CN101910943B - Layered photosensitive-resin product - Google Patents

Layered photosensitive-resin product Download PDF

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Publication number
CN101910943B
CN101910943B CN200880122943.4A CN200880122943A CN101910943B CN 101910943 B CN101910943 B CN 101910943B CN 200880122943 A CN200880122943 A CN 200880122943A CN 101910943 B CN101910943 B CN 101910943B
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photosensitive
compound
resin
substrate
corrosion
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CN101910943A (en
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西本秀昭
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Asahi Kasei Corp
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Asahi Kasei E Materials Corp
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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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • 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

Photosensitive-resin layered product
Technical field
The present invention relates to the photosensitive-resin layered product be laminated to by the photosensitive polymer combination that can be developed by alkaline aqueous solution on supporting layer, use this photosensitive-resin layered product on substrate, 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 providing applicable in following parts manufacture: the manufacture of printed-wiring board (PWB), the manufacture of flexibility printed circuit board; The manufacture of lead frame (hereinafter referred to as lead frame) of IC chip carrying; The semiconductor package body manufacture of the tinsel precision sizing, BGA (BGA Package) or CSP (chip size packages) etc. of metal mask manufacture etc.; With the manufacture that TAB (automatic carrier band bonding: TapeAutomated Bonding) or COF (covering brilliant film (Chip On Film): the material carrying semiconducter IC on the microfine circuit plate of film like) is the belt base plate of representative; The manufacture of semi-conductor projection; The manufacture of the parts such as the ITO electrode in field of flat panel displays, addressing electrode or electromagnetic wave shield.
Background technology
In the past, printed-wiring board (PWB) lithographically manufactured.So-called photolithography refers to and is coated on substrate by photosensitive polymer combination, and the exposed portion polymerizing curable of this photosensitive polymer combination is made by pattern exposure, on substrate, corrosion-resisting pattern is formed by developing solution removing unexposed portion, implement etching or plating process formation conductive pattern, then this corrosion-resisting pattern is peeled off removing from this substrate, thus on substrate, form the method for conductive pattern.
In above-mentioned photolithography, when photosensitive polymer combination is coated on substrate, any one with the following method can be made: make the method for its drying at base plate coating photoresist agent solution, or the layer that lamination is formed by supporting layer, photosensitive polymer combination successively on substrate (hereafter also claims " photo-sensitive resin ".), and the photosensitive-resin layered product of protective layer as required (hereafter also claims " dry film against corrosion ".) method.And in the manufacture of printed-wiring board (PWB), most dry film against corrosion using the latter.
The method using above-mentioned dry film against corrosion to manufacture printed-wiring board (PWB) is summarized as follows.
First, when dry film against corrosion has protective layer such as polyethylene film, peeled off by photo-sensitive resin.Then laminating machine is used on substrate such as copper clad laminate with the sequential layer pressure sensitivity photosensitive resin layer of this substrate, photo-sensitive resin, supporting layer and supporting layer.Then, by across the photomask with line pattern, with this photo-sensitive resin of ultraviolet exposure of the i ray (365nm) sent containing extra-high-pressure mercury vapour lamp, thus exposed portion polymerizing curable is made.Then supporting layer such as polyethylene terephthalate is peeled off.Then by developing solution, such as, there is the unexposed portion of weakly alkaline aqueous dissolution or dispersion removing photo-sensitive resin, make it on substrate, form corrosion-resisting pattern.
Corrosion-resisting pattern on the substrate using like this operation to be formed, is roughly divided into 2 kinds of methods as the method making metal conductor pattern, by not by the coated metallic member of resist by the method for etching removing with by the method for plating with metal.Especially nearest from simple process aspect, the former method multiplex.
In the method by etching removing metallic member, for the via that the communicating pores (through hole) for substrate is connected with interlayer, the metal in hole is avoided to be etched by covering with solidification etchant resist.This processing method is called cap bore (tenting) method.Such as cupric chloride, iron(ic) chloride, cupric ammine complex solution can be used in etching work procedure.
With the miniaturization of line segregation in printed-wiring board (PWB) in recent years, in order to manufacture the pattern of thin space with good yield rate, high resolving power and high hole covering character are required to dry film against corrosion.As putting forward high-resolution method; by making dry film against corrosion thinning; can improve easily; and it is contrary; died down by the drag of the physical property external force to film brought by the spraying of developing procedure, etching work procedure, and there is the problem can not protecting through hole, via (hole covering character is unexcellent) in developing procedure, etching work procedure.
Patent documentation 1 to disclose in the unsaturated compound in photosensitive polymer combination the photo-resist of excellence because 3 functional monomers are many.But, only describe the ratio of 3 functional monomers in unsaturated compound, within the scope of certain, there is the problem that hole covering character is unexcellent.Patent documentation 1 is in a comparative example aftermentioned.
Patent documentation 2 discloses the photo-resist of the excellence utilizing 4 functional monomers as the unsaturated compound in photosensitive polymer combination.But, in the direct description exposure using them, there is the unexcellent problem of hole covering character.
Patent documentation 3 discloses the photo-resist of the excellence utilizing 3 functional monomers in the unsaturated compound in photosensitive polymer combination.But, utilize in the direct description exposure employing their film and there is the unexcellent problem of hole covering character.
But, when comprising these polyfunctional monomers in a large number in photosensitive polymer combination, when also there is development, produce the problem of the aggregation of oily.
Therefore, even if seek directly describing hole covering character in exposure, well, in addition, aggregation during development is not oily yet, and the material that the aggregation of powdery is also few.
