CN1229692C - Photo-corrosion-resisting agent composition - Google Patents
Photo-corrosion-resisting agent composition Download PDFInfo
- Publication number
- CN1229692C CN1229692C CN 01144640 CN01144640A CN1229692C CN 1229692 C CN1229692 C CN 1229692C CN 01144640 CN01144640 CN 01144640 CN 01144640 A CN01144640 A CN 01144640A CN 1229692 C CN1229692 C CN 1229692C
- Authority
- CN
- China
- Prior art keywords
- acid
- alkyl
- methyl
- polymerization
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a photoresist. The present invention discloses a photoimaging composition containing organic acid and capable of improving a cleaning characteristic and also discloses a method for improving the cleaning characteristic of the photoimaging composition and a method of manufacturing a printed circuit board by using the photoimaing composition.
Description
Technical field
The present invention relates to the field of photoresist.Particularly, the present invention relates to have the photoresist of removing characteristic, be specially adapted to the manufacturing of printed-wiring board (PWB) through improving.
Background technology
Photoresist is in order to image is gone to the photosensitive film of substrate.On substrate, form the photoresist coating, then see through light shield and make the exposure of photoresist layer with activating radiation.It is opaque to activating radiation that light shield has some zone, and other zone is transparent to activating radiation.Be exposed to activating radiation and can provide photo-induced chemical conversion in the photoresist coating, with the image transfer of light shield to the photoresist coating base plate.After the exposure, make development of photoresist can make substrate carry out the relief image that selectivity is handled to provide.
Photoresist can be positive effect or negative effect.With regard to negative effect photoresist, be exposed to the coating area of activating radiation, produce polymerization or cross-linking reaction between the polymerization agent of its photo-corrosion-resisting agent composition and Photoactive compounds.Therefore, coating is insoluble in developer solution through exposed areas than unexposed area.With regard to positive effect photoresist, be soluble in the developer solution through exposed areas, unexposed zone is insoluble in developer relatively and is residual.Generally speaking, photo-corrosion-resisting agent composition comprises resin binder composition and photolytic activity reagent at least.
Multiple different polymerization or resin binder can be used for photoresist.This kind polymerization binder can comprise one or more sour functional monomers, as acrylic or methacrylic acid, as the polymerization composition.For example, United States Patent (USP) the 5th, 952, No. 153 (Lundy et al.) disclosed smooth imaging compositions contain enough functionality acid as the polymerization binder, and light imaging composition can be developed in alkaline aqueous solution.United States Patent (USP) the 4th, 537, No. 855 (Ide) discloses, and using polycarboxylic acid and ethene is that unsaturated compound forms polymerisable ester derivant.The polymerisable ester derivant of this kind is the polymerization binder that is used for forming light imaging composition.
Photoresist can be liquid or dry film.Photoresist liquid disposes earlier to then curing of substrate.The photoresist dry film typically can be superimposed to substrate.This kind photoresist dry film is specially adapted to the manufacturing of printed-wiring board (PWB).The problem of known photoresist dry film composition is the circuit board that is difficult to from metallide, uses known buck dissolubility to remove solution (for example, 3% sodium hydroxide solution) and removes.This problem is because the fabricator of printed circuit board (PCB) is caused by increasing its functional volume that dwindles printed circuit board (PCB).Therefore, when more the multicircuit loop need be contained in less space, the circuitry lines of circuit board and space need constantly dwindle.Simultaneously, the height of plated metal must be higher than the thickness of photoresist.And causing metal to be suspended from photoresist, the small space that causes containing photoresist is enclosed in the plated metal in fact.Photoresist is subject to the plating cantilever, and it is difficult to by known method contact and removing.If photoresist is not removed fully or removed, after etching, can cause unfavorable roughened copper circuitry lines, and cause the short circuit of plank.
Partial circuit plate fabricator increase to electroplate under the situation that height can hold, and attempts increasing the thickness of photoresist, yet this kind method is costliness and make the resolution of circuitry lines limited comparatively.Particularly, use based on the alkalescence of organic (containing amine or organic solvent) and remove solution, can produce small removing particle and help removing.Therefore, it is preferable to remove photoresist by this kind based on organic removing thing, but it is with respect to comparatively expensive based on inorganic removing thing (for example, NaOH or potassium), and has considering of more relevant offal treatment and environment aspect.Owing to the restriction of factory management rule or for reducing dispersing of solvent, can remove the also imperfect person of photoresist of solvent.
Therefore, but still expectation the photo-corrosion-resisting agent composition of a kind of use based on inorganic buck dissolubility removing solution easy removal is provided.
Summary of the invention
Shockingly find, add one or more non-polymerization organic acids, can provide to have through the removing of improvement or the light imaging composition of removing property.Find shockingly that again this kind non-polymerization organic acid can't produce adverse influence to other characteristic (for example, chemoresistance) of photoresistance binder.Therefore, composition of the present invention does not contain non-polymerization organic acid same combination with other to be compared, and shows the removing through improving under the situation of the impairment of essence not chemoresistance.
On the one hand, the invention provides a kind of photo-corrosion-resisting agent composition, this photo-corrosion-resisting agent composition comprises polymerization binder, photolytic activity composition, organic acid and crosslinking chemical optionally, and wherein, organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization.
On the other hand, the invention provides a kind of enhancement removes photo-corrosion-resisting agent composition from substrate method, comprise the step that photo-corrosion-resisting agent composition is combined with organic acid, this photo-corrosion-resisting agent composition comprises polymerization binder, photolytic activity composition and crosslinking chemical optionally, wherein, organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization.
Again on the other hand, the invention provides a kind of method of making printed-wiring board (PWB), comprise the following step: a) on the substrate of printed-wiring board (PWB), dispose photo-corrosion-resisting agent composition, this photo-corrosion-resisting agent composition comprises polymerization binder, photolytic activity composition, organic acid and crosslinking chemical optionally, wherein, organic acid and polymerization binder and crosslinking chemical optionally are non-polymerization; B) make the photoresist imaging; And c) makes development of photoresist.
Embodiment
In this instructions, except as otherwise noted, following abbreviation is following meaning: ℃=degree centigrade; The g=gram; The mg=milligram; Tg=glass transition temperature; °F=Fahrenheit temperature; Wt%=weight %; And mil=0.001 inch.
" resin " reaches " polymkeric substance " and can be used alternatingly in this manual." alkyl " speech is meant straight chain, side chain and cyclic alkyl." halogen " reaches " halogen " and comprises fluorine, chlorine, bromine and iodine.Therefore, " halogenation " be meant fluoridize, chlorination, bromination and iodate." polymkeric substance " is meant homopolymer and multipolymer and comprises dipolymer, trimer, oligomer etc." (methyl) acrylate " be meant acrylate and methacrylate the two.In like manner, " (methyl) acrylic acid " be meant acrylic acid and methacrylic acid the two." monomer " is meant to appoint and closes polymerisable ethene system or acetylene is unsaturated compound." cross-linking agent " reaches " crosslinking chemical " and can be used alternatingly in this manual." printed-wiring board (PWB) " reaches " printed circuit board (PCB) " and can be used alternatingly in this manual.
