CN101762970B - Manufacturing method of etched substrate and light-sensitive resin composition - Google Patents
Manufacturing method of etched substrate and light-sensitive resin composition Download PDFInfo
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- CN101762970B CN101762970B CN 200910215325 CN200910215325A CN101762970B CN 101762970 B CN101762970 B CN 101762970B CN 200910215325 CN200910215325 CN 200910215325 CN 200910215325 A CN200910215325 A CN 200910215325A CN 101762970 B CN101762970 B CN 101762970B
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Abstract
The invention provides a manufacturing method of etched substrate. The etched substrate has etching resistance at acidic and alkaline conditions, and is capable of taking resin pattern stripped by the alkaline stripping liquid as a mask after the etching process is finished. The inventive manufacturing method of etched substrate includes: a process of forming a light-sensitive resin layer on the substrate; a process of performing selective exposal and developing to form resin pattern; a process of taking the resin pattern as a mask, and using acidic or alkaline etching liquid with temperature lower than 45 DEG C to perform selective etching to the substrate; a process of using 50-80 DEG C of alkaline stripping liquid to strip the resin pattern. The light-sensitive resin composition includes: 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; multifunctional monomer with more than three functions; and a photopolymerization initiator.
Description
Technical field
The present invention relates to manufacture method and the photosensitive polymer combination of etched basal body.
Background technology
Plasma display panel (is designated hereinafter simply as " PDP ".) be widely used as the full-color display device of large picture.Owing to the luminous image that forms of each pixel of PDP self, therefore compare with the liquid crystal display of using bias light and color filter, have the advantage that the visual angle is wide, reaction velocity is fast, excitation is good.
Supply with one of wiring structural body that is used for luminous electric power as each pixel to PDP, the known Cr/Cu/Cr wiring structural body that stacks gradually Cr (chromium) layer, Cu (copper) layer, Cr layer at glass substrate.This wiring structural body adopts the following methods manufacturing: form the Cr/Cu/Cr stack membrane thereby form successively a Cr layer, Cu layer and the 2nd Cr tunic by vapour deposition method or sputtering method etc., then adopt photolithography to form the resin pattern that Wiring pattern forms usefulness, this resin pattern is made through the multi-stage etching operation as mask (for example, with reference to patent documentation 1).
But, in the above-mentioned patent documentation 1, when the Cr/Cu/Cr layer is carried out selective etch successively, will use the operation of acidic etching liquid, the operation combination of use alkaline etching liquid to implement.For example, the first embodiment according to patent documentation 1 record, use as the acidic etching liquid of major component the 2nd Cr layer that is positioned at the upper strata is carried out etching with aluminum chloride and phosphoric acid after, be that the acidic etching liquid of major component carries out etching to the Cu layer in order to iron sulfate and sulfuric acid again, use at last the strong basicity etching solution that contains NaOH, calcium hydroxide that a Cr layer that is positioned at lower floor is carried out etching.
Be used to form the resin pattern as etching mask of Wiring pattern, developed by alkaline-based developer, and peeled off by alkaline stripper.Therefore, the common patience that lacks alkaline liquid.Just because of this, in the said method that the first embodiment of patent documentation 1 proposes, before the Cr layer etching work procedure that under strong alkaline condition, carries out, remove first the resin pattern as etching mask.Therefore, a Cr layer is being carried out in the etched operation, the etched while of a Cr layer, the 2nd Cr layer that forms of finishing patterns also can be etched, thus must be on the operation that is pre-formed the 2nd thicker Cr layer time-consuming taking a lot of work.
Like this, since do not exist to acid and alkaline etching liquid all have patience and be used to form Wiring pattern form finish after the material of the resin pattern removed of the enough alkaline strippers of energy, therefore, present situation is in the pattern formation method that comprises acid and alkali etching operation, need to be on various operations time-consuming taking a lot of work.
Patent documentation 1: TOHKEMY 2000-11863 communique
Summary of the invention
The present invention finishes in view of above problem, purpose is to provide a kind of manufacture method of etched basal body and employed photosensitive polymer combination in the manufacture method of this etched basal body, this etched basal body has the elching resistant under acid and the alkali condition, and the resin pattern of peeling off with the enough alkaline strippers of energy after finishing at etching work procedure is as mask.
The inventor conducts in-depth research in order to solve above-mentioned problem, found that if use the photosensitive polymer combination that comprises the polyfunctional monomer more than specific alkali soluble resin and the trifunctional, and under acidity or alkalescence, carry out in the etched operation and in the operation of using alkaline stripper that resin pattern is peeled off, adopt different temperature conditions, can solve above-mentioned problem, thereby finish the present invention.Particularly, the invention provides following content.
