CN102395924A - Photosensitive resin composition, photosensitive element utilizing the composition, method for formation of resist pattern, and process for production of printed circuit board - Google Patents

Photosensitive resin composition, photosensitive element utilizing the composition, method for formation of resist pattern, and process for production of printed circuit board Download PDF

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CN102395924A
CN102395924A CN2010800171698A CN201080017169A CN102395924A CN 102395924 A CN102395924 A CN 102395924A CN 2010800171698 A CN2010800171698 A CN 2010800171698A CN 201080017169 A CN201080017169 A CN 201080017169A CN 102395924 A CN102395924 A CN 102395924A
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polymer combination
photosensitive polymer
methyl
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formula
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CN102395924B (en
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宫坂昌宏
锻治诚
印杰
姜学松
孙利达
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Shanghai Jiaotong University
Showa Denko Materials Co ltd
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Shanghai Jiaotong University
Hitachi Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Disclosed is a photosensitive resin composition comprising a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and at least one pyrazine compound selected from the group consisting of compounds each having a structure represented by formula (1), compounds each having a structure represented by formula (2) and compounds each having a structure represented by formula (3). [In formulae (1) to (3), R1 to R12 independently represent a univalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a heterocyclic group, wherein R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, or R11 and R12 may be bound to each other and, together with two carbon atoms contained in a pyrazine skeleton, form a ring. In formula (2), X and Y independently represent an atom group that constitutes an aromatic ring formed together with two carbon atoms contained in a pyrazine skeleton and having a monocyclic or condensed polycyclic structure. In formula (3), Z represents an atom group that constitutes an aromatic ring having a monocyclic or condensed polycyclic structure and formed together with four carbon atoms contained in a pyrazine skeleton or a hetero ring.

Description

The formation method of photosensitive polymer combination, the photosensitive element that uses it, resist pattern and the manufacturing approach of printed-wiring board (PWB)
Technical field
The present invention relates to photosensitive polymer combination, use its photosensitive element, the formation method of resist pattern and the manufacturing approach of printed-wiring board (PWB).
Background technology
Printed-wiring board (PWB), plasma scope with wiring plate, the manufacturing field of LCD with microelectronic circuits such as wiring plate, large scale integrated circuit, thin type transistor, semiconductor packages in; As the anticorrosive additive material that uses in etching, the plating etc., photosensitive polymer combination, photosensitive element (duplexer) are widely used.
Microelectronic circuit for example is described below and makes.At first, the photosensitive polymer combination of photosensitive element is folded (lamination) layer by layer on circuit forms with substrate.Then, peel off remove support membrane after, to the established part of photosensitive polymer combination layer irradiation active ray, exposure portion is solidified.Then, remove (development) from substrate, thereby on substrate, form the resist pattern that the solidfied material by photosensitive polymer combination constitutes unexposed.The resist pattern that obtains is implemented etch processes or plating is handled and after forming circuit on the substrate, finally peel off and remove resist, make microelectronic circuit.
As the method for above-mentioned exposure, use the method that to make public as light source, across photomask as the mercury lamp at center with wavelength 365nm all the time.In addition; Having proposed with the long-life of wavelength 405nm and the gallium nitride based semiconductor blue laser of high-output power, the Solid State Laser of wavelength 355nm in recent years is light source; The numerical data of figure directly drawn on the photosensitive polymer combination layer, directly draw exposure method (for example, with reference to non-patent literature 1).Be called as DLP (Digital Light Processing; The digit optical processing), LDI (Laser Direct Imaging; Laser direct imaging) these are directly drawn exposure method, with to compare the aligned in position precision across the exposure method of photomask better, and can obtain high meticulous figure; Therefore in order to make the high-density packages substrate, importing this technology.
In addition, also the photosensitive material that is suitable for laser explosure is being studied.For example, the photosensitive material that uses when being light source with the semiconductor bluish violet color laser discloses the photosensitive polymer combination that has used particular initiator in the patent documentation 1,2.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-296764 communique
Patent documentation 2: TOHKEMY 2004-45596 communique
Non-patent literature
Non-patent literature 1: エ レ Network ト ロ ニ Network ス real packing technique in June, 2002 number (p.74～79)
Summary of the invention
The problem that invention will solve
Yet, in exposure process,, need shorten the time shutter in order to enhance productivity as far as possible.But above-mentioned directly drawing in the exposure method is monochromatic light such as laser because light source uses, and therefore scan edge substrate limit irradiation light is compared with the present exposure method across photomask in addition, the tendency of existences longer time shutter of needs.Therefore, compared with prior art, need to improve the sensitivity of photosensitive polymer combination.
On the other hand, along with the densification of printed-wiring board (PWB) in recent years,, the requirement of high resolution and high adaptation is also improved constantly photosensitive polymer combination.And then along with the miniaturization of wiring, it is also more remarkable that the voltage due to the resistance of power lead reduces problem, and forming thickness is that the above plating layer (conductor layer) of 10 μ m has become a problem.In order to form thickness is the plating layer more than the 10 μ m, and resist must form the above thickness of 15 μ m, but then there is the tendency that resolution descends in the thickness thickening of photographic layer usually.Therefore, need a kind of photosensitive polymer combination that can satisfy thickness and this two specific character of resolution.
In addition, photosensitive polymer combination is low also very important to the contaminative of plating.If photosensitive polymer combination polluted bath, then exist and to have implemented exterior substrate that plating handles and produce variable color or plating and form property decline and cause problem such as broken string.
And then, to photosensitive polymer combination, also require the peel property of the resist behind the plating excellent.When peel property was insufficient, in the resist stripping process after plating is handled, the resist of peeling off between fine wiring became difficult, and splitting time increases, and production efficiency descends.In addition, produce the problems such as residue, decrease in yield of peeling off between the existence wiring.
Therefore, it is excellent and to the formation method of the low photosensitive polymer combination of the contaminative of plating, the photosensitive element that uses it, resist pattern and the manufacturing approach of printed-wiring board (PWB) to the object of the present invention is to provide sensitivity to the light of wavelength 350～410nm, resolution, adaptation, peel property and plating to form property.
The method of dealing with problems
The present invention provides a kind of photosensitive polymer combination, and it contains binder polymer, has the optical polymerism compound of ethene property unsaturated link and is selected from least a kind of pyrazine compound in the group of being made up of the compound with the structure shown in following formula (1), (2) or (3).
[Chemical formula 1]
Figure BPA00001447174600031
In the formula (1), R 1, R 2, R 3And R 4Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 1And R 2, or R 3And R 4Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton.
[Chemical formula 2]
Figure BPA00001447174600032
In the formula (2), R 5, R 6, R 7And R 8Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 5And R 6, or R 7And R 8Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton.X and Y represent to constitute the former subgroup of the aromatic ring of single ring architecture that 2 carbon with the pyrazine skeleton form or condensation polycyclic structure independently of one another.
[chemical formula 3]
Figure BPA00001447174600033
In the formula (3), R 9, R 10, R 11And R 12Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 9And R 10, or R 11And R 12Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton.Z representes to constitute single ring architecture or the aromatic ring of condensation polycyclic structure or the former subgroup of heterocycle that 4 carbon with the pyrazine skeleton form.
Above-mentioned pyrazine compound has stronger absorption to the light of wavelength 350～410nm, and therefore photosensitive polymer combination of the present invention can obtain good sensitivity to the light of wavelength 350～410nm.In addition, it is also excellent that fissility (peel property) and the plating that contains the photosensitive polymer combination behind the resolution, adaptation, curing of the photosensitive polymer combination of the present invention of above-mentioned pyrazine compound forms property, also low to the contaminative of plating.
In addition, above-mentioned pyrazine compound is preferably the compound with the structure shown in the above-mentioned formula (1).
In addition, in photosensitive polymer combination of the present invention, the very big absorbing wavelength of pyrazine compound is preferably in the scope of 350～410nm.Thus, the light to wavelength 350～410nm can obtain good sensitivity, the absorption of the long wavelength side more than wavelength 500nm minimizing simultaneously, having good stability under sodium yellow.
In addition, in photosensitive polymer combination of the present invention, the preferred adhesive polymkeric substance contains (methyl) acrylic acid and styrene or styrene derivative as copolymer composition.Thus, further improve alkali-developable, resolution and the adaptation of photosensitive polymer combination.
In addition, preferred photosensitive polymer combination of the present invention contains the compound shown in the following formula (4).Thus, have the resolution of keeping photosensitive polymer combination and adaptation and improve the tendency of sensitivity and imaging (colour rendering of resist).
[chemical formula 4]
In the formula (4), X representes carbon atom or nitrogen-atoms, R 13, R 14And R 15The alkyl of representing halogen atom or carbon number 1～5 independently of one another, R 13, R 14And R 15In at least one the expression halogen atom.R 16Expression hydrogen atom, the alkyl of carbon number 1～5 or the alkoxy of carbon number 1～5, l representes 0～4 integer.L is 2～4 o'clock, a plurality of R 16Can be the same or different.
In addition, photosensitive polymer combination of the present invention preferably further contains hydrogen supply property compound.Thus, improve the sensitivity of photosensitive polymer combination.
In addition, in photosensitive polymer combination of the present invention, hydrogen supply property compound preferably contains the compound shown in the following formula (5).Thus, the tendency that has the sensitivity of further raising photosensitive polymer combination.
