CN101776845A - Light-sensitive resin composition and manufacturing method of etched basal body - Google Patents
Light-sensitive resin composition and manufacturing method of etched basal body Download PDFInfo
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- CN101776845A CN101776845A CN200910215323A CN200910215323A CN101776845A CN 101776845 A CN101776845 A CN 101776845A CN 200910215323 A CN200910215323 A CN 200910215323A CN 200910215323 A CN200910215323 A CN 200910215323A CN 101776845 A CN101776845 A CN 101776845A
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Abstract
The invention provides a light-sensitive resin composition, which has sufficient medicament resistance and favorable peeling character, and can be used to obtain a resin pattern displaying good adhesivity between the metal membrane on the base material. The invention also provides a manufacturing method of the of etched basal body using the resin pattern. The inventive light-sensitive resin composition includes: an alkaline soluble resin generated by reacting part of acid group come from acrylic resin containing acid group and epoxy group come from unsaturated compound containing alicyclic epoxy group; a multifunctional monomer with more than three functions; a single function monomer containing nitrogen; and a photopolymerization initiator.
Description
Technical field
The present invention relates to the manufacture method of photosensitive polymer combination and etched basal body.
Background technology
In recent years, owing to improve day by day to the requirement that increases the picture resolution and to the requirement that electronic product is installed more to high-density, the miniaturization and the densification that therefore are used to install the distributions such as printed base plate of the distribution that drives display device such as plasma display panel, electronic product also develop.These distributions adopt following method to form: the photolithograph art forms the resin pattern that is known as etching mask being provided with on the substrate surface of even metal film, then, adopt will the not be covered metal film of etching mask of etching and processing to remove (for example with reference to patent documentation 1).Then, after etching and processing finishes, remove the resin pattern that uses as etching mask, the distribution after finishing little processing on the substrate with alkaline stripper.
Wherein, be used for the metal of distribution, can use various metals, also can use the lamination metal distribution (for example with reference to patent documentation 2) that is laminated with multiple dissimilar metals as required according to electrical specification of necessity etc.Like this, can be various as the metal of etch target, the etching solution that is used for etching and processing also can be various etching solutions such as acidity or alkalescence.And, according to circumstances,, also use multiple etching solution to carry out interim etching and processing sometimes for the lamination metal film that is laminated with multiple dissimilar metals film.Therefore, to the resin pattern that uses as etching mask, has the resistance to chemical reagents (elching resistant) that employing is acid, alkaline etching liquid also can not be stripped from even require.
When giving resistance to chemical reagents, can increase the cross-linking density of resin pattern inside to the resin pattern that uses as etching mask.Like this, can prevent medicine impregnated with resin pattern inside, and can prevent that resin pattern is stripped from etching work procedure because of medicine expands.
But if increase the cross-linking density of resin pattern, when then peeling off resin pattern in etching work procedure end back with stripper, resin pattern is difficult for peeling off.This situation can cause the residue and residual of resin pattern to stay on the substrate and the operation that produces substandard product or peel off resin pattern needs the plenty of time and causes work efficiency to reduce.And even the resistance to chemical reagents of resin pattern improves, if the tack between metal film on the base material and the resin pattern is insufficient, then etching solution can be invaded between metal film and the resin pattern, thereby causes that resist is that resin pattern is peeled off in the etching work procedure.At this moment, because the etched liquid of resin pattern is removed the distribution part to necessity, therefore cause producing substandard product.
In addition, for anti-principal vertical line (line) pollutes, need advancing at stripping process, acidity, the alkaline solution of being about to be used as etching solution washs, the operation of drying on program.In general,, dry up operation,, then can become the main cause that causes (formation dust) circuit to pollute, so not preferred if tack is insufficient and cause pattern to be peeled off in the wind operation with after the pure water washing.
Patent documentation 1: TOHKEMY 2003-131369 communique
Patent documentation 2: TOHKEMY 2000-11863 communique
Summary of the invention
The present invention finishes in view of above problem, purpose is to provide a kind of photosensitive polymer combination, this photosensitive polymer combination have sufficient resistance to chemical reagents and good fissility concurrently and be used to obtain and base material on metal film between show the resin pattern of good adhesive property, and provide a kind of manufacture method of having used the etched basal body of this resin pattern.
The inventor furthers investigate repeatedly, found that, if in the acrylic acid soluble resin that a part of acidic group of the acrylic resin that comes self-contained acidic group generates with the epoxy reaction of the unsaturated compound that comes self-contained alicyclic epoxy base, the monofunctional monomer that combination excessively increases the cross-linking density of resin pattern polyfunctional monomer that increases and the cross-linking density that suppresses resin pattern, particularly nitrogenous monofunctional monomer, and in the presence of Photoepolymerizationinitiater initiater, make these material polymerizations prepare resin pattern, the resin pattern that then obtains shows good resistance to chemical reagents and fissility, and metal film on the base material and the cohesive between the resin pattern improve, thereby have finished the present invention.
First embodiment of the present invention relates to photosensitive polymer combination, and it comprises: the acrylic acid soluble resin (A) that the epoxy reaction by a part of acidic group that makes the acrylic resin that comes self-contained acidic group and the unsaturated compound that comes self-contained alicyclic epoxy base generates; The above polyfunctional monomer of trifunctional (B); Nitrogenous monofunctional monomer (C); Photoepolymerizationinitiater initiater (D).
Second embodiment of the present invention relates to the manufacture method of etched basal body, and this method comprises: the above-mentioned photosensitive polymer combination of coating on matrix, the operation of formation photo-sensitive resin; After above-mentioned photo-sensitive resin carried out selectivity exposure, develop to form exposure, the developing procedure of resin pattern; Above-mentioned resin pattern as mask, is carried out the etching work procedure of selective etch to above-mentioned matrix; Peel off the stripping process of above-mentioned resin pattern with stripper.
According to the present invention, a kind of photosensitive polymer combination can be provided, said composition have sufficient resistance to chemical reagents and good fissility concurrently and be used to obtain and base material on metal film between show the resin pattern of good adhesive property.A kind of manufacture method of having used the etched basal body of this resin pattern is provided in addition.
Embodiment
Below, embodiments of the present invention are described, but the present invention is not subjected to any restriction of following embodiment.
