CN102144189A - Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, conductive pattern, printed wiring board, lead frame, base, and method for manufacturing semiconductor package - Google Patents

Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, conductive pattern, printed wiring board, lead frame, base, and method for manufacturing semiconductor package Download PDF

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CN102144189A
CN102144189A CN2009801347346A CN200980134734A CN102144189A CN 102144189 A CN102144189 A CN 102144189A CN 2009801347346 A CN2009801347346 A CN 2009801347346A CN 200980134734 A CN200980134734 A CN 200980134734A CN 102144189 A CN102144189 A CN 102144189A
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substrate
layered product
corrosion
photosensitive
resin layered
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CN102144189B (en
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小谷结华
山田有里
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Asahi Kasei Corp
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Asahi Chemical Co Ltd
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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
    • 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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

A photosensitive resin composition providing excellent resolution, adhesion, tinting properties and releasability. The photosensitive resin composition contains (a) a thermoplastic polymer obtained by polymerizing, as a polymerization component, at least alpha,beta-unsaturated carboxyl group-containing monomer, and having an acid equivalent weight of 100-600 and a weight average molecular weight of 5,000-500,000, (b) an addition-polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in each molecule, (c) a photopolymerization initiator and (d) a compound represented by general formula (I). In the formula, R1-R5 independently represent an H, an aryl group or an arylalkyl group, and at least one of R1-R5 represents an aryl group or an arylalkyl group; A1 represents C2H4 or C3H6, and when n1 is not less than 2, the plurality of A1's may be the same as or different from each other; and n1 represents an integer of 1-50.

Description

The manufacture method of photosensitive polymer combination, photosensitive-resin layered product, corrosion-resisting pattern formation method and conductive pattern, printed circuit board (PCB), lead frame, base material and semiconductor packages
Technical field
The photosensitive polymer combination that the present invention relates to develop by alkaline aqueous solution, this photosensitive polymer combination is laminated to the photosensitive-resin layered product that obtains on the supporter, uses this photosensitive-resin layered product to form the method for corrosion-resisting pattern and the purposes of this corrosion-resisting pattern on substrate.More specifically, relate to the photosensitive polymer combination that corrosion-resisting pattern can be provided, this corrosion-resisting pattern is applicable to: the manufacturing of printed circuit board (PCB), the manufacturing of flexible printed circuit board, the IC chip carries the manufacturing with lead frame (being designated hereinafter simply as lead frame), metal forming Precision Machining such as metal mask manufacturing, BGA (BGA Package), the manufacturing of CSP semiconductor packages such as (chip size packages), with TAB (belt is welded automatically), COF (covering brilliant film: carry semiconducter IC and form on the fine circuits plate of film like) is the manufacturing of the belt base plate of representative (tape substrate), the manufacturing of semiconductor projection (semiconductor bump), the ITO electrode of field of flat panel displays, the manufacturing of parts such as addressing electrode or electromagnetic wave shield.
Background technology
At present, printed circuit board (PCB) is made by photoetching process.In photoetching process, photosensitive polymer combination is coated on the substrate, carry out pattern exposure and make the exposure portion polymerizing curable of this photosensitive polymer combination, remove unexposed portion with developer solution, thereby on substrate, form corrosion-resisting pattern, this substrate is carried out etching or plating handle and form conductive pattern, peel off from this substrate then and remove this corrosion-resisting pattern, thereby can on substrate, form conductive pattern.
In above-mentioned photoetching process, can adopt in the following method any one: when being coated on photosensitive polymer combination on the substrate, with the solution coat of photosensitive polymer combination on substrate and make its dry method; Perhaps; lamination supporter, the layer (below be also referred to as " photo-sensitive resin ") that is formed by photosensitive polymer combination and the protective seam of deciding as required obtain photosensitive-resin layered product (below be also referred to as " dry film resist layer (dry film resist) ") successively, and photosensitive-resin layered product is laminated to method on the substrate.And, in the manufacturing of printed circuit board (PCB), use a kind of dry film resist layer in back mostly.
Below the simple method of using above-mentioned dry film resist layer to make printed circuit board (PCB) of describing.At first, when having protective seams such as polyethylene film at the dry film resist layer, this protective seam is peeled off from photo-sensitive resin.Then, use laminating machine on substrates such as copper clad laminate, to come laminated photosensitive resin bed and supporter according to the order of this substrate, photo-sensitive resin, supporter.Then, by the photomask with wiring pattern, the i ray ultraviolet rays such as (365nm) of launching with ultrahigh pressure mercury lamp exposes this photo-sensitive resin, thereby makes the exposed portion polymerizing curable.Then, peel off the supporter that forms by polyethylene terephthalate etc.Then, remove the unexposed portion of photo-sensitive resin, on substrate, form corrosion-resisting pattern by having developing solution dissolution such as weakly alkaline aqueous solution or dispersion.Then, serve as the protection mask with formed corrosion-resisting pattern, carry out known etch processes or pattern plating and handle.In remove the method for metal part by etching, by with solidifying the through hole (through-hole) of etchant resist, be used for via hole (via-hole) covering that interlayer connects, thereby make the metal in the hole not etched with substrate.This method is called masking method (tenting method).In etching work procedure, for example use the solution of cupric chloride, iron chloride or cupric ammine complex.At last, peel off this corrosion-resisting pattern from substrate, thereby make substrate, be printed circuit board (PCB) with conductive pattern with the aqueous alkali of NaOH etc.From the viewpoint of operability, the property handled and throughput rate, preferred peeling rate is very fast.
On the other hand, along with the wiring miniaturization at interval of in recent years printed circuit board (PCB), the high-resolution requirement of dry film resist layer is increased gradually.In addition, in masking method and plating method, soak between resist and the copper in order not make etching solution and plating solution, the adhesion of resist and copper is important, but along with there is the elongated problem of splitting time meeting in the raising of adhesion.
In the patent documentation 1,, record the photosensitive polymer combination of the chain multipolymer that contains oxirane and epoxypropane, but do not put down in writing the problem of fissility in order in the high resolving power of keeping photosensitive polymer combination and high adhesion force, to improve sheltering.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-20726 communique
Summary of the invention
The problem that invention will solve
Therefore, as the photosensitive polymer combination that dry film is used, the fast photosensitive polymer combination of peeling rate that resolution, adhesion and sheltering excellence and going far towards improves operability, the property handled and throughput rate does not provide yet.
The objective of the invention is to, provide: resolution, adhesion and sheltering excellence, the curing etchant resist has the photosensitive polymer combination based on the excellent fissility of aqueous alkali; Use has the photosensitive-resin layered product of this photosensitive polymer combination; Use this photosensitive-resin layered product on substrate, to form the corrosion-resisting pattern formation method of corrosion-resisting pattern; And use manufacture method this photosensitive-resin layered product, conductive pattern, printed circuit board (PCB), lead frame, base material and semiconductor packages.
The scheme that is used to deal with problems
Above-mentioned purpose can realize by following formation of the present invention.That is, the present invention is as follows.
[1] a kind of photosensitive polymer combination, it contains following (a)～(d) composition: (a) at least to contain α, β-unsaturated carboxylic monomer for the polymerization composition carry out that polymerization obtains, acid equivalent be 100～600 and weight-average molecular weight be 5000～500000 thermoplastic polymer, 20～90 quality %; (b) has the addition polymerization monomer of at least one polymerizable olefinic unsaturated link in the molecule, 3～75 quality %; (c) Photoepolymerizationinitiater initiater, 0.01～30 quality %; And (d) compound shown in the following general formula (I):
[Chemical formula 1]
Figure BPA00001328438100041
In the formula, R 1～R 5Independent separately is H, aryl or aryl alkyl, and R 1～R 5In at least one be aryl or aryl alkyl, A 1Be C 2H 4Or C 3H 6, n 1Be 2 when above, a plurality of A 1Can be the same or different each other, and n 1It is 1～50 integer.