Except as otherwise noted, all amounts are weight %, and all proportions is weight ratio.All digital scopes are and comprise and for capable of being combined.
Photo-corrosion-resisting agent composition of the present invention comprises polymerization binder, photolytic activity composition, organic acid and crosslinking chemical optionally, and wherein, organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization.
Multiple polymerization binder is applicable to the present invention.The polymerization binder that is fit to is to contain one or more ethene systems or propylene is that unsaturated monomer is as the polymeric unit person.The monomer that is fit to comprises, but non-being limited to: (methyl) acrylic acid, (methyl) acrylamide, alkyl (methyl) acrylate, thiazolinyl (methyl) acrylate, aromatic series (methyl) acrylate, vinyl aromatic monomers, nitrogen-containing compound and sulfur analogs thereof, the vinyl monomer that is substituted, cyclic olefin, the cyclic olefin that is substituted etc.Preferred monomer comprises: (methyl) acrylic acid, alkyl (methyl) acrylate and vinyl aromatic monomers.These polymerization binders can be homopolymer or multipolymer, and are good with multipolymer.Further can understand, the binder mixture of polymers also can be used for the present invention.Therefore, smooth imaging composition of the present invention can comprise one or more polymerization binders.
Particularly, can be used for alkyl of the present invention (methyl) acrylate is (C
1-C
24) alkyl (methyl) acrylate.Alkyl (methyl) acrylate that is fit to comprises, but is not limited to: " low cut (lowcut) " alkyl (methyl) acrylate, " middle cut " alkyl (methyl) acrylate and " high cut " alkyl (methyl) acrylate.
" low cut " alkyl (methyl) acrylate is meant that generally alkyl contains 1 to 6 carbon atom.Low cut alkyl (methyl) acrylate that is fit to comprises, but is not limited to: methyl methacrylate (" MMA "), methyl acrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate (" BMA "), butyl acrylate (" BA "), isobutyl methacrylate (" IBMA "), hexyl methacrylate, cyclohexyl methyl acrylate, cyclohexyl acrylate and composition thereof.
" middle cut " alkyl (methyl) acrylate is meant that generally alkyl contains 7 to 15 carbon atoms.Middle cut alkyl (methyl) acrylate that is fit to comprises, but be not limited to: (" IDMA " is with side chain (C for 2-ethylhexyl acrylate (" EHA "), 2-ethylhexyl methacrylate, octyl group methacrylate, decyl first acrylate, isodecyl methacrylate
10) the alkyl isomeric compound is main potpourri), undecyl methacrylate, dodecyl methyl acrylate (bay methacrylate just), tridecyl methacrylate, myristyl methacrylate (nutmeg methacrylate just), pentadecyl methacrylate and composition thereof.Useful especially potpourri comprises 12-ten pentamethyl acrylate (" DPMA "); 12,13,14 and the straight chain of pentadecyl methacrylate and the potpourri of side chain isomeric compound; And bay-nutmeg methacrylate (" LMA ").
" high cut " alkyl (methyl) acrylate is meant that generally alkyl contains 16 to 24 carbon atoms.High cut alkyl (methyl) acrylate that is fit to comprises, but is not limited to: cetyl methacrylate, heptadecyl methacrylate, octadecyl methyl acrylate, nonadecyl methacrylate, cosyl methacrylate, eicosyl methacrylate and composition thereof.Useful especially high cut alkyl (methyl) acrylate potpourri comprises, but is not limited to: spermaceti-eicosyl methacrylate (" CEMA "), and it is 16,18, the potpourri of cosyl and eicosyl methacrylate; And spermaceti-stearic methacrylate (" SMA "), it is 16 and the potpourri of octadecyl methyl acrylate.
Alkyl (methyl) acrylate monomer of cut and high cut in above-mentioned, it generally is esterification preparation by standard, with the long refining aliphatic alcohol preparation of technical grade, and these commercially available alcohols that get are to contain between carbon number 10 and 15 in alkyl or the potpourri of the alcohols that the refining of the difference between 16 and 20 is long.The example of these alcohols is: the various Ziegler catalysis ALFOL alcohols of Vista chemical company, i.e. ALFOL 1618 and ALFOL 1620; The various Ziegler catalyzing N EODOL alcohols of Shell chemical company, promptly NEODOL 25L reaches spontaneous alcohols such as Proctor ﹠amp; The TA-1618 of Gamble and CO-1270.Therefore, for the purposes of the present invention, alkyl (methyl) acrylate tends to not only comprise each alkyl (methyl) acrylate product of being mentioned, also comprise alkyl (methyl) acrylate and the potpourri of the main especially alkyl of mentioning (methyl) acrylate.
Used in the present invention alkyl (methyl) acrylate monomer can be monomer or the potpourri that has different number carbon atoms at moieties.In addition, used (methyl) acrylamide and alkyl (methyl) acrylate monomer of the present invention can optionally be substituted.The selectivity that is fit to be substituted (methyl) acrylamide and alkyl (methyl) acrylate monomer comprise, but be not limited to: hydroxyl (C
2-C
6) alkyl (methyl) acrylate, dialkyl amino (C
2-C
6) alkyl (methyl) acrylate, dialkyl amino (C
2-C
6) alkyl (methyl) acrylamide.
The useful especially alkyl that is substituted (methyl) acrylate monomer is meant that one or more hydroxyl is arranged in alkyl, particularly those beta-positions (2-position) in alkyl have hydroxyl.At hydroxyalkyl (methyl) the propylene ester monomer alkyl substituent that is substituted wherein with branch or there is not (the C of branch
2-C
6) alkyl is good.Hydroxyalkyl (methyl) the propylene ester monomer that is fit to comprises, but is not limited to: 2-hydroxyethyl meth acrylate (" HEMA "), 2-hydroxy ethyl methacrylate (" HEA "), 2-hydroxypropyl methyl acrylate, 1-methyl-2-hydroxyethyl meth acrylate, 2-hydroxyl-propyl group acrylate, 1-methyl-2-hydroxy ethyl methacrylate, 2-hydroxyl butyl methyl acrylate, 2-hydroxyl butylacrylic acid ester and composition thereof.Preferred hydroxyalkyl (methyl) acrylate monomer is HEMA, 1-methyl-2-hydroxyethyl meth acrylate, 2-hydroxypropyl methyl acrylate and composition thereof.The potpourri of last two kinds of monomers typically refers to " hydroxypropyl methyl acrylate " or HPMA.