[chemical formula 5]
Figure BPA00001447174600051
In the formula (5), R 17Alkyl, alkoxy or ester group, hydroxyl or the halogen atom of expression carbon number 1～6.N is 0～5 integer, and n is 2～5 o'clock, a plurality of R 17Can be the same or different.
In addition, the present invention provides and has supporter and the photosensitive element that is formed at the photosensitive polymer combination layer that is made up of above-mentioned photosensitive polymer combination on this supporter.Through using such photosensitive element, can form the excellent and resist pattern low of sensitivity, resolution, adaptation, peel property and plating formation property efficiently to the contaminative of plating.
In addition; The present invention provides a kind of formation method of resist pattern, and it comprises: thus will be stacked in range upon range of operation on the substrate by the photosensitive polymer combination that above-mentioned photosensitive polymer combination constitutes layer by layer, remove part beyond the afore mentioned rules part of photosensitive polymer combination layer forms the resist pattern that the solidfied material by photosensitive polymer combination constitutes at substrate developing procedure to the exposure process of the established part irradiation active ray of photosensitive polymer combination layer with from substrate.According to said method, can form the excellent and resist pattern low of sensitivity, resolution, adaptation, peel property and plating formation property efficiently to the contaminative of plating.
In the formation method of above-mentioned resist pattern, the wavelength of active ray is preferably 390～410nm.Thus, can form the more excellent resist pattern of sensitivity, resolution, adaptation, peel property and plating formation property.
In addition, the present invention provides a kind of manufacturing approach of printed-wiring board (PWB), and it comprises the operation of the substrate that has formed resist pattern through said method being carried out etching or plating.According to this manufacturing approach, can make the printed-wiring board (PWB) that this type of high-density packages substrate has the densification wiring efficiently.
The invention effect
According to the present invention; Can provide sensitivity, resolution, adaptation, peel property and plating formation property the excellent and photosensitive polymer combination low to the contaminative of plating to the light of wavelength 350～410nm; Use its photosensitive element, the formation method of resist pattern and the manufacturing approach of printed-wiring board (PWB).
Description of drawings
Fig. 1 is the pattern cut-open view of an example of expression photosensitive element.
Fig. 2 is the 1H-NMR spectrum of present embodiment (C-1).
Fig. 3 is the 13C-NMR spectrum of present embodiment (C-1).
Fig. 4 is the ultraviolet-visible absorption spectroscopy of present embodiment (C-1), (C-3).
Fig. 5 is the ultraviolet-visible absorption spectroscopy of present embodiment (C-1), (C-2).
Embodiment
Be elaborated in the face of the preferred embodiment for the present invention down.But the present invention is not limited by following embodiment.Explain that in this manual, (methyl) acrylic acid is meant acrylic or methacrylic acid, (methyl) acrylic ester is meant acrylic ester or methacrylate, and (methyl) acryloyl group is meant acryloyl group or methacryl.In addition, (gathering) oxygen ethylidene chain is meant oxygen ethylidene or polyoxyethylene chain, and (gathering) oxygen propylidene chain is meant oxygen propylidene or polyoxy propylidene chain.And then " EO modification " be meant the compound with (gathering) oxygen ethylidene chain, and " PO modification " is meant the compound with (gathering) oxygen propylidene chain, and " EOPO modification " is meant to have the two compound of (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
(photosensitive polymer combination)
At first, the photosensitive polymer combination to this embodiment describes.The photosensitive polymer combination of this embodiment contains (A) binder polymer, (B) optical polymerism compound and (C) Photoepolymerizationinitiater initiater.
At first, the binder polymer as (A) composition is described.As (A) binder polymer, for example can enumerating, acrylic resin, phenylethylene resin series, epoxy are that resin, acid amides are that resin, acid amides epoxy are that resin, alkyd are resin, phenol resin etc.From the position of alkali-developable, preferred acrylic resin.These can use a kind of separately or two or more combinations are used.
(A) binder polymer for example can be made through polymerizable monomer is carried out free radical polymerization.As above-mentioned polymerizable monomer; For example can enumerate out styrene, vinyltoluene, AMS, p-methylstyrene, to polymerisable styrene derivatives such as ethyl styrenes; Ester class, (methyl) alkyl acrylate, (methyl) acrylic acid cycloalkyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid chaff ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid-2 of vinyl alcohols such as acrylic amide, vinyl cyanide, vinyl-n-butyl ether; 2; 2-trifluoro ethyl ester, (methyl) acrylic acid 2; 2; 3; Maleic acid monoesters such as 3-tetrafluoro propyl ester, (methyl) acrylic acid, alpha-brominated (methyl) acrylic acid, alpha-chloro (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid etc.These can use a kind of separately or two or more combinations are used.
As above-mentioned (methyl) alkyl acrylate, for example can enumerate out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid-2-ethyl hexyl and these constitutional isomer etc.These can use a kind of separately or two or more combinations are used.
From the position of alkali-developable, (A) binder polymer preferably contains carboxyl, for example can make through making the polymerizable monomer with carboxyl carry out free radical polymerization with other polymerizable monomer.As above-mentioned preferred (methyl) acrylic acid of polymerizable monomer with carboxyl.
From improving the viewpoint of adaptation, (A) binder polymer preferably contains styrene or styrene derivative as copolymer composition.When containing above-mentioned styrene or styrene derivative as copolymer composition; From balancedly improving the viewpoint of adaptation and peel property; Its content all preferably contains 5～70 quality % with respect to the nonvolatile component of (A) composition; More preferably contain 10～65 quality %, especially preferably contain 15～60 quality %.When content during less than 5 quality %, have the tendency of adaptation difference, when surpassing 70 quality %, exist splitting time elongated, be easy to generate the tendency of peeling off residue behind the plating.
In addition, (A) binder polymer preferably contains (methyl) benzyl acrylate as copolymer composition.When containing (methyl) benzyl acrylate as copolymer composition; From balancedly improving the viewpoint of resolution and peel property; Its content preferably all contains 5～70 quality % with respect to the nonvolatile component of (A) composition; More preferably contain 10～65 quality %, especially preferably contain 15～60 quality %.When content during less than 5 quality %, have the tendency of resolution difference, when surpassing 70 quality %, exist splitting time elongated, be easy to generate the tendency of peeling off residue behind the plating.
What wherein, weight-average molecular weight among the present invention and number-average molecular weight were used is to measure the value that the column criterion polystyrene conversion of going forward side by side gets through gel permeation chromatography (GPC).
(A) weight-average molecular weight of binder polymer is preferably 5000～300000, and more preferably 10000～150000, further be preferably 20000～80000, be preferably 30000～70000 especially.When weight-average molecular weight less than 5000 the time, when surpassing 300000, there is the tendency that development time is elongated, resolution uprises or peel property descends in the tendency that exists anti-development fluidity to descend.
(A) acid number of composition is preferably 50～250mgKOH/g, more preferably 10～230mgKOH/g, more preferably 130～200mgKOH/g.When acid number during less than 50mgKOH/g, have the elongated tendency of development time, when surpassing 250mgKOH/g, have photocuring the tendency that descends of the anti-development fluidity (adaptation) of resist.In addition, when with an organic solvent being developer solution as developing procedure, preferred for preparation has the polymerizable monomer of carboxyl on a small quantity.
With regard to (A) binder polymer, preferred dispersion degree (weight-average molecular weight/number-average molecular weight) is 1.0～3.0, more preferably 1.0～2.0.When dispersion degree surpasses 3.0, the tendency that exists cementability and resolution to descend.
(A) binder polymer can use a kind of separately or two or more combinations are used.When combination more than 2 kinds and when using; As binder polymer, for example can enumerate out different binder polymer more than 2 kinds of the different binder polymer more than 2 kinds of the binder polymer more than 2 kinds, the weight-average molecular weight that constitute by different copolymer compositions, dispersion degree etc.In addition, can also use the polymkeric substance of putting down in writing in the japanese kokai publication hei 11-327137 communique with multi-modal molecular weight distribution.
In addition, (A) binder polymer can have the photonasty group as required.
Secondly, the optical polymerism compound with ethene property unsaturated link as (B) composition is described.
As (B) optical polymerism compound; As long as have the material of at least 1 ethene property unsaturated link in the molecule; Just not special restriction; For example can enumerating out, bisphenol-A is (methyl) acrylate compounds, makes α; Beta-unsaturated carboxylic acid and polyol reaction and compound, molecule in have an amino-formate bond carbamate monomer, Nonylphenoxies such as (methyl) acrylate compounds gather ethylidene oxypropylene acid esters, phthalic acid based compound, (methyl) alkyl acrylate, make α, the compound that beta-unsaturated carboxylic acid obtains with the compound reaction that contains glycidyl etc.These can use a kind of separately or two or more combinations are used.
From improving the viewpoint of resolution and peel property, (B) the optical polymerism compound preferably contains bisphenol-A system (methyl) acrylate compounds.These more preferably contain 20～80 quality % with respect to all total amounts of (B) composition, further preferably contain 30～70 quality %.
As bisphenol-A system (methyl) acrylate compounds; Can enumerate out 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy the gathers propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy the gathers butoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy polyethoxy gathers propoxyl group) phenyl) propane of 2-etc., wherein, from the viewpoint of further raising resolution and peel property; Preferred 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-.