[2] according to above-mentioned [1] described photosensitive polymer combination, wherein, the R in the above-mentioned general formula (I) 1～R 5In at least one be phenylalkyl.
[3] according to above-mentioned [2] described photosensitive polymer combination, wherein, the carbon number of the moieties in the above-mentioned phenylalkyl is 1～6.
[4] according to each above-mentioned [1]～[3] described photosensitive polymer combination, wherein, the R in the above-mentioned general formula (I) 1～R 5In 1～3 group be respectively aryl or aryl alkyl.
[5] according to each above-mentioned [1]～[3] described photosensitive polymer combination, wherein, the R in the above-mentioned general formula (I) 1～R 5In 2 or 3 groups be respectively aryl or aryl alkyl.
[6] according to each above-mentioned [1]～[5] described photosensitive polymer combination, wherein, in the above-mentioned general formula (I), n 1It is 1～35 integer.
[7] according to each above-mentioned [1]～[6] described photosensitive polymer combination, wherein, the R in the above-mentioned general formula (I) 1～R 5Independent separately is H, phenyl or 1-phenylethyl, R 1～R 5In 2 be H, and R 1～R 5In 3 independent separately be phenyl or 1-phenylethyl.
[8] according to each above-mentioned [1]～[7] described photosensitive polymer combination, wherein, with above-mentioned (a) and (b) with (c) when the total amount of composition is 100 quality %, the content of above-mentioned (d) composition is 1～20 quality %.
[9],, contain the unsaturated compound of the photopolymerization shown in following general formula (II) or the following general formula (III) as above-mentioned (b) composition according to each above-mentioned [1]～[8] described photosensitive polymer combination:
[Chemical formula 2]
Figure BPA00001328438100051
In the formula, R 6And R 7Independent separately is H or CH 3, n 2, n 3And n 4Independently be 3～20 integer separately;
[chemical formula 3]
Figure BPA00001328438100052
In the formula, R 8Or R 9Independent separately is H or CH 3, A 2Be C 2H 4, A 3Be C 3H 6, n 5And n 6Independently be 1～29 integer and n separately 5+ n 6Be 2～30 integer, n 7And n 8Independently be 0～29 integer and n separately 7+ n 8Be 0～30 integer ,-(A 2-O)-and-(A 3-O)-the arrangement mode of repetitive can be random also can be block, be arranged as under the situation of block at it, can be-(A 2-O)-and-(A 3-O)-in any one be positioned at the xenyl side.
[10] a kind of photosensitive-resin layered product, it is each above-mentioned [1]～[9] described photosensitive polymer combination is laminated on the supporter and forms.
[11] a kind of corrosion-resisting pattern formation method, this method comprises following operation: the lamination that forms above-mentioned [10] described photosensitive-resin layered product on substrate; Exposure process to this photosensitive-resin layered product exposure; And the unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern.
[12] a kind of manufacture method of conductive pattern, this method comprises following operation: form the lamination of above-mentioned [10] described photosensitive-resin layered product on substrate, wherein said substrate is sheet metal or metal film coated insulcrete; Exposure process to this photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; And by the substrate that is formed with this corrosion-resisting pattern being carried out the operation that etching or plating form conductive pattern.
[13] a kind of manufacture method of printed circuit board (PCB), this method comprises following operation: form the lamination of above-mentioned [10] described photosensitive-resin layered product on substrate, wherein said substrate is copper clad laminate or flexible base, board; Exposure process to this photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with this corrosion-resisting pattern is carried out the operation of etching or plating; And the operation of peeling off corrosion-resisting pattern from this substrate.
[14] a kind of manufacture method of lead frame, this method comprises following operation: form the lamination of above-mentioned [10] described photosensitive-resin layered product on substrate, wherein said substrate is a sheet metal; Exposure process to this photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with this corrosion-resisting pattern is carried out etched operation; And the operation of peeling off this corrosion-resisting pattern from this substrate.
[15] a kind of manufacture method with base material of relief pattern, this method comprises following operation: form the lamination of above-mentioned [10] described photosensitive-resin layered product on substrate, wherein said substrate is for being coated with the glass substrate of glass rib (ribbed glass) paste; Exposure process to this photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with this corrosion-resisting pattern is carried out the operation of blasting treatment processing; And the operation of peeling off this corrosion-resisting pattern from this substrate.
[16] a kind of manufacture method of semiconductor packages, this method comprises following operation: form the lamination of above-mentioned [10] described photosensitive-resin layered product on substrate, wherein said substrate is for having finished the circuit-formed wafer as LSI (large scale integrated circuit); Exposure process to this photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with this corrosion-resisting pattern is carried out the operation of plating; And the operation of peeling off this corrosion-resisting pattern from this substrate.
The effect of invention
The present invention can provide: resolution, adhesion and sheltering excellence, curing etchant resist have the photosensitive polymer combination based on the excellent fissility of aqueous alkali; Use has the photosensitive-resin layered product of this photosensitive polymer combination; Use the formation method of the high meticulous corrosion-resisting pattern of this photosensitive-resin layered product.In addition, use this photosensitive-resin layered product, can make high meticulous printed circuit board (PCB), lead frame, semiconductor packages or even flat-panel screens.
Embodiment
Specify the present invention below.
＜photosensitive polymer combination 〉
Photosensitive polymer combination of the present invention contains following (a)～(d) composition as neccessary composition: (a) at least to contain α, β-unsaturated carboxylic monomer for the polymerization composition carry out that polymerization obtains, acid equivalent be 100～600 and weight-average molecular weight be 5000～500000 thermoplastic polymer (below be also referred to as (a) thermoplastic polymer), 20～90 quality %; (b) has the addition polymerization monomer (below be also referred to as (b) addition polymerization monomer) of at least one polymerizable olefinic unsaturated link in the molecule, 3～75 quality %; (c) Photoepolymerizationinitiater initiater (below be also referred to as (c) Photoepolymerizationinitiater initiater), 0.01～30 quality %; And (d) compound shown in the following general formula (I) (below be also referred to as the compound shown in (d) general formula (I)).
[chemical formula 4]
Figure BPA00001328438100081
(in the formula, R 1～R 5Independent separately is H, aryl or aryl alkyl, and R 1～R 5In at least one be aryl or aryl alkyl, A 1Be C 2H 4Or C 3H 6, n 1Be 2 when above, a plurality of A 1Can be the same or different each other, and n 1It is 1～50 integer.)
(a) thermoplastic polymer
(a) thermoplastic polymer is at least containing α, β-unsaturated carboxylic monomer be polymerization composition, acid equivalent be 100～600 and weight-average molecular weight be 5000～500000 thermoplastic polymer.