＜photosensitive polymer combination 〉
At first, photosensitive polymer combination of the present invention is described.Photosensitive polymer combination of the present invention comprises: the alkali soluble resin (A) that the epoxy reaction by a part of acidic group that makes the acrylic resin that comes self-contained acidic group and the unsaturated compound that comes self-contained alicyclic epoxy base generates; The polyfunctional monomer (B) that trifunctional is above; Nitrogenous monofunctional monomer (C); Photoepolymerizationinitiater initiater (D).
[the alkali soluble resin (A) that a part of acidic group of the acrylic resin that comes self-contained acidic group is generated with the epoxy reaction of the unsaturated compound that comes self-contained alicyclic epoxy base]
The alkali soluble resin that photosensitive polymer combination of the present invention contained (below be also referred to as " (A) composition ".), be the epoxy reaction of a part of acidic group and the unsaturated compound (a2) that comes self-contained alicyclic epoxy base that makes the acrylic resin (a1) of self-contained acidic group, introduce the alkali soluble resin that is cured the unsaturated group of necessary, as to come self-contained alicyclic epoxy base unsaturated compound (a2) with active energy ray.
Each composition is as described below.
[acrylic resin (a1) that contains acidic group]
As the acrylic resin that contains acidic group (below be also referred to as " (a1) composition ".), can adopt the multipolymer that acid with ethene unsaturated link is obtained with being selected from the monomer copolymerization more than a kind or 2 kinds in the monomers such as (methyl) esters of acrylic acid, vinyl aromatic compounds, amide-type unsaturated compound, polyolefins compound.Specifically can enumerate, with (methyl) acrylic acid, (methyl) acrylic acid 2-carboxylic ethyl ester, (methyl) acrylic acid 2-carboxylic propyl ester, maleic acid (acid anhydride) etc. has the acid of ethene unsaturated link as being neccessary composition, the multipolymer that it is obtained with being selected from following monomer copolymerization more than a kind or 2 kinds: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) stearyl acrylate alcohol ester, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid ester classes such as (methyl) hydroxypropyl acrylate; Styrene, α-Jia Jibenyixi, vinyltoluene, to vinyl aromatic compounds such as chlorostyrenes; Amide-type unsaturated compounds such as (methyl) acrylamide, diacetone acrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide; The monomer of polyolefins compounds such as butadiene, isoprene, chlorbutadiene and the rare nitrile of methyl-prop, methyl isopropyl thiazolinyl ketone, vinyl acetate, ベ オ バ モ ノ マ one (シ エ Le chemicals), propionate (vinyl propionate) wait other monomer.
(a1) acid number of composition is preferably more than the 15mgKOH/g, more preferably 40～500mgKOH/g.By making (a1) composition have above-mentioned acid number, even from a part of acidic group of (a1) composition with from the epoxy reaction that contains the unsaturated compound (a2) of alicyclic epoxy base described later, and after in (A) composition, introducing the unsaturated group of aequum, (A) acidic group that also can residual q.s in the composition.Thus, (A) composition can be realized excellent development.
[unsaturated compound (a2) that contains the alicyclic epoxy base]
As the unsaturated compound that contains the alicyclic epoxy base (below be also referred to as " (a2) composition ".), preferably in a part, have the compound of an ethene unsaturated group and alicyclic epoxy base.Particularly, for example can enumerate the compound of representing by following formula (I)～(XV).
[changing 1]
[changing 2]
[changing 3]
Wherein, R
4Represent hydrogen atom or methyl respectively independently.R
5The divalence sturated aliphatic hydrocarbon base of representing carbon number 1～6 respectively independently.R
6The bivalent hydrocanbon radical of representing carbon number 1～10 respectively independently.L is 0～10 integer.R
5The alkylidene of preferred straight or branched, for example methylene, ethylidene, propylidene, tetramethylene, butenyl group, 1,5-pentylidene, 1,6-hexylidene.R
6Preference such as methylene, ethylidene, propylidene, tetramethylene, butenyl group, 1,5-pentylidene, 1,6-hexylidene, phenylene, cyclohexylidene (cyclo hexylene) ,-CH
2-Ph-CH
2-(Ph is a phenylene.)。
[preparation of alkali soluble resin (A)]
(A) composition is by making from a part of acidic group of (a1) composition and epoxy reaction from (a2) composition, introducing unsaturated group and prepare in (a1) composition.Particularly, for example, the inert organic solvents solution by making (a1) composition and (a2) composition about 20～120 ℃ down reaction prepared in about 1～5 hour.As inert organic solvents, be not particularly limited, can enumerate alcohols, ester class, aliphatics or aromatic hydrocarbon based.(a1) composition and (a2) ratio of composition can change according to the kind of the monomer that is used to synthesize (a1) composition, (a2) composition is preferably 15 moles more than the % with respect to (a1) components in proportions.If (a2) composition is 15 moles more than the % with respect to (a1) components in proportions, then can solidifies the resin pattern that obtain to the photosensitive polymer combination that will contain (A) composition and give good elching resistant.
The matter average molecular weight of Zhi Bei (A) composition can be obtained by gel permeation chromatography thus, and this value is preferably 1000～100000, more preferably 3000～70000, more preferably 9000～30000.(A) composition is owing to having two keys at side chain thereby can solidifying by light in the presence of Photoepolymerizationinitiater initiater.Therefore that is to say that resin (A) composition self has high photosensitivity, can improve the cured density when crosslinked, and can improve the state of cure of the photosensitive polymer combination that exposure causes.In addition,, can develop, perhaps remove the resin pattern of formation with alkaline stripper with alkaline-based developer in order to have acidic group at side chain.The acid number of this (A) composition is preferably 20～200mgKOH/g, more preferably 30～150mgKOH/g, 50～140mgKOH/g more preferably.Acid number by making (A) composition can obtain excellent development more than lower limit, make it below higher limit, and then elching resistant is good, and can obtain the excellent pattern shape.In addition, have alicyclic ring class group, can improve elching resistant from (a2) composition by making (A) composition.
[polyfunctional monomer (B) that trifunctional is above]
Photosensitive polymer combination of the present invention comprise the above polyfunctional monomer of trifunctional (below be also referred to as " (B) composition ".)。Wherein " polyfunctional monomer that trifunctional is above " is meant in the presence of Photoepolymerizationinitiater initiater, has the monomer component of the two keys of ethene that can carry out addition polymerization more than 3 under rayed in 1 molecule.By making photosensitive polymer combination of the present invention contain this polyfunctional monomer component, can form the resin pattern of cross-linking density height and resistance to chemical reagents excellence.
