CN101910943A - Layered photosensitive-resin product - Google Patents
Layered photosensitive-resin product Download PDFInfo
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- CN101910943A CN101910943A CN2008801229434A CN200880122943A CN101910943A CN 101910943 A CN101910943 A CN 101910943A CN 2008801229434 A CN2008801229434 A CN 2008801229434A CN 200880122943 A CN200880122943 A CN 200880122943A CN 101910943 A CN101910943 A CN 101910943A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
A layered photosensitive-resin product which includes a photosensitive-resin layer having a thickness of 3-15 mu m and which, despite the small photosensitive-layer thickness, has satisfactory tenting properties even when exposed by direct writing exposure. This layered product upon development gives aggregates which are not oily. The layered photosensitive-resin product comprises superposed layers composed of a base layer and a photosensitive-resin layer. This product is characterized in that the photosensitive-resin layer is made of a photosensitive resin composition and that the photosensitive resin composition comprises (a) 25-64 mass% alkali-soluble resin, (b) a compound having a photopolymerizable unsaturated double bond, and (c) 0.1-20 mass% photopolymerization initiator. The product is further characterized by satisfying the following (i), (ii), and (iii): (i) a specific photopolymerizable unsaturated compound is contained in an amount of 30-55 mass% based on the whole photosensitive resin composition; (ii) the alkali-soluble resin (a) has a weight-average molecular weight of 70,000-220,000 and an acid equivalent of 100-600; and (iii) the photosensitive-resin layer has a thickness of 3-15 mu m.
Description
Technical field
The present invention relates to be laminated to by the photosensitive polymer combination that alkaline aqueous solution can develop photosensitive-resin layered product on the supporting layer, use this photosensitive-resin layered product on substrate, to form the method for corrosion-resisting pattern and the purposes of this corrosion-resisting pattern.Say in further detail, relate to the photosensitive polymer combination of the corrosion-resisting pattern that in following parts manufacturing, provides suitable: the manufacturing of printed-wiring board (PWB), the manufacturing of flexibility printed circuit board; The IC chip carries the manufacturing with lead frame (hereinafter referred to as lead frame); The semiconductor package body manufacturing of the metal forming Precision Machining of metal mask manufacturing etc., BGA (BGA Package) or CSP (chip size packages) etc.; With TAB (automatic carrier band bonding: Tape Automated Bonding) or COF (cover brilliant film (Chip On Film): be the manufacturing of the belt base plate of representative the material that on the fine wiring board of film like, carries semiconducter IC); The manufacturing of semiconductor projection; The manufacturing of parts such as ITO electrode, addressing electrode or electromagnetic wave shield in the field of flat panel displays.
Background technology
In the past, printed-wiring board (PWB) was made by photoetching process.So-called photoetching process is meant photosensitive polymer combination is coated on the substrate, and make the exposed portion polymerizing curable of this photosensitive polymer combination by pattern exposure, remove unexposed portion and on substrate, form corrosion-resisting pattern by developer solution, implement etching or plating and handle the formation conductive pattern, then this corrosion-resisting pattern is peeled off from this substrate and removed, thereby on substrate, form the method for conductive pattern.
In the above-mentioned photoetching process, when being coated on photosensitive polymer combination on the substrate, in can making with the following method any: at base plate coating photoresist agent solution and make its dry method, perhaps on substrate successively the layer that forms by supporting layer, photosensitive polymer combination of lamination (hereinafter also claim " photo-sensitive resin ".) and the photosensitive-resin layered product of protective seam as required (hereinafter also claim " dry film against corrosion ".) method.And in the manufacturing of printed-wiring board (PWB), most dry films against corrosion that use the latter.
Be summarized as follows for the method for using above-mentioned dry film against corrosion to make printed-wiring board (PWB).
At first, dry film against corrosion has protective seam for example under the situation of polyethylene film, by photo-sensitive resin it is peeled off.Then use laminating machine substrate for example on the copper clad laminate with the sequential layer pressure sensitivity photosensitiveness resin bed and the supporting layer of this substrate, photo-sensitive resin, supporting layer.Then, by across photomask,, thereby make the exposed portion polymerizing curable with this photo-sensitive resin of ultraviolet exposure that contains the i ray (365nm) that extra-high-pressure mercury vapour lamp sends with line pattern.Peel off for example polyethylene terephthalate of supporting layer then.By developer solution, for example have the unexposed portion that photo-sensitive resin is removed in weakly alkaline aqueous solution dissolving or dispersion then, make it on substrate, form corrosion-resisting pattern.
Use the corrosion-resisting pattern on the substrate that operation like this forms, roughly be divided into 2 kinds of methods, method that the metal part that will be not be coated by resist is removed by etching and the method that has metal by plating as the method for making metal conductor pattern.Especially recently from the easy aspect of technology, use the former method more.
In the method for removing the metal part by etching,, etched by covering the metal of avoiding in the hole with the curing etchant resist for the via that the through hole that is used for substrate (through hole) is connected with interlayer.This process is called hole (tenting) method of covering.In etching work procedure, can use for example cupric chloride, iron chloride, cupric ammine complex solution.
Follow the miniaturization of line segregation in the printed-wiring board (PWB) in recent years,, dry film against corrosion is required high resolving power and high hole covering character in order to make the pattern of thin space with good yield rate.As the method that improves resolution; by making dry film attenuation against corrosion; can improve easily; and it is opposite; the drag of bringing by the spraying by developing procedure, etching work procedure to the physical property external force of film dies down, and exists in the problem that can not protect through hole, via (hole covering character is unexcellent) in developing procedure, the etching work procedure.
Patent documentation 1 discloses in the unsaturated compound in the photosensitive polymer combination because the many and excellent photoresist of 3 functional monomers.Yet, only recorded and narrated the ratio of 3 functional monomers in the unsaturated compound, in certain scope, there is the unexcellent problem of hole covering character.Patent documentation 1 aftermentioned is in comparative example.
Patent documentation 2 discloses the photoresist that utilizes 4 functional monomers' excellence as the unsaturated compound in the photosensitive polymer combination.Yet, use they directly describe have the unexcellent problem of hole covering character in exposing.
Patent documentation 3 discloses the photoresist that utilizes 3 functional monomers' excellence in the unsaturated compound in the photosensitive polymer combination.Yet, utilize the film used them directly describe have the unexcellent problem of hole covering character in exposing.