In order to make photosensitive polymer combination of the present invention have development, fissility to developer solution, the stripper that is made of aqueous alkali, (a) carboxyl in the thermoplastic polymer needs.(a) acid equivalent of thermoplastic polymer is 100～600, is preferably 250～450.From guarantee with solvent or photosensitive polymer combination other composition compatibility, particularly with the viewpoint of the compatibility of aftermentioned (b) addition polymerization monomer, acid equivalent is more than 100, in addition, from keeping the viewpoint of development, fissility, be below 600.Herein, acid equivalent is meant, wherein has the quality (gram) of thermoplastic polymer of the carboxyl of 1 equivalent.In addition, the mensuration of acid equivalent is for example used HIRANUMA REPORTING TITRETOR (COM-555), is undertaken by potential difference titration with the NaOH aqueous solution of 0.1mol/L.
(a) weight-average molecular weight of thermoplastic polymer is 5000～500000.From the thickness homogeneous of keeping photosensitive-resin layered product (being the dry film resist layer), obtain viewpoint to the patience of developer solution, weight-average molecular weight is more than 5000, in addition, from keeping the viewpoint of development, is below 500000.Preferably, weight-average molecular weight is 20000～100000.Weight-average molecular weight in this instructions is meant, uses the weight-average molecular weight of the standard curve determination of the polystyrene ShodexSTANDARD SM-105 of electrician's (strain) manufacturing (for example clear and) by gel permeation chromatography (GPC).The gel permeation chromatography that this weight-average molecular weight can use Japanese beam split (strain) to make is measured under the following conditions:
Differential refraction rate meter: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Post: be followed successively by KF-8025, KF-806M * 2, KF-807
Eluent: THF
Image after developing from alkali forms the viewpoint of property, preferably, (a) thermoplastic polymer is a kind of polymer of monomers in aftermentioned first monomer or the multipolymer of two or more monomers, or a kind of polymer of monomers in aftermentioned second monomer or the multipolymer of two or more monomers, or the multipolymer of more than one monomers in more than one monomers in this first monomer and this second monomer.
First monomer is carboxylic acid or the acid anhydrides that has a polymerism unsaturated group in the molecule.As first monomer, for example can list (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and maleic acid half ester.Wherein, from the viewpoint based on the development of aqueous slkali, (methyl) acrylic acid is particularly preferred.Here, (methyl) acrylic acid is represented acrylic or methacrylic acid.Below identical.
Second monomer is the monomer that has at least one polymerism unsaturated group in nonacid, the molecule.As second monomer, for example can list (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) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, the ester class of vinyl alcohols such as vinyl acetate, (methyl) vinyl cyanide, styrene and polymerisable styrene derivative.Wherein, from the viewpoint of image formation property, (methyl) methyl acrylate, (methyl) n-butyl acrylate, styrene and (methyl) benzyl acrylate are particularly preferred.
Example more specifically as (a) thermoplastic polymer, can list and contain methyl methacrylate, methacrylic acid and styrene polymkeric substance as copolymer composition, contain methyl methacrylate, methacrylic acid and n-butyl acrylate polymkeric substance, and contain benzyl methacrylate, methyl methacrylate and 2-EHA as polymkeric substance of copolymer composition etc. as copolymer composition.
The amount of contained (a) thermoplastic polymer is the scope of 20～90 quality % in the photosensitive polymer combination of the present invention, is preferably the scope of 25～70 quality %.From keeping the viewpoint of alkali-developable, this amount is more than the 20 quality %, and in addition, from given full play to the viewpoint of its etch resistant properties by the corrosion-resisting pattern that forms of exposure, this amount is below the 90 quality %.
(b) addition polymerization monomer
(b) the addition polymerization monomer has at least one polymerizable olefinic unsaturated link in molecule.From the good viewpoint of image formation property, ethylenic unsaturated bond is preferably terminal ethylenically unsaturated group.From high resolving power with suppress the viewpoint of edge-melting (edge fusion), as (b) addition polymerization monomer, preferably contain at least a following general formula (II) or (III) shown in the photopolymerization unsaturated compound.
[chemical formula 5]
Figure BPA00001328438100111
(in the formula, R 6And R 7Independent separately is H or CH 3, n 2, n 3And n 4Independently be 3～20 integer separately.)
[chemical formula 6]
Figure BPA00001328438100112
(in the formula, R 8Or R 9Independent separately is H or CH 3, A 2Be C 2H 4, A 3Be C 3H 6, n 5And n 6Independently be 1～29 integer and n separately 5+ n 6Be 2～30 integer, n 7And n 8Independently be 0～29 integer and n separately 7+ n 8Be 0～30 integer ,-(A 2-O)-and-(A 3-O)-the arrangement mode of repetitive can be random or block, be arranged as under the situation of block at it, can be-(A 2-O)-and-(A 3-O)-in any one be positioned at the xenyl side.)
In the compound shown in the above-mentioned general formula (II), n 2, n 3And n 4Independently be more than 3 and below 20 separately.From improving the viewpoint of sheltering, n 2, n 3And n 4Be more than 3, from improving the viewpoint of light sensitivity and resolution, n 2, n 3And n 4Be below 20.More preferably, n 2And n 4Be more than 3 and below 10 independently of one another, n 3Be more than 5 and below 15.
In the compound shown in the above-mentioned general formula (III), n 5And n 6Independently be 1～29 integer and n separately 5+ n 6It is 2～30 integer.From the viewpoint of the flexibility of solidifying etchant resist, n 5And n 6Being more than 1, from obtaining the viewpoint of sufficient light sensitivity, is below 29.From the viewpoint of sheltering, n 5+ n 6Being more than 2, from the viewpoint of image formation property, is below 30.In addition, in the compound shown in the above-mentioned general formula (III), n 7And n 8Independently be 0～29 integer and n separately 7+ n 8It is 0～30 integer.From obtaining the viewpoint of sufficient light sensitivity, n 7And n 8Be below 29.From the viewpoint of developer solution cohesion, n 7+ n 8Be below 30.
In the compound shown in the above-mentioned general formula (III), n 5+ n 6+ n 7+ n 8Value be preferably more than 2, in addition, be preferably below 40.The flexibility of the curing etchant resist that obtains from photosensitive polymer combination is solidified and the viewpoint of sheltering, above-mentioned value is preferably more than 2, and from the effect to resolution, above-mentioned value is preferably below 40.Object lesson as the unsaturated compound shown in the above-mentioned general formula (III), the two ends that can list bisphenol-A respectively the average 2 moles oxirane of addition and the polyglycol that obtains dimethylacrylate (for example, the NKESTER BPE-200 that Xin Zhong village chemical industry (strain) is made), the two ends of bisphenol-A are the dimethylacrylate of the average 5 moles oxirane of addition and the polyglycol that obtains (for example Xin Zhong village chemical industry (strain) make NK ESTER BPE-500) respectively, the two ends of bisphenol-A are the average 6 moles oxirane of addition and average 2 moles epoxypropane and the dimethylacrylate of the poly alkylene glycol that obtains respectively, and the two ends of bisphenol-A are the dimethylacrylate etc. of the average 15 moles oxirane of addition and average 2 moles epoxypropane and the poly alkylene glycol that obtains respectively.
From improving the viewpoint of light sensitivity, resolution, adhesion and sheltering, photopolymerization unsaturated compound shown in the above-mentioned general formula (II) shared ratio in (b) addition polymerization monomer is preferably more than the 3 quality %, from suppressing the viewpoint of edge-melting, be preferably below the 70 quality %.Aforementioned proportion is more preferably more than the 3 quality % and below the 50 quality %, more preferably more than the 3 quality % and below the 30 quality %.
From improving the viewpoint of light sensitivity, the shared ratio in (b) addition polymerization monomer of the photopolymerization unsaturated compound shown in the above-mentioned general formula (III) is preferably more than the 3 quality %, from suppressing the viewpoint of edge-melting, is preferably below the 70 quality %.Aforementioned proportion is 10～65 quality % more preferably, more preferably 15～55 quality %.