Patent documentation 1: Japanese Unexamined Patent Publication 11-119422 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2000-347400 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2002-228871 publication
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 μm, even if with directly describe exposure expose time, hole covering character is also good, in addition, oily aggregation when developing does not occur, and the aggregation of powdery is also few.
for the scheme of dealing with problems
Above-mentioned problem can be realized by the following technical scheme of the present invention.
That is, content of the present invention is as follows.
1. a photosensitive-resin layered product, is characterized in that, it is the photosensitive-resin layered product of at least lamination supporting layer and photo-sensitive resin, and this photo-sensitive resin is formed by photosensitive polymer combination, and this photosensitive polymer combination at least comprises:
(a) alkali soluble resin 25 ~ 64 quality %,
The compound with unsaturated double-bond of (b) photopolymerization,
(c) Photoepolymerizationinitiater initiater 0.1 ~ 20 quality %,
And meet following (i), (ii) and (iii) further:
I () is as the compound with unsaturated double-bond of described (b) photopolymerization, relative to the total amount of photosensitive polymer combination, the unsaturated compound being selected from least one photopolymerization in the group that compound that the compound that represented by following general formula (I) and following general formula (II) represent forms containing 30 ~ 55 quality %;
(ii) weight-average molecular weight of (a) alkali soluble resin described in is 70000 ~ 220000, acid equivalent is 100 ~ 600;
(iii) thickness of photo-sensitive resin is 3 ~ 15 μm,
(chemical formula 1)
(in formula, R 1, R 2and R 3be H or CH independently of one another 3, n 1, n 2, n 3and n 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.W is with CH 3or the group that OH represents.)
(chemical formula 2)
(in formula, R 5, R 6, R 7and R 8be H or CH independently of one another 3, m 1, m 2, m 3and m 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.)
2. the photosensitive-resin layered product according to above-mentioned 1, wherein, as the compound with unsaturated double-bond of described (b) photopolymerization, relative to the total amount of photosensitive polymer combination, the unsaturated compound being selected from least one photopolymerization in the group that compound that the compound that represented by described general formula (I) and described general formula (II) represent forms containing 35 ~ 55 quality %.
3. the photosensitive-resin layered product described in above-mentioned 1 or 2, wherein, (c) Photoepolymerizationinitiater initiater is 9-phenylacridine.
4. the photosensitive-resin layered product according to any one of above-mentioned 1 ~ 3, it is characterized in that, if relative to the ratio of above-mentioned (a) alkali soluble resin of photosensitive polymer combination total amount be A quality %, the ratio with the compound of unsaturated double-bond of above-mentioned (b) photopolymerization be B quality % time, A/B is 1.1 ~ 1.3.
5. a formation method for corrosion-resisting pattern, it comprises: the developing procedure of the unexposed portion that presses the lamination of the photo-sensitive resin of the photosensitive-resin layered product stated according to any one of 1 ~ 4 on substrate upper strata, exposes ultraviolet exposure process, removes.
6. the formation method of the corrosion-resisting pattern described in above-mentioned 5, is characterized in that, by directly describing to expose in described exposure process.
7. a manufacture method for conductive pattern, it comprises: use copper clad laminate as substrate, etch or the operation of plating to the substrate being formed with corrosion-resisting pattern by the method described in above-mentioned 5 or 6.
8. a manufacture method for printed-wiring board (PWB), is characterized in that, uses metallic cover insulcrete as substrate, etches or plating the substrate being formed with corrosion-resisting pattern by the method according to any one of above-mentioned 4 ~ 7, peel off corrosion-resisting pattern.
9. a manufacture method for lead frame, is characterized in that, uses metal sheet as substrate, etches the substrate being formed with corrosion-resisting pattern by the method described in above-mentioned 4 ~ 8 any one, peel off corrosion-resisting pattern.
10. the manufacture method of a semiconductor packages, it is characterized in that, the wafer that the circuit being used to complete large-scale integrated circuit is formed, as substrate, carries out plating to the substrate being formed with corrosion-resisting pattern by the method described in above-mentioned 4 ~ 9 any one, peels off corrosion-resisting pattern.
11. 1 kinds of manufacture method with the base material of concavo-convex pattern, is characterized in that, use Glass Rib as substrate, utilize blasting craft to process the substrate being formed with corrosion-resisting pattern by the method described in above-mentioned 4 ~ 10 any one, peel off corrosion-resisting pattern.
The effect of invention
Photosensitive-resin layered product of the present invention has following effect: although the thickness of photo-sensitive resin is as thin as 3 ~ 15 μm, even if with directly describe exposure expose time, hole covering character is also good, in addition, do not produce oily aggregation during development, 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 of at least lamination supporting layer and photo-sensitive resin, and this photo-sensitive resin is formed by photosensitive polymer combination, and this photosensitive polymer combination at least comprises:
(a) alkali soluble resin 25 ~ 64 quality %,
The compound with unsaturated double-bond of (b) photopolymerization,
(c) Photoepolymerizationinitiater initiater 0.1 ~ 20 quality %,
And meet following (i), (ii) and (iii) further:
I () is as the compound with unsaturated double-bond of described (b) photopolymerization, relative to the total amount of photosensitive polymer combination, the unsaturated compound being selected from least one photopolymerization in the group that compound that the compound that represented by following general formula (I) and following general formula (II) represent forms containing 30 ~ 55 quality %;
(ii) weight-average molecular weight of (a) alkali soluble resin described in is 70000 ~ 220000, acid equivalent is 100 ~ 600;
(iii) thickness of photo-sensitive resin is 3 ~ 15 μm,
[chemical formula 3]
(in formula, R 1, R 2, and R 3be H or CH independently of one another 3, n 1, n 2, n 3, and n 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.W is with CH 3, or the group that represents of OH.)