Other can be used for (methyl) acrylate that is substituted of the present invention and (methyl) acrylamide monomer is meant at alkyl to have dialkyl amino or dialkylaminoalkyl group.The example of (methyl) acrylate that these are substituted and (methyl) acrylamide comprises; but be not limited to: the dimethyl aminoethyl methacrylate; the dimethyl aminoethyl acrylate; N; N-dimethyl aminoethyl Methacrylamide; N; N-dimethyl-amine propyl methyl acid amides; N; N-dimethyl amine butyl methyl acrylamide; N; N-diethylamide ethyl-methyl acrylamide; N; N-diethylamide propyl methyl acid amides; N; N-diethylamide butyl methyl acrylamide; N-(1; 1-dimethyl-3-oxygen-butyl) acrylamide; N-(1,3-diphenyl-1-ethyl-3-oxygen-butyl) acrylamide; N-(1-methyl isophthalic acid-phenyl-3-oxygen-butyl) Methacrylamide and 2-hydroxyethyl acrylamide; the N methacrylamide of amine ethylethylene urea; N-methacryl oxygen ethyl morpholine; the N-of dimethyl amine propylamine is along butyryl diene imines and composition thereof.
Can be used for (methyl) acrylate monomer that other is substituted of the present invention is siliceous monomer, for example γ-propyl group three (C
1-C
6) alkoxysilane group (methyl) acrylate, γ-propyl group three (C
1-C
6) alkyl tin groups, alkyl silane groups (methyl) acrylate, γ-propyl group two (C
1-C
6) alkoxy (C
1-C
6) alkyl tin groups, alkyl silane groups (methyl) acrylate, γ-propyl group two (C
1-C
6) alkyl (C
1-C
6) alkoxysilane group (methyl) acrylate, vinyl three (C
1-C
6) alkoxysilane group (methyl) acrylate, vinyl two (C
1-C
6) alkoxy (C
1-C
6) alkyl tin groups, alkyl silane groups (methyl) acrylate, vinyl (C
1-C
6) alkoxy two (C
1-C
6) alkyl tin groups, alkyl silane groups (methyl) acrylate, vinyl three (C
1-C
6) alkyl tin groups, alkyl silane groups (methyl) acrylate, 2-propyl group silicon half oxygen alkane (methyl) acrylate and composition thereof.
The vinyl aromatic monomers that can be used as unsaturated monomer among the present invention comprises, but is not limited to: styrene (" STY "), oxybenzene ethene, α-Jia Jibenyixi, vinyltoluene, p-methylstyrene, vinyl xylene, ethyl vinyl benzene, vinyl naphthalene, vinyl-dimethyl benzene and composition thereof.Vinyl aromatic monomers also comprises its relative homologue that is substituted, and for example, halide derivative promptly contains one or more halogen radical, as fluorine, chlorine or bromine; And nitre, cyanogen, (C
1-C
10) alkoxy, halogen (C
1-C
10) alkyl, carbonyl (C
1-C
10) alkoxy, carboxylic, amine, (C
1-C
10) alkylamine derivative etc.
The nitrogen-containing compound and the sulphur-analog thereof that can be used as unsaturated monomer among the present invention comprise, but are not limited to: vinylpyridine, as 2-vinylpyridine or 4-vinylpridine; Low alkyl group (C
1-C
8) the N-vinylpyridine that replaces, as 2-methyl-5-vinylpyrine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine and 2-methyl-3-ethyl-5-vinylpyridine; Methyl substituted quinoline and isoquinoline; The N-caprolactam; The N-vinyl butyrate lactam; The N-vinyl pyrrolidone; Vinyl imidazole; The N-vinylcarbazole; N-vinyl-succinimide; (methyl) vinyl cyanide; Adjacent-,-or right-amine styrene; Maleimide; N-vinyl-oxazolidones; N, N-dimethyl aminoethyl-vinyl-ether; Ethyl-2-cyanoacrylate; Vinylacetonitrile; The adjacent dicarboximide of N-vinyl;-vinyl-pyrrolidone, as N-vinyl-sulphur-pyrrolidone, 3-methyl isophthalic acid-vinyl-pyrrolidinone, 4-methyl isophthalic acid-vinyl-pyrrolidinone, 5-methyl isophthalic acid-vinyl-pyrrolidinone, 3-ethyl-1-vinyl-pyrrolidinone, 3-butyl-1-vinyl-pyrrolidinone, 3,3-dimethyl-1-vinyl-pyrrolidinone, 4,5-dimethyl-1-vinyl-pyrrolidinone, 5,5-dimethyl-1-vinyl-pyrrolidinone, 3,3,5-trimethyl-1-vinyl-pyrrolidinone, 4-ethyl-1-vinyl-pyrrolidinone, 5-methyl-5-ethyl-1-vinyl-pyrrolidinone and 3,4,5-trimethyl-1-vinyl-pyrrolidinone; Vinyl pyrrole; Vinyl aniline and vinyl six hydrogen piperidines.
The vinyl monomer that can be used as the replacement of unsaturated monomer among the present invention comprises, but is not limited to: vinylacetate, vinyl formamide, vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride, inclined to one side dibromoethane, tetrafluoroethene, trifluoro-ethylene, trifluoromethyl vinylacetate, vinyl ether and decomposition rhizome of Chinese monkshood acid anhydride.
