CN102144189B - Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, conductive pattern, and method for manufacturing printed wiring board - Google Patents

Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, conductive pattern, and method for manufacturing printed wiring board Download PDF

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Publication number
CN102144189B
CN102144189B CN200980134734.6A CN200980134734A CN102144189B CN 102144189 B CN102144189 B CN 102144189B CN 200980134734 A CN200980134734 A CN 200980134734A CN 102144189 B CN102144189 B CN 102144189B
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photosensitive
substrate
layered product
corrosion
resisting pattern
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CN102144189A (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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  • Physics & Mathematics (AREA)
  • 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

The invention provides 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; A<1> represents C2H4 or C3H6, and when n1 is not less than 2, the plurality of A<1>'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, layered product, corrosion-resisting pattern formation method and conductive pattern, printed circuit board (PCB)
Technical field
The present invention relates to by alkaline aqueous solution development photosensitive polymer combination, this photosensitive polymer combination is laminated to supporter obtains photosensitive-resin layered product, use this photosensitive-resin layered product on substrate, form the method for corrosion-resisting pattern and the purposes of this corrosion-resisting pattern.More specifically, relate to the photosensitive polymer combination that corrosion-resisting pattern can be provided, this corrosion-resisting pattern is applicable to: the manufacture of printed circuit board (PCB), the manufacture of flexible printed circuit board, the manufacture of lead frame (hereinafter referred to as lead frame) of IC chip carrying, the metal forming Precision Machining such as metal mask manufacture, BGA(BGA Package), CSP(chip size packages) etc. the manufacture of semiconductor packages, with TAB(tape automated bonds), COF(covers brilliant film: on the fine circuits plate of film-form, carry semiconducter IC form) be the manufacture of the belt base plate (tape substrate) of representative, the manufacture of semiconductor projection (semiconductor bump), the ITO electrode of field of flat panel displays, the manufacture of the parts such as addressing electrode or electromagnetic wave shield.
Background technology
At present, printed circuit board (PCB) lithographically manufactures.In photolithography, photosensitive polymer combination is coated on substrate, carry out the exposure portion polymerizing curable that pattern exposure makes this photosensitive polymer combination, unexposed portion is removed with developer solution, thus corrosion-resisting pattern is formed on substrate, this substrate is etched or plating process to form conductive pattern, then peel off this corrosion-resisting pattern of removing from this substrate, thus conductive pattern can be formed on substrate.
In above-mentioned photoetching process, can adopt in following method any one: when photosensitive polymer combination is coated on substrate, the solution of photosensitive polymer combination is coated on substrate and makes the method for its drying; Or; lamination supporter, the layer (hereinafter also referred to " photo-sensitive resin ") formed by photosensitive polymer combination and the protective seam determined as required obtain photosensitive-resin layered product (hereinafter also referred to " dry film resist layer (dry film resist) ") successively, and photosensitive-resin layered product are laminated to the method on substrate.And, in the manufacturing of printed circuit boards, dry film resist layer a kind of after mostly using.
Simple description below uses above-mentioned dry film resist layer to manufacture the method for printed circuit board (PCB).First, when dry film resist layer has the protective seams such as polyethylene film, this protective seam is peeled off from photo-sensitive resin.Then, laminating machine is used to come laminated photosensitive resin bed and supporter according to the order of this substrate, photo-sensitive resin, supporter on the substrates such as copper clad laminate.Then, by the photomask with wiring pattern, this photo-sensitive resin exposes by the ultraviolets such as the i ray (365nm) launched with ultrahigh pressure mercury lamp, thus makes exposed portion polymerizing curable.Then, the supporter formed by polyethylene terephthalate etc. is peeled off.Then, by having the unexposed portion of the developing solution dissolution such as weakly alkaline aqueous solution or dispersion removing photo-sensitive resin, substrate forms corrosion-resisting pattern.Then, with formed corrosion-resisting pattern for protection mask, known etch processes or the process of pattern plating is carried out.Removing in the method for metallic member by etching, by with solidification etchant resist by the through hole (through-hole) of substrate, via hole (via-hole) covering that connects for interlayer, thus the metal in hole is not etched.The method is called masking method (tenting method).In etching work procedure, such as, use the solution of cupric chloride, iron chloride or cupric ammine complex.Finally, peel off this corrosion-resisting pattern with the aqueous alkali of NaOH etc. from substrate, thus manufacture substrate, the i.e. printed circuit board (PCB) with conductive pattern.From the viewpoint of operability, treatability and throughput rate, preferred peeling rate is very fast.
On the other hand, along with the miniaturization of the routing space of printed circuit board (PCB) in recent years, the high-resolution requirement of dry film resist layer is increased gradually.In addition, in masking method and plating, in order to not make etching solution and plating solution infiltrate between resist and copper, the adhesion of resist and copper is important, but there is the problem that splitting time can be elongated along with the raising of adhesion.
In patent documentation 1, in order to improve sheltering while maintaining the high resolving power of photosensitive polymer combination and high adhesion force, recording the photosensitive polymer combination of the chain multipolymer containing oxirane and epoxypropane, but not recording the problem of fissility.
prior art document
patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-20726 publication
Summary of the invention
the problem that invention will solve
Therefore, as the photosensitive polymer combination of dry film, the excellent and photosensitive polymer combination going far towards to improve the peeling rate of operability, treatability and throughput rate fast of resolution, adhesion and sheltering provides not yet.
The object of the invention is to, provide: resolution, adhesion and sheltering are excellent, solidification etchant resist has the photosensitive polymer combination of the excellent fissility based on aqueous alkali; Use the photosensitive-resin layered product having this photosensitive polymer combination; Use this photosensitive-resin layered product on substrate, form the corrosion-resisting pattern formation method of corrosion-resisting pattern; And use this photosensitive-resin layered product, the manufacture method of conductive pattern, printed circuit board (PCB), lead frame, base material and semiconductor packages.
for the scheme of dealing with problems
Above-mentioned purpose can be realized 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) is at least to contain α, β-unsaturated carboxylic monomer be polymeric composition carry out being polymerized obtain, acid equivalent is 100 ~ 600 and weight-average molecular weight is the thermoplastic polymer of 5000 ~ 500000,20 ~ 90 quality %; B there is the polyaddition monomer of at least one polymerizable ethylenic unsaturated bond, 3 ~ 75 quality % in () molecule; (c) Photoepolymerizationinitiater initiater, 0.01 ~ 30 quality %; And the compound shown in (d) following general formula (I):
[chemical formula 1]
In formula, R 1~ R 5respective is independently H, aryl or aryl alkyl, and R 1~ R 5in at least one be aryl or aryl alkyl, A 1c 2h 4or C 3h 6, n 1when being more than 2, multiple A 1can be the same or different each other, and n 1it is the integer of 1 ~ 50.
[2] photosensitive polymer combination according to above-mentioned [1] item, wherein, the R in above-mentioned general formula (I) 1~ R 5in at least one be phenylalkyl.