[chemical formula 4]
(in formula, R 5, R 6, R 7and R 8be H or CH independently of one another 3, m 1, m 2, m 3and m 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.)
When the use level of each composition in photosensitive polymer combination is recorded, the use level of each composition with by the solids component total amount in photosensitive polymer combination for quality % during benchmark records.
(a) alkali soluble resin
Alkali soluble resin refers to the vinylite containing carboxyl, such as, the multipolymer of (methyl) vinylformic acid, (methyl) acrylate, (methyl) vinyl cyanide, (methyl) acrylamide etc.
A () alkali soluble resin is preferably containing carboxyl, and acid equivalent is 100 ~ 600.So-called acid equivalent refers to the quality of the linear polymer of the carboxyl wherein with 1 equivalent.Acid equivalent more preferably less than more than 250 450.Improve resistance to developability, improve the viewpoint of resolving power and tack and set out, preferably more than 100, from the view point of raising developability and separability, preferably less than 600.The mensuration of acid equivalent is flat natural pond automatic titration device (COM-555) using Ping Zhao Industry Co., Ltd to manufacture, and uses the sodium hydroxide of 0.1mol/L to utilize potential difference titration to carry out.
The weight-average molecular weight preferably less than more than 70,000 220000 of (a) alkali soluble resin that the present invention uses.From the view point of raising developability, preferably less than 220000.From the view point of the proterties of hole covering character, aggregation, weight-average molecular weight preferably more than 70000.Further preferably less than more than 70,000 200000.More preferably less than more than 70,000 120000.Gel permeation chromatography (the GPC) (pump: Gulliver, PU-1580 type that weight-average molecular weight utilizes Japan Spectroscopy Corporation to manufacture; Post: Showa Denko K. K Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 series connection; Mobile phase solvent: tetrahydrofuran (THF); The typical curve of polystyrene standard sample (the Shodex STANDARD SM-105 that Showa Denko K. K manufactures) is utilized to use) try to achieve with polystyrene conversion.
Alkali soluble resin is preferably by the multipolymer more than at least one more than at least one in first monomer described later and in second comonomer described later formed.
First monomer is carboxylic acid or the acid anhydrides in molecule with a polymerizability unsaturated group.Can enumerate such as, (methyl) vinylformic acid, fumaric acid, TRANSCINNAMIC ACID, β-crotonic acid, methylene-succinic acid, maleic anhydride and acid half ester.Wherein particularly preferably (methyl) vinylformic acid.
At this, (methyl) vinylformic acid represents vinylformic acid and/or methacrylic acid.Identical below.
Second comonomer is the monomer at least in nonacid, molecule with a polymerizability unsaturated group.Can enumerate such as, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, the ester class of vinyl alcohol, such as vinyl acetate, (methyl) vinyl cyanide, vinylbenzene, and styrene derivatives.Wherein, preferred (methyl) methyl acrylate, (methyl) n-butyl acrylate, vinylbenzene, (methyl) benzyl acrylate.
From the proterties viewpoint of hole covering character, aggregation, (a) alkali soluble resin for be 100 ~ 600 containing carboxyl, acid equivalent, weight-average molecular weight be 70000 ~ 220000 is the preferred embodiment of the present invention.
A () alkali soluble resin is the scope of 25 ~ 64 quality %, preferably 40 ~ 60 quality % relative to the comprehensive ratio of photosensitive polymer combination.From the characteristic as resist, the viewpoint such as, in cap bore, etching and various plating operation with enough patience is set out, corrosion-resisting pattern preferably below more than the 25 quality % 64 quality % formed by exposure, development.
The unsaturated compound of (b) photopolymerization
The unsaturated compound of photopolymerization refers in molecule the compound with at least 1 ethylenic unsaturated bond.
In photosensitive polymer combination of the present invention, there is as (b) the unsaturated double-bond compound of photopolymerization, relative to the total amount of photosensitive polymer combination, be selected from containing 30 ~ 55 quality % the unsaturated compound that the compound that represented by following general formula (I) and following general formula (II) represent the photopolymerization of at least one in the group that compound forms.
[chemical formula 5]
(in formula, R 1, R 2, and R 3be H or CH independently of one another 3, n 1, n 2, n 3, and n 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.W is with CH 3, or the group that represents of OH.)
[chemical formula 6]
(in formula, R 5, R 6, R 7and R 8be H or CH independently of one another 3, m 1, m 2, m 3and m 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.)
As the concrete example of the unsaturated compound of the photopolymerization of at least one be selected from group that compound that the compound that represented by above-mentioned general formula (I) and above-mentioned general formula (II) represent forms, can enumerate such as in above-mentioned general formula (I), R 1, R 2, and R 3for H, n 1, n 2, and n 3be the integer of 1, n 4be the integer of 0, W is CH 3compound (chemical industry Co., Ltd. of Xin Zhong village manufacture NK ester A-TMPT-3PO); Identical in above-mentioned general formula (I), R 1, R 2, and R 3for H, n 1, n 2, and n 3be the integer of 3, n 4be the integer of 0, W is CH 3compound (chemical industry Co., Ltd. of Xin Zhong village manufacture NK ester A-TMPT-9PO) etc.In addition, can be set forth in above-mentioned general formula (II), R 5, R 6, R 7, and R 8for H, m 1, m 2, m 3, and m 4be the compound (chemical industry Co., Ltd. of Xin Zhong village manufacture NK ester A-TMMT) of the integer of 0, identical in above-mentioned general formula (II), R 5, R 6, R 7, and R 8for H, m 1, m 2, m 3, and m 4it is the compound (SR-494 that サ mono-ト マ mono-ジ ヤ パ Application (strain) society manufactures) of the integer of 1.