As (b) addition polymerization monomer used in the photosensitive polymer combination of the present invention, except can use above-mentioned general formula (II) and (III) shown in compound, can also use known compound with at least one polymerizable olefinic unsaturated link.As this compound, for example can list 4-nonyl phenyl seven ethylene glycol bisthioglycolate propylene glycol acrylate, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, phenoxy group six EDIAs, the half ester compound of phthalic anhydride and acrylic acid 2-hydroxypropyl acrylate and the reactant of epoxypropane (the trade name OE-A 200 that for example Japanese catalyst chemistry is made), 4-n-octyl phenoxy group five propylene glycol acrylate, 1,6-hexanediol (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, and polypropylene glycol two (methyl) acrylate, polyether polyols two (methyl) acrylate such as polyglycol two (methyl) acrylate, 2-two (p-hydroxybenzene) propane two (methyl) acrylate, glycerine three (methyl) acrylate, pentaerythrite five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, 2, two (the 4-methacryloxy five ethoxyl phenenyls) propane of 2-, the urethane thing of hexamethylene diisocyanate and nine propylene glycol monomethyl acrylate etc. contains polyfunctional group (methyl) acrylate of carbamate groups, and multifunctional (methyl) acrylate of isocyanurate compound.These compounds can use separately, also can be used in combination of two or more.
The amount of (b) addition polymerization monomer in the photosensitive polymer combination of the present invention is the scope of 3～75 quality %, and preferred scope is 15～70 quality %.The viewpoint of the delay of and development time bad from the curing that suppresses photosensitive polymer combination, this amount is more than the 3 quality %; In addition, from the viewpoint of peeling off delay that suppresses cold flow (cold flow) and solidify resist, this amount is below the 75 quality %.
(c) Photoepolymerizationinitiater initiater
As (c) Photoepolymerizationinitiater initiater, can suitably use usually material as the Photoepolymerizationinitiater initiater of photoresist, especially preferably use hexa-aryl bi-imidazole (below be also referred to as the triarylimidazoles dimer).As the triarylimidazoles dimer, for example can list 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer (below be also referred to as 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,1 '-two imidazoles), 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', 5 '-diphenyl-imidazole dimer, 2,4-pair-(Chloro-O-Phenyl)-5-(3, the 4-Dimethoxyphenyl)-the diphenyl-imidazole dimer, 2,4,5-three-(Chloro-O-Phenyl)-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-two-4,5-(3, the 4-Dimethoxyphenyl)-the imidazoles dimer, 2,2 '-two-(2-fluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,3-difluoromethyl phenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2, the 4-difluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2, the 5-difluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2, the 6-difluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,3, the 4-trifluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,3, the 5-trifluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,3, the 6-trifluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,4, the 5-trifluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,4, the 6-trifluorophenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,3,4,5-tetrafluoro phenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2,2 '-two-(2,3,4,6-tetrafluoro phenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer, and 2,2 '-two-(2,3,4,5, the 6-pentafluorophenyl group)-4,4 ', 5,5 '-four-(3-methoxyphenyl)-imidazoles dimer etc.Especially, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer are to resolution and solidify the Photoepolymerizationinitiater initiater that film strength against corrosion has high effect, are preferred the uses.These can use separately or be used in combination of two or more.
Carry out the viewpoint of photocuring well from light sensitivity, preferably contain acridine compound and/or pyrazoline compounds as (c) Photoepolymerizationinitiater initiater.As the acridine compound, can list acridine; the 9-phenylacridine; 9-(4-tolyl) acridine; 9-(4-methoxyphenyl) acridine; 9-(4-hydroxy phenyl) acridine; 9-ethyl acridine; 9-chloroethyl acridine; 9-methoxyl acridine; 9-ethoxy acridine; 9-(4-aminomethyl phenyl) acridine; 9-(4-ethylphenyl) acridine; 9-(4-n-pro-pyl phenyl) acridine; 9-(4-n-butylphenyl) acridine; 9-(4-tert-butyl-phenyl) acridine; 9-(4-ethoxyl phenenyl) acridine; 9-(4-acetylphenyl) acridine; 9-(4-dimethylaminophenyl) acridine; 9-(4-chlorphenyl) acridine; 9-(4-bromophenyl) acridine; 9-(3-aminomethyl phenyl) acridine; 9-(3-tert-butyl-phenyl) acridine; 9-(3-acetylphenyl) acridine; 9-(3-dimethylaminophenyl) acridine; 9-(3-diethylamino phenyl) acridine; 9-(3-chlorphenyl) acridine; 9-(3-bromophenyl) acridine; 9-(2-pyridine radicals) acridine; 9-(3-pyridine radicals) acridine; 9-(4-pyridine radicals) acridine etc.Wherein, from the viewpoint of image formation property, the 9-phenylacridine is desirable.
In addition, as pyrazoline compounds, carry out the viewpoint of photocuring, 1-phenyl-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1-(4-(benzoxazole-2-yl) phenyl well from light sensitivity)-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1-phenyl-3-(4-xenyl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline and 1-phenyl-3-(4-xenyl)-5-(uncle's 4-octyl group-phenyl)-pyrazoline etc. is preferred.
In addition, as the Photoepolymerizationinitiater initiater except above-mentioned, for example can list the 2-EAQ, the octaethyl anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, the 1-chloroanthraquinone, 1, the 4-naphthoquinones, 9, the 10-phenanthrenequione, the 2-methyl isophthalic acid, the 4-naphthoquinones, 2,3-dimethyl anthraquinone, and quinones such as 3-chloro-2-methylanthraquinone, benzophenone, michaelis ketone [4,4 '-two (dimethylamino) benzophenone], and 4, aromatic series ketones such as 4 '-two (diethylamino) benzophenone, benzoin, benzoin ethyl ether, the benzoin phenylate, the methylbenzene acyloin, and benzoin ethers such as ethylbenzene acyloin, the benzil dimethyl ketal, benzil diethyl ketal, the combination of thioxanthene ketone and alkyl amino benzoic ether, and, 1-phenyl-1,2-propylene glycol-2-O-cupron, and 1-phenyl-1, oxime ester classes such as 2-propanedione-2-(O-ethoxy carbonyl) oxime.In addition, as the combination of above-mentioned thioxanthene ketone and alkyl amino benzoic ether, for example can list the combination of combination, 2-clopenthixal ketone and dimethylaminobenzoic acid ethyl ester of ethyl thioxanthones and dimethylaminobenzoic acid ethyl ester and the combination of isopropyl thioxanthone and dimethylaminobenzoic acid ethyl ester.In addition, also can use the N-aryl amino acid.As the example of N-aryl amino acid, can list N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine etc.Wherein, from the viewpoint that light sensitivity raises, N-phenylglycine is particularly preferred.
The amount of (c) Photoepolymerizationinitiater initiater in the photosensitive polymer combination is the scope of 0.01～30 quality %, and preferred range is 0.05～10 quality %.From when utilizing the photopolymerization of exposure, obtaining the viewpoint of sufficient light sensitivity, above-mentioned amount is more than the 0.01 quality %, in addition, make during from photopolymerization light fully be transmitted through photosensitive polymer combination bottom surface (away from the part of light source), obtain the good resolution and the viewpoint of adhesion, be below the 30 quality %.