The first embodiment of the present invention relates to a kind of manufacture method of etched basal body, it is characterized in that the method comprises: photosensitive resin coating composition on matrix, the operation of formation photo-sensitive resin; After above-mentioned photo-sensitive resin carried out selectivity exposure, develop to form the operation of resin pattern; With above-mentioned resin pattern as mask, the etching work procedure that uses acidity below 45 ℃ or alkaline etching liquid above-mentioned matrix to be carried out selective etch; The operation of using 50～80 ℃ alkaline stripper that above-mentioned resin pattern is peeled off; Above-mentioned photosensitive polymer combination comprises: the alkali soluble resin 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 that trifunctional is above; Photoepolymerizationinitiater initiater.
The second embodiment of the present invention relates to employed photosensitive polymer combination in a kind of manufacture method of the etched basal body in the invention described above, it is characterized in that comprising: the alkali soluble resin 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 that trifunctional is above; Photoepolymerizationinitiater initiater.
According to the present invention, a kind of manufacture method of etched basal body can be provided, and in the manufacture method of this etched basal body employed photosensitive polymer combination, this etched basal body has the elching resistant under acidity and the alkali condition, and with the resin pattern can enough alkaline strippers after etching work procedure finishes peeled off as mask.
Embodiment
Below, embodiments of the present invention are described, but the present invention is not subjected to any restriction of following embodiment.
The manufacture method of＜etched basal body 〉
Below the manufacture method of etched basal body of the present invention is described.The manufacture method of etched basal body of the present invention comprises: (1) is the photosensitive resin coating composition on matrix, forms the operation of photo-sensitive resin; (2) above-mentioned photo-sensitive resin is carried out selectivity exposure after, develop to form the operation of resin pattern; (3) take above-mentioned resin pattern as mask, the etching work procedure that uses acidity below 45 ℃ or alkaline etching liquid above-mentioned matrix to be carried out selective etch; (4) operation of using 50～80 ℃ alkaline stripper that above-mentioned resin pattern is peeled off.Below each operation is described.
At first, (1) photosensitive resin coating composition on matrix is described, forms the operation of photo-sensitive resin.
In this operation, the photosensitive polymer combination that aftermentioned is illustrated is coated on the matrix, forms photo-sensitive resin.
As matrix, usually use glass substrate.Adopting vapour deposition method or sputtering method etc. to form etched object at the glass substrate that uses as matrix is metal film.Metal film can be individual layer, and 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.
Use the 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 the non-contact type apparatus for coating such as spinner (rotary apparatus for coating), curtain coater (curtain coater), photosensitive resin coating composition on above-mentioned matrix, desolventizing after dry, thus photo-sensitive resin formed at matrix.Among the present invention, when forming photo-sensitive resin, be the situation of 1～3 μ m and be in the situation of 3.5～5 μ m at the thickness that is formed at the photo-sensitive resin on the matrix, use the different photosensitive polymer combinations that form.To be elaborated after the composition about photosensitive polymer combination.
Then, illustrate that (2) carry out selectivity exposure to above-mentioned photo-sensitive resin after, develop to form the operation 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, different because of the composition of photosensitive polymer combination, preference is such as 5～2000mJ/cm
2About.
Then, by with developer solution the resin bed after exposing being developed to make resin pattern.Developing method is not particularly limited, such as using infusion process, spray-on process etc.As the concrete example of developer solution, can enumerate: the organic 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 the resin pattern after developing and be heating and curing.After preferred 150～250 ℃ of the temperature of curing.
Then, illustrate (3) with above-mentioned resin pattern as mask, the etching work procedure that uses acidity below 45 ℃ or alkaline etching liquid above-mentioned matrix to be carried out 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 acid type etching solution, can enumerate: the aqueous solution of acid ingredients such as hydrochloric acid, sulfuric acid, hydrofluorite, phosphoric acid; The mixed aqueous solution of the 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 the salt such as alkaline components and potassium permanganate etc.Also can use the alkaline components that has made up multiple alkaline components.
In the manufacture method of etched basal body of the present invention, the temperature of etching solution is below 45 ℃.Form the resin pattern that uses as etching mask among the present invention by the photosensitive polymer combination that uses the aftermentioned explanation, with the patience of performance to the acidity in the said temperature scope and 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, the manufacture method of etched basal body of the present invention is specially adapted to be formed with successively the substrate of a Cr layer, Cu layer, the 2nd Cr layer.This substrate for example, uses acidic etching liquid to carry out etching to being positioned at the most surperficial the 2nd Cr layer and Cu layer, then, uses alkaline etching liquid that the one Cr layer is carried out etching.As mentioned above, according to the manufacture method of etched basal body of the present invention, for carrying out etching work procedure under the acid condition and the matrix of the etching work procedure under the alkali condition, can not peel off resin pattern and carry out etching.