From the view point of hole covering character, the content being selected from the unsaturated compound of the photopolymerization of at least one in the group that compound that the compound that represented by above-mentioned general formula (I) and above-mentioned general formula (II) represent forms is 35 ~ 55 quality %, more preferably 40 ~ 55 quality %.In addition, in the unsaturated compound of (b) photopolymerization, except the compound that above-mentioned general formula (I), above-mentioned general formula (II) represent, the unsaturated compound of the photopolymerization of following expression can also be used.Can enumerate such as, 1,6-hexylene glycol two (methyl) acrylate, Isosorbide-5-Nitrae-cyclohexanediol two (methyl) acrylate, poly-Diethylene Glycol two (methyl) acrylate, 2-bis-(p-hydroxy phenyl) propane two (methyl) acrylate, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxyethanyl Viscoat 295, tetramethylolmethane 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 polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy gathers alkyl diol (methyl) acrylate, polypropylene glycol list (methyl) acrylate.
Also urethane compound can be enumerated in addition.As urethane compound, can enumerate such as, hexamethylene diisocyanate, benzal vulcabond or diisocyanate cpd, such as 2,2,4-trimethyl hexamethylene diisocyanate, and the compound in a part with hydroxyl and (methyl) acrylic such as vinylformic acid 2-hydroxypropyl acrylate, urethane compound with low polypropylene glycol monomethacrylate.Specifically, the reactant of hexamethylene diisocyanate and low polypropylene glycol monomethacrylate (Block レ Application マ mono-PP1000 that NOF Corp manufactures) is had.They can be used alone and also can two or more also use.
Relative to the total amount of photosensitive polymer combination, the content that (b) that comprise the unsaturated compound of photopolymerization has the unsaturated double-bond compound of photopolymerization overall is 30 ~ 55 quality %, preferably 35 quality % ~ 55 quality %.More preferably 40 ~ 55 quality %, wherein, the unsaturated compound of the photopolymerization of at least one in the group that forms for the compound being selected from the compound that represented by above-mentioned general formula (I) and above-mentioned general formula (II) and representing of the unsaturated compound (b) of described photopolymerization.
In addition, if relative to the ratio of above-mentioned (a) alkali soluble resin of photosensitive polymer combination total amount be A quality %, above-mentioned (b) ratio with the compound of the unsaturated double-bond of photopolymerization be B quality % time, A/B is 1.1 ~ 1.3, and this is the preferred embodiment of the present invention.From the view point of hole covering character, A/B preferably more than 1.1, more preferably A/B less than 1.3.
(c) Photoepolymerizationinitiater initiater
In photosensitive polymer combination, usually can use known material as (c) Photoepolymerizationinitiater initiater.The amount of (c) Photoepolymerizationinitiater initiater contained by photosensitive polymer combination is the scope of 0.1 ~ 20 quality %, and preferred scope is 0.5 ~ 10 quality %.From the view point of obtaining sufficient light sensitivity, preferably more than 0.1 quality %, in addition, being transmitted to resist bottom surface fully from making light, obtaining good high-resolution viewpoint, preferably below 20 quality %.
As this Photoepolymerizationinitiater initiater, there are 2-ethyl-anthraquinone, octaethyl anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinones, 2-phenyl anthraquinone, 2,3-phenylbenzene anthraquinones, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinones, 9,10-phenanthrenequione, 2-MNQ, 9,10-phenanthrenequione, 2-methyl isophthalic acid, the quinones such as 4-naphthoquinones, 2,3-dimethyl anthraquinones, 3-chloro-2-methyl anthraquinone; Aromatic series ketone, such as benzophenone, Michler's keton [4,4 '-bis-(dimethylamino) benzophenone], 4,4 '-bis-(diethylin) benzophenone, bitter almond oil camphor or benzoin ethers, such as bitter almond oil camphor, ethoxybenzoin, bitter almond oil camphor phenyl ether, methylbenzoin, ethyl benzoin, dialkyl group ketal class, such as benzil dimethyl ketal, benzil diethyl ketal; Thioxanthene ketone, such as diethyl thioxanthone, clopenthixal ketone; Dialkyl amido benzoate class, such as dimethylamino ethyl benzoate; Oxime ester class, such as 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime; Lophine (Lophine) dipolymer, such as 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-pair-(m-methoxyphenyl) imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer; Acridine compounds, such as 9-phenylacridine.These compounds can be used alone, and also can two or more also use.From raising hole covering character, the viewpoint of the generation of oily aggregation can be suppressed to set out, preferred acridine compounds, particularly preferably 9-phenylacridine.Think that so-called oily aggregation represents the aggregation that viscosity is high herein, the compound with unsaturated double-bond is main component.On the other hand, thinking that the aggregation of powdery is is main component by stopper and initiator, the condensation product different from oily aggregation.
(d) other composition
In order to make the operability of the photosensitive polymer combination in the present invention improve, leuco dye or fluoran dyes and coloring material also can be added.
As leuco dye, three (4-dimethylamino phenyl) methane [leuco crystal violet], two (4-dimethylamino phenyl) phenylmethane [leucogentian violet] can be listed.Wherein, when using leuco crystal violet, contrast gradient is good therefore preferred.In photosensitive polymer combination, preferably 0.1 ~ 10 quality % is contained containing content during leuco dye.From the view point of performance contrast gradient, preferably more than 0.1 quality %, in addition, from the view point of maintenance storage stability, preferably below 10 quality %.
In photosensitive polymer combination, from the view point of tack and contrast gradient, when leuco dye and following halogen compounds are combinationally used, be preferred embodiment of the present invention.