(d) compound shown in the general formula (I)
Photosensitive polymer combination of the present invention has and can keep that image forms property and sheltering, shortening utilize aqueous alkali to peel off the advantage of the time of photocuring film by containing the compound shown in one or more (d) general formulas (I).
[chemical formula 7]
Figure BPA00001328438100161
(in the formula, R 1～R 5Independent separately is H, aryl or aryl alkyl, and R 1～R 5In at least one be aryl or aryl alkyl, A 1Be C 2H 4Or C 3H 6, n 1Be 2 when above, a plurality of A 1Can be the same or different each other, and n 1It is 1～50 integer.)
In the general formula (I), R 1～R 5Independent separately is H, aryl or aryl alkyl.In this manual, aryl alkyl is meant that a hydrogen atom of alkyl is replaced the group that forms by aryl.Aryl is the general name that the nuclear from aromatic hydrocarbon removes the residue that a hydrogen atom forms, and can list to replace or unsubstituted phenyl, tolyl, xylyl, naphthyl, 2,4 6-trimethylphenyl (mesityl) etc.As aryl alkyl, can list phenylalkyls such as benzyl, phenylethyl, cumyl etc., from the good viewpoint of adhesion, phenylalkyl is preferred, and phenylethyl is preferred.
R 1～R 5In at least one be aryl or aryl alkyl.Thus, can obtain good adhesion.In addition, R 1～R 5In 1～3, particularly 2 or 3 situations that are respectively aryl or aryl alkyl, be preferred from resolution and the good viewpoint of adhesion.
In addition, R 1～R 5In at least one be preferably phenylalkyl especially.
In addition, from shortening the viewpoint of splitting time, following this R 1～R 5Combination be preferred: R 1～R 5Independent separately is H, phenyl or 1-phenylethyl, R 1～R 5In 2 be H, and R 1～R 5In 3 independent separately be phenyl or 1-phenylethyl.On the other hand, R 1～R 5The array mode except that above-mentioned, that is, following array mode is preferred from the good viewpoint of development cohesion: R 1～R 5Independent separately is H, aryl or aryl alkyl, and R 1～R 5In at least one be aryl or aryl alkyl, with R 1～R 5Combination be not R 1～R 5In 2 be H and R 1～R 5In the mode of 3 independent separately conditions that are combined as for phenyl or 1-phenylethyl.
The carbon number of aryl alkyl preferred alkyl part is 1～6, and when carbon number was this scope, cohesion was better.More preferably 1～3 of above-mentioned carbon atom.
A in the general formula (I) 1Be C 2H 4Or C 3H 6, back cohesion good this advantage thus can obtain to develop.
Repetitive-(A in the general formula (I) 1-O)-repeat number n 1Be 1～50, n 1Be 2 when above, a plurality of A 1Can be the same or different each other.From obtaining the viewpoint of good cohesion, n 1Being more than 1, from obtaining the viewpoint of preferable image formation property and adhesion, is below 50.From the better viewpoint of adhesion, n 1Be preferably 1～35 integer.In addition, repetitive-(A 1-O)-can repeat with random or block fashion.
With above-mentioned (a) and (b) with (c) when the total amount of composition is 100 quality %, the content of the compound shown in (d) general formula (I) in the photosensitive polymer combination is preferably the scope of 1～20 quality %, the more preferably scope of 2～10 quality %.Above-mentioned content is 1 quality % when above, and cohesion is good after the development of photosensitive polymer combination, is 20 quality % when following, and it is good that development and image form property.
As the compound shown in commercially available available (d) general formula (I), for example can list Newcol 610 (Japanese emulsifying agent Co., Ltd. make), Newcol 610 (80) (Japanese emulsifying agent Co., Ltd. make), Newcol 2604 (Japanese emulsifying agent Co., Ltd. make), Newcol 2607 (Japanese emulsifying agent Co., Ltd. make), Newcol 2609 (Japanese emulsifying agent Co., Ltd. make), Newcol 2614 (Japanese emulsifying agent Co., Ltd. make), Newcol 707-F (Japanese emulsifying agent Co., Ltd. make), Newcol 710-F (Japanese emulsifying agent Co., Ltd. make), Newcol 714-F (Japanese emulsifying agent Co., Ltd. make), Newcol 2608-F (Japanese emulsifying agent Co., Ltd. make), Newcol 2600-FB (Japanese emulsifying agent Co., Ltd. make), Newcol 2616-F (Japanese emulsifying agent Co., Ltd. make), Newcol 3612-FA (Japanese emulsifying agent Co., Ltd. make) etc., wherein, from the viewpoint of effective shortening splitting time, Newcol 2604 (Japanese emulsifying agent Co., Ltd. make) more preferably, Newcol 2607 (Japanese emulsifying agent Co., Ltd. make), Newcol 2609 (Japanese emulsifying agent Co., Ltd. make) and Newcol 2614 (Japanese emulsifying agent Co., Ltd. manufacturing).
In photosensitive polymer combination of the present invention, the composition as except above-mentioned (a)～(d) composition can contain various adjuvants.Particularly, for example can adopt coloring materials such as dyestuff, pigment.As this coloring material, for example can list phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock green, alkali blue 20 and malachite green (diamond green) etc.
In addition, in order to provide visual image, can make in the photosensitive polymer combination of the present invention and contain colour former by exposure.As this colour former, can list the dyestuffs such as combination of leuco dye or fluoran dyes (fluorane dye) and halogen compounds.As this halogen compounds, can enumerate amyl bromide, isoamyl bromide, bromination isobutylene, ethylene bromide, diphenyl methyl bromine, benzal bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-three chloro-2, two (rubigan) ethane of 2-, carbon trichloride and chlorination triaizine compounds etc.
The coloring material in the photosensitive polymer combination and the amount of colour former are preferably 0.01～10 quality % respectively.From obtaining the good coloring and the viewpoint of color emissivity, this content is preferably more than the 0.01 quality %, and viewpoint that storage stability good good from the contrast of exposure portion and unexposed portion is preferably below the 10 quality %.
In addition, for thermal stability and the storage stability that improves photosensitive polymer combination, preferably make more than one compounds that contain in the photosensitive polymer combination in the group that is selected from free radical polymerization polymerization inhibitor, benzotriazole and carboxyl benzotriazole class composition.
As the free radical polymerization polymerization inhibitor, for example can list p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, stannous chloride, 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 nitroso-amines etc.
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-methyl benzotriazazole 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) aminomethylene carboxyl benzotriazole and the amino ethylidene carboxyl benzotriazole of N-(N, N-two-2-ethylhexyl).
The total content of the free radical polymerization polymerization inhibitor in the photosensitive polymer combination, 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 with good storage stability, this content is preferably more than the 0.01 quality %, in addition, from keeping the viewpoint of excellent exposure sensitivity, is preferably below the 3 quality %.
In photosensitive polymer combination, can contain plastifier as required.As plastifier; for example can list polyglycol; polypropylene glycol; polyoxy propylidene polyoxyethylene ether; the polyoxyethylene monomethyl ether; polyoxy propylidene monomethyl ether; polyoxyethylene polyoxy propylidene monomethyl ether; the single ether of polyoxyethylene; polyoxy propylidene list ether; diol-lipids such as polyoxyethylene polyoxy propylidene list ether; phthalates such as diethyl phthalate, orthotoluene sulfonamide; para toluene sulfonamide; tributyl citrate; triethyl citrate; acetyl triethyl citrate; acetyl group citric acid three n-propyls; ATBC etc.