As 2; Two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-; Can enumerate out 2, two (4-((methyl) acryloyl group ethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy diethoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy triethoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy tetraethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy five ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy six ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy seven ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy eight ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy nine ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy 11 ethoxys) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten diethoxies) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten triethoxies) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten tetraethoxies) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 16 ethoxys) phenyl) propane of 2-etc.
As 2; Two (4-((methyl) acryloxy the gathers propoxyl group) phenyl) propane of 2-can enumerate out 2, two (4-((methyl) acryloxy dipropoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy tripropoxy) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy four propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy five propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy six propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy seven propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy eight propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy nine propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy 11 propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy ten dipropoxies) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy ten tripropoxies) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 14 propoxyl group) phenyl) propane, 2 of 2-; Two (4-((methyl) acryloxy 15 propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy 16 propoxyl group) phenyl) propane of 2-etc.These can use a kind of separately or two or more combination in any are used.
Among these, with regard to 2, two (4-(methacryl base oxethyl) phenyl) propane of 2-can be used as BPE-100 (Xin Zhong village chemical industry (strain) is made, the goods name) and obtain commercially.With regard to 2, two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-, (Xin Zhong village chemical industry (strain) is made to can be used as BPE-500; The goods name) or FA-321M (Hitachi changes into industry (strain) and makes; The goods name) obtain commercially, with regard to 2, two (4-(the methacryloxy 15 ethoxys) phenyl) propane of 2-; Can be used as BPE-1300 (Xin Zhong village chemical industry (strain) make, goods name) and obtain commercially.From flexible, the resolution of solidfied material and the viewpoint of adaptation, 2, the 1 intramolecular inferior ethoxyl number of two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-is preferably 4～20, and more preferably 8～15.In addition; From can further improving the viewpoint of fissility, resolution and adaptation; 2; The 1 intramolecular inferior ethoxyl number of two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-is preferably 1～3, and is preferred especially and to use 1 intramolecular inferior ethoxyl number be 4～20 compound and be 1～3 compound.
As 2; Two (4-((methyl) acryloxy polyethoxy the gathers propoxyl group) phenyl) propane of 2-; Can enumerate out 2; Two (4-((methyl) acryloxy diethoxy eight propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy tetraethoxy four propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy six ethoxys six propoxyl group) phenyl) propane of 2-etc.
As making α; Beta-unsaturated carboxylic acid and polyol reaction and compound; Can enumerate out the ethylidene number and be 2～14 polyglycol two (methyl) acrylic ester, propylidene number and be 2～14 polypropylene glycol two (methyl) acrylic ester, trimethylolpropane two (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, EO modification trimethylolpropane tris (methyl) acrylic ester, PO modification trimethylolpropane tris (methyl) acrylic ester, EO, PO modification trimethylolpropane tris (methyl) acrylic ester, tetramethylol methane three (methyl) acrylic ester, tetramethylol methane four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester etc.These can use a kind of separately or two or more combinations are used.
Among these; With regard to the tetramethylol methane triacrylate; Can obtain as A-TMM-3 (Xin Zhong village chemical industry (strain) is made, trade name), with regard to EO modification trimethylol-propane trimethacrylate commercially; Can obtain as TMPT21E, TMPT30E (Hitachi changes into industry (strain) manufacturing, sample name) commercially.
From improving the viewpoint of alkali-developable, resolution, adaptation or peel property; (B) the optical polymerism compound preferably contains in the molecule trimethylolpropane tris (methyl) acrylate compounds with (gathering) oxygen ethylidene chain or (gathering) oxygen propylidene chain, more preferably contains in the molecule trimethylolpropane tris (methyl) acrylate compounds with (gathering) oxygen ethylidene chain.These more preferably contain 5～50 quality % with respect to all total amounts of (B) composition, further preferably contain 10～40 quality %.
In addition; From the flexible viewpoint of the solidfied material (cured film) that improves photosensitive polymer combination, (B) the optical polymerism compound preferably contains in the molecule and has the two PAG two (methyl) acrylic ester of (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.These more preferably contain 5～50 quality % with respect to all total amounts of (B) composition, further preferably contain 10～40 quality %.
As above-mentioned PAG two (methyl) acrylic ester,, have (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain ((gathering) oxygen-Ya n-pro-pyl) chain or (gathering) oxygen isopropylidene chain preferably as intramolecular (gathering) oxyalkylene chain) the two.In addition, PAG two (methyl) acrylic ester can also further have as the inferior normal-butyl chain of (gathering) oxygen, (gathering) oxygen-Ya n-pentyl chain, (gathering) oxygen-n-hexyl chain, these (gathering) oxyalkylene chain of carbon number about 4～6 of constitutional isomer etc.
In the molecule of PAG two (methyl) acrylic ester, (gathering) oxygen ethylidene chain both can have been distinguished continuous block ground with (gathering) oxygen propylidene chain and exist, and also can randomly exist.In addition, in (gathering) oxygen isopropylidene chain, both can be that the secondary carbon of propylidene combines with oxygen atom, also can be primary carbon combines with oxygen atom.
As PAG two (methyl) acrylic ester, the compound shown in preferred especially following formula (6), (7) or (8).These can use a kind of separately or two or more combinations are used.
[chemical formula 6]
Figure BPA00001447174600111
[chemical formula 7]
Figure BPA00001447174600112
[chemical formula 8]
Figure BPA00001447174600121
In above-mentioned formula (6), (7) and (8), R 18～R 23Represent hydrogen atom or methyl independently of one another, EO representes the oxygen ethylidene, and PO representes the oxygen propylidene.m 1, m 2, m 3And m 4The repeat number of the structural unit that expression is made up of the oxygen ethylidene, n 1, n 2, n 3And n 4The repeat number of the structural unit that expression is made up of the oxygen propylidene, the repetition sum m of oxygen ethylidene 1+ m 2, m 3And m 4(mean value) is represented 1～30 integer independently of one another, the repetition sum n of oxygen propylidene 1, n 2+ n 3And n 4(mean value) is represented 1～30 integer independently of one another.
In the compound shown in above-mentioned formula (6), (7) or (8), the repetition of oxygen ethylidene sum m 1+ m 2, m 3And m 4Be 1～30 integer, be preferably 1～10 integer, more preferably 4～9 integer is preferably 5～8 integer especially.When the sum of this repeat number surpasses 30, there are resolution and adaptation variation, are difficult to obtain the tendency of good shape against corrosion.
In addition, the repetition of oxygen propylidene sum n 1, n 2+ n 3And n 4Be 1～30 integer, be preferably 5～20 integer, more preferably 8～16 integer is preferably 10～14 integer especially.The sum of this repeat number surpasses at 30 o'clock, exists to be difficult to the tendency that obtains sufficient resolution, be easy to generate dregs.
As the compound shown in the above-mentioned formula (6), can enumerate out R 18And R 19=methyl, m 1+ m 2=6 (mean values), n 1(Hitachi changes into industry (strain) manufacturing, trade name: FA-023M) etc. to the vinyl compound of=12 (mean values).As the compound shown in the above-mentioned formula (7), can enumerate out R 20And R 21=methyl, m 3=6 (mean values), n 2+ n 3The vinyl compound of=12 (mean values) (Hitachi changes into industry (strain) manufacturing, trade name FA-024M) etc.As the compound shown in the above-mentioned formula (8), can enumerate out R 22And R 23=hydrogen atom, m 4=1 (mean value), n 4The vinyl compound of=9 (mean values) (make, sample name: NK ester HEMA-9P) etc. by Xin Zhong village chemical industry (strain).These can use a kind of separately or two or more combinations are used.
As (methyl) acrylate compounds that has amino-formate bond in the above-mentioned molecule; Can enumerate out (methyl) acrylic monomer and the diisocyanate cpd (IPDI, 2 that have the OH base in the β position; 6-toluene diisocyanate, 2; 4-toluene diisocyanate, 1; 6-hexamethylene diisocyanate etc.) addition compound product, three ((methyl) acryloxy TEG isocyanates) hexa-methylene chlorinated isocyanurates, EO modified amido formic ether two (methyl) acrylic ester, EO, PO modified amido formic ether two (methyl) acrylic ester etc.As EO modified amido formic ether two (methyl) acrylic ester, can enumerate out UA-11 (Xin Zhong village chemical industry (strain) is made, the goods name).In addition, as EO, PO modified amido formic ether two (methyl) acrylic ester can be enumerated out UA-13 (Xin Zhong village chemical industry (strain) is made, the goods name).These can use a kind of separately or two or more combinations are used.
Gather ethylidene oxypropylene acid esters as above-mentioned Nonylphenoxy, can enumerate out for example Nonylphenoxy four ethylidene oxypropylene acid esters, Nonylphenoxy five ethylidene oxypropylene acid esters, Nonylphenoxy six ethylidene oxypropylene acid esters, Nonylphenoxy seven ethylidene oxypropylene acid esters, Nonylphenoxy eight ethylidene oxypropylene acid esters, Nonylphenoxy nine ethylidene oxypropylene acid esters, Nonylphenoxy ten ethylidene oxypropylene acid esters, Nonylphenoxy 11 ethylidene oxypropylene acid esters.These can use a kind of separately or two or more combination in any are used.