As coloring material, (soil conservation ケ paddy chemistry (strain) is made can to enumerate such as magenta, phthalocyanine green, auramine alkali, pararosaniline chloride, Viola crystallina, tropeolin-D, Nile blue-2B, victoria blue, malachite green, ア イ ゼ Application (registered trademark) MALACHITEGREEN), alkali blue 20, diamond green (soil conservation ケ paddy chemistry (strain) make, ア イ ゼ Application (registered trademark) DIAMOND GREEN GH).Preferably in photosensitive polymer combination, 0.001 ~ 1 quality % is contained containing addition during coloring material.When the content of more than 0.001 quality %, there is the effect that operability improves, when the content of below 1 quality %, there is the effect maintaining storage stability.
In photosensitive polymer combination of the present invention, from the view point of light sensitivity, also N-aryl-alpha-amino acid compound can be contained.As N-aryl-alpha-amino acid compound, preferred N-phenylglycine.Containing content preferably below more than 0.01 quality % 30 quality % during N-aryl-alpha-amino acid compound.
In photosensitive polymer combination of the present invention, also halogen compounds can be contained.As halogen compounds, can enumerate such as, bromo pentane, bromo iso-pentane, brominated isobutylene, vinyl bromide, brominated diphenyl methane, benzal bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2,3-dibromopropyl) phosphoric acid ester, trichloroacetamide, iodo-pentane, iodo isobutane, 1,1,1-tri-chloro-2,2-two (rubigan) ethane, halogenation triaizine compounds, wherein, particularly preferably use trisbromomethyl phenyl sulfone.Be 0.01 ~ 3 quality % in photosensitive polymer combination containing content during halogen compounds.
And then, in order to improve thermostability, the storage stability of photosensitive polymer combination of the present invention, the compound of more than at least a kind in the group being selected from and being made up of radical polymerization inhibitor, benzotriazole category and carboxyl benzotriazole class can be added in photosensitive polymer combination.
As such radical polymerization inhibitor, can list such as, p methoxy phenol, quinhydrones, pyrogallol, naphthylamines, tert-butyl catechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitrosophenylhydroxylamine aluminium salt and phenylbenzene nitrosamine.
In addition, as benzotriazole category, can list such as, 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-1,2,3-benzotriazole.
In addition, as carboxyl benzotriazole class, can list such as, 4-carboxyl-1,2,3-benzotriazole, 5-carboxyl-1,2,3-benzotriazole, N-(N, N-bis--2-ethylhexyl) aminomethylene carboxyl benzotriazole, N-(N, N-bis--2-hydroxyethyl) aminomethylene carboxyl benzotriazole and N-(N, N-bis--2-ethylhexyl) aminoethylene carboxyl benzotriazole.
The summation addition of radical polymerization inhibitor, benzotriazole category and carboxyl benzotriazole class is preferably 0.01 ~ 3 quality %, is more preferably 0.05 ~ 1 quality %.From the view point of imparting photosensitive polymer combination storage stability, this amount is preferably more than 0.01 quality %, in addition, from the view point of maintenance light sensitivity, is more preferably below 3 quality %.
In photosensitive polymer combination of the present invention, softening agent can also be contained as required.Can list such as this type of softening agent, polyoxyethylene glycol, polypropylene glycol, polyoxytrimethylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxytrimethylene monomethyl ether, polyoxyethylene polyoxytrimethylene monomethyl ether, polyoxyethylene list ether, polyoxytrimethylene list ether, glycol and the ester classes such as polyoxyethylene polyoxytrimethylene list ether, the phthalates such as diethyl phthalate, o-methyl-benzene sulphonamide, p-methylphenyl sulphonylamine, tributyl citrate, triethyl citrate, CitroflexA-2, acetyl citrate three n-propyl, acetyl tributyl citrate.
As the content of softening agent, preferably in photosensitive polymer combination, contain 5 ~ 50 quality %, more preferably 5 ~ 30 quality %.From the view point of suppressing the delay of development time, giving cured film flexibility, preferably more than 5 quality %, in addition, from the view point of suppression solidification, not enough and cold flow, is preferably below 50 quality %.
Photosensitive-resin layered product of the present invention contains the photo-sensitive resin and supporting layer that are made up of photosensitive polymer combination.The surface of side that also can be contrary in the supporting layer side of photo-sensitive resin as required has protective layer.As supporting layer used herein, it is desirable to the clear support layer that can make the light therethrough radiated by exposure light source.As such supporter, polyethylene terephthalate thin film, PVA (PVOH) FILM, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrol copolymer film, polyamide layer and cellulose derivative film can be enumerated.These films can also use the film of drawn as required.Preferred turbidity is less than 5.About the thickness of film, the thin film of thickness is favourable in image formative and economy, owing to maintaining intensity, so preferably use the thickness of 10 ~ 30 μm.
In addition, as the key property of protective layer used in photosensitive-resin layered product, with regard to the sticking power of photo-sensitive resin with regard to, compared to supporting layer, the sticking power of protective layer aspect is enough little and can easily peel off.Such as, can preferably use polyethylene film and polypropylene film etc. as protective layer.In addition, the film of the separability excellence shown in Japanese Laid-Open Patent Publication 59-202457 publication can be used.The thickness of protective layer is preferably 10 ~ 100 μm, is more preferably 10 ~ 50 μm.The thickness of the photo-sensitive resin in photosensitive-resin layered product is different according to purposes, is preferably 5 ~ 100 μm, is more preferably 7 ~ 60 μm.Thickness is thinner, and resolving power is higher, and in addition, thickness is thicker, and film toughness more improves.