The content of the plastifier in the photosensitive polymer combination is preferably 5～50 quality %, more preferably 5～30 quality %.From the delay that suppresses development time, give and solidify the viewpoint of etchant resist with flexibility, above-mentioned content is preferably more than the 5 quality %, in addition, from suppressing to solidify viewpoint not enough, cold flow, is preferably below the 50 quality %.
＜photosensitive polymer combination blending liquid 〉
The form of the photosensitive polymer combination blending liquid that photosensitive polymer combination of the present invention also can form to add solvent in this photosensitive polymer combination is used for various uses.As The suitable solvent, can list with MEK (MEK) is the ketone and the alcohols such as methyl alcohol, ethanol and isopropyl alcohol of representative.Preferably be adjusted at the amount of the solvent that adds in the photosensitive polymer combination, so that the viscosity of photosensitive polymer combination blending liquid is 500～4000mPasec under 25 ℃.
＜photosensitive-resin layered product 〉
The present invention also provides above-mentioned this photosensitive polymer combination of the present invention is laminated to the photosensitive-resin layered product that forms on the supporter.Photosensitive-resin layered product can have protective seam on the surface of the opposite side in support side of the layer (below be also referred to as photo-sensitive resin) that is formed by photosensitive polymer combination.
As supporter, it is desirable to see through transparent material by the light of exposure light source emission.As this supporter, can list pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, plasticon, polyacrylonitrile film, styrol copolymer film, polyamide film and cellulose derivative film etc.As these films, can use the material that stretched as required.The mist degree of supporter is preferably below 5.The supporter of thinner thickness is being favourable aspect image formation performance and the economy, and owing to need keep intensity, preferably uses the material of 10～30 μ m.
When in photosensitive-resin layered product, forming protective seam; the key property of this protective seam is; with respect to the adhesion of photo-sensitive resin and supporter, the adhesion of photo-sensitive resin and protective seam is enough little, can easily peel off protective seam from photo-sensitive resin.For example can preferably use polyethylene film and polypropylene film etc. as protective seam.In addition, can preferably use the film of disclosed fissility excellence 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 preferably 5～100 μ m, more preferably 7～60 μ m.The thin more resolution of this thickness is high more, and in addition, thick more then film strength is high more, so this thickness can suitably be selected according to purposes.
By with supporter, photo-sensitive resin and as required and fixed protective seam successively the lamination method of making photosensitive-resin layered product of the present invention can adopt known method at present.
For example, use used photosensitive polymer combination in photo-sensitive resin prepares aforementioned photosensitive polymer combination blending liquid, at first using rod to be coated with device or roller coat device coats it on supporter and carries out drying, the photo-sensitive resin that lamination is formed by this photosensitive polymer combination on supporter.Then, lamination protective seam on this photo-sensitive resin as required.By said method, can make photosensitive-resin layered product.
＜corrosion-resisting pattern formation method 〉
The present invention also provides the corrosion-resisting pattern formation method of the photosensitive-resin layered product that uses the invention described above.This corrosion-resisting pattern formation method comprises following operation: the lamination that forms photosensitive-resin layered product on substrate; Exposure process to this photosensitive-resin layered product exposure; And the unexposed portion of removing the photoresist in this photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern.The following describes the object lesson of corrosion-resisting pattern formation method.
At first, use laminating machine to carry out lamination.Have at photosensitive-resin layered product under the situation of protective seam, peel off protective seam and with laminating machine the photo-sensitive resin heating is crimped on the substrate surface afterwards, carry out lamination.At this moment, photo-sensitive resin is lamination on a surface of substrate only, as required also can be at the two sides lamination.The heating-up temperature of this moment is generally 40～160 ℃.In addition, add thermo-compressed by carrying out twice above this, the gained corrosion-resisting pattern can improve the adhesion of substrate.At this moment, crimping can use the two-stage type laminating machine with duplex roller to carry out, and photosensitive-resin layered product and substrate repeated multiple times are connected on layered photosensitive-resin on the substrate surface by roller.
Then, use exposure machine to carry out exposure process.Peel off supporter as required, photo-sensitive resin is exposed by active light by photomask then.Exposure was decided by light illumination and time shutter.Can use quantometer to measure exposure.
In exposure process, can use maskless exposure method.Maskless exposure does not use photomask and exposes on substrate by direct drawing apparatus.As light source, can use semiconductor laser, ultrahigh pressure mercury lamp of wavelength 350～410nm etc.Describe pattern by computer control, exposure is in this case decided by the illumination of exposure light source and the translational speed of substrate.
Then, use developing apparatus to carry out developing procedure.After the exposure, be removed when on the photo-sensitive resin supporter being arranged.Then, use the developer solution that constitutes by aqueous alkali that the unexposed portion development of photoresist is removed, obtain corrosion-resisting pattern.As aqueous alkali, Na 2CO 3Or K 2CO 3Deng aqueous solution be preferred.These can cooperate the characteristic of photo-sensitive resin to select, and are generally the Na of concentration 0.2～2 quality % 2CO 3Aqueous solution.In this aqueous alkali, can sneak into surfactant, defoamer, be used to promote a small amount of organic solvent that develops etc.In addition, the temperature of this developer solution in the developing procedure preferably keeps temperature certain 20～40 ℃ of scopes.
Can obtain corrosion-resisting pattern by above-mentioned operation, and according to circumstances also can further carry out 100～300 ℃ heating process.By implementing this heating process, can further improve chemical-resistant.Heating can be used the heating furnace of modes such as hot blast, infrared ray or far infrared.
The manufacture method of＜conductive pattern and the manufacture method of printed circuit board (PCB) 〉
The present invention also provides and uses above-mentioned photosensitive-resin layered product to make the method for conductive pattern and use above-mentioned photosensitive-resin layered product to make the method for printed circuit board (PCB).The manufacture method of conductive pattern comprises following operation: form the lamination of the photosensitive-resin layered product of the invention described above on substrate, wherein said substrate is sheet metal or metal film coated insulcrete; Exposure process to the photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; And by the substrate (for example, for copper clad laminate, being the copper face of substrate) that is formed with corrosion-resisting pattern being carried out the operation that etching or plating form conductive pattern.In lamination, exposure process and developing procedure, can preferably adopt and identical method and the condition described in the corrosion-resisting pattern formation method.
In addition, the manufacture method of printed circuit board (PCB) comprises following operation: form the lamination of the photosensitive-resin layered product of the invention described above on substrate, wherein said substrate is copper clad laminate or flexible base, board; Exposure process to the photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with corrosion-resisting pattern is carried out the operation of etching or plating; And the operation of peeling off corrosion-resisting pattern from substrate.Be typically, with same method described in the corrosion-resisting pattern formation method and condition under carry out lamination, exposure process and developing procedure, handle the substrate that exposes with known method such as etching method or plating method then, and then, the aqueous solution that is better than developer solution with alkalescence is peeled off the stripping process of corrosion-resisting pattern from substrate, thereby can obtain desired printed circuit board (PCB).The aqueous alkali of peeling off usefulness (below be also referred to as " stripper ") is not particularly limited the NaOH of general working concentration 2～5 quality % or the aqueous solution of KOH.In stripper, also can add a spot of water-soluble solvent.In addition, the temperature of this stripper in the stripping process is preferably 40～70 ℃ scope.