The cycloolefin monomers that is fit among the present invention is (C
5-C
10) cycloolefin, for example cyclopentene, cyclopentadiene, two cyclopentene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, cyclo-octadiene, norborene, maleic anhydride etc.This kind cycloolefin also comprises spirocyclic olefin monomer, for example volution norborny monomer, volution cyclohexene monomer, volution cycloheptene monomer and potpourri.The cycloolefin monomers that is substituted that is fit to comprises, but is not limited to: have one or more following substituent cycloolefins that are selected from: hydroxyl, aryloxy group, halogen, (C
1-C
12) alkyl, (C
1-C
12) alkylhalide group, (C
1-C
12) hydroxyalkyl, (C
1-C
12) the halogen hydroxyalkyl, as (CH
2)
N 'C (CF
3)
2OH, n ' are 0 to 4, (C
1-C
12) alkoxy, sulfenyl, amido, (C
1-C
6) alkyl amine, (C
1-C
6) dialkylamine, (C
1-C
12) alkyl sulfide, carbonyl (C
1-C
20) alkoxy, carbonyl (C
1-C
20) halogen alkoxy, (C
1-C
12) acyl group, (C
1-C
6) alkyl oxycarbonyl (C
1-C
6) alkyl etc.The cycloolefin of particularly suitable replacement comprises: maleic anhydride and contain one or more hydroxyl, aryloxy group, (C
1-C
12) alkyl, (C
1-C
12) alkylhalide group, (C
1-C
12) hydroxyalkyl, (C
1-C
12) halogen hydroxyalkyl, carbonyl (C
1-C
20) alkoxy and carbonyl (C
1-C
20) cycloolefin of halogen alkoxy.Those skilled in the art know, and alkyl and alkoxy substituent can optionally be substituted, for example with halogen, hydroxyl, cyanogen, (C
1-C
6) alkoxy, sulfhydryl, (C
1-C
6) replacement such as alkyl sulfide, amido, sour unstable leaving group.Carbonyl (the C that is fit to
1-C
20) alkoxy substituted comprising, but be not limited to: formula C (O) O-LG those shown, wherein LG is a leaving group, including but not limited to: have 4 or above carbon atom and the direct bond of at least one quaternary carbon atom alkyl to carbonylation oxygen, tertiary butyl ester, 2 for example, 3-dimethylbutyl ester, 2-methyl amyl ester, 2,3,4-tri-methyl-amyl ester, alicyclic ester, the formed acetal of vinyl ether or ketal or enol, for example-O-(CH (CH
3) OC
2H
5) or-O-(CH
2OC
2H
5), oxinane (" THP ").Be suitable as the alicyclic ester of leaving group, comprise adamantyl, methyl adamantane base, ethyl adamantyl, methyl norborny, ethyl norborny, ethyl-trimethyl norborny, ethyl fenchol etc.
Preferred again polymerization binder contains enough functionality acid, makes the bonding polymkeric substance solvable and removable after development." functionality acid " is meant with after alkaline developer contacts, can forms any functionality of salt; Alkaline developer, for example Xi Shi NaOH or potash aqueous solution are as the solution of 1 to 3 weight %.The functionality acid that is fit to comprises, but is not limited to: carboxylic acids, sulfonic acid class, phosphonic acid based and phenols.Generally speaking, binding acid number that polymkeric substance had can be up to about 250, being good up to about 200.Typical acid number scope from 15 to 250 is good with 50 to 250.This acid number be in and the amount (milligram) of the required KOH (potassium hydroxide) of bonding polymkeric substance of 1 gram (dry weight).
The polymer bonding agent that is fit to can be buied by various commercially available source, for example Rohm and Haas company (Philadelphia is Pennsylvania) or with prepared in various methods known in the document.Particularly, the content of the polymerization binder in the light imaging composition with total restatement of composition, up to 90 weight %, is good with 20 to 90 weight %, and is preferable with 25 to 85 weight %, better with 30 to 80 weight %.
Multiple different organic acid can be used for the present invention, and this organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization, binds polymkeric substance or crosslinking chemical and incorporate into.Being used for organic acid of the present invention and being essentially non-incorporating into, is good not incorporate bonding polymerizer or crosslinking chemical into.
The organic acid that is fit to comprises, but is not limited to: carboxylic acids, and as alkane carboxylic acids and aralkyl carboxylic acid class, sulfonic acid class, as alkyl sulfonic acid class and aromatic sulfonic acid class, phosphonic acid based, as alkylphosphines acids and aryl phosphine acids etc.The example of carboxylic acids comprises, but is not limited to: (C
1-C
12) the alkyl carboxylic acid class; (C
1-C
12) alkyl dicarboxylic aid's class; (C
1-C
12) alkyl tricarboxylic acids; (the C that replaces
1-C
12) the alkyl carboxylic acid class; (the C that replaces
1-C
12) alkyl dicarboxylic aid's class; (the C that replaces
1-C
12) alkyl tricarboxylic acids; The amine carboxylic acids is as ethylenediamine tetraacetic acid; The aralkyl carboxylic acid class is as fragrant monocarboxylic acid class, fragrant omega-dicarboxylic acids and fragrant tricarboxylic acids; And the aralkyl carboxylic acid class that replaces.Preferred organic acid comprises: formic acid, acetate, propionic acid, ethane diacid, malonic acid, succinic acid, glutaric acid, hexane diacid, glycolic, lactic acid, tartrate, citric acid or malic acid, ethylenediamine tetraacetic acid, acid, benzene tricarbonic acid, salicylic acid, cyclohexane-carboxylic acid, 1,4-cyclohexane dicarboxylic acid and decanedioic acid.
Those skilled in the art know, and should use more than one organic acid in composition of the present invention.Therefore, smooth imaging composition of the present invention can comprise one or more organic acids.Be familiar with this skill person and also should know, in composition of the present invention, increase this kind non-polymerization organic acid content, can substantially not detract and remove under the effectiveness, use polymerization binder with less functionality acid.Therefore, have other characteristic (as chemoresistance), but lack the polymerization binder of required removing characteristic, can be used in combination with organic acid of the present invention, so that the light imaging that easily removes composition to be provided through promoting through improving.
This organic acid generally can be buied by multiple different commercially available source, and for example (Milwaukee Wisconsin), and need not be further purified when using AldrichChemical Co..Generally speaking, composition of the present invention comprises one or more organic acid content, to bind the polymkeric substance gross dry weight, can be up to about 10 weight %, and content to be being good up to about 8 weight %, being preferable up to about 5 weight %.Particularly, the amount that exists of one or more organic acids be 0.125 weight % or more than.The amount that this organic acid exists, based on dry weight/weight, per 40 parts of polymerization binders are 0.5 to 5 part.
Be suitable for crosslinking chemical of the present invention comprise two-, three-, four-or more multi-functional ethene be unsaturated monomer.The example that is used for crosslinking chemical of the present invention comprises, but be not limited to: trivinylbenzene, divinyl toluene, the divinyl pyridine, divinyl naphthalene and divinyl dimethylbenzene, and as the ethylene glycol diacrylate, trimethylolpropane triacrylate (" TMPTA "), the diethylene glycol divinyl ether, the trivinyl cyclohexane, allyl methyl acrylate (" ALMA "), ethylene glycol dimethacrylate (" EGDMA "), diethylene glycol dimethylacrylate (" DEGDMA "), the propylene glycol dimethylacrylate, propylene glycol diacrylate, trimethylol-propane trimethacrylate (" TMPTMA "), divinylbenzene (" DVB "), glycidyl methacrylate, 2,2-dimethylpropane 1, the 3-diacrylate, 1, the 3-butanediol diacrylate, 1, the 3-butanediol dimethylacrylate, 1, the 4-butanediol diacrylate, diethylene glycol diacrylate, the diethylene glycol dimethylacrylate, 1, the 6-hexanediyl ester, 1, the 6-hexanediol dimethacrylate, tripropylene glycol diacrylate, the triethylene glycol dimethylacrylate, tetraethylene glycol diacrylate, the Macrogol 200 diacrylate, the TEG dimethylacrylate, polyethylene glycol dimethacrylate, bisphenol a diacrylate through ethoxyquin, bisphenol a dimethacrylate through oxidation, the Macrogol 600 dimethylacrylate, poly-(butylene glycol) diacrylate, isoamyl tetrol triacrylate, trimethylolpropane tris ethoxy triacrylate, the glyceryl third oxygen triacrylate, isoamyl tetrol tetraacrylate, isoamyl tetrol tetramethyl acrylate, diisoamyl tetrol monohydroxy five acrylate, diacrylate through ethoxyquin, triacrylate (as ethoxyquin TMPTA and ethoxyquin TMPTMA) through ethoxyquin, tetraacrylate through ethoxyquin, divinyl silane, trivinyl silane, dimethyl divinyl silane, the divinyl methyl-monosilane, methyl trivinyl silane, diphenyl divinyl silane, the divinyl phenyl silane, the trivinyl phenyl silane, the divinyl aminomethyl phenyl silane, tetrem thiazolinyl silane, dimethyl vinyl disiloxane, poly-(ethylene methacrylic radical siloxane), poly-(vinyl hydrogen siloxane), poly-(phenyl vinyl siloxane), glycosyl (comprise two-, three-and four-glycosyl urea), epoxies and composition thereof.These crosslinking chemicals are general commercially available getting.