Yet, when in photosensitive polymer combination, comprising these polyfunctional monomers in a large number, also have the problem that produces the aggregation of oily when developing.
Therefore, though seek directly describe the exposure in hole covering character also good, in addition, the aggregation during development is not an oily, and the yet few material of the aggregation of powdery.
Patent documentation 1: Japanese kokai publication hei 11-119422 communique
Patent documentation 2: TOHKEMY 2000-347400 communique
Patent documentation 3: TOHKEMY 2002-228871 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of photosensitive-resin layered product, even if when the thickness of photo-sensitive resin is as thin as 3～15 μ m, even if when directly describing to expose, hole covering character is also good, in addition, the oily aggregation when not taking place to develop, and the aggregation of powdery is also few.
The scheme that is used to deal with problems
Above-mentioned problem can realize by the following technical scheme of the present invention.
That is of the present invention theing contents are as follows.
1. a photosensitive-resin layered product is characterized in that, it is the photosensitive-resin layered product that lamination supporting layer at least and photo-sensitive resin form, and this photo-sensitive resin is formed by photosensitive polymer combination, and this photosensitive polymer combination comprises at least:
(a) alkali soluble resin 25～64 quality %,
(b) compound with unsaturated double-bond of photopolymerization,
(c) Photoepolymerizationinitiater initiater 0.1～20 quality %,
And further satisfy following (i), (ii) and (iii):
(i) as the compound with unsaturated double-bond of described (b) photopolymerization, with respect to the total amount of photosensitive polymer combination, contain the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound of the compound of following general formula (I) expression and following general formula (II) expression of 30～55 quality %;
The weight-average molecular weight of (ii) described (a) alkali soluble resin is 70000～220000, acid equivalent is 100～600;
(iii) the thickness of photo-sensitive resin is 3～15 μ m,
(Chemical formula 1)
(in the formula, R
1, R
2And R
3Be H or CH independently of one another
3, n
1, n
2, n
3And n
4Being 0～4 integer independently of one another, can be 0 simultaneously also.W is with CH
3The perhaps group represented of OH.)
(Chemical formula 2)
(in the formula, R
5, R
6, R
7And R
8Be H or CH independently of one another
3, m
1, m
2, m
3And m
4Being 0～4 integer independently of one another, can be 0 simultaneously also.)
2. according to above-mentioned 1 described photosensitive-resin layered product, wherein, compound as described (b) photopolymerization with unsaturated double-bond, with respect to the total amount of photosensitive polymer combination, contain the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound of the compound of described general formula (I) expression and described general formula (II) expression of 35～55 quality %.
3. above-mentioned 1 or 2 described photosensitive-resin layered products, wherein, (c) Photoepolymerizationinitiater initiater is the 9-phenylacridine.
4. each described photosensitive-resin layered product in above-mentioned 1～3, it is characterized in that, if with respect to the ratio of above-mentioned (a) alkali soluble resin of photosensitive polymer combination total amount is the ratio of the compound with unsaturated double-bond of A quality %, above-mentioned (b) photopolymerization when being B quality %, A/B is 1.1～1.3.
5. the formation method of a corrosion-resisting pattern, it comprises: press lamination, the ultraviolet exposure process that exposes of stating the photo-sensitive resin of each described photosensitive-resin layered product in 1～4, the developing procedure of removing unexposed portion on the substrate upper strata.
6. the formation method of above-mentioned 5 described corrosion-resisting patterns is characterized in that, exposes by directly describing in described exposure process.
7. the manufacture method of a conductive pattern, it comprises: use copper clad laminate as substrate, the substrate that is formed with corrosion-resisting pattern by above-mentioned 5 or 6 described methods is carried out the operation of etching or plating.
8. the manufacture method of a printed-wiring board (PWB) is characterized in that, uses the metallic cover insulcrete as substrate, and the substrate that is formed with corrosion-resisting pattern by each described method in above-mentioned 4～7 is carried out etching or plating, peels off corrosion-resisting pattern.
9. the manufacture method of a lead frame is characterized in that, uses sheet metal as substrate, and the substrate that is formed with corrosion-resisting pattern by above-mentioned 4～8 each described methods is carried out etching, peels off corrosion-resisting pattern.
10. the manufacture method of a semiconductor packages, it is characterized in that, the circuit-formed wafer that has been used to complete large scale integrated circuit carries out plating as substrate to the substrate that is formed with corrosion-resisting pattern by above-mentioned 4～9 each described methods, peels off corrosion-resisting pattern.
11. the manufacture method with base material of relief pattern is characterized in that, uses the glass rib as substrate, utilizes blasting craft that the substrate that is formed with corrosion-resisting pattern by above-mentioned 4～10 each described methods is processed, and peels off corrosion-resisting pattern.
The effect of invention
Photosensitive-resin layered product of the present invention has following effect: although the thin thickness to 3 of photo-sensitive resin～15 μ m, even if when directly describing to expose, hole covering character is also good, in addition, do not produce the oily aggregation when developing, and the aggregation of powdery is also few.
Embodiment
Below the present invention is specifically described.
＜photosensitive-resin layered product 〉
Photosensitive-resin layered product of the present invention is characterized in that, it is the photosensitive-resin layered product that lamination supporting layer at least and photo-sensitive resin form, and this photo-sensitive resin is formed by photosensitive polymer combination, and this photosensitive polymer combination comprises at least:
(a) alkali soluble resin 25～64 quality %,
(b) compound with unsaturated double-bond of photopolymerization,
(c) Photoepolymerizationinitiater initiater 0.1～20 quality %,
And further satisfy following (i), (ii) and (iii):
(i) as the compound with unsaturated double-bond of described (b) photopolymerization, with respect to the total amount of photosensitive polymer combination, contain the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound of the compound of following general formula (I) expression and following general formula (II) expression of 30～55 quality %;
The weight-average molecular weight of (ii) described (a) alkali soluble resin is 70000～220000, acid equivalent is 100～600;
(iii) the thickness of photo-sensitive resin is 3～15 μ m,
[chemical formula 3]
(in the formula, R
1, R
2, and R
3Be H or CH independently of one another
3, n
1, n
2, n
3, and n
4Being 0～4 integer independently of one another, can be 0 simultaneously also.W is with CH
3, or the group represented of OH.)
[chemical formula 4]
(in the formula, R
5, R
6, R
7And R
8Be H or CH independently of one another
3, m
1, m
2, m
3And m
4Being 0～4 integer independently of one another, can be 0 simultaneously also.)