The operation that (4) use 50～80 ℃ alkaline stripper that above-mentioned resin pattern is peeled off then, is described.
The manufacture method of etched basal body of the present invention when the resin pattern that uses as etching mask is peeled off, is used 50～80 ℃ alkaline stripper.As mentioned above, because therefore the etching solution of use below 45 ℃ in the etching work procedure of the present invention, exist fluid temperature poor between etching work procedure and resin pattern stripping process.The resin pattern that adopts photosensitive polymer combination used in the present invention to make is because the alkaline stripper more than 50 ℃ has swelling properties.Therefore, the existence that said temperature is poor can prevent peeling off of resin pattern in the etching work procedure, and can peel off resin pattern in the stripping process of resin pattern.
Stripping means as resin pattern does not have particular determination, for example can enumerate under 50～80 ℃ the method for flooding 5～30 minutes in the alkaline stripper of substrate in stirring.As alkaline stripper, such as enumerating the inorganic alkaline compositions such as NaOH, potassium hydroxide are dissolved in alkaline stripper in water, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or their mixed solution.Can use the stripper of organic basic compositions such as containing organic amine, organic ammonium salt, but consider from the cost aspect, the preferred stripper that contains the inorganic alkaline composition that uses.Also can peel off resin pattern by above-mentioned strippers of usefulness such as spray-on process, spray process, puddlings.
＜photosensitive polymer combination 〉
Then, employed photosensitive polymer combination describes in the manufacture method to above-mentioned etched basal body.Employed photosensitive polymer combination also is one of content of the present invention in the manufacture method of above-mentioned etched basal body.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; Photoepolymerizationinitiater initiater (C).
[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 contained alkali soluble resin of photosensitive polymer combination of the present invention (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 one kind or two or more monomer copolymerization 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 one kind or two or more monomer copolymerization: (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-methyl styrene, vinyltoluene, to vinyl aromatic compounds such as chlorostyrenes; The amide-type unsaturated compounds such as (methyl) acrylamide, diacetone acrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide; Other monomers such as the monomer of the 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).
(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 introducing the unsaturated group of aequum in (A) composition, acidic group that (A) 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 that is represented by following formula (I)～(XV).
[changing 1]
[changing 2]
[changing 3]
Wherein, R
1Be hydrogen atom or methyl.R
2Divalence sturated aliphatic hydrocarbon base for carbon number 1～6.R
3Bivalent hydrocanbon radical for carbon number 1～10.1 is 0～10 integer.R
2The alkylidene of preferred straight or branched, for example methylene, ethylidene, propylidene, tetramethylene, butenyl group, 1,5-pentylidene, 1,6-hexylidene.R
3Preference 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 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, introduces unsaturated group in (a1) composition to prepare.Particularly, for example, the inert organic solvents solution by making (a1) composition prepared in about 20～120 ℃ of lower reactions with (a2) composition 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 for the synthesis of the monomer of (a1) composition, (a2) composition is preferably more than 15 % by mole with respect to the ratio of (a1) composition.If (a2) composition is more than 15 % by mole with respect to the ratio of (a1) composition, then can solidifies the resin pattern that obtains to the photosensitive polymer combination that will contain (A) composition and give good elching resistant.
The matter average molecular weight of (A) composition of preparation 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, have acidic group in order to make side chain, can develop with alkaline-based developer, perhaps remove the resin pattern of formation with alkaline stripper.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 excellent pattern form.In addition, have alicyclic ring class group from (a2) composition by making (A) composition, can improve elching resistant.
[monomer (B)]
The contained monomer component of photosensitive polymer combination of the present invention (below be also referred to as " (B) composition ".) must contain the above monomer component of trifunctional (below be also referred to as " (b1) composition ".)。Wherein " monomer component that trifunctional is above " refers 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 irradiation in 1 molecule.In the manufacture method of etched basal body of the present invention, the film thickness of the resin pattern that forms as etching mask is in the situation that is 1～3 μ m and be in the situation of 3.5～5 μ m, and the composition of (B) composition that photosensitive polymer combination is contained is not identical.Below the film thickness of the resin pattern that forms as etching mask is described respectively.
The film thickness of the resin pattern that forms as etching mask is the situation of 1～3 μ m
Film thickness at resin pattern is under the film condition of 1～3 μ m, is advantage for peel off resin pattern with alkaline stripper after etching.But, because resin pattern is film, therefore from elching resistant namely to the viewpoint of the patience of acid, alkaline etching liquid, can be described as harsh and disadvantageous condition.