Those skilled in the art know, by making light imaging composition have required characteristic in conjunction with two kinds or above crosslinking chemical.Therefore, should use the crosslinking chemical potpourri in the present invention.Photo-corrosion-resisting agent composition of the present invention is good to comprise one or more crosslinking chemicals.Particularly, in the smooth imaging composition of the present invention, the content of this kind crosslinking chemical from 5 to 75 weight % are good with 15 to 70 weight %, with 20 to 65 weight % for more preferably.
In another instantiation, one or more monomers should combine with one or more crosslinking chemicals, so that curative system to be provided.In this curative system, select one or more monomers, so that in the photoresist that solidifies, provide some required characteristic.For example, (methyl) acrylate-functional crosslinking chemical can with can combine with one or more monomers, be good with one or more (methyl) acrylate monomer." (methyl) acrylate-functional crosslinking chemical " is meant to have one or more (methyl) acrylate-based crosslinking chemical, and acrylate-based for good to have two or more (methyl), (methyl) is acrylate-based to be formula H
2C=C (H or CH
3) shown in C (O)-O-.Particularly, in curative system, select the amount of crosslinking chemical and monomer, so that required clean (methyl) acrylate-functional is provided." clean (methyl) acrylate-functional " is meant in the curing agent component, the functionality of average (methyl) acrylate.Clean (methyl) acrylate-functional of this kind is based on weight, will be many-amount of (methyl) acrylate-functional compound (being crosslinking chemical) and list-(methyl) acrylate-functional compound (i.e. (methyl) acrylate monomer) on average determines.For example, when triacrylate crosslinking chemical (as TMPTA) mixed use with acrylate monomer (promptly having a substituent compound of acrylate) with 1: 1 weight, clean (methyl) acrylate functionalities was about 2.In smooth imaging composition of the present invention, use curative system preferred as crosslinking chemical.
By selecting clean (methyl) acrylate-functional, with balance tool easy-clear or remove the light group thinner resistance of this photoresist.Generally speaking, increase the branch (promptly increasing crosslinked amount) of solidifying photoresist, can increase chemoresistance.Reduce the branch (promptly reducing crosslinked amount) of solidifying photoresist, can increase the removing of solidifying photoresist and render a service, can lower the chemoresistance of solidifying photoresist simultaneously.Surprisingly finding, is about 2 the time when clean (methyl) acrylic acid refers to functionality, and splendid chemoresistance is provided, and provides simultaneously to solidify the removing that photoresist promotes and render a service.When clean (methyl) when acrylate functionalities is higher than 2, the chemoresistance of solidifying photoresist can increase, and solidifies removing of photoresists but be unfavorable for carrying out these.When clean (methyl) when acrylate-functional is lower than 2, solidify removing effectiveness and can increasing of photoresist, but the chemoresistance that is unfavorable for solidifying photoresist.
Therefore, the invention provides a kind of enhancement and remove the method for photo-corrosion-resisting agent composition, comprise that to make clean (methyl) acrylate-functional be about 2 or the step that combines with the photo-corrosion-resisting agent composition that comprises polymerization binder and photolytic activity composition of higher hardening agent from substrate.When hardening agent comprises acrylate-functional, clean acrylate-functional with about 2 or above be good, serve as preferred with about 2.When hardening agent comprised the methacrylate functionality, clean methacrylate functionality was being good below 2.Hardening agent should comprise one or more acrylate cross linked dose, and one or more non-crosslinked acrylate monomer.Hardening agent is to comprise the triacrylate crosslinking chemical, and it is good reaching the non-crosslinked acrylate monomer.Preferred hardening agent is that the TMPTA that comprises ethoxyquin reaches 6-caprolactone and HEA reaction product as monomer as crosslinking chemical.Better again person, the weight ratio of triacrylate crosslinking chemical and non-crosslinked acrylate monomer is about 1: 1.Hardening agent is not to contain the methacrylate functionality for better.
The present invention provides a kind of smooth imaging composition again, said composition comprises one or more polymerization binder, one or more photolytic activity composition and curative system, and curative system comprises one or more crosslinking chemical and one or more monomer, and wherein clean (methyl) acrylate functionalities of curative system is about 2.
Smooth imaging composition of the present invention contains one or more photolytic activity compositions.Be used for photolytic activity composition of the present invention and can be light acid producing agent, the generation agent of light alkali or free-radical generating agent.Smooth imaging composition of the present invention can be positive effect or negative effect, act as good with negative.Those skilled in the art should know, and the photolytic activity constituents mixt can make the photolytic activity of said composition, close in specific application.
The light acid producing agent that is fit to comprises halogenation triazines, salt, sulfonated ester class, halogenation sulfonyloxy dicarboxylic acid imides class, diazonium two sulfone classes, α-cyanogen oxygen amine sulfonic acid esters, acid imide sulfonic acid esters, ketone diazonium sulfone class, sulfonyl diazo ester class, 1,2-(arylsulfonyl) class etc.Useful especially halogenation triazines comprises halomethyl-S-triazines.