During to the record of the use level of each composition in the photosensitive polymer combination, the quality % of the use level of each composition so that the solid constituent total amount in the photosensitive polymer combination is benchmark puts down in writing.
(a) alkali soluble resin
Alkali soluble resin is meant the vinylite that contains carboxyl, for example, the multipolymer of (methyl) acrylic acid, (methyl) acrylate, (methyl) vinyl cyanide, (methyl) acrylamide etc.
(a) alkali soluble resin preferably contains carboxyl, and acid equivalent is 100～600.So-called acid equivalent is meant the quality of the linear polymer of the carboxyl that wherein has 1 equivalent.Acid equivalent is more preferably more than 250 below 450.Improve the viewpoint of anti-development, raising resolution and tack and set out, preferred more than 100, from improving the viewpoint of development and fissility, preferred below 600.The flat natural pond automatic titration device (COM-555) that the mensuration of acid equivalent is to use flat natural pond Industry Co., Ltd to make uses the NaOH of 0.1mol/L to utilize potential difference titration to carry out.
The weight-average molecular weight of (a) alkali soluble resin that the present invention uses is preferred more than 70000 below 220000.From improving the viewpoint of development, preferred below 220000.From the viewpoint of the proterties of hole covering character, aggregation, weight-average molecular weight is preferred more than 70000.Further preferred more than 70000 below 200000.More preferably more than 70000 below 120000.Gel permeation chromatography (GPC) (pump: Gulliver, PU-1580 type that weight-average molecular weight utilizes Japanese beam split Co., Ltd. to make; Post: 4 series connection of the system Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) of Showa Denko K. K; Mobile phase solvent: tetrahydrofuran; Utilize the typical curve of polystyrene standard sample (the Shodex STANDARD SM-105 that Showa Denko K. K makes) to use) try to achieve with polystyrene conversion.
Alkali soluble resin is preferably by at least a above multipolymer of forming at least a above and second monomer described later in first monomer described later.
First monomer is carboxylic acid or the acid anhydrides that has a polymerism unsaturated group in the molecule.For example can enumerate (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and maleic acid half ester.Wherein preferred especially (methyl) acrylic acid.
At this, (methyl) acrylic acid is represented acrylic acid and/or methacrylic acid.Below identical.
Second monomer is the monomer that has a polymerism unsaturated group in nonacid, the molecule at least.For example can enumerate ester class, for example vinyl acetate, (methyl) vinyl cyanide, styrene and the styrene derivative of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, vinyl alcohol.Wherein, preferred (methyl) methyl acrylate, (methyl) n-butyl acrylate, styrene, (methyl) benzyl acrylate.
From the proterties viewpoint of hole covering character, aggregation, (a) alkali soluble resin is 100～600 for containing carboxyl, acid equivalent, weight-average molecular weight is 70000～220000th, preferred implementation of the present invention.
(a) alkali soluble resin is the scope of 25～64 quality % with respect to the comprehensive ratio of photosensitive polymer combination, preferred 40～60 quality %.From characteristic, for example cover the viewpoint that has enough patience in hole, etching and the various plating operation and set out, by more than exposure, the preferred 25 quality % of corrosion-resisting pattern that develop to form below the 64 quality % as resist.
(b) unsaturated compound of photopolymerization
The unsaturated compound of photopolymerization is meant the compound that has at least 1 ethylenic unsaturated bond in the molecule.
In photosensitive polymer combination of the present invention, the unsaturated double-bond compound that has photopolymerization as (b), with respect to the total amount of photosensitive polymer combination, contain the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound and following general formula (II) the expression compound of following general formula (I) expression of 30～55 quality %.
[chemical formula 5]
(in the formula, R
1, R
2, and R
3Be H or CH independently of one another
3, n
1, n
2, n
3, and n
4Being 0～4 integer independently of one another, can be 0 simultaneously also.W is with CH
3, or the group represented of OH.)
[chemical formula 6]
(in the formula, R
5, R
6, R
7And R
8Be H or CH independently of one another
3, m
1, m
2, m
3And m
4Being 0～4 integer independently of one another, can be 0 simultaneously also.)
As the concrete example of the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound of the compound of above-mentioned general formula (I) expression and above-mentioned general formula (II) expression, for example can enumerate in above-mentioned general formula (I) R
1, R
2, and R
3Be H, n
1, n
2, and n
3Be 1 integer, n
4Be 0 integer, W is CH
3Compound (Xin Zhong village chemical industry Co., Ltd. make NK ester A-TMPT-3PO); Identical in above-mentioned general formula (I), R
1, R
2, and R
3Be H, n
1, n
2, and n
3Be 3 integer, n
4Be 0 integer, W is CH
3Compound (Xin Zhong village chemical industry Co., Ltd. make NK ester A-TMPT-9PO) etc.In addition, can be set forth in the above-mentioned general formula (II) R
5, R
6, R
7, and R
8Be H, m
1, m
2, m
3, and m
4Be the compound (the NK ester A-TMMT that Xin Zhong village chemical industry Co., Ltd. makes) of 0 integer, identical in above-mentioned general formula (II), R
5, R
6, R
7, and R
8Be H, m
1, m
2, m
3, and m
4It is the compound (SR-494 that サ one ト マ one ジ ヤ パ Application (strain) society makes) of 1 integer.
Viewpoint from hole covering character, the content that is selected from the unsaturated compound of at least a photopolymerization in the group of being made up of the compound of the compound of above-mentioned general formula (I) expression and above-mentioned general formula (II) expression is 35～55 quality %, more preferably 40～55 quality %.In addition, (b) in the unsaturated compound of photopolymerization, except the compound of above-mentioned general formula (I), above-mentioned general formula (II) expression, can also use the unsaturated compound of the photopolymerization of following expression.For example can enumerate, 1,6-hexanediol two (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, poly-diethylene glycol two (methyl) acrylate, 2-two (p-hydroxy phenyl) propane two (methyl) acrylate, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxy ethyl trimethylolpropane triacrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, beta-hydroxy propyl group-β '-(acryloxy) propyl group terephthalate, phenoxy group polyglycol (methyl) acrylate, Nonylphenoxy polyglycol (methyl) acrylate, Nonylphenoxy gathers alkyl diol (methyl) acrylate, polypropylene glycol list (methyl) acrylate.