The manufacture method of＜lead frame 〉
The present invention also provides the photosensitive-resin layered product that uses the invention described above to make the method for lead frame.This method comprises following operation: form the lamination of the photosensitive-resin layered product of the invention described above on substrate, wherein said substrate is a sheet metal; Exposure process to the photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with corrosion-resisting pattern is carried out etched operation; And the operation of peeling off corrosion-resisting pattern from substrate.Be typically, the sheet metal that uses copper, aldary or iron-based alloy etc. is as substrate, with same method described in the corrosion-resisting pattern formation method and condition under carry out lamination, exposure process and developing procedure, the substrate that exposes of etching forms the operation of conductive pattern then.After this, use with the same method of the manufacture method of above-mentioned printed circuit board (PCB) and peel off the stripping process of corrosion-resisting pattern, thereby can obtain desired lead frame.
＜have a manufacture method of the base material of relief pattern 〉
The present invention also provides and uses above-mentioned photosensitive-resin layered product manufacturing to have the method for the base material of relief pattern.This method comprises following operation: form the lamination of the photosensitive-resin layered product of the invention described above on the substrate of substrate, wherein said substrate is the glass substrate that is coated with glass rib paste; The exposure process that on photosensitive-resin layered product, exposes; The unexposed portion of removing the photoresist in the photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with corrosion-resisting pattern is carried out the operation of blasting treatment processing; And the operation of peeling off corrosion-resisting pattern from substrate.In lamination, exposure process and developing procedure, can preferably adopt and same method and the condition described in the above-mentioned corrosion-resisting pattern formation method.The corrosion-resisting pattern that forms in the manufacture method of this base material can be used as and with blasting method the protection mask parts that substrate adds man-hour used.
In addition, except the above-mentioned glass substrate that is coated with glass rib paste, can also use substrates such as glass, silicon chip, amorphous silicon, polysilicon, pottery, sapphire, metal material.Be typically, on the substrate that is coated with glass rib paste, carry out lamination, exposure process and developing procedure, form corrosion-resisting pattern by the method identical with aforementioned corrosion-resisting pattern formation method.After this, through on formed corrosion-resisting pattern, spray sand-blast material be cut to target depth the blasting treatment operation, remove the corrosion-resisting pattern stripping process partly that remains on the substrate with alkali stripper etc. from substrate, can form the base material that has fine relief pattern on the substrate.The sand-blast material that uses in the blasting treatment operation can use material known, for example can use SiC, SiO 2, Al 2O 3, CaCO 3, ZrO, glass, stainless steel etc. particle diameter 2～100 μ m about particulate.
The manufacture method of＜semiconductor packages 〉
The present invention also provides the method for using above-mentioned photosensitive-resin layered product to make semiconductor packages.This method comprises following operation: form the lamination of the photosensitive-resin layered product of the invention described above on substrate, wherein said substrate is the circuit-formed wafer of having finished as LSI; Exposure process to the photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with corrosion-resisting pattern is carried out the operation of plating; And the operation of peeling off corrosion-resisting pattern from substrate.Be typically, with same method described in the corrosion-resisting pattern formation method and condition under carry out lamination, exposure process and developing procedure, carry out the plating that the peristome that exposes is implemented the column of copper, scolder etc. is formed the operation of conductive pattern then.After this, with peeling off the stripping process of corrosion-resisting pattern with the same method of the manufacture method of above-mentioned printed circuit board (PCB), and then, carry out coming the operation of the thin metal layer of the part except that removing the column plating, thereby can obtain desired semiconductor packages by etching.
Embodiment
Further specify the present invention with embodiment below, but the invention is not restricted to this.The evaluation that the following describes embodiment and comparative example is with the method for making of sample and at the evaluation method and the evaluation result of gained sample.
(embodiment 1～13, comparative example 1 and 2)
Press the mass parts shown in table 2 and the table 3 with the compound shown in the table 1, obtain photosensitive polymer combination.In addition, in table 2 and table 3, MEK represents MEK, and the mass parts in the proportion of composing of the compound except that MEK is meant that total amount comprises the value that calculates behind the MEK.
1. estimate making with sample
Photosensitive-resin layered product in following making embodiment and the comparative example.
The making of＜photosensitive-resin layered product 〉
The photosensitive polymer combination of each embodiment and each comparative example is fully stirred and mix, using rod to be coated with device is coated on described each composition on the surface as the thick pet film of 16 μ m of supporter equably, drying is 4 minutes in 95 ℃ dryer, forms photo-sensitive resin.The thickness of photo-sensitive resin is 40 μ m.
Then, on the surface that does not have the lamination pet film of photo-sensitive resin, fit, obtain photosensitive-resin layered product as the thick polyethylene film of 22 μ m of protective seam.
＜substrate surface leveling 〉
Evaluation substrate as light sensitivity, resolution and adhesion, use lamination that the thick copper clad laminate of 1.2mm of the thick rolled copper foil of 35 μ m is arranged, the wet type polishing roll is carried out on the surface grind (Scotch-Brite (registered trademark) HD#600 that 3M company makes is by twice).
Use substrate for estimating, prepared under the expulsion pressure of 0.20MPa, to carry out the substrate of jet polishing (jet scrub polishing) (Japan grinds and cuts SAKURUNDUM A (registered trademark) #F220P that whetstone grain (strain) is made).
＜lamination 〉
When peeling off the polyethylene film of photosensitive-resin layered product, hot-roll lamination machine (AL-70 that Asahi Chemical Industry's (strain) makes) is used on leveling aforesaid substrate surface then, with 105 ℃ roll temperatures it is laminated to and is preheated to 60 ℃ copper clad laminate.Making gaseous tension is that 0.35MPa, laminate speed are 1.5m/min.
＜exposure 〉
The mask that the evaluation of photo-sensitive resin is required is placed on the pet film as supporter, by ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. the HMW-201KB of Zhi Zaoing), with 6 sections in 21 sections stage metraster that Stouffer the is made exposures that take place to solidify expose (unit in the table 2 and 3 is stage metraster hop count).
＜develop
Peel off pet film, use alkali developing machine (Fuji Kiko Co., the dry film developing machine that Ltd. makes) then, with the Na of stipulated time with 30 ℃ 1 quality % 2CO 3Aqueous solution is sprayed on the photo-sensitive resin, with 2 times of unexposed portions of removing photo-sensitive resin to the dissolving of the time of minimum development time.At this moment, dissolving the required shortest time fully with the photo-sensitive resin of unexposed portion is minimum development time.
2. evaluation method
(1) light sensitivity evaluation
Use brightness from transparent to black take place 21 sections stage metraster that the Stouffer of 21 grades of variations makes to lamination after through light sensitivity, the resolution evaluation after 15 minutes expose with substrate.After the exposure, develop, with the complete residual stage metraster hop count value that is light sensitivity of etchant resist with 2 times of development times to minimum development time.
(2) resolution evaluation
Width by exposure portion and unexposed portion be 1: 1 the line style pattern mask of ratio to lamination after through the resolution evaluation after 15 minutes expose with substrate.Develop with 2 times of development times to minimum development time, the minimum mask width that solidifies line against corrosion with normal formation is the value of resolution, following resolution is carried out classification.
A: the value of resolution is below the 30 μ m.
B: the value of resolution is above 30 μ m and below the 40 μ m.
C: the value of resolution surpasses 40 μ m.
(3) adhesion evaluation
Width by exposure portion and unexposed portion be 1: 1 the line style pattern mask of ratio to lamination after through light sensitivity, the resolution evaluation after 15 minutes expose with substrate.Develop with 2 times of development times to minimum development time, the minimum mask live width of solidifying line against corrosion with normal formation is the value of adhesion.
A: the value of adhesion is below the 30 μ m.