Therefore, among the present invention, when under the film thickness of resin pattern is the film condition of 1～3 μ m, carrying out etching work procedure, preferably use the above monomer of six senses as above-mentioned (b1) composition.By making photosensitive polymer combination contain this monomer component, can improve the cross-linking density of the inside that makes the resin pattern that this photosensitive polymer combination photocuring obtains, and can improve patience acid, alkaline etching liquid.
As (b1) composition in this case, can enumerate: dipentaerythritol six (methyl) acrylate, make polyisocyanate compounds and hydroxyl (methyl) acrylate monomer reaction and the condensation product etc. of multifunctional polyurethane (methyl) acrylate (urethane (metha) crylate), polyvalent alcohol and N-methylol (methyl) acrylamide.The above monomer of these six senses can use separately or be used in combination more than 2 kinds.Wherein, preferably use dipentaerythritol acrylate (DPHA) in order to form the high firm resin pattern of elching resistant; In order in the flexibility that improves resin pattern, to improve resin pattern to the tack of etched base material, preferably use multifunctional polyurethane (methyl) acrylate.
In addition, when the film thickness of resin pattern is 1～3 μ m, as (B) composition preferably contain nitrogen atom monofunctional monomer (below be also referred to as " (b2) composition ".)。Monofunctional monomer refers to have the monomer of 1 ethene unsaturated group.By making photosensitive polymer combination of the present invention contain (b2) composition, can give flexibility to the film that photosensitive polymer combination solidifies the resin pattern of gained, and can improve resin pattern to the tack of base material.
(b2) to be preferably the glass temperature (Tg) that makes the homopolymer that this (b2) composition polymerization obtains be monomer more than 80 ℃ to composition.By making (b2) composition satisfy above-mentioned condition, 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 (b2) composition; can enumerate: acrylamide (Tg:179 of homopolymer ℃, below identical); Methacrylamide (171 ℃); N methacrylamide (171 ℃); DMAA (119 ℃); NIPA (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 acryloyl morpholine more than 140 ℃.
With respect to (A) composition 100 mass parts, the content of above-mentioned (b1) composition is preferably 110～300 mass parts, more preferably 115～200 mass parts, more preferably 115～170 mass parts.Be more than the lower limit by making its content, can obtain excellent elching resistant; Be below the higher limit by making its content, can after etching work procedure finishes, remove well resin pattern with alkaline stripper.
In addition, with respect to (A) composition 100 mass parts, the content of above-mentioned (b2) composition is preferably 10～80 mass parts, more preferably 20～75 mass parts, more preferably 30～70 mass parts.Be more than the lower limit by making its content, can give the good flexibility of resin pattern and to the tack of base material; Be below the higher limit by making its content, can obtain good elching resistant.
As (B) composition, above-mentioned (b1) composition except containing or (b1) and (b2) the composition also can contain various monomer components.As this monomer component, can enumerate the compound with ethene unsaturated group, can enumerate the monofunctional monomer with 1 ethene unsaturated group and the polyfunctional monomer with 2～5 ethene unsaturated groups.According to suitable one kind or two or more these compositions of choice for use of the required characteristic of the photosensitive polymer combinations such as viscosity of polymerisation reactivity, monomer.In addition, with respect to (A) composition 100 mass parts, (b1) composition and (b2) below preferred 80 mass parts of addition of the monomer component beyond the composition, more preferably 1～60 mass parts.Be below the higher limit by making its addition, can be at the enough cross-linking densities of resin pattern inner sustain, and can improve patience acid, alkaline etching liquid.
The film thickness of the pattern that forms as etching mask is the situation of 3.5～5 μ m
Film thickness at resin pattern is under the thick film condition of 3.5～5 μ m, is advantage for obtaining sufficient elching resistant.But, because the film thickness of resin pattern is thicker, if therefore the resin pattern internal crosslinking excessively carries out, then after etching work procedure finishes, can not fully removes resin pattern and produce the residue problem.Therefore, to be lower than the film thickness of resin pattern be the above-mentioned situation of 1～3 μ m to preferred internal crosslinking density.
Therefore, when under the film thickness of resin pattern is the condition of 3.5～5 μ m, carrying out etching work procedure among the present invention, above-mentioned (b1) composition is the monomer of trifunctional, further contain in preferred (B) composition the following monomer of difunctionality (below be also referred to as " (b3) composition ".)。By with above-mentioned (b1) composition and (b3) composition add in the photosensitive polymer combination as (B) composition, can prevent from making the cross-linking density of inside of the resin pattern that this photosensitive polymer combination photocuring obtains too high, even and form resin pattern by thicker film, also available stripper is removed well after etching work procedure finishes.
At this moment; as (b1) composition, can enumerate: trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (methyl) acrylic acid glyceride, triacryl formal (Tracrylformal) etc.These trifunctional monomers can use separately or be used in combination more than 2 kinds.