Also can enumerate urethane compound in addition.As urethane compound, for example can enumerate, hexamethylene diisocyanate, benzal diisocyanate or diisocyanate cpd, for example 2,2, the compound that has hydroxyl and (methyl) acrylic in 4-trimethyl hexamethylene diisocyanate and a part for example acrylic acid 2-hydroxypropyl acrylate, with the urethane compound of oligomeric propylene glycol monomethyl acrylate.The reactant that hexamethylene diisocyanate and oligomeric propylene glycol monomethyl acrylate (Block レ Application マ one PP1000 that NOF Corp makes) particularly, arranged.They can use separately also and can more than 2 kinds and use.
With respect to the total amount of photosensitive polymer combination, the overall content of unsaturated double-bond compound that (b) that comprises the unsaturated compound of photopolymerization has photopolymerization is 30～55 quality %, preferred 35 quality %～55 quality %.More preferably 40～55 quality %, wherein, the unsaturated compound of described photopolymerization (b) is for being selected from the unsaturated compound of at least a photopolymerization in the group of being made up of the compound of the compound of above-mentioned general formula (I) expression and above-mentioned general formula (II) expression.
In addition, if with respect to the ratio of above-mentioned (a) alkali soluble resin of photosensitive polymer combination total amount is that the ratio of the compound of unsaturated double-bond with photopolymerization of A quality %, above-mentioned (b) is when being B quality %, A/B is 1.1～1.3, and this is a preferred implementation of the present invention.From the viewpoint of hole covering character, A/B is preferred more than 1.1, and more preferably A/B is below 1.3.
(c) Photoepolymerizationinitiater initiater
In the photosensitive polymer combination, can use known substances usually as (c) Photoepolymerizationinitiater initiater.The amount of (c) Photoepolymerizationinitiater initiater that photosensitive polymer combination is contained is the scope of 0.1～20 quality %, and preferred scope is 0.5～10 quality %.From obtaining the viewpoint of sufficient light sensitivity, more than the preferred 0.1 quality %, in addition, from making light be transmitted to the resist bottom surface fully, obtain good high-resolution viewpoint, below the preferred 20 quality %.
As this Photoepolymerizationinitiater initiater, 2-EAQ, octaethyl anthraquinone, 1 are arranged, 2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinones, 9,10-phenanthrenequione, 2-methyl isophthalic acid, 4-naphthoquinones, 9,10-phenanthrenequione, 2-methyl isophthalic acid, 4-naphthoquinones, 2, quinones such as 3-dimethyl anthraquinone, 3-chloro-2-methylanthraquinone; Aromatic series ketone, for example benzophenone, Michler's keton [4,4 '-two (dimethylamino) benzophenone], 4,4 '-two (lignocaine) benzophenone, benzoin or benzoin ethers, for example benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzene acyloin, ethylbenzene acyloin, dialkyl group ketal class, for example benzil dimethyl ketal, benzil diethyl ketal; Thioxanthene ketone, for example diethyl thioxanthone, clopenthixal ketone; Dialkyl amido benzoate class, for example dimethylamino ethyl benzoate; Oxime ester class, for example 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-phenyl-1,2-propanedione-2-(O-carbethoxyl group) oxime; Lophine (Lophine) dipolymer, 2-(Chloro-O-Phenyl)-4 for example, 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-is two-(m-methoxyphenyl) imidazole dimer, 2-(p-anisyl)-4,5-diphenyl-imidazole dipolymer; Acridine compound, for example 9-phenylacridine.These compounds can use separately, also can more than 2 kinds and use.From improving hole covering character, can suppress the viewpoint of the generation of oily aggregation and set out, preferred acridine compound, preferred especially 9-phenylacridine.Think that so-called oily aggregation represents the aggregation that viscosity is high herein, the compound with unsaturated double-bond is a principal ingredient.On the other hand, think that the aggregation of powdery is is principal ingredient with polymerization inhibitor and initiating agent, the condensation product different with the oily aggregation.
(d) other composition
For the operability that makes the photosensitive polymer combination among the present invention improves, also can add leuco dye or fluoran dyes and coloring material.
As leuco dye, can list three (4-dimethylamino phenyl) methane [leuco crystal violet], two (4-dimethylamino phenyl) phenylmethane [procrypsis malachite green].Wherein, when using leuco crystal violet, so contrast is good preferred.Content when containing leuco dye preferably contains 0.1～10 quality % in photosensitive polymer combination.From the viewpoint of performance contrast, more than the preferred 0.1 quality %, in addition, from keeping the viewpoint of storage stability, below the preferred 10 quality %.
In photosensitive polymer combination,, when leuco dye and following halogen compounds are used in combination, be preferred embodiment of the present invention from the viewpoint of tack and contrast.
As coloring material, for example can enumerate basic fuchsin, phthalocyanine green, auramine alkali, paramagenta, crystal violet, methyl orange, Nile blue-2B, Victoria blue, malachite green and (protect native ケ paddy chemistry (strain) system, ア イ ゼ Application (registered trademark) MALACHITE GREEN), alkali blue 20, diamond green (protecting native ケ paddy chemistry (strain) system, ア イ ゼ Application (registered trademark) DIAMOND GREEN GH).Addition when containing coloring material preferably contains 0.001～1 quality % in photosensitive polymer combination.During content more than 0.001 quality %, have the effect that operability improves, during content below 1 quality %, have the effect of keeping storage stability.
In photosensitive polymer combination of the present invention,, also can contain N-aryl-alpha-amino acid compound from the viewpoint of light sensitivity.As N-aryl-alpha-amino acid compound, preferred N-phenylglycine.Below the above 30 quality % of the preferred 0.01 quality % of content when containing N-aryl-alpha-amino acid compound.
In photosensitive polymer combination of the present invention, also can contain halogen compounds.As halogen compounds, for example can enumerate, bromo pentane, bromo isopentane, bromo isobutylene, bromoethylene, bromo diphenyl methane, benzal bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, iodo-pentane, iodo isobutane, 1,1,1-three chloro-2, two (rubigan) ethane of 2-, halogenation triaizine compounds wherein, especially preferably use trisbromomethyl phenyl sulfone.Content when containing halogen compounds is 0.01～3 quality % in photosensitive polymer combination.
And then, for thermal stability, the storage stability that improves photosensitive polymer combination of the present invention, can in photosensitive polymer combination, add the compound more than at least a kind that is selected from the group of forming by radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class.
As such radical polymerization inhibitor, for example can list, p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, protochloride ketone, 2,6-di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso-phenyl azanol aluminium salt and diphenyl nitrosamine.