[3] photosensitive polymer combination according to above-mentioned [2] item, wherein, the carbon number of the moieties in above-mentioned phenylalkyl is 1 ~ 6.
[4] photosensitive polymer combination according to any one of above-mentioned [1] ~ [3] item, wherein, the R in above-mentioned general formula (I) 1~ R 5in 1 ~ 3 group be respectively aryl or aryl alkyl.
[5] photosensitive polymer combination according to any one of above-mentioned [1] ~ [3] item, wherein, the R in above-mentioned general formula (I) 1~ R 5in 2 or 3 groups be respectively aryl or aryl alkyl.
[6] photosensitive polymer combination according to any one of above-mentioned [1] ~ [5] item, wherein, in above-mentioned general formula (I), n 1it is the integer of 1 ~ 35.
[7] photosensitive polymer combination according to any one of above-mentioned [1] ~ [6] item, wherein, the R in above-mentioned general formula (I) 1~ R 5respective is independently H, phenyl or 1-phenylethyl, R 1~ R 5in 2 be H, and R 1~ R 5in 3 separately independent be phenyl or 1-phenylethyl.
[8] photosensitive polymer combination according to any one of above-mentioned [1] ~ [7] item, wherein, when being 100 quality % with above-mentioned (a), (b) with the total amount of (c) composition, the content of above-mentioned (d) composition is 1 ~ 20 quality %.
[9] photosensitive polymer combination according to any one of above-mentioned [1] ~ [8] item, as above-mentioned (b) composition, the unsaturated compound containing the photopolymerization shown in following general formula (II) or following general formula (III):
[chemical formula 2]
In formula, R 6and R 7respective is independently H or CH 3, n 2, n 3and n 4respective be independently 3 ~ 20 integer;
[chemical formula 3]
In formula, R 8or R 9respective is independently H or CH 3, A 2c 2h 4, A 3c 3h 6, n 5and n 6respective be independently 1 ~ 29 integer and n 5+ n 6the integer of 2 ~ 30, n 7and n 8respective be independently 0 ~ 29 integer and n 7+ n 8the integer of 0 ~ 30 ,-(A 2-O)-and-(A 3-O)-the arrangement mode of repetitive can be random also can be block, when it is arranged as block, can be-(A 2-O)-and-(A 3-O)-in any one be positioned at xenyl side.
[10] photosensitive-resin layered product, it is laminated to by the photosensitive polymer combination described in any one of above-mentioned [1] ~ [9] item on supporter to be formed.
[11] a kind of corrosion-resisting pattern formation method, the method comprises following operation: the lamination operation forming the photosensitive-resin layered product described in above-mentioned [10] item on substrate; To the exposure process that this photosensitive-resin layered product exposes; And the unexposed portion removing the photoresist in this photosensitive-resin layered product is to form the developing procedure of corrosion-resisting pattern.
[12] manufacture method for conductive pattern, the method comprises following operation: the lamination operation forming the photosensitive-resin layered product described in above-mentioned [10] item on substrate, and wherein said substrate is sheet metal or metal film coated insulcrete; To the exposure process that this photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in this photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; And by etch the substrate being formed with this corrosion-resisting pattern or plating forms the operation of conductive pattern.
[13] manufacture method for printed circuit board (PCB), the method comprises following operation: the lamination operation forming the photosensitive-resin layered product described in above-mentioned [10] item on substrate, and wherein said substrate is copper clad laminate or flexible base, board; To the exposure process that this photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in this photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; The substrate being formed with this corrosion-resisting pattern is etched or the operation of plating; And the operation of corrosion-resisting pattern is peeled off from this substrate.
[14] manufacture method for lead frame, the method comprises following operation: the lamination operation forming the photosensitive-resin layered product described in above-mentioned [10] item on substrate, and wherein said substrate is sheet metal; To the exposure process that this photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in this photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; To the operation that the substrate being formed with this corrosion-resisting pattern etches; And the operation of this corrosion-resisting pattern is peeled off from this substrate.
[15] a kind of manufacture method with the base material of relief pattern, the method comprises following operation: the lamination operation forming the photosensitive-resin layered product described in above-mentioned [10] item on substrate, and wherein said substrate is for being coated with the glass substrate of Glass Rib (ribbed glass) paste; To the exposure process that this photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in this photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; The substrate being formed with this corrosion-resisting pattern is carried out to the operation of blasting treatment processing; And the operation of this corrosion-resisting pattern is peeled off from this substrate.
[16] a kind of manufacture method of semiconductor packages, the method comprises following operation: the lamination operation forming the photosensitive-resin layered product described in above-mentioned [10] item on substrate, the wafer that wherein said substrate is formed for the circuit completed as LSI (large scale integrated circuit); To the exposure process that this photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in this photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; The substrate being formed with this corrosion-resisting pattern is carried out to the operation of plating; And the operation of this corrosion-resisting pattern is peeled off from this substrate.
the effect of invention
The present invention can provide: the photosensitive polymer combination that resolution, adhesion and sheltering are excellent, solidification etchant resist has the excellent fissility based on aqueous alkali; Use the photosensitive-resin layered product having this photosensitive polymer combination; Use the formation method of the corrosion-resisting pattern of the fine of this photosensitive-resin layered product.In addition, use this photosensitive-resin layered product, fine printed circuit board (PCB), lead frame, semiconductor packages or even flat-panel screens can be manufactured.
Embodiment
Illustrate the present invention below.
< photosensitive polymer combination >
Photosensitive polymer combination of the present invention contains following (a) ~ (d) composition as neccessary composition: (a) is at least to contain α, β-unsaturated carboxylic monomer be polymeric composition carry out being polymerized obtain, acid equivalent be 100 ~ 600 and weight-average molecular weight be 5000 ~ 500000 thermoplastic polymer (hereinafter also referred to (a) thermoplastic polymer), 20 ~ 90 quality %; B there is the polyaddition monomer (hereinafter also referred to (b) polyaddition monomer) of at least one polymerizable ethylenic unsaturated bond, 3 ~ 75 quality % in () molecule; (c) Photoepolymerizationinitiater initiater (hereinafter also referred to (c) Photoepolymerizationinitiater initiater), 0.01 ~ 30 quality %; And the compound (compound hereinafter also referred to shown in (d) general formula (I)) shown in (d) following general formula (I).
[chemical formula 4]
(in formula, R 1~ R 5respective is independently H, aryl or aryl alkyl, and R 1~ R 5in at least one be aryl or aryl alkyl, A 1c 2h 4or C 3h 6, n 1when being more than 2, multiple A 1can be the same or different each other, and n 1it is the integer of 1 ~ 50.)
(a) thermoplastic polymer
A () thermoplastic polymer is that at least to contain, α, β-unsaturated carboxylic monomer is polymeric composition, acid equivalent is 100 ~ 600 and weight-average molecular weight is the thermoplastic polymer of 5000 ~ 500000.