As (b3) composition, can enumerate: (methyl) acrylamide, methylol (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxyl group methyl (methyl) acrylamide, butoxy methoxy (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methylol (methyl) acrylamide, (methyl) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methyl propane sulfonic acid, N-tert-butyl acrylamide sulfonic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid-2-phenoxy group-2-hydroxy propyl ester, phthalic acid-2-(methyl) acryloxy-2-hydroxy propyl ester, single (methyl) acrylic acid glyceride, (methyl) tetrahydrofurfuryl acrylate, amino (methyl) acrylic acid dimethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid-2,2, the 2-trifluoro ethyl ester, (methyl) acrylic acid-2,2,3,3-tetrafluoro propyl ester, the monofunctional monomers such as half (methyl) acrylate of phthalic acid derivatives; Ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, six ethylene glycol (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, two (methyl) acrylic acid glyceride, pentaerythrite two (methyl) acrylate, two (4-(methyl) the acryloxy polyethoxy phenyl) propane of 2,2-, (methyl) acrylic acid-2-hydroxyl-3-(methyl) acryloxy propyl ester, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, polyurethane (methyl) acrylate (being toluene diisocyanate), the reactant of trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate and (methyl) acrylic acid 2-hydroxyl ethyl ester, di-2-ethylhexylphosphine oxide (methyl) acrylamide, the bifunctional monomers such as (methyl) acrylamide methylene ether.Above-mentioned monomer can use separately or be used in combination more than 2 kinds.
In above-mentioned (b3) composition of enumerating, preferably use the straight chain bifunctional monomer of EO modification, particularly preferably use triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, six glycol diacrylates etc.
With respect to (A) composition 100 mass parts, the content of above-mentioned (b1) composition is preferably 30～200 mass parts, more preferably 35～160 mass parts.Be more than the lower limit by making its content, can obtain excellent elching resistant; Be below the higher limit by making its content, can be after etching work procedure finishes with stripper good remove resin pattern.
With respect to (A) composition 100 mass parts, the content of above-mentioned (b3) composition is preferably 1～60 mass parts, more preferably 2～55 mass parts.Be more than the lower limit by making its content, between etching work procedure and resin pattern stripping process, be provided with in the manufacture method of etched basal body of the present invention for the treatment of fluid temperature difference, can realize simultaneously the easy removability of elching resistant and resin pattern.That is, in the etching work procedure that carries out under the low temperature (for example, 20 ℃～45 ℃) expansion of resin pattern little, so can prevent peeling off of resin pattern; Because the expansion of resin pattern is large in the stripping process of the resin pattern that carries out under the high temperature (for example, being preferably 50 ℃～65 ℃), therefore can promote peeling off of resin pattern.In addition, be below the higher limit by making its content, can obtain excellent elching resistant.
[Photoepolymerizationinitiater initiater (C)]
The contained Photoepolymerizationinitiater initiater of photosensitive polymer combination of the present invention (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; CTX; 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,α-dichloro-4-phenoxy acetophenone; thioxanthones; 2-methyl thioxanthones; ITX; 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.
(C) content of composition can suitably be adjusted according to the content of (B) 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.Be above-mentioned scope by making its content, can obtain sufficient thermotolerance, resistance to chemical reagents, also can improve filming performance, it is bad to suppress photocuring.
[sensitizer]
Photosensitive polymer combination of the present invention can contain have mercapto compound as sensitizer.When irradiating ultraviolet light, this sensitizer produces the S free radical by alkene-thiol reactant (ene-thiol reaction).The polyreaction that the S free radical causes is not subjected to the impact of oxygen resistance and promotes therefore can improve the curing of photosensitive polymer combination the residual film ratio of pattern when developing, and improve elching resistant.As this compound, can enumerate: the ester classes such as trimethylolpropane tris (3-mercaptopropionic acid ester); The alcohols such as 2 mercapto ethanol, 1-sulfo-glycol, single mercaptoacetic acid glyceride (glycerol monothioglycollate), 4-mercapto-phenol; Mercaptoacetic acid, 3-mercaptopropionic acid, 2 mercaptopropionic acid, thiomalic acid, mercaptoisobutyric acid, internal compensation-2, the carboxylic acidss such as 3-dimercapto isobutyric acid, thiosalicylic acid; The amines such as 2-aminoothyl mercaptan, 2-amino thiophenol, 4-amino thiophenol; Halfcystine etc.
The content of the sensitizer in the photosensitive polymer combination, can according to (A) composition and (B) content of composition suitably adjust, 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 particularly preferably 1～15 mass parts.Be above-mentioned scope by making its content, can improve development and elching resistant.