In addition, as benzotriazole, for example can list, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, two (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, two (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole and two (N-2-hydroxyethyl) aminomethylene-1,2, the 3-benzotriazole.
In addition, as the carboxyl benzotriazole class, for example can list 4-carboxyl-1,2,3-benzotriazole, 5-carboxyl-1,2,3-benzotriazole, N-(N, N-two-2-ethylhexyl) aminomethylene carboxyl benzotriazole, N-(N, N-two-2-hydroxyethyl) the amino ethylidene carboxyl benzotriazole of aminomethylene carboxyl benzotriazole and N-(N, N-two-2-ethylhexyl).
The summation addition of radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class is preferably 0.01～3 quality %, more preferably 0.05～1 quality %.From giving the viewpoint of photosensitive polymer combination storage stability, this amount is preferably more than the 0.01 quality %, in addition, and from keeping the viewpoint of light sensitivity, more preferably below the 3 quality %.
In photosensitive polymer combination of the present invention, can also contain plastifier as required.For example can list as this type of plastifier; polyglycol; polypropylene glycol; PPOX polyoxyethylene ether; the polyoxyethylene monomethyl ether; the PPOX monomethyl ether; polyoxyethylene PPOX monomethyl ether; polyoxyethylene list ether; PPOX list ether; two pure and mild ester classes such as polyoxyethylene PPOX list ether; phthalates such as diethyl phthalate, the o-methyl-benzene sulfonamide; to methyl benzenesulfonamide; tributyl citrate; triethyl citrate; CitroflexA-2; acetyl group citric acid three n-propyls; the acetyl group tri-n-butyl citrate.
As the content of plastifier, preferably in photosensitive polymer combination, contain 5～50 quality %, more preferably 5～30 quality %.From the delay that suppresses development time, the viewpoint of giving the cured film flexibility, more than the preferred 5 quality %, in addition,, be preferably below the 50 quality % from suppressing to solidify the viewpoint of not enough and cold flow.
Photosensitive-resin layered product of the present invention contains photo-sensitive resin and the supporting layer of being made up of photosensitive polymer combination.Also can have protective seam on the surface of the opposite side of the supporting layer side of photo-sensitive resin as required.As supporting layer used herein, the clear support layer that it is desirable to make the light that radiates by exposure light source to see through.As such supporter, can enumerate polyethylene terephthalate thin film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, Vingon film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, plasticon, polyacrylonitrile film, styrol copolymer film, polyamide film and cellulose derivative film.These films can also use the film of drawn as required.Preferred turbidity is below 5.About the thickness of film, the film of thin thickness is being favourable aspect image formation property and the economy, owing to must keep intensity, so preferably use the thickness of 10～30 μ m.
In addition, as the key property of protective seam used in photosensitive-resin layered product, with regard to regard to the adhesion of photo-sensitive resin, compared to supporting layer, the adhesion of protective seam aspect is enough little and can easily peel off.For example, can preferably use polyethylene film and polypropylene film etc. as protective seam.In addition, can use the film of the fissility excellence shown in the Japanese kokai publication sho 59-202457 communique.The thickness of protective seam is preferably 10～100 μ m, more preferably 10～50 μ m.The thickness of the photo-sensitive resin in the photosensitive-resin layered product is according to purposes and difference is preferably 5～100 μ m, more preferably 7～60 μ m.Thickness is thin more, and resolution is high more, and in addition, thickness is thick more, and film strength improves more.
Lamination supporting layer, photo-sensitive resin and the protective seam that is provided with as required and prepare the method for photosensitive-resin layered product of the present invention can adopt known method at present successively.For example, the photosensitive polymer combination that will be used for photo-sensitive resin is in advance made and is dissolved their the uniform solution of solvent, elder generation uses rod to be coated with machine or roll coater is applied to it on supporting layer, drying, the photo-sensitive resin that lamination is made up of this photosensitive polymer combination on supporting layer.Then, as required,, thereby can prepare photosensitive-resin layered product by lamination protective seam on this photo-sensitive resin.
As above-mentioned solvent, can enumerate MEK (MEK) is the alcohols of representative for the ketone of representative and with methyl alcohol, ethanol and isopropyl alcohol.Be that the mode of 500～4000mPa is added in the photosensitive polymer combination at 25 ℃ preferably with the solution viscosity that is coated on the photosensitive polymer combination on the supporting layer.
＜corrosion-resisting pattern formation method 〉
Used the corrosion-resisting pattern of photosensitive-resin layered product of the present invention to form by the operation that comprises lamination, exposure process and developing procedure.The following example that concrete method is shown.
As processed base material, be used for to enumerate copper clad laminate when printed-wiring board (PWB) is made, the glass baseplate that is used for the manufacturing of concavo-convex base material in addition, for example can enumerate, plasma display device with base material and surperficial electrolysis display substrate, organic EL seal closure with or, form the Silicon Wafer and the ceramic base material of through hole.Plasma display is meant behind formation electrode on glass that with base material the coating dielectric layer is coated with next door glass paste then, is implementing the base material that the next door is partly carried out sandblast processing with the glass paste and formed the next door.Is concavo-convex base material to these processed base materials through the product of shot blasting procedure.
At first, use laminating machine to carry out lamination.Have at photosensitive-resin layered product under the situation of protective seam and peel off protective seam, then, use laminating machine that photo-sensitive resin is added thermo-compressed and be laminated on the substrate surface.At this moment, photo-sensitive resin can only be laminated on the single face of substrate surface, also can be laminated on the two sides as required.The heating-up temperature of this moment is generally 40～160 ℃.In addition, add thermo-compressed by carrying out more than the secondary this, and improve adhesion and chemical proofing.At this moment, crimping can be used the two-period form laminating machine with two company's rollers, also can repeated multiple times carry out crimping by roller.
Then, use exposure machine to carry out exposure process.When needing, peel off supporter, and use active light to expose by photomask.Exposure was decided by light illumination and time shutter.Can also use quantometer to measure.
In exposure process, can also use and directly describe exposure method in addition.Directly describe the exposure be to need not to use photomask, and on substrate the mode by directly describing to expose.As light source, for example using wavelength is the semiconductor laser of 350～410nm or ultrahigh pressure mercury lamp etc.Describe pattern and controlled by computer, the exposure under this situation is decided by the translational speed of light illumination and substrate.