In order to make photosensitive polymer combination of the present invention have developability, fissility to the developer solution be made up of aqueous alkali, stripper, the carboxyl in (a) thermoplastic polymer is needs.A the acid equivalent of () thermoplastic polymer is 100 ~ 600, be preferably 250 ~ 450.From guarantee with the compatibility of other composition solvent or photosensitive polymer combination, particularly with the viewpoint of the compatibility of aftermentioned (b) polyaddition monomer, acid equivalent is more than 100, in addition, from the viewpoint maintaining developability, fissility, be less than 600.Herein, acid equivalent refers to, wherein has the quality (gram) of the thermoplastic polymer of the carboxyl of 1 equivalent.In addition, the measurement example of acid equivalent is as used HIRANUMA REPORTING TITRETOR (COM-555), being undertaken by potential difference titration by the NaOH aqueous solution of 0.1mol/L.
A the weight-average molecular weight of () thermoplastic polymer is 5000 ~ 500000.Homogeneous from the thickness maintaining photosensitive-resin layered product (i.e. dry film resist layer), to obtain the patience to developer solution viewpoint, weight-average molecular weight is more than 5000, in addition, from the viewpoint maintaining developability, is less than 500000.Preferably, weight-average molecular weight is 20000 ~ 100000.Weight-average molecular weight in this instructions refers to, is used the weight-average molecular weight of the standard curve determination of polystyrene (the ShodexSTANDARD SM-105 that such as Showa electrician (strain) manufactures) by gel permeation chromatography (GPC).The gel permeation chromatography that this weight-average molecular weight can use Japanese light splitting (strain) to manufacture measures 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
From the viewpoint of the image formative after alkali development, preferably, a () thermoplastic polymer is a kind of polymkeric substance of monomer in aftermentioned first monomer or the multipolymer of two or more monomer, or a kind of polymkeric substance of monomer in aftermentioned second comonomer or the multipolymer of two or more monomer, or the multipolymer of more than one monomers in this first monomer and more than one monomers in this second comonomer.
First monomer is carboxylic acid or the acid anhydrides in molecule with a polymerism unsaturated group.As the first monomer, include, for example out (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and acid half ester.Wherein, from the viewpoint of the developability based on aqueous slkali, (methyl) acrylic acid is particularly preferred.Here, (methyl) acrylic acid represents acrylic or methacrylic acid.Identical below.
Second comonomer is the monomer in non-acid, molecule with at least one polymerism unsaturated group.As second comonomer, include, for example out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) 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 the vinyl alcohols such as vinyl acetate, (methyl) vinyl cyanide, styrene and polymerisable styrene derivative.Wherein, from the viewpoint of image formative, (methyl) methyl acrylate, (methyl) n-butyl acrylate, styrene and (methyl) benzyl acrylate are particularly preferred.
As the example more specifically of (a) thermoplastic polymer, can list containing methyl methacrylate, methacrylic acid and the styrene polymkeric substance as copolymer composition, containing methyl methacrylate, methacrylic acid and the n-butyl acrylate polymkeric substance as copolymer composition, and containing benzyl methacrylate, methyl methacrylate and the 2-EHA polymkeric substance etc. as copolymer composition.
The amount of (a) thermoplastic polymer contained in photosensitive polymer combination of the present invention is the scope of 20 ~ 90 quality %, is preferably the scope of 25 ~ 70 quality %.From the viewpoint maintaining alkali-developable, this amount is more than 20 quality %, and in addition, give full play to the viewpoint of its etch resistant properties from the corrosion-resisting pattern formed by exposure, this amount is below 90 quality %.
(b) polyaddition monomer
B () polyaddition monomer has at least one polymerizable ethylenic unsaturated bond in molecule.From the viewpoint that image formative is good, ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group.From high resolving power and the viewpoint suppressing edge-melting (edge fusion), as (b) polyaddition monomer, preferably containing the following general formula of at least one (II) or the photopolymerization unsaturated compound shown in (III).
[chemical formula 5]
(in formula, R 6and R 7respective is independently H or CH 3, n 2, n 3and n 4respective be independently 3 ~ 20 integer.)
[chemical formula 6]
(in formula, R 8or R 9respective is independently H or CH 3, A 2c 2h 4, A 3c 3h 6, n 5and n 6respective be independently 1 ~ 29 integer and n 5+ n 6the integer of 2 ~ 30, n 7and n 8respective be independently 0 ~ 29 integer and n 7+ n 8the integer of 0 ~ 30 ,-(A 2-O)-and-(A 3-O)-the arrangement mode of repetitive can be random or block, when it is arranged as block, can be-(A 2-O)-and-(A 3-O)-in any one be positioned at xenyl side.)
In the compound shown in above-mentioned general formula (II), n 2, n 3and n 4independently be more than 3 and less than 20 separately.From the viewpoint improving sheltering, n 2, n 3and n 4be more than 3, from the viewpoint improving light sensitivity and resolution, n 2, n 3and n 4be less than 20.It is further preferred that n 2and n 4be more than 3 independently of one another and less than 10, n 3be more than 5 and less than 15.
In the compound shown in above-mentioned general formula (III), n 5and n 6respective be independently 1 ~ 29 integer and n 5+ n 6it is the integer of 2 ~ 30.From the viewpoint of the flexibility of solidification etchant resist, n 5and n 6being more than 1, from the viewpoint obtaining sufficient light sensitivity, is less than 29.From the viewpoint of sheltering, n 5+ n 6being more than 2, from the viewpoint of image formative, is less than 30.In addition, in the compound shown in above-mentioned general formula (III), n 7and n 8respective be independently 0 ~ 29 integer and n 7+ n 8it is the integer of 0 ~ 30.From the viewpoint obtaining sufficient light sensitivity, n 7and n 8be less than 29.From the viewpoint of developer solution cohesion, n 7+ n 8be less than 30.
In the compound shown in above-mentioned general formula (III), n 5+ n 6+ n 7+ n 8value be preferably more than 2, in addition, be preferably less than 40.The flexibility of solidification etchant resist obtained from making photosensitive polymer combination solidify and the viewpoint of sheltering, above-mentioned value is preferably more than 2, and from the effect to resolution, above-mentioned value is preferably less than 40.As the object lesson of the unsaturated compound shown in above-mentioned general formula (III), the oxirane of average 2 moles of addition and the dimethylacrylate of the polyglycol obtained be (such as respectively at the two ends that can list bisphenol-A, the NKESTER BPE-200 that Xin Zhong village chemical industry (strain) manufactures), the two ends of the bisphenol-A oxirane of average 5 moles of addition and the dimethylacrylate (the NK ESTER BPE-500 that such as Xin Zhong village chemical industry (strain) manufactures) of the polyglycol obtained respectively, the two ends of the bisphenol-A oxirane of average 6 moles of addition and the epoxypropane of average 2 moles and the dimethylacrylate of the poly alkylene glycol obtained respectively, the two ends of the bisphenol-A oxirane of average 15 moles of addition and the epoxypropane of average 2 moles and the dimethylacrylate etc. of the poly alkylene glycol obtained respectively.