Lamination supporting layer, photo-sensitive resin and the protective layer that arranges as required and prepare the method for photosensitive-resin layered product of the present invention successively, can adopt method known at present.Such as, in advance the photosensitive polymer combination being used for photo-sensitive resin is made solution uniform with the solvent of dissolving them, bar coater or roller coating machine is first used to be applied on supporting layer, dry, the photo-sensitive resin that lamination is made up of this photosensitive polymer combination on supporting layer.Then, as required, by lamination protective layer on this photo-sensitive resin, thus photosensitive-resin layered product can be prepared.
As above-mentioned solvent, the ketone that methylethylketone (MEK) is representative and the alcohols being representative with methyl alcohol, ethanol and Virahol can be enumerated.Preferably add in photosensitive polymer combination in the mode that 25 DEG C is 500 ~ 4000mPa with the soltion viscosity being coated on the photosensitive polymer combination on supporting layer.
< corrosion-resisting pattern formation method >
The corrosion-resisting pattern employing photosensitive-resin layered product of the present invention is formed by the operation comprising lamination, exposure process and developing procedure.The following example that concrete method is shown.
As processed base material, copper clad laminate can be enumerated when manufacturing for printed-wiring board (PWB), in addition for the glass baseplate of the manufacture of concavo-convex base material, can enumerate such as, plasma display device base material and surperficial electrolysis display substrate, organic EL seal closure with or, form Silicon Wafer and the ceramic base material of communicating pores.After plasma display base material refers to and form electrode on glass, coating dielectric layer, is then coated with next door glass paste, and in enforcement next door, glass paste part is carried out sandblasting processing and forms the base material in next door.Be concavo-convex base material to these processed base materials through the product of shot blasting procedure.
First, laminating machine is used to carry out lamination.Peel off protective layer when photosensitive-resin layered product has protective layer, then, use laminating machine photo-sensitive resin is added thermo-compressed and is laminated on substrate surface.Now, photo-sensitive resin can only be laminated on the one side of substrate surface, also can be laminated on two sides as required.Heating temperature is now generally 40 ~ 160 DEG C.In addition, add thermo-compressed by this carrying out more than secondary, and improve sticking power and chemical proofing.Now, crimping can use has the two-section type laminating machine that two connect roller, also can repeated multiple timesly be crimped by roller.
Then, exposure machine is used 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.Quantorecorder can also be used to measure.
In addition in exposure process, can also use and directly describe exposure method.Direct description exposure is without the need to using photomask, and by directly describing the mode of carrying out exposing on substrate.As light source, such as, wavelength is used to be the semiconductor laser of 350 ~ 410nm or ultrahigh pressure mercury lamp etc.Depicting pattern is by conputer controlled, and the exposure in this situation is decided by the translational speed of light illumination and substrate.
Then, developing apparatus is used to carry out developing procedure.After exposure, when photo-sensitive resin having supporter, this supporter is removed.Then, use the developing solution of alkaline aqueous solution, by unexposed portion development removing, obtain resist pattern picture.As alkaline aqueous solution, preferably use Na 2cO 3or K 2cO 3the aqueous solution.These suitably can be selected according to the characteristic of photo-sensitive resin, normally concentration 0.2 ~ 2 quality %, the Na of 20 ~ 40 DEG C 2cO 3the aqueous solution.Can also be mixed in this alkaline aqueous solution tensio-active agent, defoamer, for promote develop a small amount of organic solvent etc.
Obtain corrosion-resisting pattern by above-mentioned operation, but according to circumstances can also carry out the heating process this corrosion-resisting pattern being heated to 100 ~ 300 DEG C.By carrying out this heating process, chemical reagent resistance can be improved further.Heating can use the process furnace of the mode of hot blast, infrared rays or far infrared rays.
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 then uses copper clad laminate or flexible substrate as the above-mentioned corrosion-resisting pattern formation method of substrate, carries out through following operation.
First, known method such as etching method or plating is used to form conductive pattern the copper face by the substrate exposed that develops.
Then, use there is the alkalescence stronger than developing solution the aqueous solution by corrosion-resisting pattern from strippable substrate, thus obtain the printed-wiring board (PWB) expected.For the alkaline aqueous solution peeled off (hereinafter also referred to " stripping liquid ".) have no particular limits, usually use 2 ~ 5 quality % concentration, the aqueous solution of NaOH or KOH of 40 ~ 70 DEG C.Also a small amount of water-soluble solvent can be added in stripping liquid.
The manufacture method > of < lead frame
Lead frame manufacture method of the present invention then uses metal plate if copper, copper alloy, iron-based alloy are as the above-mentioned corrosion-resisting pattern formation method of substrate, carries out through following operation.
First, etch by the substrate exposed that develops thus form conductive pattern.Then, peel off corrosion-resisting pattern by the method same with the manufacture method of above-mentioned printed-wiring board (PWB), thus obtain the lead frame expected.
The manufacture method > of < semiconductor packages
The manufacture method of semiconductor package body of the present invention has then been used to complete wafer that the circuit as LSI formed as the formation method of the above-mentioned corrosion-resisting pattern of substrate, carries out through following operation.
First, for by the opening portion exposed of developing, implement the column plating utilizing copper or soldering, thus form conductive pattern.Then, by utilizing the method same with the manufacture method of above-mentioned printed-wiring board (PWB) to carry out stripping corrosion-resisting pattern, recycling etching removes the thin metal layer of the part beyond column plating, thus obtains the semiconductor package body expected.
Embodiment
Based on embodiment, the present invention will be described.
The making method that the sample for evaluation of embodiment and comparative example is below shown and the evaluation method of sample obtained and evaluation result.