As above-mentioned phthalic acid based compound, can enumerate out γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloyl group oxygen ethyl-phthalic ester, beta-hydroxy alkyl-β '-(methyl) acryloyl group oxyalkyl-phthalic ester etc.These can use a kind of separately or two or more combinations are used.
In addition; Viewpoint from the peel property of the solidfied material (cured film) that improves photosensitive polymer combination; (B) the optical polymerism compound preferably contains the optical polymerism compound that has 1 ethene property unsaturated link in the molecule; Its content more preferably contains 3～30 quality % with respect to all total amounts of (B) composition, further preferably contains 5～20 quality %.
With regard to the content of (B) composition, be benchmark with (A) composition with (B) total amount 100 mass parts of composition, preferably be made as 30～70 mass parts, more preferably be made as 35～65 mass parts, especially preferably be made as 40～60 mass parts.When this content during less than 30 mass parts, there is the tendency that is difficult to obtain sufficient sensitivity and resolution, when surpassing 70 mass parts, there is the tendency that is difficult to form film, existence is difficult to obtain the tendency of good shape against corrosion in addition.
Secondly, to describing as (C) composition Photoepolymerizationinitiater initiater.
Contain the pyrazine compound that the pyrazine compound that is selected from (C1) and has the structure shown in the following formula (1) (below be sometimes referred to as " (C1) composition "), (C2) have the structure shown in the following formula (2) (below be sometimes referred to as " (C2) composition ") and (C3) have at least a kind of pyrazine compound in the group that the pyrazine compound (below be sometimes referred to as " (C3) composition ") of the structure shown in the following formula (3) forms as the Photoepolymerizationinitiater initiater of (C) composition.
[chemical formula 9]
Figure BPA00001447174600141
In the formula (1), R 1, R 2, R 3And R 4Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 1And R 2, or R 3And R 4Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton.
[Chemical formula 1 0]
Figure BPA00001447174600142
In the formula (2), R 5, R 6, R 7And R 8Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 5And R 6, or R 7And R 8Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton.X and Y represent to constitute the former subgroup of the aromatic ring of single ring architecture that 2 carbon with the pyrazine skeleton form or condensation polycyclic structure independently of one another, and 2 aromatic rings combine through the singly-bound between the constituting atom of regulation.
[Chemical formula 1 1]
Figure BPA00001447174600143
In the formula (3), R 9, R 10, R 11And R 12Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 9And R 10, or R 11And R 12Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton.Z representes to constitute single ring architecture or the aromatic ring of condensation polycyclic structure or the former subgroup of heterocycle that 4 carbon with the pyrazine skeleton form.
As pyrazine compound, (C1) among composition, (C2) composition, (C3) composition,, can use (C1) composition from the viewpoint of the sensitivity that improves photosensitive polymer combination.
In above-mentioned formula (1)～(3), as alkyl, the straight chain shape or the branched-chain alkyl of preferred carbon number 1～10 can be enumerated out for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and these constitutional isomer.As naphthenic base, the naphthenic base of preferred carbon number 4～10 can be enumerated out cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl.In addition, the hydrogen atom that can enumerate out naphthenic base replaced by substituting group arbitrarily and group.As the hetero ring type base, can enumerate out for example furyl, thienyl, imidazole radicals 、 oxazolyl, pyridine radicals etc.In addition, the hydrogen atom of phenyl, naphthyl and hetero ring type base can be by substituting group replacement arbitrarily.
As above-mentioned substituting group arbitrarily, can enumerate out straight chain shape or the branched alkoxy of straight chain shape or branched-chain alkyl, the carbon number 1～10 of carbon number 1～10 for example, the ester group of carbon number 1～10, alkyl amino of carbon number 1～10 etc.
R 1～R 4, R 5～R 8Or R 9～R 12When comprising 1 valency organic group of phenyl, naphthyl or hetero ring type base, from improving dissolubility, the light absorption wavelength of compound being adjusted to the viewpoint of visible region (405nm) near, preferably R 1～R 4In at least 1, R 5～R 8In at least 1 or R 9～R 12In at least 1 straight chain shape or branched alkoxy that contains carbon number 1～10.
Aromatic ring as single ring architecture or condensation polycyclic structure; The hydrogen atom that can enumerate out for example benzene, naphthalene, anthracene, aphthacene, pentacene, phenanthrene, three adjacent inferior benzene, pyrene and these aromatic rings is by the substituted product of substituting group arbitrarily etc.; From price, deliquescent viewpoint when synthetic, be preferably benzene or naphthalene.
As heterocycle, the hydrogen atom that can enumerate out for example pyridine, pyrimidine, pyrazine, pyrroles, furans, thiophene and these heterocycles is by the substituted product of substituting group arbitrarily etc., cheap viewpoint from synthetic, is preferably pyridine.
In addition, R 1And R 2, R 3And R 4, R 5And R 6, R 7And R 8, R 9And R 10, or R 11And R 12Mutually combine and when forming ring with 2 carbon of pyrazine skeleton; The ring that forms can be the aliphatics ring; Also can be aromatic ring,, be preferably aromatic ring from improving dissolubility, the light absorption wavelength of compound being adjusted to the viewpoint of visible region (405nm) near.As aromatic rings, more preferably phenyl ring or naphthalene nucleus.
With regard to the pyrazine compound shown in the above-mentioned formula (1), work as R 3And R 4Form when ring with mutually combining with 2 carbon of pyrazine skeleton, the ring of formation is preferably aromatic rings, more preferably naphthalene nucleus.In addition, R 1And R 2Be preferably phenyl, more preferably the hydrogen atom of phenyl is replaced by the straight chain shape of carbon number 1～10 or branched alkoxy.In addition, substituent position is arbitrarily.As the pyrazine compound shown in the above-mentioned formula (1), can enumerate out the compound shown in for example following formula (9), (10), (11), (12) etc.
[Chemical formula 1 2]
Figure BPA00001447174600161
[Chemical formula 1 3]
Figure BPA00001447174600162
[Chemical formula 1 4]
Figure BPA00001447174600163
[Chemical formula 1 5]
Figure BPA00001447174600164
In addition, as the pyrazine compound shown in the above-mentioned formula (2), can enumerate out the compound shown in for example following formula (13), (14) etc.
[Chemical formula 1 6]
Figure BPA00001447174600171
[Chemical formula 1 7]
Figure BPA00001447174600172
In addition, as the pyrazine compound shown in the above-mentioned formula (3), can enumerate out the compound shown in for example following formula (15), (16) etc.
[Chemical formula 1 8]
Figure BPA00001447174600173
[Chemical formula 1 9]
Figure BPA00001447174600181
In addition, in this photosensitive polymer combination, (C1), (C2) and (C3) the very big absorbing wavelength of composition preferably in the scope of 350～410nm.Thus, the light to wavelength 350～410nm can obtain good sensitivity, the absorption of the long wavelength side more than wavelength 500nm minimizing simultaneously, having good stability under gold-tinted.
Especially use wavelength 405nm with many photoheads directly draw exposure device the time, (C1), (C2) and (C3) the very big absorbing wavelength of composition preferably in the scope of 380～410nm.By making very big absorbing wavelength in the scope of 380～410nm, thus an even emission wavelength chromatic dispersion in the light source of each photohead! the development optical wavelength is disperseed) have under the situation of some differences, near the absorbing amount wavelength 405nm is also almost constant.Consequently, can reduce the possibility that each photohead produces sensitivity variations.And then, owing to can stably obtain high sensitivity, therefore can also reduce the addition of Photoepolymerizationinitiater initiater.
With regard to above-mentioned (C1), (C2) with (C3) with regard to the content of composition, be preferably 50～100 quality % with respect to all total amounts of (C) composition, more preferably 70～100 quality % further are preferably 80～100 quality %.When its content during less than 50 quality %, the tendency that exists sensitivity and resolution to descend.In addition, alleged here " content " is comprising (C1), (C2) and (C3) among the composition more than 2 kinds the time, is being meant their total content.
Do not damaging (C1), (C2) and (C3) in the degree of the effect brought of composition, (C) Photoepolymerizationinitiater initiater can also contain other Photoepolymerizationinitiater initiater.As other Photoepolymerizationinitiater initiater, can enumerate out for example benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-aromatic ketone such as 2-morpholine-acetone-1 grade, benzoin ether compounds such as quinones such as alkyl-anthraquinone, benzoin alkylether, benzoin compounds such as benzoin, alkyl benzene acyloin; Benzil derivants such as benzil dimethyl ketal, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(adjacent fluorophenyl)-4; 5-diphenyl-imidazole dipolymer etc. 2,4,5-triarylimidazoles dipolymer; 9-phenylacridine, 1, acridine derivatives such as 7-(9,9 '-acridinyl) heptane etc.These can use a kind of separately or two or more combinations are used.
In addition, above-mentioned 22,4, the aryl substituent of 5-triarylimidazoles can be identical, also can be different.These can use separately or two or more combinations are used.
In addition, as other Photoepolymerizationinitiater initiater, can enumerate out the compound shown in the following formula (4).