From the viewpoint improving light sensitivity, resolution, adhesion and sheltering, the ratio of photopolymerization unsaturated compound shown in above-mentioned general formula (II) shared by (b) polyaddition monomer is preferably more than 3 quality %, from the viewpoint suppressing edge-melting, be preferably below 70 quality %.Aforementioned proportion is more preferably more than 3 quality % and below 50 quality %, more preferably more than 3 quality % and below 30 quality %.
From the viewpoint improving light sensitivity, the ratio of photopolymerization unsaturated compound shown in above-mentioned general formula (III) shared by (b) polyaddition monomer is preferably more than 3 quality %, from the viewpoint suppressing edge-melting, be preferably below 70 quality %.Aforementioned proportion is more preferably 10 ~ 65 quality %, more preferably 15 ~ 55 quality %.
As (b) polyaddition monomer used in photosensitive polymer combination of the present invention, except can using the compound shown in above-mentioned general formula (II) and (III), the known compound with at least one polymerizable ethylenic unsaturated bond can also be used.As this compound, include, for example out 4-nonyl phenyl seven ethylene glycol bisthioglycolate methacrylatoethyl, acrylic acid 2-hydroxyl-3-phenoxy-propyl, phenoxy group six EDIA, the half ester compound of phthalic anhydride and acrylic acid 2-hydroxypropyl acrylate and the reactant (the trade name OE-A 200 that such as Japanese catalyst chemistry manufactures) of epoxypropane, 4-n-octyl phenoxy group five methacrylatoethyl, 1,6-hexanediol (methyl) acrylate, Isosorbide-5-Nitrae-cyclohexanediol two (methyl) acrylate, and polypropylene glycol two (methyl) acrylate, polyether polyols two (methyl) acrylate such as polyglycol two (methyl) acrylate, 2-bis-(p-hydroxybenzene) propane two (methyl) acrylate, glycerine three (methyl) acrylate, pentaerythrite five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, two (the 4-methacryloxy five ethoxyl phenenyl) propane of 2,2-, polyfunctional group (methyl) acrylate containing carbamate groups such as the carbamate compound of hexamethylene diisocyanate and nine propylene glycol monomethyl acrylate, and multifunctional (methyl) acrylate of isocyanurate compound.These compounds can be used alone, and also can be used in combination of two or more.
The amount of (b) polyaddition monomer in photosensitive polymer combination of the present invention is the scope of 3 ~ 75 quality %, and preferred scope is 15 ~ 70 quality %.From the viewpoint of delay suppressing the bad and development time of the solidification of photosensitive polymer combination, this amount is more than 3 quality %; In addition, from the viewpoint suppressing the stripping of cold flow (cold flow) and solidification resist to postpone, this amount is below 75 quality %.
(c) Photoepolymerizationinitiater initiater
As (c) Photoepolymerizationinitiater initiater, suitably can use the material of the Photoepolymerizationinitiater initiater being typically used as photoresist, particularly preferably use hexa-aryl bi-imidazole (hereinafter also referred to triarylimidazoles dimer).As triarylimidazoles dimer, include, for example out 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dimer is (hereinafter also referred to 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl-1, 1 '-bis-imidazoles), 2, 2 ', 5-tri--(Chloro-O-Phenyl)-4-(3, 4-Dimethoxyphenyl)-4 ', 5 '-diphenyl-imidazole dimer, 2, 4-pair-(Chloro-O-Phenyl)-5-(3, 4-Dimethoxyphenyl)-diphenyl-imidazole dimer, 2, 4, 5-tri--(Chloro-O-Phenyl)-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-bis--4, 5-(3, 4-Dimethoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2-fluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 3-difluoromethyl phenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 4-difluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 5-difluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 6-difluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 3, 4-trifluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 3, 5-trifluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 3, 6-trifluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 4, 5-trifluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 4, 6-trifluorophenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 3, 4, 5-tetrafluoro phenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, 2, 2 '-bis--(2, 3, 4, 6-tetrafluoro phenyl)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer, and 2, 2 '-bis--(2, 3, 4, 5, 6-pentafluorophenyl group)-4, 4 ', 5, 5 '-four-(3-methoxyphenyl)-imidazoles dimer etc.Especially, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer is Photoepolymerizationinitiater initiater resolution and solidification film strength against corrosion to high effect, is preferably use.These can be used alone or are used in combination of two or more.
Carry out the viewpoint of photocuring well from light sensitivity, preferably containing acridine compounds and/or pyrazoline compounds as (c) Photoepolymerizationinitiater initiater.As acridine compounds, acridine can be listed, 9-phenylacridine, 9-(4-tolyl) acridine, 9-(4-methoxyphenyl) acridine, 9-(4-hydroxy phenyl) acridine, 9-ethyl acridine, 9-chloroethyl acridine, 9-methoxyacridine, 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 formative, 9-phenylacridine is desirable.
In addition, as pyrazoline compounds, the viewpoint of photocuring is carried out well, 1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline, 1-(4-(benzoxazole-2-base) phenyl from light sensitivity)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline, 1-phenyl-3-(4-xenyl)-5-(4-tbutyl-phenyl)-pyrazoline and 1-phenyl-3-(4-xenyl)-5-(the tertiary Octyl-phenyl of 4-)-pyrazoline etc. be preferred.
In addition, as Photoepolymerizationinitiater initiater in addition to the foregoing, include, for example out 2-EAQ, octaethyl anthraquinone, 1, 2-benzo anthraquinone, 2, 3-benzo anthraquinone, 2-phenyl anthraquinone, 2, 3-diphenyl anthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinones, 9, 10-phenanthrenequione, 2-methyl isophthalic acid, 4-naphthoquinones, 2, 3-dimethyl anthraquinone, and the quinones such as 3-chloro-2-methyl anthraquinone, benzophenone, michaelis ketone [4, 4 '-bis-(dimethylamino) benzophenone], and 4, the aromatic series ketones such as 4 '-bis-(diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenylate, methylbenzoin, and the benzoin ethers such as ethyl benzoin, 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, the 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, include, for example out the combination of ethyl thioxanthones and dimethyl amino benzoate, CTX and the combination of dimethyl amino benzoate and the combination of isopropyl thioxanthone and dimethyl amino benzoate.In addition, also N-aryl amino acid can be used.As the example of N-aryl amino acid, N-phenylglycine, N-Methyl-N-phenyl glycocoll, N-ethyl, N-phenyl glycocoll etc. can be listed.Wherein, from the viewpoint that light sensitivity raises, N-phenylglycine is particularly preferred.
The amount of (c) Photoepolymerizationinitiater initiater in photosensitive polymer combination is the scope of 0.01 ~ 30 quality %, and preferred scope is 0.05 ~ 10 quality %.From the viewpoint obtaining sufficient light sensitivity when utilizing the photopolymerization of exposure, above-mentioned amount is more than 0.01 quality %, in addition, from make during photopolymerization light be fully transmitted through photosensitive polymer combination bottom surface (part away from light source), obtain good resolution and the viewpoint of adhesion, be below 30 quality %.