The free-radical generating agent that is fit to comprises, but be not limited to: n-phenyl Gly, aromatic series ketone, as diphenylketone, N, N '-tetramethyl-4,4 '-diamines diphenylketone " Michler ' s ketone ", N, N '-tetraethyl-4,4 '-diamines diphenylketone, 4-methoxyl-4 '-dimethyl amine diphenylketone, 3,3 '-dimethyl-4-methoxyl diphenylketone, p, p '-two (dimethyl amine) diphenylketone, p, p '-two (diethylamide) diphenylketone, anthraquinone, 2-EAQ, naphthoquinones and phenanthrenequione; The diphenylhydroxyethanone class is as diphenylhydroxyethanone, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ethylether, diphenylhydroxyethanone isopropyl ether, diphenylhydroxyethanone n-butyl ether, diphenylhydroxyethanone phenyl ether, methyldiphenyl ethanol ketone and ethyl diphenylhydroxyethanone; The benzyl derivant is as benzhydryl, benzyl phenyl disulfide and benzyl dimethyl ketal; Acridine derivatives, as 9-phenylacridine and 1, two (9-acridinyl) heptane of 7-; The 9-oxygen dibenzo sulphur croak class of muttering, as 2-chloro-9-oxygen dibenzo sulphur croak mutter, 2-methyl-9-oxygen dibenzo sulphur croak is muttered, 2,4-diethyl-9-oxygen dibenzo sulphur croak mutters, 2, the 4-dimethyl-9-oxygen dibenzo sulphur croak is muttered and 2-isopropyl-9-oxygen dibenzo sulphur croak is muttered; The acetophenone class, as 1,1-ww-dichloroacetophenone, p-tributyl two chloro-acetophenones, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone and 2,2-two chloro-4-phenoxy group acetophenones; 2,4,5-triarylimidazoles dipolymer, as 2-(neighbour-chlorphenyl)-4,5 diphenyl-imidazole dipolymers, 2-(neighbour-chlorphenyl)-4,5-two (-anisyl) imidazole dimer, 2-(ortho-fluorophenyl base)-4,5-diphenyl-imidazole dipolymer, 2-(neighbour-anisyl)-4,5-diphenyl-imidazole dipolymer, 2-(right-anisyl)-4,5-diphenyl-imidazole dipolymer, 2,4-two (right-anisyl)-5-phenylimidazole dipolymer, 2-(2, the 4-dimethoxy phenyl)-4,5-diphenyl-imidazole dipolymer and 2-(right-methyl hydrogen sulfenyl phenyl)-4,5-diphenyl-imidazole dipolymer etc.Yet free-radical generating agent (triphenylphosphine) is not to be contained in the photolytic activity chemical system as catalyzer.This kind free-radical generating agent is suitable for negative to do to use with light imaging composition, does to use preferred with light imaging composition dry film in negative of the present invention.
Particularly, the amount of this photoreactive compositions is counted 0.05 to 10 weight % with the composition gross weight, is good with 0.1 to 5 weight %, and is preferred with 0.1 to 2 weight %.
Smooth imaging composition of the present invention, visual need contain solvent.The solvent that is fit to comprises, but is not limited to: the ketone solvent class, as ethyl ketone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; Polyalcohols and derivant thereof, as ethylene glycol, glycol monomethyl ethyl ester, diethylene glycol, diethylene glycol mono ethyl ester, propylene glycol, propylene glycol mono ethyl ester, dipropylene glycol and dipropylene glycol mono ethyl ester, with and monomethyl, single ethyl, single propyl group, monobutyl and single phenyl fan; The cyclic ethers kind solvent is as diox; Esters solvent is as methyllactic acid ester, Solactol ester, methyl acetic acid ester, ethylhexoate, butylacetic acid ester, methyl acetone acid esters, ethyl acetone acid esters, methyl methoxy base propionic ester and ethyl ethoxy-c acid esters; Amide solvent, as N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-; 3-ethoxyethyl propionic ester; The 2-heptanone; Gamma-butyrolacton and composition thereof.
The adjuvant that optionally can be used for smooth imaging composition of the present invention comprises, but is not limited to: anti-striped agent, plasticiser, speed promoting agent, filling material, dyestuff, plastic film agent, the photoresist that contains the hydrophobicity trihalomethyl remove to be promoted thing etc.The plasticiser that is fit to comprises the ester class, as benzoate.Smooth imaging composition of the present invention should add one or more photoresist that contains the hydrophobicity trihalomethyl and remove the enhancement thing.The photoresist that contains the hydrophobicity trihalomethyl that is fit to is removed the enhancement thing and is comprised the multiple different compounds that contain trihalomethyl, is hydrolyzed to the carboxylate anion in the photoresistance reset procedure.The photoresist removing enhancement thing that this kind contains the hydrophobicity trihalomethyl is preferably α-trisbromomethyl phenylmethyl acetic acid ester.These adjuvants optionally can be present in the photo-corrosion-resisting agent composition with multiple concentration.For example, filling material and dyestuff can use with a large amount of relatively concentration, and for example with total restatement of composition dry ingredients, its amount is about 5 to 30 weight %.
Photo-corrosion-resisting agent composition of the present invention typically with any order in conjunction with polymerization binder, photolytic activity composition, organic acid, optionally crosslinking chemical, optionally solvent and adjuvant optionally and prepare.
The processing procedure of smooth imaging of the present invention or photo-corrosion-resisting agent composition can be any known method.In the typical method, be applied to the photoresist layer of substrate, can form or transfer the photoresist layer to by fluid composition by dry film.When using the liquid photoresist composition, can as methods such as spin coating, dip-coating, roller coating, it be applied to substrate by any known method.
Photo-corrosion-resisting agent composition of the present invention can be used for making the used multiple substrate of electronic original part (as printed-wiring board (PWB) and integrated circuit).The substrate that is fit to comprises: the wafer that the copper surface of copper coating plate, the internal layer of printed-wiring board (PWB) and skin, manufacturing integrated circuit are used etc.
After photoresist is applied to substrate, make its imaging or see through suitable pattern to be exposed to the activating radiation source.In the example of negative effect photoresist, the activating radiation source can make the crosslinking chemical polymerization of exposure area, produces the cross-linked structure of anti-developer.The person of connecing utilizes the alkaline aqueous solution of dilution that composition is developed.The developer that is fit to comprises NaOH or the potassium hydroxide aqueous solution of 1 to 3 weight %.Can use based on organic developer (as, tetraalkylammonium hydroxides alkaline developer), but this not preferred person.In the process of developing, the acidic groups that binds polymkeric substance can form salt, and makes the bonding polymkeric substance solvable or removable.
Negative effect photoresist is applied in the example on copper surface of copper coating plate, can use etchant after development, and the zone that copper oneself is removed photoresist removes, and forms P.e.c..Then remove residual photoresist with scavenger.
Therefore, the invention provides a kind of method of making printed-wiring board (PWB), comprise the following step: a) on the substrate of printed-wiring board (PWB), dispose photo-corrosion-resisting agent composition, said composition comprises polymerization binder, photolytic activity composition, organic acid and crosslinking chemical optionally, wherein, organic acid and polymerization binder and crosslinking chemical optionally are non-polymerization; B) make the photoresist imaging; And c) makes development of photoresist.