[Chemical formula 2 0]
Figure BPA00001447174600191
In the formula (4), X representes carbon atom or nitrogen-atoms, R 13, R 14And R 15The alkyl of representing halogen atom or carbon number 1～5 independently of one another, R 13, R 14And R 15In at least one the expression halogen atom.R 16Expression hydrogen atom, the alkyl of carbon number 1～5 or the alkoxy of carbon number 1～5, l representes 0～4 integer.L is 2～4 o'clock, a plurality of R 16Can be the same or different.
In photosensitive polymer combination of the present invention; As (C) Photoepolymerizationinitiater initiater; Through with the compound shown in the above-mentioned formula (4) and (C1) composition or (C2) composition combination use, has the tendency of keeping resolution and adaptation and raising sensitivity and imaging (colour rendering of resist).
As the content of the Photoepolymerizationinitiater initiater of (C) composition, with respect to (A) composition and (B) total amount 100 mass parts of composition, preferably be made as 0.01～10 mass parts, more preferably be made as 0.05～6 mass parts, especially preferably be made as 0.1～4 mass parts.When its content during less than 0.01 mass parts, existence can't obtain good sensitivity, the tendency of resolution, and when surpassing 10 mass parts, existence can't obtain the tendency of good shape.
In addition, photosensitive polymer combination of the present invention preferably further contains (D) hydrogen supply property compound.As hydrogen supply property compound; The compound shown in for example two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane, leuco crystal violet, 2-mercaptobenzoxazole, the following formula (5) etc. can be enumerated out, sensitivity can be further improved.From the viewpoint of further raising sensitivity, more preferably contain the compound shown in the following formula (5).As the compound shown in the formula (5), can enumerate out for example N-phenylglycine etc.
[Chemical formula 2 1]
Figure BPA00001447174600201
In the formula (5), R 17Alkyl, alkoxy or ester group, hydroxyl or the halogen atom of expression carbon number 1～6.N is 0～5 integer, and n is 2～5 o'clock, a plurality of R 17Can be the same or different.R 17Alkyl, alkoxy or ester group, hydroxyl or the halogen atom of expression carbon number 1～6.N is 0～5 integer, and n is 2～5 o'clock, a plurality of R 17Can be the same or different.In photosensitive polymer combination of the present invention, use the compound shown in the above-mentioned formula (5) and (C1) composition or (C2) composition through combination, have the tendency of raising to the sensitivity of the light of wavelength 350～410nm.
With regard to the content of (D) hydrogen donor compound, with respect to (A) composition and (B) total amount 100 mass parts of composition, preferably be made as 0.01～10 mass parts, more preferably be made as 0.05～5 mass parts, especially preferably be made as 0.1～2 mass parts.When its use level during less than 0.01 mass parts, existence can't obtain the tendency of good sensitivity, when surpassing 10 mass parts, form film after, have the tendency of separating out as foreign matter.These can use a kind of separately or two or more combinations are used.
In addition, the purpose from further improving sensitivity can also contain (E) sensitizing coloring matter.Sensitizing coloring matter can select to have the pigment with the matched absorbing wavelength of wavelength of the active ray that uses, and preferred greatly absorbing wavelength is the compound of 370nm～420nm.Through using such sensitizing coloring matter, photosensitive polymer combination particularly has fully high sensitivity to the exposure light of directly drawing exposure method of wavelength 405nm.When the very big absorbing wavelength of sensitizing coloring matter during less than 370nm, there is the tendency that the sensitivity of directly drawing exposure light is descended, when being 420nm when above, exist in the tendency of the stability decreases under the gold-tinted.
As (E) sensitizing coloring matter, can enumerate out for example dialkyl amido benzophenone, pyrazolines, anthracene class, Coumarins, xanthene ketone, oxazole class, Benzooxazole kind, thiazoles, benzothiazoles, triazole type, stibene class, triazines, thiophene-based, naphthalimide class, triaryl amine etc.Sensitizing coloring matter can use a kind of separately or two or more combinations are used.
When particularly using the active ray of 390～420nm that the photosensitive polymer combination layer is made public; Viewpoint from sensitivity and adaptation; (E) sensitizing coloring matter preferably contains at least a kind in the group that is selected from pyrazolines, anthracene class, Coumarins and triaryl amine composition, wherein more preferably contains pyrazolines, anthracene class or triaryl amine.
With regard to the content of (E) sensitizing coloring matter, with respect to (A) composition and (B) total amount 100 mass parts of composition, preferably be made as 0.01～10 mass parts, more preferably be made as 0.05～5 mass parts, especially preferably be made as 0.1～2 mass parts.When its use level during less than 0.01 mass parts, existence can't obtain good sensitivity, the tendency of resolution, and when surpassing 10 mass parts, existence can't obtain the tendency of good shape.
In the photosensitive polymer combination of this embodiment, light developers such as dyestuff, leuco crystal violet such as optical polymerism compound (oxetane compound etc.), cationic polymerization initiators, peacock green, the heat colour developing that can contain the ring-type ether that has at least 1 cationically polymerizable in the molecule as required prevent plastifier such as agent, para toluene sulfonamide, pigment, filler, foam-breaking agent, fire retardant, stabilizing agent, adaptation imparting agent, levelling agent, peel off promoter, anti-oxidant, spices, preparation, thermal cross-linking agent etc.These can use a kind of separately or two or more combinations are used.With regard to these content,, preferably be made as about 0.01～20 mass parts respectively with respect to (A) composition (binder polymer) and (B) total amount 100 mass parts of composition (optical polymerism compound).
The photosensitive polymer combination of above-mentioned embodiment is dissolved in the organic solvent; Processing solid constituent is the photosensitive polymer combination solution (coating fluid) about 30～60 quality %; Coat on the surface of sheet metal etc. for example; Drying, thus the photosensitive polymer combination layer that the photosensitive polymer combination by this embodiment constitutes can be formed.As organic solvent, can enumerate out methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, dinethylformamide, propylene glycol monomethyl ether or these mixed solvent.In addition, as sheet metal, can enumerate iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, preferably copper, copper series alloy, iron-based alloy.
The thickness of photosensitive polymer combination layer is according to its purposes and difference is preferably counted about 1～100 μ m with dried thickness.Can also the surface with the sheet metal opposition side of photosensitive polymer combination layer be covered with diaphragm.As diaphragm, can enumerate out polymer films such as tygon, polypropylene etc.
(photosensitive element)
Secondly, photosensitive polymer combination layer and the photosensitive element to this embodiment describes.Fig. 1 is the pattern cut-open view of an example of expression photosensitive element.Photosensitive element 1 is for stacking gradually the duplexer that support membrane 2, photosensitive polymer combination layer 3 and diaphragm according to circumstances 4 form.
As support membrane 2, the polymer film that can use polyester, polypropylene, tygon etc. such as polyethylene terephthalate to have thermotolerance and solvent resistance.The thickness of support membrane (polymer film) is preferably 1～100 μ m, more preferably 5～50 μ m, further preferred 5～30 μ m.When its thickness during less than 1 μ m, there is the crackly tendency of support membrane when peeling off support membrane, when surpassing 100 μ m, existence can't fully obtain the tendency of resolution.
With the photosensitive polymer combination solution coat of above-mentioned embodiment on support membrane 2, drying, thus can on support membrane 2, form the photosensitive polymer combination layer 3 that constitutes by above-mentioned photosensitive polymer combination.
The coating of photosensitive polymer combination solution on support membrane 2 can be carried out through known method such as roll coater, unfilled corner wheel coating machine, intaglio plate coating machine, Kohler coater, die coater, scraping strip coating machines.
The drying of photosensitive polymer combination solution is preferably being carried out about 5～30 minutes under 70～150 ℃.The viewpoint of organic solvent diffusion from prevent subsequent handling, after the drying, preferably making the remaining organic solvent amount in the photosensitive polymer combination layer 3 is below the 2 quality %.
The thickness of the photosensitive polymer combination layer 3 in the photosensitive element 1 is according to purposes and difference is preferably counted 1～100 μ m with dried thickness, and more preferably 1～50 μ m further is preferably 5～50 μ m, is preferably 10～40 μ m especially.When its thickness during less than 1 μ m, exist and be difficult to the tendency that is coated with in the industry, when surpassing 100 μ m, there is the tendency that is difficult to fully obtain adaptation and resolution.
To with regard to the transmitance of photosensitive polymer combination layer 3, under the ultraviolet ray of wavelength 405nm, be preferably 5～75% with regard to ultraviolet ray, more preferably 10～65%, be preferably 15～55% especially.When this transmitance less than 5% the time, have the tendency that is difficult to obtain sufficient adaptation, when surpassing 75%, have the tendency that is difficult to obtain sufficient resolution.Above-mentioned transmitance can be measured through the UV spectrometer.As the UV spectrometer, can enumerate out the system 228A of Hitachi type W light beam spectrophotometer.
Photosensitive element 1 can possess the lining photosensitive polymer combination layer diaphragm 4 with surfaces support membrane 2 opposition sides 3 as required.
As diaphragm 4, preferably to the bonding force of photosensitive polymer combination layer 3 the little diaphragm of bonding force than 2 pairs of photosensitive polymer combination layers of support membrane, in addition, the preferred few film of shrinkage cavity (fisheye).Here, " shrinkage cavity " is meant: with the material heat fusing, through mixing, extrude, when biaxial stretch-formed, casting method etc. is made film, the foreign matter of material, melt, oxidative degradation thing etc. are not comprised in the film.That is, " shrinkage cavity is few " means that above-mentioned foreign matter in the film etc. is few.