[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, DPE, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) the alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether; (gathering) the 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; The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone; The 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, the 3-methoxy methyl propionate, 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, propyl butyrate, 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; The arene such as toluene, dimethylbenzene; The amide-types such as 1-METHYLPYRROLIDONE, DMF, DMA etc.These solvents can be used singly or in combination.
The content of organic solvent is not particularly limited, and can under concentration that can coated substrates etc., suitably select according to coated film thickness.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 the 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 the compounds such as anionic species, cationic, nonionic class.
[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 〉
Photosensitive polymer combination according to table 1～table 4 Preparation Example 1～17 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 configuration alkali soluble resin (A) are used for the preparation of photosensitive polymer combination.Wherein, table 1～table 4 neutral and alkali soluble resin (A-1 or A-2) 100 mass parts refer to 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 (1), formula (2) and the formula (3) 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 4]
[in the formula (1), R
4Expression alkyl or hydroxy alkyl, in formula (1), formula (2) and the formula (3), 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: tetraethylene glycol diacrylate (bifunctional monomer)
B-2: tricyclodecane methanol diacrylate (tricyclo deccan methanol diacrylate) (bifunctional monomer)
B-3:TMPTA (trimethylolpropane triacrylate, trifunctional monomer)
B-4:DPHA (dipentaerythritol acrylate, six functional monomers)
B-5:CN9006 (サ one ト マ one society's system, urethane acrylate, six functional monomers)
B-6: acryloyl morpholine (nitrogenous monofunctional monomer)
B-7:CN2300 (サ one ト マ one society's system, eight functional monomers)
B-8:CN2302 (サ one ト マ one society's system, 16 functional monomers)
B-9: acrylic acid 2-phenoxy ethyl
Photoepolymerizationinitiater initiater (C)
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 (soil conservation ケ paddy chemical industry Co., Ltd. system)
[table 1]
[table 2]
[table 3]
[table 4]
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 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 ℃ lower dry 6 minutes, obtain having 2.0 μ m, the evaluation substrate of the photo-sensitive resin of 2.5 μ m or 5 μ m film thicknesses.Then, the process negative mask is with 75mJ/cm
2Exposure to the ultraviolet ray of these photo-sensitive resin elective irradiations (light source: extra-high-pressure mercury vapour lamp), the sodium carbonate liquor that uses 0.25 quality % as developer solution 30 ℃ of lower 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 (in order to estimate patience with estimating substrate, dip time is longer than common program), carry out etching to being positioned at the 2nd the most surperficial Cr layer, wash with pure water.Then, adjust the HCl/FeCl of 0.3/0.3/0.3 (mol/L ratio)
3/ Cu
2+Aqueous solution is as acidic etching liquid, with estimating substrate and be immersed in 30 ℃ the acidic etching liquid, while shake Cu layer etching 60 seconds, washs with pure water.At last, to the Na of 5 quality %
2SiO
3Add the potassium permanganate of 5 quality % in the aqueous solution and make alkaline etching liquid, with estimating substrate and be immersed in this alkaline etching liquid of 40 ℃ 10 minutes, carry out etching to being positioned at a undermost Cr layer, wash with pure water.
After etching work procedure finishes, 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
According to said sequence, with embodiment 1,3～6 and the photosensitive polymer combination of comparative example 1～3 make the evaluation substrate of the resin pattern with 5 μ m film thicknesses; The photosensitive polymer combination of embodiment 7～16 is made the evaluation substrate of the resin pattern with 2.5 μ m film thicknesses; Embodiment 2,7,10 and 17 photosensitive polymer combination are made the evaluation substrate of the resin pattern with 2.0 μ m film thicknesses.Then, respectively each is estimated substrate and carry out etching, estimate residual film ratio after developing, peel off after patience (elching resistant), the etching of liquid finished and have or not residue after needed time of resin pattern and resin pattern are peeled off.Its result is shown in table 5～table 9.Evaluation method and the metewand of projects are as described below.In addition, use the embodiment 1 that estimates with 5 μ m film thicknesses and 3～6 photosensitive polymer combination, make the evaluation substrate of the resin pattern with 2.5 μ m film thicknesses, when estimating, all do not obtain acid, alkali patience (being evaluated as following △).
[residual film during development]
By photo-sensitive resin is exposed 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]
Resin pattern after finishing by the etching work procedure of observing the 2nd Cr layer, Cu layer and a Cr layer peel off situation evaluation.
◎: etching work procedure is not observed peeling off of resin pattern after finishing.
Zero: peel off (released part is in area occupation ratio less than 5%) that does not almost observe resin pattern after etching work procedure finishes.
△: resin pattern had occured to peel off after etching work procedure finished.(released part with area occupation ratio count more than 5%, less than 30%).