As (B) composition, for example, the above acrylate of trifunctionals such as pentaerythrite four (methyl) acrylate, oxirane modification pentaerythrite four (methyl) acrylate, epoxy pronane modification pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate; The reaction of (methyl) acrylate monomer of polyisocyanate compounds and hydroxyl and multifunctional polyurethane (methyl) acrylate (urethane (metha) crylate); The condensation product of polyvalent alcohol and N-methylol (methyl) acrylamide etc.These polyfunctional monomers can use separately or be used in combination more than 2 kinds.In addition, by multifunctional polyurethane (methyl) acrylate and other polyfunctional monomers are used in combination, can improve the flexibility of resin bed.
In addition, in the time of will making film thickness and be the film of 1～3 μ m as the resin pattern of etching mask, in above-mentioned (B) composition of enumerating, especially preferably use the above monomer of six senses.When forming resin pattern with film, from elching resistant promptly to the viewpoint of resistance to chemical reagents of acid, alkali, be harsh conditions, under such condition, by using monomer conduct (B) composition more than six senses, can improve the cross-linking density of resin pattern inside, can give resin pattern good resistance to chemical reagents.For example can enumerate as the monomer more than this six senses: the reaction of (methyl) acrylate monomer of dipentaerythritol six (methyl) acrylate, polyisocyanate compounds and hydroxyl and the condensation product etc. of multifunctional polyurethane (methyl) acrylate, polyvalent alcohol and N-methylol (methyl) acrylamide.Wherein, preferably use dipentaerythritol acrylate (DPHA) in order to form the high firm resin pattern of elching resistant.The above monomer of these six senses can use separately or be used in combination more than 2 kinds, also the combination of monomers more than the above-mentioned trifunctional can be used.
With respect to (A) composition 100 mass parts, the content of above-mentioned (B) composition is preferably 110～300 mass parts, more preferably 115～200 mass parts.By making its content is more than the lower limit, can obtain excellent elching resistant; By making its content is below the higher limit, can finish the back at etching work procedure and remove resin pattern well with alkaline stripper.
[nitrogenous monofunctional monomer (C)]
Photosensitive polymer combination of the present invention contain nitrogenous monofunctional monomer (below be also referred to as " (C) composition ".)。Monofunctional monomer is meant the monomer with 1 ethene unsaturated group.By making photosensitive polymer combination of the present invention contain i.e. (C) composition of simple function, can prevent that the cross-linking density of resin pattern inside is too high, can give flexibility to the film of resin pattern, to the good fissility of alkaline stripper.In addition, because (C) composition is a simple function, and molecule contains nitrogen-atoms, if therefore (C) composition be introduced in the molecular resin because of polyreaction, then the resin backbone that contains with respect to resin pattern inside of the contained nitrogen-atoms of (C) composition disposes towards the outside.Therefore, (C) the contained nitrogen-atoms of composition can be used for improving and base material on stickability between the metal film, thereby improve the tack between the metal film on resin pattern and the base material.
(C) the represented compound of the preferred following general formula of composition (1).
[changing 4]
(in the general formula (1), A represents the alkylidene of singly-bound or carbon number 1～5; R
1Expression hydrogen atom or methyl; R
2, R
3Represent hydrogen atom respectively independently, maybe can have substituent alkyl.R
2, R
3When being alkyl, the formation ring structure can mutually combine.)
In the above-mentioned general formula (1), R
2, R
3In alkyl can be aromatic hydrocarbyl or aliphatic alkyl.The carbon number of alkyl is preferably 1～10, and more preferably 1～6.As aliphatic alkyl, more specifically can enumerate the straight or branched aliphatic alkyl, contain the aliphatic alkyl of ring etc. in the structure.As the alkyl of the preferred carbon number 1～10 of this aliphatic alkyl, the more preferably alkyl of carbon number 1～5.In addition, as the substituting group that this alkyl can have, for example can enumerate: alkyl, alkoxy, halogen atom, halogenated alkyl, hydroxyl, oxygen atom (=O ,-O-), hydroxy alkyl, cyano group etc.
In the above-mentioned general formula (1), R
2And R
3Interosculate when forming ring structure R
2And R
3The preferred carbon number of divalent alkyl be 3～6, more preferably carbon number is 4～5.R
2And R
3The divalent alkyl can have oxygen atom (O-), nitrogen-atoms (N=,-NH-).
(C) to be preferably the glass temperature (Tg) that makes the homopolymer that this (C) composition polymerization obtains be monomer more than 80 ℃ to composition.As mentioned above, (C) composition is the composition with the effect that prevents that the resin pattern cross-linking density from increasing, and from the viewpoint of cross-linking density, aspect the reduction resistance to chemical reagents effect is being arranged.But, satisfy the Tg condition by making (C) composition, can give the fastness of resin pattern to medicine, therefore the resistance to chemical reagents of resin pattern can be improved, and elching resistant can be improved.As this (C) composition; can enumerate: acrylamide (Tg:179 of homopolymer ℃, below identical); Methacrylamide (171 ℃); N methacrylamide (171 ℃); DMAA (119 ℃); N-N-isopropylacrylamide (134 ℃); acryloyl morpholine (acryloyl morpholine) (145 ℃); N tert butyl acrylamide (135 ℃); N-propenyl benzene acid amides (160 ℃); diacetone acrylamide (86 ℃); acryloyl group piperidines (116 ℃); diethyl acrylamide (81 ℃); 2-hydroxyethyl acrylamide (98 ℃); dimethylamino propyl acrylamide (134 ℃) etc.Wherein more preferably the Tg of homopolymer is acrylamide, Methacrylamide, N methacrylamide, acryloyl morpholine, N-propenyl benzene acid amides, most preferably an acryloyl morpholine more than 140 ℃.
With respect to (A) composition 100 mass parts, the content of above-mentioned (C) composition is preferably 10～80 mass parts, more preferably 20～75 mass parts, more preferably 30～70 mass parts.By making its content is more than the lower limit, can give the good flexibility of resin pattern, fissility and to the tack of base material; By making its content is below the higher limit, thereby the cross-linking density that can prevent resin pattern is crossed the low good medicament patience that obtains.