Then, use developing apparatus to carry out developing procedure.After exposure, have on the photo-sensitive resin under the situation of supporter this supporter is removed.Then, use the developer solution of alkaline aqueous solution, unexposed portion is developed remove, obtain the resist pattern picture.As alkaline aqueous solution, preferably use Na
2CO
3Or K
2CO
3Aqueous solution.These can suitably be selected according to the characteristic of photo-sensitive resin, normally concentration 0.2～2 quality %, 20～40 ℃ Na
2CO
3Aqueous solution.Can also in this alkaline aqueous solution, sneak into surfactant, defoamer, be used to promote a small amount of organic solvent that develops etc.
Obtain corrosion-resisting pattern by above-mentioned operation, but can also according to circumstances carry out this corrosion-resisting pattern is heated to 100～300 ℃ heating process.By carrying out this heating process, can further improve chemical reagent resistance.Heating can be used the heating furnace of the mode of hot blast, infrared ray or far infrared.
The manufacture method of the manufacture method printed-wiring board (PWB) of＜conductive pattern 〉
The manufacture method of printed-wiring board (PWB) of the present invention is then to use copper clad laminate or flexible substrate as the above-mentioned corrosion-resisting pattern formation method of substrate, carries out through following operation.
At first, the copper face of the substrate that will expose by development uses known method for example etching method or plating method forms conductive pattern.
Then, use have the alkalescence stronger than developer solution aqueous solution with corrosion-resisting pattern from strippable substrate, thereby obtain the printed-wiring board (PWB) of expectation.For the alkaline aqueous solution of peeling off usefulness (below be also referred to as " stripper ".) have no particular limits, use 2～5 quality % concentration, 40～70 ℃ NaOH or the aqueous solution of KOH usually.In stripper, also can add a spot of water-soluble solvent.
The manufacture method of＜lead frame 〉
Lead frame manufacture method of the present invention is then to use sheet metal for example copper, aldary, iron-based alloy carry out through following operation as the above-mentioned corrosion-resisting pattern formation method of substrate.
At first, thus the substrate that exposes by development is carried out etching forms conductive pattern.Then, by peeling off corrosion-resisting pattern, thereby obtain the lead frame of expectation with the same method of the manufacture method of above-mentioned printed-wiring board (PWB).
The manufacture method of＜semiconductor packages 〉
The manufacture method of semiconductor package body of the present invention is then to be used to complete as the circuit-formed wafer of the LSI formation method as the above-mentioned corrosion-resisting pattern of substrate, carries out through following operation.
At first,, implement to utilize the column plating of copper or soldering, thereby form conductive pattern for the peristome that has exposed by development.Then, peel off corrosion-resisting pattern, utilize etching to remove the thin metal layer of column plating part in addition again, thereby obtain the semiconductor package body of expectation by the method that the utilization and the manufacture method of above-mentioned printed-wiring board (PWB) are same.
Embodiment
The present invention will be described based on embodiment.
The evaluation that embodiment and comparative example below be shown is with the evaluation method and the evaluation result of the method for making of sample and the sample that obtains.
1) estimates the making of using sample
Photosensitive-resin layered product in embodiment and the comparative example carries out following making.
The making of＜photosensitive-resin layered product 〉
The solution of the composition shown in the modulometer 1 is so that the solid constituent amount reaches 50 quality %, and fully stir, mix, on as the thick pet film of the 16 μ m that support film (the system R340-G16 of Mitsubishi Chemical society), use and mix the evenly photosensitive polymer combination shown in the coating table 1 of coating machine, drying is 1 minute under 95 ℃.The thickness of dried photo-sensitive resin is 10 μ m.Then on the surface on the photo-sensitive resin, fit, obtain photosensitive-resin layered product as the thick polyethylene film of 35 μ m of protective seam (the system GF-858 of タ マ Port リ society).
＜substrate 〉
Use on insulating resin lamination the thick copper clad laminate of 0.4mm of 35 μ m Copper Foils estimate.Put down in writing its order when in addition, below using other substrate.
＜lamination 〉
The protective seam limit that photosensitive-resin layered product of the present invention is peeled off on the limit is by hot-roll lamination machine (エ of Asahi Chemical Industry Application ジ ニ ア リ Application グ (strain) society makes, AL-700), carries out lamination under 105 ℃ of roll temperatures.Air pressure is 0.35MPa, and laminate speed is 1.5m/min.
＜exposure 〉
Utilize directly describe exposure machine (オ Le ボ テ Star Network society system, Paragon9000) under 8W with 12mJ/cm
2Exposure photo-sensitive resin is exposed.
＜develop
30 ℃ the 1.0 quality %Na of spray stipulated time
2CO
3Aqueous solution, the unexposed portion of photo-sensitive resin is removed in dissolving.Actual development time developed with 24 seconds, and then, the washing time washed with 36 seconds.
2) evaluation method
Except the method that the making to above-mentioned assess sample describes, performance is separately estimated by following method.
＜hole covering character 〉
To on copper clad laminate, carrying out the substrate of two sides lamination by said method, utilizing above-mentioned exposure method to carry out whole directly retouches exposure and obtains cured film, described copper clad laminate is that 0.2mm is thick and be manufactured with the copper clad laminate of 500mm * 500mm of through hole of 2500 0.3mm diameter, develops by above-mentioned developing method.After development, calculate the number of breaking of cured film, according to classification as described below.
◎: the number of breaking is below 25
Zero: the number of breaking surpasses 25 and be below 75
*: the number of breaking is above 75.
The generation of＜oily aggregation 〉
Only the photo-sensitive resin of photosensitive-resin layered product is assembled 2.4m
2, be immersed in the 200ml developer solution, stirred 2 hours down at 30 ℃, make its dissolving.Leave standstill then, carry out classification as described below by the situation of the solution after 72 hours.
Zero: the aggregation, the powdery aggregation that do not produce oily.
△: the aggregation of oily, powdery aggregation are few.
*: the aggregation of oily, powdery aggregation are many.
The peel strength of＜supporting layer (PET) 〉
The substrate of single sided lamination is carried out the photo-sensitive resin of photosensitive-resin layered product by said method in preparation, under 23 ℃, 50% relative humidity, placed 24 hours, then the supporting layer of 1 inch width (being PET herein) being carried out 180 ° peels off, its intensity is measured with テ Application シ ロ Application RTM-500 (the smart machine manufacturing of Japan), carries out classification as described below.
Zero: the very big mean value of peel strength is more than the 3gf.