Compound shown in (d) general formula (I)
Photosensitive polymer combination of the present invention is by maintaining image formative and sheltering, shortening utilize aqueous alkali to peel off the advantage of the time of photocuring film containing the compound shown in one or more (d) general formula (I) and having.
[chemical formula 7]
(in formula, R 1~ R 5respective is independently H, aryl or aryl alkyl, and R 1~ R 5in at least one be aryl or aryl alkyl, A 1c 2h 4or C 3h 6, n 1when being more than 2, multiple A 1can be the same or different each other, and n 1it is the integer of 1 ~ 50.)
In general formula (I), R 1~ R 5respective is independently H, aryl or aryl alkyl.In this manual, aryl alkyl refers to the group that a hydrogen atom of alkyl is replaced by aryl.Aryl is the general name of the residue removing a hydrogen atom from the core of aromatic hydrocarbon, can list substituted or unsubstituted phenyl, tolyl, xylyl, naphthyl, 2,4,6-trimethylphenyls (mesityl) etc.As aryl alkyl, can list the phenylalkyl such as benzyl, phenylethyl, cumyl etc., from the viewpoint that adhesion is good, phenylalkyl is preferred, and phenylethyl is preferred.
R 1~ R 5in at least one be aryl or aryl alkyl.Thus, good adhesion can be obtained.In addition, R 1~ R 5in 1 ~ 3, particularly 2 or 3 be respectively the situation of aryl or aryl alkyl, be preferred from resolution and the good viewpoint of adhesion.
In addition, R 1~ R 5in at least one be particularly preferably phenylalkyl.
In addition, from the viewpoint shortening splitting time, following this R 1~ R 5combination be preferred: R 1~ R 5respective is independently H, phenyl or 1-phenylethyl, R 1~ R 5in 2 be H, and R 1~ R 5in 3 separately independent be phenyl or 1-phenylethyl.On the other hand, R 1~ R 5array mode than that described above, that is, following array mode is preferred from the good viewpoint of development cohesion: R 1~ R 5respective is independently 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 respective independent conditions that are combined as phenyl or 1-phenylethyl.
The carbon number of aryl alkyl preferred alkyl part is 1 ~ 6, and when carbon number is this scope, cohesion is better.Above-mentioned carbon atom is more preferably 1 ~ 3.
A in general formula (I) 1c 2h 4or C 3h 6, the rear cohesion of development this advantage good can be obtained thus.
Repetitive-(A in general formula (I) 1-O)-repeat number n 11 ~ 50, n 1when being more than 2, multiple A 1can be the same or different each other.From the viewpoint obtaining good cohesion, n 1being more than 1, from obtaining good image formative and the viewpoint of adhesion, is less than 50.From the viewpoint that adhesion is better, n 1be preferably the integer of 1 ~ 35.In addition, repetitive-(A 1-O)-can repeat with random or block fashion.
When being 100 quality % with above-mentioned (a), (b) with the total amount of (c) composition, the content of the compound shown in (d) general formula (I) in photosensitive polymer combination is preferably the scope of 1 ~ 20 quality %, is more preferably the scope of 2 ~ 10 quality %.When above-mentioned content is more than 1 quality %, after the development of photosensitive polymer combination, cohesion is good, when being below 20 quality %, developability and image formative good.
As the compound shown in commercially available available (d) general formula (I), include, for example out Newcol 610 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 610 (80) (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2604 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2607 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2609 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2614 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 707-F (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 710-F (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 714-F (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2608-F (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2600-FB (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2616-F (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 3612-FA (Japanese emulsifying agent Co., Ltd. manufactures) etc., wherein, from the viewpoint effectively shortening splitting time, more preferably Newcol 2604 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2607 (Japanese emulsifying agent Co., Ltd. manufactures), Newcol 2609 (Japanese emulsifying agent Co., Ltd. manufactures) and Newcol 2614 (Japanese emulsifying agent Co., Ltd. manufactures).
In photosensitive polymer combination of the present invention, as the composition except above-mentioned (a) ~ (d) composition, various adjuvant can be contained.Specifically, such as the coloring material such as dyestuff, pigment can be adopted.As this coloring material, include, for example out 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 visual image can be provided by exposure, can make in photosensitive polymer combination of the present invention containing colour former.As this colour former, the dyestuffs such as the combination of leuco dye or fluoran dyes (fluorane dye) and halogen compounds can be listed.As this halogen compounds, amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, diphenyl methyl bromine, benzal bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2 can be enumerated, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-tri-chloro-2,2-two (rubigan) ethane, carbon trichloride and chlorination triaizine compounds etc.
Coloring material in photosensitive polymer combination and the amount of colour former are preferably 0.01 ~ 10 quality % respectively.From obtaining good coloring and the viewpoint of color emissivity, this content is preferably more than 0.01 quality %, from the viewpoint that contrast is good and storage stability is good in exposure portion and unexposed portion, is preferably below 10 quality %.
In addition, in order to improve thermal stability and the storage stability of photosensitive polymer combination, preferably make in photosensitive polymer combination containing more than one compounds be selected from the group of free radical polymerization polymerization inhibitor, benzotriazole and carboxyl benzotriazole class composition.
As free radical polymerization polymerization inhibitor, include, for example out 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-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitrosophenylhydroxylamine aluminium salt and diphenyl nitroso-amines etc.
In addition, as benzotriazole, include, for example out 1,2, chloro-1,2, the 3-benzotriazole of 3-benzotriazole, 1-, 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-1,2,3-benzotriazole.
In addition, as carboxyl benzotriazole class, include, for example out 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 total content of the free radical polymerization polymerization inhibitor in photosensitive polymer combination, benzotriazole and carboxyl benzotriazole class is preferably 0.01 ~ 3 quality %, is more preferably 0.05 ~ 1 quality %.From imparting photosensitive polymer combination with the viewpoint of good storage stability, this content is preferably more than 0.01 quality %, in addition, from the viewpoint maintaining good exposure sensitivity, is preferably below 3 quality %.
In photosensitive polymer combination, plastifier can be contained as required.As plastifier, include, for example out polyglycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene list ether, polyoxypropylene list ether, the diol-lipids such as polyoxyethylene polyoxypropylene list ether, the phthalates such as diethyl phthalate, orthotoluene sulfonamide, para toluene sulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate three n-propyl, ATBC etc.
The content of the plastifier in photosensitive polymer combination is preferably 5 ~ 50 quality %, is more preferably 5 ~ 30 quality %.From suppressing the delay of development time, giving solidification etchant resist with the viewpoint of flexibility, above-mentioned content is preferably more than 5 quality %, and in addition, from suppressing, solidification is not enough, the viewpoint of cold flow, is preferably below 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 be formed to add solvent in this photosensitive polymer combination is for various uses.As suitable solvent, can list with MEK (MEK) alcohols such as ketone and methyl alcohol, ethanol and isopropyl alcohol that is representative.The amount of the solvent that preferred adjustment is added in photosensitive polymer combination, to make the viscosity of photosensitive polymer combination blending liquid at 25 DEG C for 500 ~ 4000mPasec.