[Photoepolymerizationinitiater initiater (D)]
The Photoepolymerizationinitiater initiater that photosensitive polymer combination of the present invention contained (below be also referred to as " (C) composition ".) be not particularly limited; for example can enumerate: 1-hydroxy-cyclohexyl phenyl ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone; two (4-dimethylamino phenyl) ketone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; ethyl ketone (ethanone)-1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-yl]-1-(adjacent acetyl oxime); 2; 4; 6-trimethylbenzene acyl group diphenyl phosphine oxide; 4-benzoyl group-4 '-methyl dimethoxy sulphur; the 4-dimethylaminobenzoic acid; 4-dimethylaminobenzoic acid methyl esters; the 4-dimethyl ethyl aminobenzoate; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylamino-2-ethylhexyl benzoic acid; 4-dimethylamino-2-isoamyl benzene formic acid; benzyl-'beta '-methoxy ethyl acetals; benzyl dimethyl ketal; 1-phenyl-1; 2-propanedione-2-(adjacent carbethoxyl group) oxime; adjacent benzoyl group methyl benzoate; 2; the 4-diethyl thioxanthone; the 2-clopenthixal ketone; 2; 4-dimethyl thioxanthones; 1-chloro-4-propoxyl group thioxanthones; thioxanthene; 2-diuril ton; 2; 4-diethyl thioxanthene; 2-methyl thioxanthene; 2-isopropyl thioxanthene; the 2-EAQ; the prestox anthraquinone; 1; 2-benzo anthraquinone (benzanthraquinone); 2; 3-diphenyl anthraquinone; azo diisobutyl nitrile; benzoyl peroxide; the peroxidating cumene; 2-mercaptobenzimidazole; the 2-mercaptobenzoxazole; 2-mercaptobenzothiazole; 2-(Chloro-O-Phenyl)-4; 5-two (m-methoxyphenyl)-imidazoles dimer; benzophenone; the 2-chlorobenzophenone; p; p '-two dimethylamino benzophenone; 4; 4 '-two lignocaine benzophenone; 4; 4 '-dichloro benzophenone; 3; 3-dimethyl-4-methoxy benzophenone; benzil; benzoin; benzoin methylether; benzoin ethyl ether; benzoin iso-propylether; benzoin n-butylether; the benzoin isobutyl ether; the benzoin butyl ether; acetophenone; 2; the 2-diethoxy acetophenone; to dimethyl acetophenone; to the dimethylamino propiophenone; dichloroacetophenone; trichloroacetophenone; p-tert.-butyl acetophenone; to the dimethylamino acetophenone; to tert-butyl group trichloroacetophenone; to tert-butyl group dichloroacetophenone; α; α-Er Lv-4-Ben Yangjibenyitong; thioxanthones; 2-methyl thioxanthones; the 2-isopropyl thioxanthone; Dibenzosuberone (dibenzosuberone); amyl group-4-dimethylaminobenzoic acid ester; the 9-phenylacridine; 1; 7-pair-(9-acridinyl) heptane; 1; 5-pair-(9-acridinyl) pentane; 1; 3-pair-(9-acridinyl) propane; to the methoxyl triazine; 2; 4; 6-three (trichloromethyl)-secondary triazine; 2-methyl-4; two (the trichloromethyl)-secondary triazines of 6-; 2-[2-(5-methylfuran-2-yl) vinyl]-4; two (the trichloromethyl)-secondary triazines of 6-; 2-[2-(furans-2-yl) vinyl]-4; two (the trichloromethyl)-secondary triazines of 6-; 2-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-4; two (the trichloromethyl)-secondary triazines of 6-; 2-[2-(3; the 4-Dimethoxyphenyl) vinyl]-4; two (the trichloromethyl)-secondary triazines of 6-; 2-(4-methoxyphenyl)-4; two (the trichloromethyl)-secondary triazines of 6-; 2-(4-ethoxybenzene vinyl)-4; two (the trichloromethyl)-secondary triazines of 6-; 2-(4-n-butoxy phenyl)-4; two (the trichloromethyl)-secondary triazines of 6-; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) phenyl-secondary triazine; 2; 4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) phenyl-secondary triazine; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) styryl phenyl-secondary triazine; 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) styryl phenyl-secondary triazine etc.These Photoepolymerizationinitiater initiaters can use separately or be used in combination more than 2 kinds.
(D) content of composition can suitably be adjusted according to the content of (A)～(C) composition, with respect to alkali soluble resin (A) 100 mass parts, is preferably 1～30 mass parts, more preferably 5～25 mass parts, more preferably 10～20 mass parts.By making its content is above-mentioned scope, can obtain sufficient thermotolerance, resistance to chemical reagents, also can improve filming performance, and it is bad to suppress photocuring.
[sensitizer (E)]
Photosensitive polymer combination of the present invention can contain compound with mercapto as sensitizer (below be also referred to as " (E) composition ").When irradiating ultraviolet light, (E) composition generates the S free radical by alkene-thiol reactant (ene-thiol reaction).The polyreaction that the S free radical causes is not subjected to the influence of oxygen resistance and promotes therefore can improve the curing of photosensitive polymer combination the residual film ratio of pattern when developing, and improve the resistance to chemical reagents of resin pattern.As this (E) composition, can enumerate: trimethylolpropane tris ester classes such as (3-mercaptopropionic acid esters); Alcohols such as 2 mercapto ethanol, 1-sulfo-glycol, single mercaptoacetic acid glyceride (glycerolmonothioglycollate), 4-mercapto-phenol; Mercaptoacetic acid, 3-mercaptopropionic acid, 2 mercaptopropionic acid, thiomalic acid, mercaptoisobutyric acid, internal compensation-2, carboxylic acidss such as 3-dimercapto isobutyric acid, thiosalicylic acid; Amines such as 2-aminoothyl mercaptan, the amino thiophenol of 2-, the amino thiophenol of 4-; Halfcystine etc.
The content of (E) composition in the photosensitive polymer combination, can suitably adjust according to the content of (A)～(C) composition, with respect to alkali soluble resin (A) 100 mass parts, be preferably 0.1～30 mass parts, 0.5～25 mass parts more preferably, more preferably 0.8～20 mass parts is preferably 1～15 mass parts especially.By making its content is above-mentioned scope, can improve development and elching resistant.