*: in the etching work procedure, (released part is counted more than 30% with area occupation ratio) occured to peel off in the major part of resin pattern.
[splitting time]
Estimate by peeling off the needed time of resin pattern with alkaline stripper after the etching work procedure end.
Zero: peeling off the needed time is less than 100 seconds
△: peeling off the needed time is more than 100 seconds, below 150 seconds
*: peel off the needed time above 150 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 rear resin pattern has a little residual.
*: peeling off rear resin pattern has residual in a large number.
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
Can be confirmed that by the above results embodiment 1～17 has good acid, alkali patience (elching resistant) with respect to comparative example 2～3.Hence one can see that, contains the composition of the specific alkali soluble resin of the present invention by use, can improve the elching resistant that makes photosensitive polymer combination solidify the resin pattern of gained.
Can also confirm that by the above results embodiment 2 and 7～17 compares with embodiment 1 and 3～6, its film (2.5 μ m or 2.0 μ m) has more excellent acid, alkali patience.Hence one can see that, when making the resin pattern of film and carrying out etching, and the preferred photosensitive polymer combination that contains the above monomer of six senses that uses.
Shown in the result of embodiment 2 and 7～17, because with respect to alkali soluble resin 100 mass parts, the content of above-mentioned polyfunctional monomer is in the scope of 110～200 mass parts, even therefore film (2.5 μ m or 2.0 μ m) also can obtain good acid, alkali patience.
In addition, shown in the result of embodiment 13～16, namely contain the photosensitive polymer combination of acryloyl morpholine by using nitrogenous monofunctional monomer, can improve acid, alkali patience.Supposition is because not only monofunctional monomer has the effect that improves the resin pattern flexibility, and by by the existence of being introduced the nitrogen-atoms of resin by acryloyl morpholine, also has the effect that improves tack between substrate and the resin pattern.
Can confirm in addition, embodiment 1,3 and 4, the splitting time of thick film (5 μ m) is short.Hence one can see that, as long as with respect to resin 100 mass parts, multifunctional (trifunctional) monomer is that 30～100 mass parts, the following monomer of difunctionality are 1～60 mass parts, can improve the resin pattern fissility.
These results are discussed, then can infer, the such polyfunctional monomer of six functional monomers increases the cross-linking density of resin, therefore not only can improve acid, alkali patience, also plays the effect that the delayed resin pattern is peeled off.Therefore be appreciated that at film resin pattern (1～3 μ m) like this with respect to the existence of acid, alkaline liquid be harsh conditions and resin pattern peel off in the easier situation the preferred photosensitive polymer combination that contains six functional monomers that uses.On the other hand, the resin pattern of thick film for (3.5～5 μ m) with respect to the existence of acid, alkaline liquid be like this peeling off of the condition that relatively relaxes but resin pattern can the situation of difficult under, the preferred photosensitive polymer combination that contains the less monomer of this functional group's number of trifunctional monomer that uses.In addition, by using these photosensitive polymer combinations, and carrying out etching work procedure below 45 ℃, and the operation of under 50～80 ℃, peeling off resin pattern, can satisfy simultaneously the liquid patience (acid, alkali patience) of resin pattern and these two kinds of opposite performance requirements of fissility that resin pattern is produced by alkaline stripper.
Claims (9)
1. the manufacture method of an etched basal body is characterized in that the method comprises:
Photosensitive resin coating composition on matrix, the operation of formation photo-sensitive resin;
After described photo-sensitive resin carried out selectivity exposure, develop to form the operation of resin pattern; And
With described resin pattern as mask, the etching work procedure that uses acidity below 45 ℃ or alkaline etching liquid described matrix to be carried out selective etch;
The operation of using 50～80 ℃ alkaline stripper that described resin pattern is peeled off;
Described photosensitive polymer combination comprises: the alkali soluble resin 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 that trifunctional is above; Photoepolymerizationinitiater initiater;
The above polyfunctional monomer of described trifunctional refers in the presence of Photoepolymerizationinitiater initiater to have the monomer component of the two keys of ethene that can carry out addition polymerization more than 3 under irradiation in 1 molecule;
The film thickness of described photo-sensitive resin is 1～3 μ m;
Described polyfunctional monomer is the above monomers of six senses.
2. the manufacture method of etched basal body as claimed in claim 1, it is characterized in that: described alkaline stripper contains inorganic alkaline compound.
3. the manufacture method of etched basal body as claimed in claim 1, it is characterized in that: with respect to described alkali soluble resin 100 mass parts, described polyfunctional monomer content is 110～300 mass parts.
4. the manufacture method of etched basal body as claimed in claim 1, it is characterized in that: described photosensitive polymer combination further contains nitrogenous monofunctional monomer.