< photosensitive-resin layered product >
The present invention also provides the photosensitive-resin layered product be laminated to by above-mentioned this photosensitive polymer combination of the present invention on supporter.Photosensitive-resin layered product can have protective seam on the surface of the support side opposite side of the layer formed by photosensitive polymer combination (hereinafter also referred to photo-sensitive resin).
As supporter, it is desirable to the transparent material that can pass through the light launched by exposure light source.As this supporter, 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. can be listed.As these films, stretched material can be used as required.The mist degree of supporter is preferably less than 5.The supporter of thinner thickness is favourable in image forming property and economy, and due to needs maintenance intensity, preferably uses the material of 10 ~ 30 μm.
When forming protective seam in photosensitive-resin layered product; the key property of this protective seam is; relative to the adhesion of photo-sensitive resin and supporter, the adhesion of photo-sensitive resin and protective seam is enough little, easily can peel off protective seam from photo-sensitive resin.Such as can preferably use polyethylene film and polypropylene film etc. as protective seam.In addition, the film of fissility excellence disclosed in Japanese Laid-Open Patent Publication 59-202457 publication can preferably be used.The thickness of protective seam is preferably 10 ~ 100 μm, is more preferably 10 ~ 50 μm.
The thickness of the photo-sensitive resin in photosensitive-resin layered product is preferably 5 ~ 100 μm, is more preferably 7 ~ 60 μm.The thinner resolution of this thickness is higher, and in addition, thicker then film strength is higher, and therefore this thickness suitably can be selected according to purposes.
By by supporter, photo-sensitive resin and as required and the fixed protective seam method that lamination makes photosensitive-resin layered product of the present invention successively can adopt method known at present.
Such as, be used in photosensitive polymer combination used in photo-sensitive resin to prepare photosensitive resin combination blending liquid, first use rod coaters or sized roller applicator to be coated on supporter and carry 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, photosensitive-resin layered product can be made.
< corrosion-resisting pattern formation method >
The present invention also provides the corrosion-resisting pattern formation method of the photosensitive-resin layered product using the invention described above.This corrosion-resisting pattern formation method comprises following operation: the lamination operation forming photosensitive-resin layered product on substrate; To the exposure process that this photosensitive-resin layered product exposes; And the unexposed portion removing the photoresist in this photosensitive-resin layered product is to form the developing procedure of corrosion-resisting pattern.The following describes the object lesson of corrosion-resisting pattern formation method.
First, laminating machine is used to carry out lamination operation.When photosensitive-resin layered product has protective seam, with laminating machine, photo-sensitive resin heating is crimped on the surface of the substrate after peeling off protective seam, carry out lamination.Now, photo-sensitive resin can only lamination on a surface of substrate, as required also can at two sides lamination.Heating-up temperature is now generally 40 ~ 160 DEG C.In addition, add thermo-compressed by this carrying out more than twice, gained corrosion-resisting pattern can improve the adhesion of substrate.Now, crimping can use the two-stage type laminating machine with duplex roller to carry out, and also can make photosensitive-resin layered product and substrate is repeated multiple times is connect on the surface of the substrate by layered photosensitive-resin by roller.
Then, exposure machine is used to carry out exposure process.Peel off supporter as required, then by active light, photo-sensitive resin is exposed by photomask.Exposure was decided by light illumination and time shutter.Quantometer can be used to measure exposure.
In exposure process, maskless exposure method can be used.Maskless exposure is not used photomask and is exposed on substrate by direct drawing apparatus.As light source, the semiconductor laser of wavelength 350 ~ 410nm, ultrahigh pressure mercury lamp etc. can be used.Depicting pattern is controlled by computing machine, and exposure is in this case decided by the illumination of exposure light source and the translational speed of substrate.
Then, developing apparatus is used to carry out developing procedure.After exposure, photo-sensitive resin has during supporter and be removed.Then, use the developer solution be made up of aqueous alkali by the unexposed portion of photoresist development removing, obtain corrosion-resisting pattern.As aqueous alkali, Na 2cO 3or K 2cO 3deng aqueous solution be preferred.These can coordinate 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 be mixed into surfactant, defoamer, for promote develop a small amount of organic solvent etc.In addition, the temperature of this developer solution in developing procedure preferably keeps temperature certain 20 ~ 40 DEG C of scopes.
Can corrosion-resisting pattern be obtained by above-mentioned operation, and according to circumstances also can carry out the heating process of 100 ~ 300 DEG C further.By implementing this heating process, chemical-resistant can be improved further.Heating can use the heating furnace of the 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 manufacture the method for conductive pattern and to use above-mentioned photosensitive-resin layered product to manufacture the method for printed circuit board (PCB).The manufacture method of conductive pattern comprises following operation: the lamination operation forming the photosensitive-resin layered product of the invention described above on substrate, and wherein said substrate is sheet metal or metal film coated insulcrete; To the exposure process of photosensitive-resin layered product exposure; The unexposed portion of the photoresist in removing photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; And by carry out etching to the substrate (such as, for copper clad laminate, the copper face for substrate) being formed with corrosion-resisting pattern or plating to form the operation of conductive pattern.In lamination operation, exposure process and developing procedure, can preferably adopt and the identical method described in corrosion-resisting pattern formation method and condition.
In addition, the manufacture method of printed circuit board (PCB) comprises following operation: the lamination operation forming the photosensitive-resin layered product of the invention described above on substrate, and wherein said substrate is copper clad laminate or flexible base, board; To the exposure process of photosensitive-resin layered product exposure; The unexposed portion of the photoresist in removing photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate being formed with corrosion-resisting pattern is etched or the operation of plating; And the operation of corrosion-resisting pattern is peeled off from substrate.Typically, lamination operation, exposure process and developing procedure is being carried out with under the same method described in corrosion-resisting pattern formation method and condition, then with the substrate that the method process that etching method or plating etc. are known is exposed, and then, the aqueous solution being better than developer solution by alkalescence peels off the stripping process of corrosion-resisting pattern from substrate, thus can obtain desired printed circuit board (PCB).The aqueous alkali (hereinafter also referred to " stripper ") peeled off is not particularly limited, the aqueous solution of NaOH or KOH of general working concentration 2 ~ 5 quality %.Also a small amount of water-soluble solvent can be added in stripper.In addition, the temperature of this stripper in stripping process is preferably the scope of 40 ~ 70 DEG C.
The manufacture method > of < lead frame
The present invention also provides and uses the photosensitive-resin layered product of the invention described above to manufacture the method for lead frame.The method comprises following operation: the lamination operation forming the photosensitive-resin layered product of the invention described above on substrate, and wherein said substrate is sheet metal; To the exposure process of photosensitive-resin layered product exposure; The unexposed portion of the photoresist in removing photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; To the operation that the substrate being formed with corrosion-resisting pattern etches; And the operation of corrosion-resisting pattern is peeled off from substrate.Typically, use the sheet metal of copper, aldary or iron-based alloy etc. as substrate, carry out lamination operation, exposure process and developing procedure with under the same method described in corrosion-resisting pattern formation method and condition, then etch the substrate that exposes to form the operation of conductive pattern.After this, carry out by the method same with the manufacture method of above-mentioned printed circuit board (PCB) the stripping process peeling off corrosion-resisting pattern, thus desired lead frame can be obtained.