[monomer component]
Photosensitive polymer combination of the present invention also can contain various monomer components except that containing above-mentioned each composition.As this monomer component, can enumerate compound with ethene unsaturated group, can enumerate monofunctional monomer with 1 ethene unsaturated group (but (C) composition except) and have the polyfunctional monomer of 2 ethene unsaturated groups.Can suitably select to use these monomer components more than a kind or 2 kinds according to the characteristic that the photosensitive polymer combinations such as viscosity of polymerisation reactivity, monomer are required.With respect to (A) composition 100 mass parts, below preferred 80 mass parts of the addition of these monomer components, more preferably 1～60 mass parts.By making its addition is below the higher limit, can be at the enough cross-linking densities of resin pattern inner sustain, and can improve patience acid, alkaline etching liquid.
[organic solvent]
In order to improve coating, to adjust viscosity, photosensitive polymer combination of the present invention preferably contains organic solvent.As this machine solvent, for example can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, the diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether; (gathering) alkylene glycol monoalkyl ethers acetate esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol MEE, diethylene glycol diethyl ether, tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester; 2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-ethyl acetoacetate; Arene such as toluene, dimethylbenzene; N-Methyl pyrrolidone, N, amide-types such as dinethylformamide, N,N-dimethylacetamide etc.These solvents can be used singly or in combination.
The content of organic solvent is not particularly limited, and can suitably select according to coated film thickness under concentration that can coated substrates etc.At this moment, solid component concentration is preferably 5～70 quality %, more preferably 10～60 quality %.
[other composition]
Other composition as photosensitive polymer combination of the present invention can contain adjuvants such as defoamer, surfactant as required.As defoamer, be not particularly limited, can enumerate silicone, fluoride compound etc.As surfactant, be not particularly limited, can enumerate compounds such as anionic species, cationic, nonionic class.
The manufacture method of＜etched basal body 〉
Then, the manufacture method to the etched basal body of the photosensitive polymer combination that used the invention described above describes.The manufacture method of having used the etched basal body of above-mentioned photosensitive polymer combination also is one of content of the present invention.The manufacture method of etched basal body of the present invention comprises: (1) is coated with photosensitive polymer combination of the present invention on matrix, forms the operation of photo-sensitive resin; (2) above-mentioned photo-sensitive resin is carried out selectivity exposure after, develop to form exposure, the developing procedure of resin pattern; (3) be mask with above-mentioned resin pattern, above-mentioned matrix carried out the etching work procedure of selective etch; (4) stripping process that uses stripper that above-mentioned resin pattern is peeled off.In addition, " matrix " among the present invention is meant the matrix that is formed with the film of etch target on substrates such as glass.Film as etch target can be enumerated metal film.
At first, illustrate that (1) is coated with photosensitive polymer combination of the present invention on matrix, form the operation of photo-sensitive resin.
In this operation, the photosensitive polymer combination of the invention described above is coated on the matrix, forms photo-sensitive resin.
As the substrate that is used to make matrix, use glass substrate usually.Adopting vapour deposition method or sputtering method etc. to form etched object on glass substrate is the matrix that metal film is made as etch target.The metal that forms metal film also contains metal oxide with electric conductivity etc. except containing metal, for example can enumerate: metal, the alloy of these metals, In such as Ni, Cr, Au, Mo, W, Pt, Ti, Cu, Pd, Ag
2O
3-SnO
2Deng semiconductor of metal oxide, polysilicon etc. etc.Metal film can be an individual layer, and one of unique point of the present invention is, can be to carrying out selective etch by the film formed composite metal membrane of the multiple layer metal under the different etching conditions.As this composite metal membrane, can enumerate the Cr/Cu/Cr stack membrane that is formed with a Cr (chromium) layer, Cu (copper) layer, the 2nd Cr layer.
By using contact transfer printing type apparatus for coating such as roll coater (roll coater), reverse coating machine (reverse coater), bar coating machine (bar coater), slit coater (slit coater), or spinner (rotary apparatus for coating), curtain coater non-contact type apparatus for coating such as (curtain coater), photosensitive resin coating composition on above-mentioned matrix, dry back is removed and is desolvated, thereby forms photo-sensitive resin on matrix.
The thickness of photo-sensitive resin does not have particular determination, is 1～5 μ m but preferably make the thickness as the resin pattern of etching mask.By making its thickness is more than the lower limit, can give resin pattern good resistance to chemical reagents; By making its thickness is below the higher limit, can give resin pattern good fissility.
Then, illustrate that (2) carry out selectivity exposure to above-mentioned photo-sensitive resin after, develop to form exposure, the developing procedure of resin pattern.
When above-mentioned photo-sensitive resin is carried out the selectivity exposure, can be via light-shielding pattern, irradiation ultraviolet radiation, excimer laser isoreactivity energy line expose.For exposure, can use the ultraviolet light sources of emission such as high-pressure mercury-vapor lamp, xenon lamp, carbon arc lamp.The energy line amount of irradiation, because of the composition difference of photosensitive polymer combination, but preference is as 5～2000mJ/cm
2About.
Then, make resin pattern by the resin bed after exposing being developed with developer solution.Developing method is not particularly limited, and for example can use infusion process, spray-on process etc.As the concrete example of developer solution, can enumerate: organic class developer solutions such as monoethanolamine, diethanolamine, triethanolamine; The aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc.And, cure (post bake) after also can carrying out and be heating and curing the resin pattern after developing.After preferred 150～250 ℃ of the temperature of curing.
Then, illustrate (3) with above-mentioned resin pattern as mask, above-mentioned matrix is carried out the etching work procedure of selective etch.
As etching method, for example can enumerate the wet etching that is impregnated in the etching solution commonly used.The employed etching solution of wet etching is so long as according to etched object and the acid type of suitably selecting or the etching solution of alkaline type get final product.As the etching solution of acid type, can enumerate: the aqueous solution of single acid ingredients such as hydrochloric acid, sulfuric acid, hydrofluorite, phosphoric acid; The mixed aqueous solution of salt such as acid ingredient and iron chloride, ammonium fluoride, potassium permanganate etc.Also can use the acid ingredient that has made up multiple acid ingredient.In addition, as the etching solution of alkaline type, can enumerate: the aqueous solution of the single alkaline components such as salt of NaOH, potassium hydroxide, ammonia, organic amine, this class organic amine of tetramethylphosphonihydroxide hydroxide amine; The mixed aqueous solution of salt such as alkaline components and potassium permanganate etc.Also can use the alkaline components that has made up multiple alkaline components.
The manufacture method of etched basal body of the present invention is not particularly limited, and the temperature of etching solution is preferably below 45 ℃.Form the resin pattern that uses as etching mask among the present invention by the photosensitive polymer combination that uses the invention described above, to bring into play to acidity in the said temperature scope and the excellent especially patience of alkaline etching liquid.Therefore, can prevent that resin pattern is peeled off in the etching work procedure, thereby the part that does not have resin pattern is carried out selective etch.