1) making of sample for evaluation
Photosensitive-resin layered product in embodiment and comparative example carries out following making.
The making > of < photosensitive-resin layered product
The solution of the composition shown in modulometer 1 reaches 50 quality % to make solids component amount, and fully stir, mix, on the pet film (society of Mitsubishi Chemical R340-G16) that 16 μm as support film are thick, use the photosensitive polymer combination shown in mixing coating machine even spread table 1, drying 1 minute at 95 DEG C.The thickness of dried photo-sensitive resin is 10 μm.Then, on the surface on photo-sensitive resin, fit as 35 μm of protective layer thick polyethylene films (タ マ Port リ society GF-858), obtain photosensitive-resin layered product.
< substrate >
The thick copper clad laminate of 0.4mm being used in the 35 μm of Copper Foils of lamination on insulating resin is evaluated.In addition, below use during other substrate and describe its order.
< lamination >
While the protective layer limit of peeling off photosensitive-resin layered product of the present invention is by hot roll laminator (Asahi Chemical Industry エ Application ジ ニ ア リ Application グ (strain) society manufactures, AL-700), at roll temperature 105 DEG C, carry out lamination.Air pressure is 0.35MPa, and laminate speed is 1.5m/min.
< exposes >
Utilize and directly describe exposure machine (オ Le ボ テ ツク society system, Paragon9000) under 8W with 12mJ/cm 2exposure photo-sensitive resin is exposed.
< develops >
The 1.0 quality %Na of 30 DEG C of spray specified time 2cO 3the aqueous solution, dissolves the unexposed portion of removing photo-sensitive resin.The development in 24 seconds of actual development time, then, washing time washing in 36 seconds.
2) evaluation method
Except the method that the making of above-mentioned assess sample is described, respective performance is evaluated by following method.
< hole covering character >
To the substrate being carried out two sides lamination on copper clad laminate by aforesaid method, utilize above-mentioned exposure method to carry out whole directly to retouch and expose and obtain cured film, described copper clad laminate is that 0.2mm is thick and be manufactured with the copper clad laminate of the 500mm × 500mm of the through hole of the 0.3mm diameter of 2500, is developed by above-mentioned developing method.Calculate the number of breaking of cured film after development, according to classification as described below.
◎: the number of breaking is less than 25
Zero: the number of breaking is more than 25 and be less than 75
×: the number of breaking is more than 75.
The generation > of < oily aggregation
Only the photo-sensitive resin of photosensitive-resin layered product assembles 2.4m 2, be immersed in 200ml developing solution, stir 2 hours at 30 DEG C, make it dissolve.Then leave standstill, carry out classification as described below by the situation of the solution after 72 hours.
Zero: do not produce the aggregation of oily, powdery aggregation.
△: aggregation, the powdery aggregation of oily are few.
×: aggregation, the powdery aggregation of oily are many.
The stripping strength > of < supporting layer (PET)
Prepare the substrate by aforesaid method, the photo-sensitive resin of photosensitive-resin layered product being carried out single sided lamination, 23 DEG C, place 24 hours under 50% relative humidity, then 180 ° of strippings are carried out to the supporting layer (being PET) of 1 inch in width herein, its intensity テ Application シ ロ Application RTM-500 (Toyo Seiki manufacture) measures, and carries out classification as described below.
Zero: the very big mean value of stripping strength is more than 3gf.
△: the very big mean value of stripping 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 the B-1 ~ B-4 in table 1 is the mass parts of solids component, not containing solvent.In order to modulate photosensitive polymer combination, the solid component concentration making B-1 ~ B-4 is in advance the methyl ethyl ketone solution of 50 quality %, coordinates the solution of each B-1 ~ B-4 to reach the solids component of table 1.
[table 1]
< nomenclature >
B-1: methacrylic acid 25 quality %, the terpolymer (weight-average molecular weight 100000, acid equivalent 344) of methyl methacrylate 65 quality %, butyl acrylate 10 quality %
B-2: methacrylic acid 25 quality %, the terpolymer (weight-average molecular weight 200000, acid equivalent 370) of methyl methacrylate 65 quality %, butyl acrylate 10 quality %
B-3: methacrylic acid 25 quality %, the terpolymer (weight-average molecular weight 50000, acid equivalent 344) of methyl methacrylate 50 quality %, vinylbenzene 25 quality %
B-4: methacrylic acid 25 quality %, the terpolymer (weight-average molecular weight 70000, acid equivalent 344) of methyl methacrylate 50 quality %, butyl acrylate 25 quality %
B-5: benzyl methacrylate 80 quality %, the copolymer (weight-average molecular weight 100000, acid equivalent 430) of methacrylic acid 20 quality %
M-1: to the tetraacrylate (サ mono-ト マ mono-ジ ヤ パ Application (strain) society manufactures SR-494) of the oxyethane of 4 ends difference addition 1 mole of tetramethylolmethane
M-2: by the tetraacrylate of 4 of tetramethylolmethane terminal acrylate
M-3: to the triacrylate (Xin Zhong village chemistry manufactures A-TMPT-3EO) of the oxyethane of the average addition of TriMethylolPropane(TMP) 3 moles
M-4: to the triacrylate of the propylene oxide of the average addition of TriMethylolPropane(TMP) 3 moles
M-5: to the dimethacrylate of the polyoxyethylene glycol of the oxyethane of two ends difference each 2 moles of the average addition of dihydroxyphenyl propane
M-6: polypropyleneglycol diacrylate
I-1:9-phenylacridine
I-2:N-phenylglycocoll
I-3:2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer
I-4:1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline
Two (m-methoxyphenyl) imidazole dimer of I-5:2-(Chloro-O-Phenyl)-4,5-
D-1: diamond green
D-2: Viola crystallina
F-1: methylethylketone
In comparative example 1, when using the polymkeric substance of mean molecule quantity not sufficient 70,000 as alkali soluble resin, produce oily aggregation during development, undesirable condition occurs.