Particularly, as diaphragm 4, can use polyester such as polyethylene terephthalate, polypropylene, tygon etc. has the polymer film of thermotolerance and solvent resistance.As commercially available film, can enumerate out polyethylene terephthalate films such as PS series of the polypropylene screen of ALPHAN (the ア Le Off ア Application) MA-410, E-200C, SHIN-ETSU HANTOTAI's film manufactured etc. of Oji Paper manufactured, PS-25 of Supreme Being people's manufactured etc. etc.In addition, diaphragm 4 can be the film identical with support membrane.
The thickness of diaphragm 4 is preferably 1～100 μ m, and more preferably 5～50 μ m further are preferably 5～30 μ m, are preferably 15～30 μ m especially.When its thickness during less than 1 μ m, exist photosensitive polymer combination layer 2 diaphragm 4 crackly tendencies when diaphragm 4 range upon range of (lamination) is on substrate, when surpassing 100 μ m, have cheapness property aspect tendency fully inadequately.
Photosensitive element can further have middle layers such as cushion, adhesive linkage, light absorbing zone, barrier layer for gases etc.
The photosensitive element 1 that obtains can or be wound into the roller shape with sheet and take care of on the volume core.When being wound into the roller shape, the mode outside preferably becoming according to support membrane 2 is reeled.As the volume core, can enumerate out polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin plastics such as (acrylonitrile-butadiene-styrene copolymers).From the position of end face protection, the end face of the photosensitive element of the roller shape that obtains so preferably is provided with the end face dividing plate, from the position on refractory limit, damp proof end face dividing plate is set preferably.As bundling method, preferably wrap in the little sheet steel of moisture-penetrability (Black sheet) and pack.
(the formation method of resist pattern)
Use above-mentioned photosensitive polymer combination can form resist pattern.The formation method of the resist pattern of this embodiment has (i) thereby will be stacked in range upon range of operation on the substrate by the photosensitive polymer combination that above-mentioned photosensitive polymer combination constitutes layer by layer, (ii) to the exposure process of the established part irradiation active ray of photosensitive polymer combination layer with (iii) remove part beyond the afore mentioned rules part of photosensitive polymer combination layer forms the resist pattern that the solidfied material by photosensitive polymer combination constitutes at substrate developing procedure from substrate.
(i) range upon range of operation
At first, will be stacked on the substrate layer by layer by the photosensitive polymer combination that photosensitive polymer combination constitutes.As substrate, can use to possess insulation course and the substrate that is formed at the conductor layer on this insulation course (circuit forms and uses substrate).
Range upon range of on the photosensitive polymer combination course substrate for example can be after removing the diaphragm of above-mentioned photosensitive element, and the photosensitive polymer combination layer limit through limit heating photosensitive element is crimped on it on aforesaid substrate carries out.Thus, can obtain by substrate, photosensitive polymer combination layer and support membrane constitutes and these stack gradually the duplexer that forms.
From the position of adaptation and tracing ability, this range upon range of operation is preferably under reduced pressure carried out.During crimping,, preferably under 70～130 ℃ temperature, carry out, preferably with (1～10kgf/cm about 0.1～1.0MPa to not special restrictions of condition such as the temperature of photosensitive polymer combination layer and/or substrate heating, pressure 2About) pressure carry out crimping.In addition,, then in advance substrate is carried out thermal pretreatment and inessential, but, also can carry out the thermal pretreatment of substrate in order further to improve stackability if the photosensitive polymer combination layer is heated to 70～130 ℃.
(ii) exposure process
Then, the established part irradiation active ray to the photosensitive polymer combination layer on the substrate makes public, solidifies this established part.At this moment; When the support membrane on being present in the photosensitive polymer combination layer has permeability to active ray, can see through support membrane irradiation active ray, when support membrane has light-proofness to active ray; After removing support membrane, to photosensitive polymer combination layer irradiation active ray.
As exposure method, can enumerate out minus or the method (mask exposure method) of eurymeric mask graph image shape ground irradiation active ray through being called as wiring diagram (ART WORK).In addition, can also adopt through LDI (Laser Direct Imaging, laser direct imaging) exposure method, DLP (Digital Light Processing, digit optical is handled) exposure method etc. and directly draw exposure method, image shape ground shines the method for active ray.
Light source as active ray; Can use known light source, for example Solid State Laser, semiconductor lasers etc. such as gas lasers such as carbon arc lamp, mercury vapour arc lamp, high-pressure sodium lamp, xenon lamp, argon laser, YAG laser effectively radiate the light source of ultraviolet ray, visible light etc.
As the wavelength (exposure wavelength) of active ray, from can more positively obtaining the viewpoint of effect of the present invention, preferably be located in the scope of 350～410nm, more preferably be located in the scope of 390～410nm.
(iii) developing procedure
And then, through the part beyond the afore mentioned rules part of removing the photosensitive polymer combination layer from substrate, on substrate, form the resist pattern that the solidfied material by photosensitive polymer combination constitutes.When having support membrane on the photosensitive polymer combination layer, remove remove (development) of carrying out afore mentioned rules part (exposed portion) part (unexposed portion) in addition behind the support membrane.Developing method has wet developing and dry process development, and wet developing is widely used.
Utilize under the situation of wet developing, use and the corresponding developer solution of photosensitive polymer combination, develop through known developing method.As developing method; Can enumerate and send as an envoy to impregnation method, stirring (バ ト Le) mode, spray pattern, the method for scrubbing, patting (slapping), blade coating (scrapping), shaking impregnating; From improving the viewpoint of resolution, optimal is the high-pressure fog mode.Also can the combination of the method more than 2 kinds in these be developed.
As developer solution, can enumerate alkaline water solution, water system developer solution, organic solvent is developer solution etc.
When using alkaline aqueous solution as developer solution, safety and stable, operability is good.Alkali as alkaline aqueous solution; Can use the alkali metal hydroxides such as oxyhydroxide of lithium, sodium or potassium; The carbonate of lithium, sodium, potassium or ammonia or supercarbonate, alkali metal phosphates such as potassium phosphate, sodium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate etc.
As alkaline aqueous solution, preferred 0.1 quality %～5 quality % sodium carbonate lean solutions, 0.1 quality %～5 quality % sal tartari lean solutions, 0.1 quality %～5 quality % dilute solution of sodium hydroxide, 0.1 quality %～5 quality % sodium tetraborate lean solutions etc.The pH of alkaline aqueous solution preferably is made as 9～11 scope, and its temperature can be regulated according to the alkali-developable of photo-sensitive resin.Can also sneak into surfactant, foam-breaking agent in the alkaline aqueous solution, be used to promote organic solvent that develops etc. on a small quantity.
The water system developer solution is the developer solution for being made up of water or alkaline aqueous solution and the organic solvent more than a kind for example.At this,, except that aforementioned substances, can also enumerate out for example borax, sodium silicate, TMAH, monoethanolamine, ethylenediamine, diethylene triamine, 2-amino-2-methylol-1, ammediol, morpholine etc. as the alkali of alkaline aqueous solution.The pH of water system developer solution preferably is made as as far as possible little in the scope that can fully develop, preferably is made as pH8～12, more preferably is made as pH9～10.
As the organic solvent that uses in the water system developer solution, can enumerate out for example acetone, ethyl acetate, alkoxyethanol, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether etc. with alkoxy of carbon number 1～4.These can use a kind of separately or two or more combinations are used.The concentration of the organic solvent in the water system developer solution preferably is made as 2～90 quality % usually, and its temperature can be adjusted according to alkali-developable.Also can sneak into surfactant, foam-breaking agent etc. on a small quantity in the water system developer solution.
As organic solvent is developer solution, for example can enumerate out 1,1,1-trichloroethanes, N-Methyl pyrrolidone, N, organic solvents such as dinethylformamide, cyclohexanone, methyl isobutyl ketone, gamma-butyrolacton.On fire for preventing, preferably the scope with 1～20 quality % adds water in these organic solvents.
After removing unexposed portion, can also carry out heating or the 0.2～10J/cm about 60 ℃～250 ℃ as required 2About exposure, thereby resist pattern is further solidified.
(manufacturing approach of printed-wiring board (PWB))
Through the substrate that utilizes said method to form resist pattern is carried out etching or plating, can make printed-wiring board (PWB).To be mask with the resist pattern that forms carry out the conductor layer of substrate etc. for the etching of substrate or plating.
Etching solution when carrying out etching can be enumerated out copper chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, from the good viewpoint of etching factor, and the preferred ferric chloride solution that uses among these.
Method for plating when carrying out plating; Can enumerate out copper platings such as copper sulphate plating, pyrophosphoric acid acid copper plating; Scolding tin platings such as high evenly scolding tin (high-throw solder) plating; Watt is bathed nickel platings such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid, golden platings such as hard gold plating, soft golden plating etc.