△: the very big mean value of peel strength is less than 3gf.
3) evaluation result
The evaluation result of embodiment and comparative example is shown in Table 1.The mass parts of B-1～B-4 in the table 1 is the mass parts of solid constituent, does not contain solvent.In order to modulate photosensitive polymer combination, the solid component concentration of making B-1～B-4 in advance is the methyl ethyl ketone solution of 50 quality %, and the solution that cooperates each B-1～B-4 is to reach the solid constituent of table 1.
[table 1]
＜symbol description 〉
B-1: the terpolymer (weight-average molecular weight 100000, acid equivalent 344) of methacrylic acid 25 quality %, methyl methacrylate 65 quality %, butyl acrylate 10 quality %
B-2: the terpolymer (weight-average molecular weight 200000, acid equivalent 370) of methacrylic acid 25 quality %, methyl methacrylate 65 quality %, butyl acrylate 10 quality %
B-3: the terpolymer (weight-average molecular weight 50000, acid equivalent 344) of methacrylic acid 25 quality %, methyl methacrylate 50 quality %, styrene 25 quality %
B-4: the terpolymer (weight-average molecular weight 70000, acid equivalent 344) of methacrylic acid 25 quality %, methyl methacrylate 50 quality %, butyl acrylate 25 quality %
B-5: the bipolymer of benzyl methacrylate 80 quality %, methacrylic acid 20 quality % (weight-average molecular weight 100000, acid equivalent 430)
M-1: to 4 terminal tetraacrylate (サ one ト マ one ジ ヤ パ Application (strain) society makes SR-494) of distinguishing the oxirane of 1 mole of addition of pentaerythrite
M-2: with the tetraacrylate of 4 terminal acrylateization of pentaerythrite
M-3: to the triacrylate (Xin Zhong village chemistry is made A-TMPT-3EO) of the oxirane of 3 moles of the average additions of trimethylolpropane
M-4: to the triacrylate of the epoxypropane of 3 moles of the average additions of trimethylolpropane
M-5: the dimethylacrylate of the two ends of bisphenol-A being distinguished the polyglycol of each oxirane of 2 moles of average addition
M-6: polypropyleneglycol diacrylate
The I-1:9-phenylacridine
The I-2:N-phenylglycine
I-3:2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer
I-4:1-phenyl-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline
I-5:2-(Chloro-O-Phenyl)-4, two (m-methoxyphenyl) imidazole dimers of 5-
D-1: diamond green
D-2: crystal violet
F-1: MEK
In comparative example 1, when using the polymkeric substance of mean molecule quantity not sufficient 70,000, produce the oily aggregation during development as alkali soluble resin, undesirable condition takes place.
In comparative example 2, the ratio of the compound of above-mentioned general formula (II) expression in the photosensitive polymer combination becomes the result that hole covering character worsens less than 30 quality %.
In comparative example 3, the ratio of the compound of above-mentioned general formula (II) expression in the photosensitive polymer combination is greater than 55 quality %, in addition, the ratio of establishing above-mentioned (a) alkali soluble resin with respect to the photosensitive polymer combination total amount is that the ratio of the compound with unsaturated double-bond of A quality %, above-mentioned (b) photopolymerization is when being B quality %, A/B becomes the result that hole covering character worsens less than 1.1.Comparative example 4 is the experiments of appending of Japanese kokai publication hei 11-119422.In comparative example 4, use is equivalent to the unsaturated compound of the polyfunctional photopolymerization of the compound of above-mentioned general formula (I) expression and the compound that above-mentioned general formula (II) is represented, so hole covering character worsens, becomes the result who produces the oily aggregation.
Utilizability on the industry
Photosensitive-resin layered product of the present invention by by lamination substrate expose; protect through hole not to be subjected to the impact of alkaline-based developer, etching solution; thereby can simplify follow-up operation; and because the aggregation of oily is few in developer solution; so the washing of device is few; in addition, be useful in the printed substrate manufacturing of developing by alkali.
Claims (11)
1. a photosensitive-resin layered product is characterized in that, it is the photosensitive-resin layered product that lamination supporting layer at least and photo-sensitive resin form, and this photo-sensitive resin is formed by photosensitive polymer combination, and this photosensitive polymer combination comprises at least:
(a) alkali soluble resin 25～64 quality %,
(b) compound with unsaturated double-bond of photopolymerization,
(c) Photoepolymerizationinitiater initiater 0.1～20 quality %,
And further satisfy following (i), (ii) and (iii):
(i) as the compound with unsaturated double-bond of described (b) photopolymerization, with respect to the total amount of photosensitive polymer combination, contain the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound of the compound of following general formula (I) expression and following general formula (II) expression of 30～55 quality %;
The weight-average molecular weight of (ii) described (a) alkali soluble resin is 70000～220000, acid equivalent is 100～600;
(iii) the thickness of photo-sensitive resin is 3～15 μ m,
[Chemical formula 1]
In the formula, R
1, R
2And R
3Be H or CH independently of one another
3, n
1, n
2, n
3And n
4Being 0～4 integer independently of one another, can be 0 simultaneously also, and W is with CH
3The perhaps group represented of OH,
[Chemical formula 2]
In the formula, R
5, R
6, R
7And R
8Be H or CH independently of one another
3, m
1, m
2, m
3And m
4Being 0～4 integer independently of one another, can be 0 simultaneously also.
2. photosensitive-resin layered product according to claim 1, wherein, compound as described (b) photopolymerization with unsaturated double-bond, with respect to the total amount of photosensitive polymer combination, contain the unsaturated compound that is selected from least a photopolymerization in the group of forming by the compound of the compound of described general formula (I) expression and described general formula (II) expression of 35～55 quality %.
3. claim 1 or 2 described photosensitive-resin layered products, wherein, (c) Photoepolymerizationinitiater initiater is the 9-phenylacridine.
4. photosensitive-resin layered product according to claim 1 and 2, it is characterized in that, if with respect to the ratio of above-mentioned (a) alkali soluble resin of photosensitive polymer combination total amount is the ratio of the compound with unsaturated double-bond of A quality %, above-mentioned (b) photopolymerization when being B quality %, A/B is 1.1～1.3.
5. the formation method of a corrosion-resisting pattern, it comprises: on substrate the lamination of the photo-sensitive resin of lamination claim 1 or 2 described photosensitive-resin layered products, the ultraviolet exposure process that exposes, remove the developing procedure of unexposed portion.