In comparative example 2, the ratio of the compound that the above-mentioned general formula (II) in photosensitive polymer combination represents is less than 30 quality %, becomes the result that hole covering character worsens.
In comparative example 3, the ratio of the compound that the above-mentioned general formula (II) in photosensitive polymer combination represents is greater than 55 quality %, in addition, relative to photosensitive polymer combination total amount set the ratio of above-mentioned (a) alkali soluble resin as the ratio with the compound of unsaturated double-bond of A quality %, above-mentioned (b) photopolymerization be B quality % time, A/B is less than 1.1, becomes the result that hole covering character worsens.Comparative example 4 is additional experiments of Japanese Unexamined Patent Publication 11-119422.In comparative example 4, do not use the unsaturated compound of the polyfunctional photopolymerization being equivalent to compound that above-mentioned general formula (I) represents and the compound that above-mentioned general formula (II) represents, so hole covering character worsens, become the result producing oily aggregation.
Utilizability in industry
Photosensitive-resin layered product of the present invention by exposing on the substrate be laminated; protect through hole not by the impact of alkaline-based developer, etching solution; thus follow-up operation can be simplified; and due in developing solution the aggregation of oily few; so the washing of device is few; in addition, the printed-wiring board (PWB) manufacture of being developed by alkali is useful.

Claims (11)

1. a photosensitive-resin layered product, is characterized in that, it is the photosensitive-resin layered product of at least lamination supporting layer and photo-sensitive resin, and this photo-sensitive resin is formed by photosensitive polymer combination, and this photosensitive polymer combination at least comprises:
(a) alkali soluble resin 25 ~ 64 quality %,
The compound with unsaturated double-bond of (b) photopolymerization,
(c) Photoepolymerizationinitiater initiater 0.1 ~ 20 quality %,
And meet following (i), (ii), (iii) and (iv) further:
I () is as the compound with unsaturated double-bond of described (b) photopolymerization, relative to the total amount of photosensitive polymer combination, the unsaturated compound being selected from least one photopolymerization in the group that compound that the compound that represented by following general formula (I) and following general formula (II) represent forms containing 30 ~ 55 quality %;
(ii) weight-average molecular weight of (a) alkali soluble resin described in is 70000 ~ 220000, acid equivalent is 100 ~ 600;
(iii) thickness of photo-sensitive resin is 3 ~ 15 μm,
(iv) set relative to above-mentioned (a) alkali soluble resin of photosensitive polymer combination total amount ratio as the ratio with the compound of unsaturated double-bond of A quality %, above-mentioned (b) photopolymerization be B quality % time, A/B is 1.1 ~ 1.31
[chemical formula 1]
In formula, R 1, R 2and R 3be H or CH independently of one another 3, n 1, n 2, n 3and n 4be the integer of 0 ~ 4 independently of one another, can be also 0, W be with CH simultaneously 3or the group that OH represents,
[chemical formula 2]
In formula, R 5, R 6, R 7and R 8be H or CH independently of one another 3, m 1, m 2, m 3and m 4be the integer of 0 ~ 4 independently of one another, can be also 0 simultaneously.
2. photosensitive-resin layered product according to claim 1, wherein, as the compound with unsaturated double-bond of described (b) photopolymerization, relative to the total amount of photosensitive polymer combination, the unsaturated compound being selected from least one photopolymerization in the group that compound that the compound that represented by described general formula (I) and described general formula (II) represent forms containing 35 ~ 55 quality %.
3. the photosensitive-resin layered product described in claim 1 or 2, wherein, (c) Photoepolymerizationinitiater initiater is 9-phenylacridine.
4. photosensitive-resin layered product according to claim 1 and 2, is characterized in that, the A/B in above-mentioned (iv) is 1.1 ~ 1.3.
5. a formation method for corrosion-resisting pattern, it comprises: the lamination of the photo-sensitive resin of the photosensitive-resin layered product on substrate described in any one of lamination Claims 1 to 4, expose the developing procedure of ultraviolet exposure process, removing unexposed portion.
6. the formation method of corrosion-resisting pattern according to claim 5, is characterized in that, by directly describing to expose in described exposure process.
7. a manufacture method for conductive pattern, it comprises: use copper clad laminate as substrate, etch or the operation of plating to the substrate being formed with corrosion-resisting pattern by the method described in claim 5 or 6.
8. a manufacture method for printed-wiring board (PWB), is characterized in that, uses metallic cover insulcrete as substrate, etches or plating the substrate being formed with corrosion-resisting pattern by the method described in claim 5 or 6, peel off corrosion-resisting pattern.
9. a manufacture method for lead frame, is characterized in that, uses metal sheet as substrate, etches the substrate being formed with corrosion-resisting pattern by the method described in claim 5 or 6, peel off corrosion-resisting pattern.
10. a manufacture method for semiconductor packages, is characterized in that, the wafer that the circuit being used to complete large-scale integrated circuit is formed, as substrate, carries out plating to the substrate being formed with corrosion-resisting pattern by the method described in claim 5 or 6, peels off corrosion-resisting pattern.
11. 1 kinds of manufacture method with the base material of concavo-convex pattern, is characterized in that, use Glass Rib as substrate, utilize blasting craft to process the substrate being formed with corrosion-resisting pattern by the method described in claim 5 or 6, peel off corrosion-resisting pattern.
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