In addition, owing to the resin pattern that uses as etching mask in the manufacture method of etched basal body of the present invention has aforesaid high resistance to chemical reagents, therefore, even for example on base material, form multiple metal film, and use different types of etching solution to carry out repeatedly under the such exacting terms of etching successively to these metal films, the manufacture method of etched basal body of the present invention also preferably is suitable for.
As such example, can enumerate the situation of the above-mentioned substrate that is formed with a Cr layer, Cu layer, the 2nd Cr layer successively being carried out etching and processing.In this substrate, for example use acidic etching liquid to carry out etching, use alkaline etching liquid that the one Cr layer is carried out etching then being positioned at the most surperficial the 2nd Cr layer and Cu layer.According to the manufacture method of etched basal body of the present invention, must carry out the etching work procedure under the acid condition and the matrix of the etching work procedure under the alkali condition for above-mentioned, can not peel off resin pattern and carry out etching.
After above-mentioned etching,, can carry out washing procedure, drying process as required for anti-principal vertical line pollutes.For washing procedure, for example, washed substrate 10～300 seconds with pure water at normal temperatures; For drying process,, suitably adjust wind and press (0.1～5kg/cm as long as use wind
2About) get final product.
The stripping process that (4) use stripper that above-mentioned resin pattern is peeled off then, is described.
Stripping means as resin pattern does not have particular determination, for example can enumerate under 30～80 ℃, under preferred 50～80 ℃ with alkaline stripper dipping 5～30 minute the method for substrate in stirring.The resin pattern that uses as etching mask among the present invention is showing excellent resistance fluidity as mentioned above below 45 ℃, if fluid temperature is more than 50 ℃ then shows swelling properties because of alkaline stripper.According to this character, if used 50～80 ℃ stripper to carry out stripping process would have that activity time shortens, resin pattern peel off the advantage that residue reduces.That is to say, poor by between above-mentioned etching work procedure and stripping process, fluid temperature being set, the resin pattern that uses as etching mask among the present invention is brought into play in etching work procedure in the good resistance fluidity, in stripping process, show good fissility, thereby can satisfy resistance fluidity and these two kinds of opposite characteristics of fissility simultaneously.
As stripper, for example can enumerate organic basic compositions such as inorganic alkaline composition, tertiary amine, quaternary ammonium salt such as NaOH, potassium hydroxide, be dissolved in the stripper in water, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or their mixed solution.Can peel off resin pattern by above-mentioned strippers of use such as spray-on process, spray process, puddlings.
[embodiment]
According to following examples the present invention is described more specifically.But these embodiment are example of the present invention, can not limit scope of the present invention.
The preparation of＜photosensitive polymer combination 〉
According to table 1 and table 2, the photosensitive polymer combination of preparation embodiment 1～14 and comparative example 1～3.Each composition that table 1 is put down in writing is as described below.In addition, 45 quality %DPGME (dipropylene glycol monomethyl ether) solution of preparation alkali soluble resin (A) are used for the preparation of photosensitive polymer combination.The numeric representation mass parts that table 1 and table 2 are put down in writing.Wherein, the alkali soluble resin of table 1 (A-1 or A-2) 100 mass parts are meant that the solid constituent of alkali soluble resin is 100 mass parts.
Alkali soluble resin (A)
A-1: サ イ Network ロ マ one ACA Z250 (ダ イ セ Le chemical industry Co., Ltd. system, the resin of the structural unit that following formula (2), formula (3) and the formula (4) that matter average molecular weight 20000, acid number 101.7mgKOH/g, the acrylic resin that contains acidic group generate with the unsaturated compound reaction that contains the alicyclic epoxy base is represented.)
[changing 5]
[in the formula (2), R
7Expression alkyl or hydroxy alkyl, in formula (2), formula (3) and the formula (4), X represents hydrogen atom or methyl.]
A-2: the multipolymer of benzyl methacrylate and methacrylic acid (benzyl methacrylate/methacrylic acid=80: 20 (mass ratio), matter average molecular weight 60000)
Monomer (B)
B-1:DPHA (dipentaerythritol acrylate, six functional monomers)
B-2:CN9006 (サ one ト マ one society's system, urethane acrylate, six functional monomers)
Nitrogenous monofunctional monomer (C)
C-1: acryloyl morpholine
Other monomer
B '-1: acrylic acid 2-phenoxy ethyl
B '-2: isobornyl acrylate
Photoepolymerizationinitiater initiater (D)
IR369: イ Le ガ キ ユ ア 369 (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ society system)
EAB-F:4,4 '-two (lignocaine) benzophenone (protect native ケ paddy chemical industry Co., Ltd. system)
Sensitizer (E)
E-1: trimethylolpropane tris mercaptopropionic acid ester
[table 1]
[table 2]
The preparation of＜etched basal body 〉
Make the glass substrate (thickness 1.8mm) that is laminated with the 2nd Cr layer/Cu layer/Cr layer by sputtering method, as estimating substrate.Estimate in the substrate, the 2nd a Cr layer and a Cr layer lay respectively at the most surperficial and orlop, and the Cu layer is positioned in the middle of them.The thickness of each layer, the 2nd Cr layer are that 100nm, Cu layer are that 2.0 μ m, a Cr layer are 50nm.Use photoresist spinner that this is estimated the base plate coating photosensitive polymer combination, 65 ℃ dry 6 minutes down, obtain having the evaluation substrate of the photo-sensitive resin of 2.5 μ m film thicknesses.Then, the process negative mask is with 25mJ/cm
2(composition that contains sensitizer) or 50mJ/cm
2The exposure of (composition that does not contain sensitizer) is to these photo-sensitive resin elective irradiation ultraviolet ray (light sources: extra-high-pressure mercury vapour lamp), the sodium carbonate liquor that uses 0.25 quality % as developer solution 30 ℃ of following spray development 120 seconds to form resin pattern, with the pure water washing, dry up.Then to the resin pattern that forms with 300mJ/cm
2Exposure irradiation ultraviolet radiation (light source: extra-high-pressure mercury vapour lamp) carry out post-exposure.