B: the value of adhesion is above 30 μ m and below the 40 μ m.
C: the value of adhesion surpasses 40 μ m.
(4) fissility evaluation
The mask of the pattern by having 6cm * 6cm to lamination after through the fissility evaluation after 15 minutes expose with substrate.Develop with 2 times of development times, be immersed in then in 50 ℃, the aqueous sodium carbonate of 3 quality %, measure the time that etchant resist is peeled off, followingly carry out classification to minimum development time.
A: splitting time is below 45 seconds.
B: splitting time surpasses below 45 seconds and 50 seconds.
C: splitting time was above 50 seconds.
(5) sheltering evaluation
At the two sides laminated photosensitive resin laminate of the base material in the hole thick copper clad laminate of 1.6mm, that have diameter 6mm, expose by the exposure of regulation in table 2 and the table 3, develop washing and drying with 4 times of development times to minimum development time.Then, measure the hole number that breaks, calculate the masking film rupture rate by following mathematical expression.
Masking film rupture rate (%)=[breaking and count (individual)/all hole counts (individual) in the hole] * 100
According to this masking film rupture rate (%), carry out classification as follows.
A: be lower than 3%
B:3% is above and be lower than 10%
More than the C:10%
3. evaluation result
The evaluation result of embodiment and comparative example is shown in table 2 and 3.
[table 1]
Figure BPA00001328438100301
[table 2]
Figure BPA00001328438100311
[table 3]
Figure BPA00001328438100321
Utilizability on the industry
Photosensitive polymer combination of the present invention can be applied to aptly: the manufacturing of printed circuit board (PCB), the manufacturing of lead frame of IC chip carrying, the metal forming Precision Machining such as metal mask manufacturing, the manufacturing of the encapsulation such as BGA or CSP, the manufacturing of the belt base plate such as COF, TAB, the manufacturing of semiconductor projection, the manufacturing of the partition of the flat-panel monitors such as ITO electrode, addressing electrode, electromagnetic wave shield etc.

Claims (16)

1. photosensitive polymer combination, it contains following (a)～(d) composition: (a) at least to contain α, β-unsaturated carboxylic monomer for the polymerization composition carry out that polymerization obtains, acid equivalent be 100～600 and weight-average molecular weight be 5000～500000 thermoplastic polymer, 20～90 quality %; (b) has the addition polymerization monomer of at least one polymerizable olefinic unsaturated link in the molecule, 3～75 quality %; (c) Photoepolymerizationinitiater initiater, 0.01～30 quality %; And (d) compound shown in the following general formula (I),
[Chemical formula 1]
Figure FPA00001328438000011
In the formula, R 1～R 5Independent separately is H, aryl or aryl alkyl, and R 1～R 5In at least one be aryl or aryl alkyl, A 1Be C 2H 4Or C 3H 6, n 1Be 2 when above, a plurality of A 1Can be the same or different each other, and n 1It is 1～50 integer.
2. photosensitive polymer combination according to claim 1, wherein, the R in the described general formula (I) 1～R 5In at least one be phenylalkyl.
3. photosensitive polymer combination according to claim 2, wherein, the carbon number of the moieties in the described phenylalkyl is 1～6.
4. according to each described photosensitive polymer combination of claim 1～3, wherein, the R in the described general formula (I) 1～R 5In 1～3 group be respectively aryl or aryl alkyl.
5. according to each described photosensitive polymer combination of claim 1～3, wherein, the R in the described general formula (I) 1～R 5In 2 or 3 groups be respectively aryl or aryl alkyl.
6. according to each described photosensitive polymer combination of claim 1～5, wherein, in the described general formula (I), n 1It is 1～35 integer.
7. according to each described photosensitive polymer combination of claim 1～6, wherein, the R in the described general formula (I) 1～R 5Independent separately is H, phenyl or 1-phenylethyl, R 1～R 5In 2 be H, and R 1～R 5In 3 independent separately be phenyl or 1-phenylethyl.
8. according to each described photosensitive polymer combination of claim 1～7, wherein, when with described (a) and (b) and (c) total amount of composition was 100 quality %, the content of described (d) composition was 1～20 quality %.
9. according to each described photosensitive polymer combination of claim 1～8,, contain the unsaturated compound of the photopolymerization shown in following general formula (II) or the following general formula (III) as described (b) composition,
[Chemical formula 2]
In the formula, R 6And R 7Independent separately is H or CH 3, n 2, n 3And n 4Independently be 3～20 integer separately;
[chemical formula 3]
Figure FPA00001328438000022
In the formula, R 8And R 9Independent separately is H or CH 3, A 2Be C 2H 4, A 3Be C 3H 6, n 5And n 6Independently be 1～29 integer and n separately 5+ n 6Be 2～30 integer, n 7And n 8Independently be 0～29 integer and n separately 7+ n 8Be 0～30 integer ,-(A 2-O)-and-(A 3-O)-the arrangement mode of repetitive can be random also can be block, be arranged as under the situation of block at it, can be-(A 2-O)-and-(A 3-O)-in any one be positioned at the xenyl side.
10. photosensitive-resin layered product, it is that each described photosensitive polymer combination with claim 1～9 is laminated on the supporter and forms.
11. a corrosion-resisting pattern formation method, this method comprises following operation: the lamination that forms the described photosensitive-resin layered product of claim 10 on substrate; Exposure process to described photosensitive-resin layered product exposure; And the unexposed portion of removing the photoresist in the described photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern.
12. the manufacture method of a conductive pattern, this method comprises following operation: form the lamination of the described photosensitive-resin layered product of claim 10 on substrate, wherein said substrate is sheet metal or metal film coated insulcrete; Exposure process to described photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the described photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; And by the substrate that is formed with described corrosion-resisting pattern being carried out the operation that etching or plating form conductive pattern.
13. the manufacture method of a printed circuit board (PCB), this method comprises following operation: form the lamination of the described photosensitive-resin layered product of claim 10 on substrate, wherein said substrate is copper clad laminate or flexible base, board; Exposure process to described photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the described photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with described corrosion-resisting pattern is carried out the operation of etching or plating; And the operation of peeling off described corrosion-resisting pattern from described substrate.
14. the manufacture method of a lead frame, this method comprises following operation: form the lamination of the described photosensitive-resin layered product of claim 10 on substrate, wherein said substrate is a sheet metal; Exposure process to described photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the described photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with described corrosion-resisting pattern is carried out etched operation; And the operation of peeling off described corrosion-resisting pattern from described substrate.
15. the manufacture method with base material of relief pattern, this method comprises following operation: form the lamination of the described photosensitive-resin layered product of claim 10 on substrate, wherein said substrate is the glass substrate that is coated with glass rib paste; Exposure process to described photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the described photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with described corrosion-resisting pattern is carried out the operation of blasting treatment processing; And the operation of peeling off described corrosion-resisting pattern from described substrate.
16. the manufacture method of a semiconductor packages, this method comprises following operation: form the lamination of the described photosensitive-resin layered product of claim 10 on substrate, wherein said substrate is the circuit-formed wafer of having finished as large scale integrated circuit; Exposure process to described photosensitive-resin layered product exposure; The unexposed portion of removing the photoresist in the described photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate that is formed with described corrosion-resisting pattern is carried out the operation of plating; And the operation of peeling off described corrosion-resisting pattern from described substrate.
CN200980134734.6A 2008-09-04 2009-09-04 Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, conductive pattern, and method for manufacturing printed wiring board Active CN102144189B (en)

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