< has the manufacture method > of the base material of relief pattern
The present invention also provides the method using above-mentioned photosensitive-resin layered product to manufacture the base material with relief pattern.The method comprises following operation: the lamination operation forming the photosensitive-resin layered product of the invention described above on the substrate of substrate, and wherein said substrate is the glass substrate being coated with Glass Rib paste; The exposure process that photosensitive-resin layered product exposes; The unexposed portion of the photoresist in removing photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate being formed with corrosion-resisting pattern is carried out to the operation of blasting treatment processing; And the operation of corrosion-resisting pattern is peeled off from substrate.In lamination operation, exposure process and developing procedure, can preferably adopt and the same method described in above-mentioned corrosion-resisting pattern formation method and condition.The corrosion-resisting pattern formed in the manufacture method of this base material can as using the protection mask parts that substrate adds man-hour with blasting method.
In addition, except the above-mentioned glass substrate being coated with Glass Rib paste, the substrates such as glass, silicon chip, amorphous silicon, polysilicon, pottery, sapphire, metal material can also be used.Typically, on the substrate being coated with Glass Rib paste, carry out lamination operation, exposure process and developing procedure by the method identical with aforementioned corrosion-resisting pattern formation method, form corrosion-resisting pattern.After this, through spraying sand-blast material to be cut to the blasting treatment operation of target depth, to remove the stripping process of the corrosion-resisting pattern part remained on substrate with alkali stripper etc. from substrate on formed corrosion-resisting pattern, base material substrate with fine relief pattern can be formed.The sand-blast material used in blasting treatment operation, can use known material, such as, can use SiC, SiO 2, Al 2o 3, CaCO 3, ZrO, glass, stainless steel etc. the particulate of particle diameter about 2 ~ 100 μm.
The manufacture method > of < semiconductor packages
The present invention also provides and uses above-mentioned photosensitive-resin layered product to manufacture the method for semiconductor packages.The method comprises following operation: the lamination operation forming the photosensitive-resin layered product of the invention described above on substrate, and wherein said substrate is complete the wafer that the circuit as LSI formed; To the exposure process of photosensitive-resin layered product exposure; The unexposed portion of the photoresist in removing photosensitive-resin layered product forms the developing procedure of corrosion-resisting pattern; The substrate being formed with corrosion-resisting pattern is carried out to the operation of plating; And the operation of corrosion-resisting pattern is peeled off from substrate.Typically, carrying out lamination operation, exposure process and developing procedure with under the same method described in corrosion-resisting pattern formation method and condition, then carrying out implementing the plating of the column of copper, solder etc. to form the operation of conductive pattern to the peristome exposed.After this, the stripping process peeling off corrosion-resisting pattern is carried out by the method same with the manufacture method of above-mentioned printed circuit board (PCB), and then, carry out the operation of the thin metal layer by the part of etching except removing column plating, thus desired semiconductor packages can be obtained.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited thereto.The following describes the sample for evaluation of embodiment and comparative example method for making and for the evaluation method of gained sample and evaluation result.
(embodiment 1 ~ 13, comparative example 1 and 2)
By the mass parts shown in table 2 and table 3 by the compound mixing shown in 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 MEK refers to, the value that total amount calculates after comprising MEK.
1. the making of sample for evaluation
Photosensitive-resin layered product in following making embodiment and comparative example.
The making > of < photosensitive-resin layered product
By the abundant Agitation and mixing of photosensitive polymer combination of each embodiment and each comparative example, rod coaters is used to be coated on equably by described each composition as on the surface of 16 μm of supporter thick pet films, in the dryer of 95 DEG C, drying 4 minutes, forms photo-sensitive resin.The thickness of photo-sensitive resin is 40 μm.
Then, do not have to fit in the surface of lamination pet film as 22 μm of protective seam thick polyethylene films at photo-sensitive resin, obtain photosensitive-resin layered product.
< substrate surface leveling >
As the evaluation substrate of light sensitivity, resolution and adhesion, lamination is used to have the copper clad laminate that the 1.2mm of 35 μm of thick rolled copper foils is thick, effects on surface carries out wet type polishing roll grinding (Scotch-Brite (registered trademark) HD#600 that 3M company manufactures, by twice).
For evaluation substrate, prepare the substrate having carried out Jet Polishing (jet scrub polishing) (SAKURUNDUM A (registered trademark) #F220P that Japanese grinding whetstone grain (strain) manufactures) under the expulsion pressure of 0.20MPa.
< lamination >
While the polyethylene film peeling off photosensitive-resin layered product, leveling aforesaid substrate surface, then use hot roll laminator (AL-70 that Asahi Chemical Industry's (strain) manufactures), be laminated to the copper clad laminate being preheated to 60 DEG C with the roll temperature of 105 DEG C.Make that gaseous tension is 0.35MPa, laminate speed is 1.5m/min.
< exposes >
Mask needed for the evaluation of photo-sensitive resin is placed on as on the pet film of supporter, by ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. the HMW-201KB manufactured), 6 sections in the 21 sections of stage metraster manufactured with the making Stouffer exposures that solidification occurs carry out exposing (unit in table 2 and 3 is stage metraster hop count).
< develops >
Peel off pet film, then use alkali developing machine (the dry film developing machine that Fuji Kiko Co., Ltd. manufactures), with the Na of stipulated time by the 1 quality % of 30 DEG C 2cO 3aqueous solution is sprayed on photo-sensitive resin, dissolves the unexposed portion of removing photo-sensitive resin with 2 times of times to minimum development time.Now, dissolving the required shortest time completely with the photo-sensitive resin of unexposed portion is minimum development time.
2. evaluation method
(1) light sensitivity evaluation
Brightness is used 21 sections of stage metraster of the Stouffer manufacture of 21 grades of changes to occur to the light sensitivity that have passed through after lamination after 15 minutes, resolution evaluation base board to explosure from transparent to black.After exposure, develop with 2 times of development times to minimum development time, the value being light sensitivity with the stage metraster hop count that etchant resist is completely residual.
(2) resolution evaluation
Be that the line style pattern mask of the ratio of 1: 1 is to have passed through the resolution evaluation base board to explosure after 15 minutes after lamination by the width in exposure portion and unexposed portion.Develop with 2 times of development times to minimum development time, normally to form the value that the minimum mask width that solidifies line against corrosion is resolution, as follows classification is carried out to resolution.
A: the value of resolution is less than 30 μm.
B: the value of resolution is more than 30 μm and less than 40 μm.
C: the value of resolution is more than 40 μm.
(3) adhesion evaluation
Be that the line style pattern mask of the ratio of 1: 1 is to the light sensitivity that have passed through after lamination after 15 minutes, resolution evaluation base board to explosure by the width in exposure portion and unexposed portion.Develop with 2 times of development times to minimum development time, normally to form the value that the minimum mask live width of solidifying line against corrosion is adhesion.