After etching or plating finish, for example can be through peeling off resist pattern than the stronger WS of alkaline aqueous solution alkalescence that uses in developing.As this alkaline WS, can use for example 1～10 quality % sodium hydrate aqueous solution, 1～10 quality % potassium hydroxide aqueous solution etc.Wherein, preferably use 1～10 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution, more preferably use 1～5 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
As the mode of peeling off of resist pattern, can enumerate out impregnation method, spray pattern etc., these can use separately also and can and use.In addition, the printed-wiring board (PWB) that has formed resist pattern both can be a multilayer printed circuit board, also can have the minor diameter through hole.
More than preferred implementation of the present invention is illustrated, but the present invention does not receive any qualification of above-mentioned embodiment.
Below enumerating embodiment explains the present invention more specifically.But the present invention is not limited by following examples.
< embodiment 1～13 and comparative example 1 >
[modulation of photosensitive polymer combination solution]
Below table 1 and the composition shown in the table 2 are mixed according to the use level shown in this table, thus the photosensitive polymer combination solution of modulation embodiment 1～13 and comparative example 1.In addition, the use level of (A) composition shown in table 1 and the table 2 is the quality (solid constituent amount) of nonvolatile component.Below table 1 and each composition shown in the table 2 are specifically as shown in following.
(A) binder polymer
[synthesizing of binder polymer (A-1)]
To mix with the 9.0g azobis isobutyronitrile as 150g methacrylic acid, 125g benzyl methacrylate, 25g methyl methacrylate and the 200g styrene (mass ratio is 30/25/5/40) of polymerizable monomer (monomer), with the solution of gained as " solution a ".
The solution that gets with dissolving 1.2g azobis isobutyronitrile in the mixed liquor (mass ratio is 3: 2) of 60g methyl cellosolve and 40g toluene is as " solution b ".
In the flask that possesses stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, drop into the mixed liquor (mass ratio is 3: 2) of 270g methyl cellosolve and 180g toluene, the limit is blown into the stirring of nitrogen limit in flask, heat temperature raising to 80 ℃.
In the above-mentioned mixed liquor in flask, dripped above-mentioned solution a with 4 hours after, while stirring 80 ℃ of insulations 2 hours down.Then, be added drop-wise to above-mentioned solution b in the solution in the flask with 10 minutes after, the solution limit in the stirred flask of limit is 80 ℃ of insulations 3 hours down.And then, with 30 minutes the solution in the flask is warming up to 90 ℃,, cool off after 2 hours in insulation under 90 ℃, obtain containing the liquid of binder polymer (A-1).
The nonvolatile component (solid constituent) of binder polymer (A-1) is 47.8 quality %, and weight-average molecular weight is 30,000, and acid number is 196mgKOH/g.In addition, weight-average molecular weight derivation thereby the calibration curve of mensuration and use polystyrene standard converts through gel permeation chromatography (GPC).The condition of GPC is as follows.
(GPC condition)
Pump: the L-6000 of Hitachi type [(strain) Hitachi system]
Post: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (totally 3) (above all make trade name) for Hitachi changes into industry (strain)
Eluant: tetrahydrofuran
Measure temperature: 40 ℃
Flow: 2.05mL/ minute
Detecting device: the L-3300 of Hitachi type RI [(strain) Hitachi system]
< (B) optical polymerism compound >
TMPT21E: trimethylolpropane polyoxyethylene ether trimethyl acrylic ester (Hitachi changes into industrial group and makes, trade name)
FA-321M:2, two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-) (Hitachi changes into industrial group and makes, trade name)
FA-024M: R in the compound shown in the above-mentioned formula (7) 20And R 21=methyl, m 3=6 (mean values), n 2+ n 3The compound of=12 (mean values) (Hitachi changes into industrial group and makes, trade name)
M-114:4-n-nonyl phenoxy group eight EDIAs (East Asia synthetic (strain) made trade name)
BPE-100:2, two (4-(methacryloxy polyethoxy) phenyl) propane of 2-) (2.6 moles of the inferior ethoxyl chain average out to that contains in 1 molecule) (Xin Zhong village chemical company makes, trade name)
< Photoepolymerizationinitiater initiater (C) >
[synthesizing of Photoepolymerizationinitiater initiater (C-1)]
With 20mL ethanol, 2mmol 3,3 ', 4,4 '-xenyl tetramine and 4mmol 3,3 '-benzil of dimethoxy join in the flask and mix, the air in the flask is carried out the nitrogen displacement after, with potpourri 80 ℃ of refluxed 12 hours.Be cooled to room temperature, behind the water of adding 200mL, obtain product (C-1) through filtration under diminished pressure.
Confirmed the compound of product (C-1) by 1H-NMR spectrum shown in Figure 2 and 13C-NMR spectrum shown in Figure 3 for the structure shown in the following formula (13).
[Chemical formula 2 2]
Figure BPA00001447174600281
[synthesizing of Photoepolymerizationinitiater initiater (C-2)]
Use 4,4 '-benzil of dimethoxy replacement 3, in addition 3 '-benzil of dimethoxy is likewise operated with above-mentioned (C-1), obtains the compound of the structure shown in the following formula (14).
[Chemical formula 2 3]
Figure BPA00001447174600291
[synthesizing of Photoepolymerizationinitiater initiater (C-3)]
Use 2mmol 2,3-diaminonaphthalene and 2mmol 3,3 '-benzil of dimethoxy replaces 2mmol 3; 3 ', 4,4 '-xenyl tetramine and 4mmol 3; 3 '-benzil of dimethoxy is likewise operated with above-mentioned (C-1) in addition, obtains the compound of the structure shown in the following formula (11).
[Chemical formula 2 4]
Figure BPA00001447174600292
[synthesizing of Photoepolymerizationinitiater initiater (C-4)]
Use 2mmol 2,3-diaminonaphthalene and 2mmol 4,4 '-benzil of dimethoxy replaces 2mmol 3; 3 ', 4,4 '-xenyl tetramine and 4mmol 3; 3 '-benzil of dimethoxy is likewise operated with above-mentioned (C-1) in addition, obtains the compound of the structure shown in the following formula (12).
[Chemical formula 2 5]
Figure BPA00001447174600301
[other Photoepolymerizationinitiater initiater]
(C-1), (C-2), (C-3) and (C-4) in addition Photoepolymerizationinitiater initiater as shown in following.
BCIM:2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole (Hampford manufactured, trade name)
TPS: α, α, α-trisbromomethyl phenyl sulfone
(mensuration of absorption spectrum)
Carry out the mensuration of the ultraviolet-visible absorption spectroscopy of product (C-1), (C-2), (C-3) with being described below.
The film of making among film of making among the use embodiment 1 that contains product (C-1) and the embodiment 8 that contains product (C-3) uses Tianjin, island corporate system ultraviolet-visible pectrophotometer UV2550, measures the ultraviolet-visible absorption spectroscopy of each sample film.The result who obtains is shown in Fig. 4.
In addition, take by weighing product (C-1), (C-2) is 1 * 10 to chloroform -5Mol/L adds in the silica dish, uses Tianjin, island corporate system ultraviolet-visible pectrophotometer UV2550, measures the ultraviolet-visible absorption spectroscopy of each sample solution.The result who obtains is shown in Fig. 5.
According to Fig. 4 and spectrum shown in Figure 5, confirmed product (C-1), (C-2) and (C-3) in the scope of 350～410nm, had a very big absorbing wavelength.
< (D) hydrogen supply property compound >
LCV: leuco crystal violet
NPG:N-phenylglycine (R 17=hydrogen atom)
(D-1): the 2-mercaptobenzoxazole
(E) sensitizing coloring matter
Nikka Flow MC (ニ Star カ Off ロ one MC): 7-diethylamino-4-methylcoumarin (Japanese chemical industry institute manufactured, trade name)
DBA:9,10-dibutoxy anthracene (Kawasaki changes into industrial group and makes, trade name)
(E-1): 1-phenyl-3-(4-cumene vinyl)-5-(4-isopropyl phenyl) pyrazoline (Japanese chemical industry institute corporate system)
Table 1
Figure BPA00001447174600311
Table 2
Figure BPA00001447174600321
(photosensitive element)
The photosensitive polymer combination solution of the foregoing description 1～13 and comparative example 1 is coated on the polyethylene terephthalate film that thickness is 16 μ m (Supreme Being people's (strain) manufacturing respectively equably; Goods name " HTF-01 ") on; Hot air convection formula exsiccator through 70 ℃ and 110 ℃ carries out drying, and forming dried thickness is the photosensitive polymer combination layer of 40 μ m.Diaphragm (TAMAPOLY (タ マ Port リ) CO. fits on this photosensitive polymer combination layer; LTD makes; Goods name " NF-15 "), obtain to have stacked gradually the embodiment 1～13 of polyethylene terephthalate film (support membrane), photosensitive polymer combination layer and diaphragm and the photosensitive element of comparative example 1.
(multilayer board)
Use has the muller (three open (strain) system) of the brush that is equivalent to #600; (Hitachi changes into industry (strain) manufacturing to the copper-clad laminated board by glass epoxide material and Copper Foil (thickness the is 35 μ m) formation that is formed on its two sides; Goods name MCL-E-67) after copper surface is ground, washed, dry through airflow.Heat this copper-clad laminated board (below be called " substrate ".) and after being warming up to 80 ℃, the photosensitive element lamination (range upon range of) of embodiment 1～13 and comparative example 1 is surperficial to the copper of substrate.Lamination with the limit remove photosensitive polymer combination layer driving fit that the diaphragm limit makes each photosensitive element to the mode on the copper surface of substrate at 120 ℃ of temperature, lamination pressure 4kgf/cm 2Condition under carry out.Like this, the multilayer board of obtained laminated photosensitive polymer combination layer and polyethylene terephthalate film on the copper surface of substrate.