Then, the evaluation substrate that is formed with resin pattern is carried out etching.At first, in 35 ℃ the acidic etching liquid that the aqueous hydrochloric acid solution by about 15 quality % forms, flood 5 minutes (※ is in order to estimate patience, and dip time is longer than common program), carry out etching, wash with pure water to being positioned at the 2nd the most surperficial Cr layer with estimating substrate.Then, the HCl/FeCl of preparation 0.3/0.3/0.3 (mol/L ratio)
3/ Cu
2+Aqueous solution is as acidic etching liquid, with estimating in this acidic etching liquid that substrate is immersed in 30 ℃, while shake Cu layer etching 60 seconds, washs with pure water.At last, to the Na of 5 quality %
2SiO
3The potassium permanganate that adds 5 quality % in the aqueous solution is made alkaline etching liquid, floods 10 minutes in this alkaline etching liquid of 40 ℃ estimating substrate, carries out etching to being positioned at a undermost Cr layer, washs with pure water.
Etching work procedure dries up with air gun after finishing (comprising the operation with pure water washing (under 23 ℃, 60 seconds)).Then, use alkaline stripper to peel off and be present in the resin pattern of estimating on the substrate.Stripper uses the sodium hydrate aqueous solution heat to 60 ℃ 12 quality %.
＜estimate
The photosensitive polymer combination of embodiment 1～14 and comparative example 1～3 is made the evaluation substrate of the resin pattern with 2.5 μ m film thicknesses as mentioned above, estimate carry out etching and develop after residual film ratio, resistance fluidity (elching resistant), etching wash, dry up after finishing to peel off after pattern stickability, etching after the operation finishes and have or not residue after needed time of resin pattern and resin pattern are peeled off.Its result is shown in table 3 and table 4.The evaluation method and the metewand of projects are as described below.
[residual film during development]
By observe to photo-sensitive resin expose and spray development after the residual rate of resin pattern film estimate.
Zero: the residual film ratio after the resin pattern of photocuring develops is more than 90%
△: the residual film ratio after the resin pattern of photocuring develops is more than 50%, less than 90%
*: the residual film ratio less than 50% after the resin pattern of photocuring develops
[acid, alkali patience]
Peel off situation evaluation by what the etching work procedure of observing the 2nd Cr layer, Cu layer and a Cr layer finished the back resin pattern.
◎: etching work procedure is not observed peeling off of resin pattern after finishing.
Zero: etching work procedure does not almost observe peeling off of resin pattern after finishing.
△: the part of resin pattern in the etching work procedure (counting less than 30% with area occupation ratio) has taken place to peel off.
*: in the etching work procedure, the major part of resin pattern (counting more than 30% with area occupation ratio) has taken place to peel off.
[etching, the back pattern tack of blowing]
The pattern tack that etching work procedure finishes after the back dries up with pure water washing (under 23 ℃, 60 seconds) and with air gun is estimated.
◎: exposure 25mJ/cm
2, wire spoke 20 μ m spacings 80 μ m pattern dimension under, pattern adheres to and does not observe pattern and peel off.
Zero: exposure 50mJ/cm
2Below, under the pattern dimension of wire spoke 30 μ m spacings 90 μ m, pattern adheres to and does not observe pattern and peel off.
*: exposure 25mJ/cm
2Below, under the pattern dimension of wire spoke 30 μ m spacings 90 μ m, can be observed pattern and peel off.
[etching, the back pattern rectilinearity of blowing]
According to following benchmark, the pattern rectilinearity that etching work procedure finishes after the back dries up with pure water washing (under 23 ℃, 60 seconds) and with air gun is estimated.In addition, estimate employed pattern and be of a size of wire spoke 30 μ m spacings 90 μ m.
Zero: do not observe wave (the ripple ろ Chi) shape of pattern, the rectilinearity height.
△: observing has some wave-likes in the pattern.
*: observing has wave-like in the pattern, rectilinearity is low.
[splitting time]
Peeling off the needed time of resin pattern by etching work procedure end back with alkaline stripper estimates.
Zero: peeling off the needed time is below 120 seconds
*: peel off the needed time above 120 seconds
[fissility]
After peeling off resin pattern with alkaline stripper, observe the residue of resin pattern residual on the substrate and estimate.
Zero: the residue that does not have resin pattern after peeling off.
△: peeling off the back resin pattern has a little residual.
*: peeling off the back resin pattern has residual in a large number.
[table 3]
[table 4]
Resistance to acids and bases owing to comparative example 1 in the table 4 is insufficient, so does not carry out the evaluation behind the etching work procedure.In addition, the pattern tack after the etching of comparative example 2～5, the wind operation is insufficient, and a part of pattern is stripped from, the evaluation of the stripping process after therefore not carrying out, but for the pattern rectilinearity of residual pattern, charge in the lump in () with for referencial use.
Shown in table 3 and table 4, with respect to comparative example 1～5, embodiment 1～8 has good acid, alkaline patience (resistance to chemical reagents), also has sufficient pattern tack in the washing behind etching work procedure, the wind operation.Hence one can see that, acrylic acid soluble resin and nitrogenous monofunctional monomer that epoxy reaction by a part of acidic group that will make the acrylic resin that comes self-contained acidic group and the unsaturated compound that comes self-contained alicyclic epoxy base generates are used for photosensitive polymer combination, can improve the resistance to chemical reagents of resin pattern.In general, if interpolation monofunctional monomer, resin internal crosslinking density after then solidifying reduces, therefore consider that this point expectation of setting out can be unfavorable for resistance to chemical reagents, if but use nitrogenous monofunctional monomer used in the present invention, then opposite with above-mentioned expectation, can improve aforesaid resistance to chemical reagents and tack.Supposition is that the contained nitrogen-atoms of monomer makes due to resin pattern improves the tack of substrate surface.At this on the one hand, use the tack of comparative example 4 and 5 after etching, wind operation of monofunctional monomer of nonnitrogenous atom insufficient.
But as mentioned above, if use polyfunctional monomer in a large number, then the cross-linking density of resin inside improves, though therefore favourable aspect resistance to chemical reagents, unfavorable aspect fissility.At this on the one hand, nitrogenous monofunctional monomer in the photosensitive polymer combination of the application of the invention, can excessively not improve the cross-linking density of resin inside, and can give resin pattern resistance to chemical reagents and tack, therefore can realize these opposite performances of resistance to chemical reagents, tack and fissility simultaneously.