A: the value of adhesion is less than 30 μm.
B: the value of adhesion is more than 30 μm and less than 40 μm.
C: the value of adhesion is more than 40 μm.
(4) fissility evaluation
By there is the mask of the pattern of 6cm × 6cm to have passed through the fissility evaluation base board to explosure after 15 minutes after lamination.Develop with 2 times of development times to minimum development time, be then immersed in 50 DEG C, in the aqueous sodium carbonate of 3 quality %, measure the time that etchant resist is peeled off, carry out classification as follows.
A: splitting time is less than 45 seconds.
B: splitting time is more than 45 seconds and less than 50 seconds.
C: splitting time was more than 50 seconds.
(5) sheltering evaluation
The thick copper clad laminate of 1.6mm, the two sides laminated photosensitive resin laminate of the base material in the hole with diameter 6mm, expose by the exposure of regulation in table 2 and table 3, develop with 4 times of development times to minimum development time, washing drying.Then, break number in mensuration hole, calculates masking film rupture rate by following mathematical expression.
Masking film rupture rate (%)=[breaking and count (individual)/all hole counts (individual) in hole] × 100
According to this masking film rupture rate (%), carry out classification as follows.
A: lower than 3%
More than B:3% and lower than 10%
More than C:10%
3. evaluation result
The evaluation result of embodiment and comparative example is shown in table 2 and 3.
[table 1]
[table 2]
[table 3]
utilizability in industry
Photosensitive polymer combination of the present invention can be applied to aptly: the manufacture of printed circuit board (PCB), the manufacture of IC chip carrying lead frame, the metal forming Precision Machining such as metal mask manufacture, the manufacture of the encapsulation such as BGA or CSP, the manufacture of the belt base plates such as COF, TAB, the manufacture of semiconductor projection, the manufacture etc. of the partition of the flat-panel monitors such as ITO electrode, addressing electrode, electromagnetic wave shield.

Claims (15)

1. a photosensitive polymer combination, it contains following (a) ~ (d) composition: (a) is at least to contain α, β-unsaturated carboxylic monomer be polymeric composition carry out being polymerized obtain, acid equivalent is 100 ~ 600 and weight-average molecular weight is the thermoplastic polymer of 5000 ~ 500000,20 ~ 90 quality %; B there is the polyaddition monomer of at least one polymerizable ethylenic unsaturated bond, 3 ~ 75 quality % in () molecule; (c) Photoepolymerizationinitiater initiater, 0.01 ~ 30 quality %; And the compound shown in (d) following general formula (I),
In formula, R 1~ R 5respective is independently H, aryl or aryl alkyl, and R 1~ R 5in at least one be aryl or aryl alkyl, A 1c 2h 4or C 3h 6, n 1when being more than 2, multiple A 1be same to each other or different to each other, and n 1the integer of 1 ~ 50,
As described (b) composition, the unsaturated compound containing the photopolymerization shown in following general formula (III),
In formula, R 8and R 9respective is independently H or CH 3, A 2c 2h 4, A 3c 3h 6, n 5and n 6respective be independently 1 ~ 29 integer and n 5+ n 6the integer of 2 ~ 30, n 7and n 8respective be independently 0 ~ 29 integer and n 7+ n 8the integer of 0 ~ 30 ,-(A 2-O)-and-(A 3-O)-the arrangement mode of repetitive be random or block, when it is arranged as block ,-(A 2-O)-and-(A 3-O)-in any one be positioned at xenyl side.
2. photosensitive polymer combination according to claim 1, wherein, the R in 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 described phenylalkyl is 1 ~ 6.
4. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, the R in described general formula (I) 1~ R 5in 1 ~ 3 group be respectively aryl or aryl alkyl.
5. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, the R in described general formula (I) 1~ R 5in 2 or 3 groups be respectively aryl or aryl alkyl.
6. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, in described general formula (I), n 1it is the integer of 1 ~ 35.
7. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, the R in described general formula (I) 1~ R 5respective is independently H, phenyl or 1-phenylethyl, R 1~ R 5in 2 be H, and R 1~ R 5in another 3 separately independent be phenyl or 1-phenylethyl.
8. the photosensitive polymer combination according to any one of claims 1 to 3, wherein, when being 100 quality % with described (a), (b) with the total amount of (c) composition, the content of described (d) composition is 1 ~ 20 quality %.
9. a photosensitive-resin layered product, it is laminated to by the photosensitive polymer combination described in any one of claim 1 ~ 8 on supporter to be formed.
10. a corrosion-resisting pattern formation method, the method comprises following operation: the lamination operation forming photosensitive-resin layered product according to claim 9 on substrate; To the exposure process that described photosensitive-resin layered product exposes; And the unexposed portion removing the photoresist in described photosensitive-resin layered product is to form the developing procedure of corrosion-resisting pattern.
The manufacture method of 11. 1 kinds of conductive patterns, the method comprises following operation: the lamination operation forming photosensitive-resin layered product according to claim 9 on substrate, and wherein said substrate is sheet metal or metal film coated insulcrete; To the exposure process that described photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in described photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; And by etch the substrate being formed with described corrosion-resisting pattern or plating forms the operation of conductive pattern.
The manufacture method of 12. 1 kinds of printed circuit board (PCB)s, the method comprises following operation: the lamination operation forming photosensitive-resin layered product according to claim 9 on substrate, and wherein said substrate is copper clad laminate or flexible base, board; To the exposure process that described photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in described photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; The substrate being formed with described corrosion-resisting pattern is etched or the operation of plating; And the operation of described corrosion-resisting pattern is peeled off from described substrate.
The manufacture method of 13. 1 kinds of lead frames, the method comprises following operation: the lamination operation forming photosensitive-resin layered product according to claim 9 on substrate, and wherein said substrate is sheet metal; To the exposure process that described photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in described photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; To the operation that the substrate being formed with described corrosion-resisting pattern etches; And the operation of described corrosion-resisting pattern is peeled off from described substrate.
14. 1 kinds of manufacture methods with the base material of relief pattern, the method comprises following operation: the lamination operation forming photosensitive-resin layered product according to claim 9 on substrate, and wherein said substrate is the glass substrate being coated with Glass Rib paste; To the exposure process that described photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in described photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; The substrate being formed with described corrosion-resisting pattern is carried out to the operation of blasting treatment processing; And the operation of described corrosion-resisting pattern is peeled off from described substrate.
The manufacture method of 15. 1 kinds of semiconductor packages, the method comprises following operation: the lamination operation forming photosensitive-resin layered product according to claim 9 on substrate, and wherein said substrate is complete the wafer that the circuit as large scale integrated circuit formed; To the exposure process that described photosensitive-resin layered product exposes; Remove the unexposed portion of the photoresist in described photosensitive-resin layered product to form the developing procedure of corrosion-resisting pattern; The substrate being formed with described corrosion-resisting pattern is carried out to the operation of plating; And the operation of described corrosion-resisting pattern is peeled off 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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