5. the manufacture method of etched basal body as claimed in claim 4, it is characterized in that: described nitrogenous monofunctional monomer is acryloyl morpholine.
6. the manufacture method of an etched basal body is characterized in that the method comprises:
Photosensitive resin coating composition on matrix, the operation of formation photo-sensitive resin;
After described photo-sensitive resin carried out selectivity exposure, develop to form the operation of resin pattern; And
With described resin pattern as mask, the etching work procedure that uses acidity below 45 ℃ or alkaline etching liquid described matrix to be carried out selective etch;
The operation of using 50～80 ℃ alkaline stripper that described resin pattern is peeled off;
Described photosensitive polymer combination comprises: the alkali soluble resin 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 that trifunctional is above; Photoepolymerizationinitiater initiater;
The above polyfunctional monomer of described trifunctional refers in the presence of Photoepolymerizationinitiater initiater to have the monomer component of the two keys of ethene that can carry out addition polymerization more than 3 under irradiation in 1 molecule;
The film thickness of described photo-sensitive resin is 3.5～5 μ m;
Described polyfunctional monomer is trifunctional monomer;
Described photosensitive polymer combination further contains the following monomer of difunctionality.
7. the manufacture method of etched basal body as claimed in claim 6, it is characterized in that: with respect to described alkali soluble resin 100 mass parts, the content that contains described polyfunctional monomer is 30～100 mass parts, and the content that contains the following monomer of described difunctionality is 1～60 mass parts.
8. the manufacture method of etched basal body as claimed in claim 1 is characterized in that:, the described alicyclic epoxy base unsaturated compound that contains is more than 15 % by mole with respect to the described ratio that contains the acidic group acrylic resin.
9. the manufacture method of etched basal body as claimed in claim 1 is characterized in that:
Described matrix is the matrix that is formed with successively a Cr layer, Cu layer, the 2nd Cr layer on substrate;
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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| JP5697965B2 (en) * | 2010-06-08 | 2015-04-08 | 住友化学株式会社 | Photosensitive resin composition |
| CN103365087B (en) * | 2012-03-28 | 2019-03-08 | 东京应化工业株式会社 | Insulating film forms the forming method with photosensitive polymer combination, insulating film and insulating film |
| CN104216227A (en) * | 2013-05-28 | 2014-12-17 | 株式会社田村制作所 | Photosensitive resin composition |
| TWI480697B (en) * | 2013-06-10 | 2015-04-11 | Chi Mei Corp | Photosensitive resin composition and applications thereof |
| KR101505187B1 (en) | 2014-05-12 | 2015-03-23 | 주식회사 티지오테크 | Method for forming pattern on the basis of peeling phenomenon and method for manufacturing solar cell using the same |
| TWI550348B (en) * | 2015-07-03 | 2016-09-21 | 臻鼎科技股份有限公司 | Composition, tape, and film and circuit board using the same |
| CN108017747B (en) * | 2016-10-31 | 2021-03-05 | 固安鼎材科技有限公司 | Alkali-soluble resin polymer, preparation method thereof and photosensitive resin composition |
| JP2020076945A (en) * | 2018-09-21 | 2020-05-21 | 旭化成株式会社 | Photosensitive resin composition |
| KR20210149691A (en) * | 2019-03-29 | 2021-12-09 | 다이요 잉키 세이조 가부시키가이샤 | Photoresist composition and cured product thereof |
| CN112759976A (en) * | 2019-11-04 | 2021-05-07 | 北京氦舶科技有限责任公司 | Touch screen conductive circuit protection ink and preparation method and construction process thereof |
| CN110824841A (en) * | 2019-11-20 | 2020-02-21 | 叶顺闵 | Method for improving yield of wafer edge device |
| CN113956715A (en) * | 2021-12-10 | 2022-01-21 | 北京大华博科智能科技有限公司 | Anti-etching ink for ink-jet printing |
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2008
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1276011A1 (en) * | 2000-03-29 | 2003-01-15 | Kanagawa University | Photocurable/thermosetting resin composition, photosensitive dry film formed therefrom, and method of forming pattern with the same |
| CN1965267A (en) * | 2004-05-26 | 2007-05-16 | 昭和电工株式会社 | Photosensitive resin composition, and cured product and use thereof |
| JP2006133378A (en) * | 2004-11-04 | 2006-05-25 | Tokyo Ohka Kogyo Co Ltd | Photosensitive resin composition and photosensitive dry film using the same |
| JP2007322546A (en) * | 2006-05-30 | 2007-12-13 | Taiyo Ink Mfg Ltd | Photosetting and thermosetting solder resist composition, and printed wiring board using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101762970A (en) | 2010-06-30 |
| JP2010152154A (en) | 2010-07-08 |
| JP5404028B2 (en) | 2014-01-29 |
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