In addition, if embodiment 7 is compared with comparative example 3, then can improve the acid of resin pattern, alkaline patience by the existence of nitrogenous monofunctional monomer as can be known.The reason that the existence of nitrogenous monofunctional monomer improves the acid of resin pattern, alkaline patience is because can prevent that by the tack that improves resin pattern and base material etching solution from immersing between resin pattern and the base material.
In addition, if embodiment 6 and embodiment 7 are compared, both all do not have peeling off of resin pattern behind etching work procedure as can be known.But compare with embodiment 7, etching, pattern tack wind after of embodiment 6 under low exposure is more excellent.About this point, thereby think, even so the pattern of smaller szie influence that soup brings also can not be subjected to etching the time because make susceptibility well make polyreaction abundant by adding sensitizer.
Claims (8)
1. photosensitive polymer combination comprises: the alkali soluble resin (A) that a part of acidic group of the acrylic resin by making self-contained acidic group and the epoxy reaction of the unsaturated compound that comes self-contained alicyclic epoxy base generate; The polyfunctional monomer (B) that trifunctional is above; Nitrogenous monofunctional monomer (C); Photoepolymerizationinitiater initiater (D).
2. photosensitive polymer combination as claimed in claim 1 is characterized in that: described nitrogenous monofunctional monomer (C) is the compound by following general formula (1) expression,
In the general formula (1), A represents the alkylidene of singly-bound or carbon number 1～5; R
1Expression hydrogen atom or methyl; R
2, R
3Represent hydrogen atom respectively independently, maybe can have substituent alkyl.R
2, R
3When being alkyl, the formation ring structure can mutually combine.
3. photosensitive polymer combination as claimed in claim 1 is characterized in that:
With respect to described alkali soluble resin (A) 100 mass parts, the content of described nitrogenous monofunctional monomer (C) is 10～60 mass parts.
4. photosensitive polymer combination as claimed in claim 1 is characterized in that: described polyfunctional monomer (B) is the above monomers of six senses.
5. photosensitive polymer combination as claimed in claim 4 is characterized in that: with respect to described alkali soluble resin (A) 100 mass parts, the content of described polyfunctional monomer (B) is 110～300 mass parts.
6. photosensitive polymer combination as claimed in claim 1 is characterized in that: said composition further contains sensitizer (E).
7. the manufacture method of an etched basal body is characterized in that this method comprises:
Each described photosensitive polymer combination in the coating claim 1 to 6 on matrix, the operation of formation photo-sensitive resin;
After described photo-sensitive resin carried out selectivity exposure, develop to form exposure, the developing procedure of resin pattern;
Described resin pattern as mask, is carried out the etching work procedure of selective etch to described matrix;
Peel off the stripping process of described resin pattern with stripper.
8. the manufacture method of etched basal body as claimed in claim 7 is characterized in that:
Described matrix is the matrix that is formed with a Cr layer, Cu layer, the 2nd Cr layer on substrate successively;
Described etching work procedure comprises: use acidic etching liquid described the 2nd Cr layer to be carried out the operation of selective etch; Use acidic etching liquid described Cu layer to be carried out the operation of selective etch; And use alkaline etching liquid a described Cr layer to be carried out the operation of selective etch.
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| CN104797982A (en) * | 2013-05-02 | 2015-07-22 | 富士胶片株式会社 | Pattern forming method, method for manufacturing electronic device, and electronic device |
| CN107075283A (en) * | 2014-09-29 | 2017-08-18 | 爱克发-格法特公司 | The numerical DC speed of metallic article |
| CN110941140A (en) * | 2018-09-21 | 2020-03-31 | 旭化成株式会社 | Photosensitive resin composition |
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| CN102534621B (en) * | 2012-02-21 | 2013-11-13 | 上海正帆科技有限公司 | Method for treating acidic etching solution |
| US10095110B2 (en) | 2015-11-26 | 2018-10-09 | Jsr Corporation | Photosensitive resin composition, method for forming resist pattern, and method for producing metallic pattern |
| JP6819160B2 (en) | 2015-11-26 | 2021-01-27 | Jsr株式会社 | Photosensitive resin composition, resist pattern forming method, and metal pattern manufacturing method |
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| EP0234430A2 (en) * | 1986-02-27 | 1987-09-02 | Kohjin Co., Ltd. | Diluent for UV and EB curable resins |
| KR100725249B1 (en) * | 2005-12-20 | 2007-06-04 | (주)디피아이 홀딩스 | Ultraviolet curable paint for steels coating |
| CN101044434A (en) * | 2004-11-04 | 2007-09-26 | 东京应化工业株式会社 | Photosensitive resin composition and photosensitive dry film by the use thereof |
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| JPH11302342A (en) * | 1998-04-21 | 1999-11-02 | Kansai Paint Co Ltd | Active energy ray-curable resin composition and formation of coating film using the same |
| JP2000011863A (en) * | 1998-06-19 | 2000-01-14 | Hitachi Ltd | MANUFACTURE OF Cr/Cu/Cr WIRING STRUCTURE, MANUFACTURE OF PLASMA DISPLAY PANEL USING THE BODY AND IMAGE DISPLAY DEVICE USING THE STRUCTURE |
| JP2003131380A (en) * | 2001-10-24 | 2003-05-09 | Toppan Printing Co Ltd | Photosensitive resin composition |
| JP3997753B2 (en) * | 2001-10-24 | 2007-10-24 | 凸版印刷株式会社 | Photosensitive resin composition |
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| EP0234430A2 (en) * | 1986-02-27 | 1987-09-02 | Kohjin Co., Ltd. | Diluent for UV and EB curable resins |
| CN101044434A (en) * | 2004-11-04 | 2007-09-26 | 东京应化工业株式会社 | Photosensitive resin composition and photosensitive dry film by the use thereof |
| KR100725249B1 (en) * | 2005-12-20 | 2007-06-04 | (주)디피아이 홀딩스 | Ultraviolet curable paint for steels coating |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797982A (en) * | 2013-05-02 | 2015-07-22 | 富士胶片株式会社 | Pattern forming method, method for manufacturing electronic device, and electronic device |
| CN107075283A (en) * | 2014-09-29 | 2017-08-18 | 爱克发-格法特公司 | The numerical DC speed of metallic article |
| CN110941140A (en) * | 2018-09-21 | 2020-03-31 | 旭化成株式会社 | Photosensitive resin composition |
| CN110941140B (en) * | 2018-09-21 | 2023-09-15 | 旭化成株式会社 | Photosensitive resin composition |
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