6. the formation method of corrosion-resisting pattern according to claim 5 is characterized in that, exposes by directly describing in described exposure process.
7. the manufacture method of a conductive pattern, it comprises: use copper clad laminate as substrate, the substrate that is formed with corrosion-resisting pattern by claim 5 or 6 described methods is carried out the operation of etching or plating.
8. the manufacture method of a printed-wiring board (PWB) is characterized in that, uses the metallic cover insulcrete as substrate, and the substrate that is formed with corrosion-resisting pattern by claim 5 or 6 described methods is carried out etching or plating, peels off corrosion-resisting pattern.
9. the manufacture method of a lead frame is characterized in that, uses sheet metal as substrate, and the substrate that is formed with corrosion-resisting pattern by claim 5 or 6 described methods is carried out etching, peels off corrosion-resisting pattern.
10. the manufacture method of a semiconductor packages is characterized in that, the circuit-formed wafer that has been used to complete large scale integrated circuit carries out plating as substrate to the substrate that is formed with corrosion-resisting pattern by claim 5 or 6 described methods, peels off corrosion-resisting pattern.
11. the manufacture method with base material of relief pattern is characterized in that, uses the glass rib as substrate, utilizes blasting craft that the substrate that is formed with corrosion-resisting pattern by claim 5 or 6 described methods is processed, and peels off corrosion-resisting pattern.
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| JP2007332226 | 2007-12-25 | ||
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| PCT/JP2008/073391 WO2009081925A1 (en) | 2007-12-25 | 2008-12-24 | Layered photosensitive-resin product |
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Cited By (3)
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| CN110036341A (en) * | 2016-12-05 | 2019-07-19 | 旭化成株式会社 | Photosensitive polymer combination, photoresist lamination body, the manufacturing method of resin pattern and cured film method of manufacturing pattern |
| CN111694218A (en) * | 2014-05-21 | 2020-09-22 | 旭化成株式会社 | Photosensitive resin composition and method for forming circuit pattern |
| CN114437251A (en) * | 2015-04-08 | 2022-05-06 | 旭化成株式会社 | Photosensitive resin composition |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI424269B (en) * | 2011-01-25 | 2014-01-21 | Chunghwa Picture Tubes Ltd | Hydrophilic monomer, hydrophilic photoresist composition containing the same, and resist pattern formation method |
| JP5990366B2 (en) * | 2011-03-31 | 2016-09-14 | 旭化成株式会社 | Laminated body and roll using the same |
| JP2012215787A (en) * | 2011-04-01 | 2012-11-08 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, method for manufacturing resist pattern, and printed wiring board and method for manufacturing the same |
| CN103064253B (en) * | 2012-12-05 | 2015-04-08 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing acridine oxide |
| KR101662706B1 (en) | 2014-10-10 | 2016-10-05 | 율촌화학 주식회사 | Cushioned released composite films and method of matufacturing the same |
| US20230375930A1 (en) * | 2020-10-23 | 2023-11-23 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin multilayer body |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6424247A (en) * | 1987-07-21 | 1989-01-26 | Hitachi Chemical Co Ltd | Photosensitive resin composition |
| JPS6425147A (en) * | 1987-07-22 | 1989-01-27 | Hitachi Chemical Co Ltd | Photosensitive resin composition |
| JPH06214400A (en) * | 1993-01-18 | 1994-08-05 | Sekisui Chem Co Ltd | Production of image display board |
| JP3100039B2 (en) * | 1997-07-04 | 2000-10-16 | 日本合成化学工業株式会社 | Dry film resist for tenting |
| JP2000344812A (en) * | 1999-06-07 | 2000-12-12 | Toyo Ink Mfg Co Ltd | Polymerizable composition |
| JP4609824B2 (en) * | 2001-07-02 | 2011-01-12 | 太陽ホールディングス株式会社 | Photosensitive resin composition |
| JP2004037518A (en) * | 2002-06-28 | 2004-02-05 | Hitachi Chem Co Ltd | Surface irregularities forming method, optical film obtained thereby and diffuse reflector plate and manufacture method for diffuse reflector plate |
| JP2004198993A (en) * | 2002-12-20 | 2004-07-15 | Hitachi Chem Co Ltd | Energy-sensitive negative resin composition and photosensitive element used for organic layer having roughened surface for liquid crystal display device |
| TW200622486A (en) * | 2004-10-14 | 2006-07-01 | Sumitomo Chemical Co | Radiation sensitive resin composition |
| TWI377440B (en) * | 2004-10-14 | 2012-11-21 | Sumitomo Chemical Co | Radiation sensitive resin composition |
| CN1896872A (en) * | 2005-07-12 | 2007-01-17 | 富士胶片电子材料有限公司 | Photo setting composition, color filter and its preparation method |
| JP4761909B2 (en) * | 2005-10-05 | 2011-08-31 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and laminate |
| JP4697031B2 (en) * | 2006-04-21 | 2011-06-08 | Ｊｓｒ株式会社 | Inorganic particle-containing photosensitive resin composition, photosensitive film, and inorganic pattern forming method |
-
2008
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111694218A (en) * | 2014-05-21 | 2020-09-22 | 旭化成株式会社 | Photosensitive resin composition and method for forming circuit pattern |
| CN111694218B (en) * | 2014-05-21 | 2023-09-08 | 旭化成株式会社 | Photosensitive resin composition and method for forming circuit pattern |
| CN114437251A (en) * | 2015-04-08 | 2022-05-06 | 旭化成株式会社 | Photosensitive resin composition |
| CN114437251B (en) * | 2015-04-08 | 2024-02-20 | 旭化成株式会社 | Photosensitive resin composition |
| CN110036341A (en) * | 2016-12-05 | 2019-07-19 | 旭化成株式会社 | Photosensitive polymer combination, photoresist lamination body, the manufacturing method of resin pattern and cured film method of manufacturing pattern |
| CN110036341B (en) * | 2016-12-05 | 2023-06-09 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, method for producing resin pattern, and method for producing cured film pattern |
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| WO2009081925A1 (en) | 2009-07-02 |
| TW200949433A (en) | 2009-12-01 |
| TWI536094B (en) | 2016-06-01 |
| JPWO2009081925A1 (en) | 2011-05-06 |
| KR20100082852A (en) | 2010-07-20 |
| KR101207242B1 (en) | 2012-12-03 |
| JP5107367B2 (en) | 2012-12-26 |
| CN101910943B (en) | 2015-03-25 |
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