Photo-corrosion-resisting agent composition of the present invention is compared to generally not containing the removing property that non-polymerization organic acid photoresist shows enhancement.Therefore, the present invention also provides a kind of enhancement to remove the method for photo-corrosion-resisting agent composition from substrate, comprise the step that photo-corrosion-resisting agent composition is combined with organic acid, this photo-corrosion-resisting agent composition comprises polymerization binder, photolytic activity composition and crosslinking chemical optionally, wherein, organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization.
Find shockingly that again this kind non-polymerization organic acid can't produce adverse influence to other characteristic (for example, chemoresistance) of photoresistance binder.Therefore, photo-corrosion-resisting agent composition of the present invention is compared to containing non-polymerization organic acid same combination, shows the removing through improving under the situation of essence impairment chemoresistance not.
Following embodiment further describes various viewpoint of the present invention, is not to limit the scope of the invention anyways.
Embodiment
Embodiment 1
The amount of associative list 1 listed each composition prepares three kinds of negative effect photo-corrosion-resisting agent composition dry film sample A-C.Polymeric binder is functionality acid.The potpourri that uses ethoxyquin TMPTA is as hardening agent, and 6-caprolactone and HEA reaction product be as hydroxyl functionality list-acrylate monomer, and with 1: 1 part by weight mixing, making its clean acrylate functionalities was about 2.Use the potpourri of three kinds of free-radical generating agent to open the beginning system as light.In each sample, use two kinds and adhere to the potpourri that promotes thing.The photoresist that add trichloromethyl phenylmethyl acetic acid ester (" TCMBA ") in sample C, contains the hydrophobicity trihalomethyl is removed and is promoted thing.Used dyestuff bag is a phototropy agent dye mixture.Sample A to C is prepared as the photoresist dry film respectively according to known process technique.
Table 1
| Sample | A | B | C |
| (methyl) acrylic ester adhesive polymkeric substance 1 (g) | 0 | 0 | 40 |
| (methyl) acrylic ester adhesive polymkeric substance 3 (g) | 30 | 30 | 0 |
| (methyl) acrylic ester adhesive polymkeric substance 4 (g) | 10 | 10 | 0 |
| Hardening agent (g) | 30 | 30 | 28 |
| Light initiator system (g) | 4 | 4 | 6 |
| Decanedioic acid (g) | 0 | 3 | 0 |
| 1,4-cyclohexane dicarboxylic acid (g) | 3 | 0 | 2 |
| TCMBA(g) | 0 | 0 | 0 |
| Adhesion promoter (g) | 0.1 | 0.1 | 0.1 |
| Dyestuff bag (g) | 0.6 | 0.6 | 0.6 |
| Other compound (g) | 0.3 | 0.3 | 0.3 |
Embodiment 2
The sample A to C of embodiment 1 is applied to the separation panel.Comparative sample C-1 and C-2 are applied to the separation panel.Each panel is handled in an identical manner, also promptly uses identical preplating program, cleaning procedure etc.Comparative sample C1 is that the commercially available negative effect that gets is electroplated the photoresist dry film (available from (Marlborough of Shipley company, MA)), the light that comprises sour functionality (methyl) acrylate binder, the hardening agent that comprises crosslinking chemical and single (methyl) acrylate, generation free radical opens the beginning system, reaches the dyestuff bag.Comparative sample C1 does not contain the non-polymerization organic acid, does not contain any photoresist that contains the hydrophobicity trihalomethyl yet and removes the enhancement thing.Comparative sample C2 is the commercially available plating photoresist dry film (RISTON that gets
TM9020) (, and do not contain non-polymerization organic acid and the contained any photoresist removing enhancement thing that contains the hydrophobicity trihalomethyl of C1 available from Dupont PrintedCircuits (Wilmingto, DE)).
Electroplate usefulness and photoresist checkout time with photoresist sidewall outward appearance, copper/tin after the development limit, exposure rate (photospeed), the contrast of exposure back, the development, assessment contains the panel of the photoresist of sample A to C and comparative sample C-1 and C-2.Assessment result is listed in table 2.With Stouffer 21 step wedges (copper 9) in 50% (be that eccysis is unexposed cause resist midway, see through the development chamber) judge exposure rate.The contrast of exposure back is the aberration with visual examination panel exposure region and unexposed area, grade " 1 " expression the best.
Photoresist sidewall outward appearance after the development is to judge with sweep electron microscope.Scanning electron micrograph after the exposure of assessment panel corrodes and/or the pedestal grade with the side of judging the photoresist sidewall.Sidewall grade " 1 " expression does not have side in fact corrodes or pedestal, and grade " 2 " or " 3 " expression photoresist sidewall have the part side to corrode or pedestal.
It is the plating of measuring photoresist that copper/tin (" Cu/Sn ") is electroplated usefulness.According to this kind effect test, check that whether vertical electro-coppering trace judge photoresist eccysis.Eccysis with bottom electrical copper facing decidable photoresist.Each panel is washed into one square centimeter, by the amount of optical microscope with the plating of visual examination bottom.Grade " 1 " expression does not have the bottom in fact electroplates, and electroplate grade " 2 " or " 3 " expression bottom in various degree.
The photoresist checkout time is to use 3% sodium hydroxide in 130 °F, removes or remove the required second number of photoresist fully.
Table 2
| Sample | A | B | C | C-1 * | C-2 * |
| The development limit (second) | 35.9 | 31.5 | 25.9 | 24.8 | 25.1 |
| Exposure rate (Cu 9,50%) (mj/cm 2) | 120 | 84 | 60 | 84 | 84 |
| The contrast of exposure back | 1 | 1 | 1 | 3 | 2 |
| Post-develop causes resist sidewall outward appearance | 1 | 1 | 1 | 3 | 1 |
| Copper/tin is electroplated usefulness | 1 | 1 | 1 | 1 | 2 |
| Photoresist checkout time (second) | 31.7 | 35.8 | 35.7 | 50.3 | 52.2 |
Above-mentioned data clearly illustrate that the dry film photoresist that photo-corrosion-resisting agent composition of the present invention is more known has the performance of improvement, and more known photoresist can obviously remove apace.
Claims (9)
1. photo-corrosion-resisting agent composition, comprise polymerization binder, photolytic activity composition, organic acid and crosslinking chemical optionally, wherein, organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization, and described organic acid is selected from carboxylic acid or sulfonic acid, wherein based on the dry weight of polymerization binder, per 40 parts of polymerization binders are 0.5 to 5 part.
2. composition as claimed in claim 1 is characterized in that described organic acid is selected from alkanoic acid, aralkyl carboxylic acid, alkanesulfonic acid or aromatic sulfonic acid.
3. composition as claimed in claim 2 is characterized in that described organic acid is selected from (C
1-C
12) alkyl carboxylic acid, (C
1-C
12) alkyl dicarboxylic aid, (C
1-C
12) (the C of alkyl tricarboxylic acids, replacement
1-C
12) (the C of alkyl carboxylic acid, replacement
1-C
12) (the C of alkyl dicarboxylic aid, replacement
1-C
12) aralkyl carboxylic acid of alkyl tricarboxylic acids, amine carboxylic acid, fragrant dicarboxylic acid or replacement.
4. an enhancement removes the method for photo-corrosion-resisting agent composition from substrate, comprise the step that photo-corrosion-resisting agent composition is combined with organic acid, this photo-corrosion-resisting agent composition comprises polymerization binder, photolytic activity composition and crosslinking chemical optionally, it is characterized in that organic acid and polymerization binder, crosslinking chemical optionally or both are non-polymerization, and described organic acid is selected from carboxylic acid or sulfonic acid, wherein based on the dry weight of polymerization binder, per 40 parts of polymerization binders are 0.5 to 5 part.
5. method as claimed in claim 4 is characterized in that described organic acid is selected from alkanoic acid, aralkyl carboxylic acid, alkanesulfonic acid or aromatic sulfonic acid.
6. method as claimed in claim 5 is characterized in that described organic acid is selected from (C
1-C
12) alkyl carboxylic acid, (C
1-C
12) alkyl dicarboxylic aid, (C
1-C
12) (the C of alkyl tricarboxylic acids, replacement
1-C
12) (the C of alkyl carboxylic acid, replacement
1-C
12) (the C of alkyl dicarboxylic aid, replacement
1-C
12) aralkyl carboxylic acid of alkyl tricarboxylic acids, amine carboxylic acid, fragrant dicarboxylic acid or replacement.
7. method of making printed-wiring board (PWB), comprise the following steps: a) on the substrate of printed-wiring board (PWB), to dispose photo-corrosion-resisting agent composition, this photo-corrosion-resisting agent composition comprises polymerization binder, photolytic activity composition, organic acid and crosslinking chemical optionally, it is characterized in that organic acid and polymerization binder and crosslinking chemical optionally are non-polymerization, and described organic acid is selected from carboxylic acid or sulfonic acid, wherein based on the dry weight of polymerization binder, per 40 parts of polymerization binders are 0.5 to 5 part; B) make the photoresist imaging; And c) makes development of photoresist.
8. method as claimed in claim 7 is characterized in that described organic acid is selected from alkanoic acid, aralkyl carboxylic acid, alkanesulfonic acid or aromatic sulfonic acid.
9. method as claimed in claim 8 is characterized in that described organic acid is selected from (C
1-C
12) alkyl carboxylic acid, (C
1-C
12) alkyl dicarboxylic aid, (C
1-C
12) (the C of alkyl tricarboxylic acids, replacement
1-C
12) (the C of alkyl carboxylic acid, replacement
1-C
12) (the C of alkyl dicarboxylic aid, replacement
1-C
12) aralkyl carboxylic acid of alkyl tricarboxylic acids, amine carboxylic acid, fragrant dicarboxylic acid or replacement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01144640 CN1229692C (en) | 2001-12-21 | 2001-12-21 | Photo-corrosion-resisting agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01144640 CN1229692C (en) | 2001-12-21 | 2001-12-21 | Photo-corrosion-resisting agent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1427307A CN1427307A (en) | 2003-07-02 |
| CN1229692C true CN1229692C (en) | 2005-11-30 |
Family
ID=4677727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01144640 Expired - Lifetime CN1229692C (en) | 2001-12-21 | 2001-12-21 | Photo-corrosion-resisting agent composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1229692C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105301904B (en) * | 2015-11-16 | 2017-05-31 | 北京中科紫鑫科技有限责任公司 | A kind of photoetching compositions and preparation method thereof |
-
2001
- 2001-12-21 CN CN 01144640 patent/CN1229692C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1427307A (en) | 2003-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1170207C (en) | Phenol-alicyclic copolymer and photoresist | |
| CN1171125C (en) | Copolymer with nitrile and alcyl group and photoresist composite containing the copolymer | |
| CN100343758C (en) | Electroplating method | |
| WO2005098541A1 (en) | Top coat composition | |
| TW201005440A (en) | Positive radiation-sensitive composition and process for producing resist pattern using the same | |
| KR20000047909A (en) | Itaconic anhydride polymers and photoresist compositions comprising same | |
| CN102109760A (en) | Resist pattern forming method | |
| KR20120012792A (en) | Radiation-sensitive resin composition, polymer used therein, and compound used therein | |
| CN1252541C (en) | Photoresist composition containing cycloolefine polymer and hydrophobic-non-stero superfatted cyclic additive | |
| CN1975577A (en) | Photosensitive composition | |
| CN1384399A (en) | Photoresist composition | |
| TW201106103A (en) | Radiation-sensitive resin composition, polymer and method for forming resist pattern | |
| TW201831997A (en) | Active light sensitive or radiation sensitive resin composition, resist film, method for forming pattern, and method for manufacturing electronic device | |
| CN1229692C (en) | Photo-corrosion-resisting agent composition | |
| CN1335945A (en) | Composition for antireflection coating | |
| JP3743986B2 (en) | Radiation sensitive resin composition | |
| CN1232884C (en) | Photoresisting agent composition | |
| US20030022098A1 (en) | Photoresist composition | |
| EP1209528B1 (en) | Photoresist composition | |
| JP2548016B2 (en) | Photopolymerizable laminate | |
| CN1310090C (en) | Polymers and photoresist compositions | |
| JP2690494B2 (en) | Photoresist composition | |
| JP4488601B2 (en) | Photosensitive resin laminate | |
| JPH07140650A (en) | Photosensitive resin composition and photosensitive film using the same | |
| JP3795872B2 (en) | Photosensitive resin composition and photosensitive element using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ETERNAL TECHNOLOGIES CO., LTD. Free format text: FORMER OWNER: ROHM AND HAAS ELECTRONIC MATERIALS, LLC Effective date: 20100826 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee |
Owner name: ROHM AND HAAS ELECTRONIC MATERIALS, LLC Free format text: FORMER NAME: HIPPLY CO. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: MASSACHUSETTS, U.S.A. TO: VIRGINIA, U.S.A. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Massachusetts, USA Patentee after: Rohm and Haas Electronic Materials Address before: Massachusetts, USA Patentee before: SHIPLEY CO.,LLC |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100826 Address after: Virginia Patentee after: Changxin Technology Co. Address before: Massachusetts, USA Patentee before: Rohm and Haas Electronic Materials |
|
| CX01 | Expiry of patent term |
Granted publication date: 20051130 |
|
| CX01 | Expiry of patent term |