(evaluation of sensitivity)
The multilayer board that obtains is placed cooling; In the moment that reaches 23 ℃; On the polyethylene terephthalate film of multilayer board, the size that driving fit has concentration range 0.00～2.00, concentration stage 0.05, a metraster is that the size in 20mm * 187mm, each stage is the optical tool (phototool) of 41 sections stage metraster of 3mm * 12mm.Use with the bluish-violet color laser diode of wavelength 405nm the machine of directly retouching " DE-1AH " (trade name), across optical tool and polyethylene terephthalate film the photosensitive polymer combination layer is made public with the energy fluence (exposure) of regulation as the Via Mechanics of the Hitachi manufactured of light source.In addition, the mensuration of luminous intensity uses the ultraviolet photometer of having used with the corresponding probe of 405nm (USHIO motor (strain) is made, trade name " UIT-150 ") to carry out.
After the exposure, peel off the polyethylene terephthalate film, the photosensitive polymer combination layer is exposed from multilayer board, injection quality % aqueous sodium carbonate in 60 second 1 under 30 ℃, thus remove unexposed portion.Like this, on the copper surface of substrate, form the cured film that the solidfied material by photosensitive polymer combination constitutes.Exposure (mJ/cm when the remaining hop count through the stage metraster that obtains as cured film is 20 sections 2), estimate the sensitivity of photosensitive polymer combination.This numerical value is more little to mean that then sensitivity is good more.The result is shown in table 3 and table 4.
(evaluation of resolution and adaptation)
Use line width (L)/gap width (S) (below be designated as " L/S ".) be 5/5～30/30 (and unit: μ m) draw figure, the energy fluence that with the remaining hop count of 41 sections stage metraster is 20 sections is to the photosensitive polymer combination layer of above-mentioned multilayer board make public (drawing).After the exposure, carry out the development treatment same with the evaluation of above-mentioned sensitivity.
After the development, thoroughly removed and line part (exposed portion) does not produce among distortion, damaged the resist pattern that forms at gap portion (unexposed portion), through the value evaluation resolution and the adaptation of minimum line width/gap width.More little resolution and the adaptation of then meaning of this numerical value is all good.The result is shown in table 3 and table 4.
(evaluation of peel property)
The formation that obtains in the evaluation with above-mentioned resolution and adaptation the multilayer board of resist pattern impregnated in the plating solution of copper sulphate/aqueous sulfuric acid, carry out 15 minutes electrolytic copper platings with total current value 2A.The copper facing thickness that obtains is about 15 μ m.Multilayer board behind the plating is sprayed 50 ℃ 3 quality % sodium hydrate aqueous solutions, resist is removed from strippable substrate.Use the multilayer board after observation by light microscope is peeled off, have or not the residue of peeling off of cured film between investigation plating figure (copper wiring).The result is shown in table 3 and table 4.
(evaluation of plating formation property)
Use the multilayer board after the peeling off that observation by light microscope obtains in the evaluation of above-mentioned peel property, the plating width that has a minimum that broken string or short circuit ground forms through the plating figure is estimated plating and is formed property.This numerical value is more little to mean that then plating formation property is good more.The result is shown in table 3 and table 4.
(to the evaluation of the preventing property of the pollution of plating)
Cutting out the size of 40cm * 50cm from each photosensitive element, remove diaphragm, is that 20 sections exposure is made public to the photosensitive polymer combination layer with the stage metraster, peels off the polyethylene terephthalate film, obtains cured film.This cured film was flooded 3 days in the plating solution 1L of copper sulphate/aqueous sulfuric acid.Use conspicuous coomb's test Coomb bath (Hull cell) (the gold-plated testing machine corporate system in Yamamoto), above-mentioned copper-clad laminated board (substrate) is carried out 15 minutes electrolytic copper platings with total current value 2A.
Plating when not flooding the plating solution of cured film to use is as reference, uses the outward appearance of plating when having flooded the plating solution of cured film through visualization.Will be judged as nonstaining property with reference to comparing plating outward appearance no change person, will exist variation person such as variable color to be judged as contaminative.The result is shown in table 3 and table 4.
Table 3
Figure BPA00001447174600341
*1 ... Exposure when the remaining hop count of stage metraster is 20 sections
Table 4
Figure BPA00001447174600351
*1 ... Exposure when the remaining hop count of stage metraster is 20 sections
The photosensitive polymer combination of embodiment 1～15 is compared with comparative example 1, to wavelength 405nm directly to draw exposure sensitivity higher, and resolution, adaptation and plating to form property good.In addition, the peel property of resist and the preventing property of the pollution of plating also is maintained well.Particularly use (C1) composition or (C2) composition as Photoepolymerizationinitiater initiater, only use the N-phenylglycine shown in the above-mentioned formula (5) to improve as the sensitivity of the embodiment 2,8 of hydrogen supply property compound.In addition, through with the α shown in the above-mentioned formula (4), α, α-trisbromomethyl phenyl sulfone and (C1) composition or (C2) composition and usefulness, with independent use (C1) composition or (C2) during composition mutually specific sensitivity also improve.In addition; And with the α shown in the above-mentioned formula (4); α; During α-trisbromomethyl phenyl sulfone, used the embodiment 15 of (C1) composition shown in the formula (C-4) to compare with the embodiment 9 that has used (C2) composition shown in the formula (C-1) with the embodiment 14 that has used (C1) composition shown in the formula (C-3), sensitivity further improves.
Know according to above, can obtain excellent and photosensitive polymer combination and the photosensitive element low of sensitivity, resolution, adaptation, peel property and plating formation property the contaminative of plating.
Symbol description
1 ... Photosensitive element, 2 ... Support membrane, 3 ... Photosensitive polymer combination, 4 ... Diaphragm.

Claims (11)

1. photosensitive polymer combination, it contains binder polymer, has the optical polymerism compound of ethene property unsaturated link and is selected from least a kind of pyrazine compound in the group of being made up of the compound with the structure shown in following formula (1), (2) or (3);
Figure FPA00001447174500011
In the formula (1), R 1, R 2, R 3And R 4Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 1And R 2, or R 3And R 4Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton;
Figure FPA00001447174500012
In the formula (2), R 5, R 6, R 7And R 8Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 5And R 6, or R 7And R 8Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton, X and Y represent to constitute the former subgroup of the aromatic ring of single ring architecture that 2 carbon with the pyrazine skeleton form or condensation polycyclic structure independently of one another;
In the formula (3), R 9, R 10, R 11And R 12Expression independently of one another comprises 1 valency organic group of alkyl, naphthenic base, phenyl, naphthyl or hetero ring type base, R 9And R 10, or R 11And R 12Can mutually combine and form ring with 2 carbon atoms of pyrazine skeleton, Z representes to constitute single ring architecture or the aromatic ring of condensation polycyclic structure or the former subgroup of heterocycle that 4 carbon with the pyrazine skeleton form.
2. photosensitive polymer combination according to claim 1, the compound of said pyrazine compound for having the structure shown in the said formula (1).
3. photosensitive polymer combination according to claim 1 and 2, the very big absorbing wavelength of said pyrazine compound is in the scope of 350～410nm.
4. according to any described photosensitive polymer combination in the claim 1～3, said binder polymer contains (methyl) acrylic acid and styrene or styrene derivative as copolymer composition.
5. according to any described photosensitive polymer combination in the claim 1～4, contain the compound shown in the following formula (4);
Figure FPA00001447174500021
In the formula (4), X representes carbon atom or nitrogen-atoms, R 13, R 14And R 15The alkyl of representing halogen atom or carbon number 1～5 independently of one another, R 13, R 14And R 15In at least one the expression halogen atom, R 16Expression hydrogen atom, the alkyl of carbon number 1～5 or the alkoxy of carbon number 1～5, l representes 0～4 integer, l is 2～4 o'clock, a plurality of R 16Can be the same or different.
6. according to any described photosensitive polymer combination in the claim 1～5, further contain hydrogen supply property compound.
7. photosensitive polymer combination according to claim 6, said hydrogen supply property compound contains the compound shown in the following formula (5);
Figure FPA00001447174500022
In the formula (5), R 17Alkyl, alkoxy or ester group, hydroxyl or the halogen atom of expression carbon number 1～6, n is 0～5 integer, n is 2～5 o'clock, a plurality of R 17Can be the same or different.
8. photosensitive element possesses supporter and the photosensitive polymer combination layer that is made up of any described photosensitive polymer combination in the claim 1～7 that is formed on this supporter.
9. the formation method of a resist pattern, it comprises:
To be stacked in layer by layer by the photosensitive polymer combination that any described photosensitive polymer combination in the claim 1～7 constitutes range upon range of operation on the substrate,
To the exposure process of the established part of said photosensitive polymer combination layer irradiation active ray and
Remove the part beyond the said established part of said photosensitive polymer combination layer from said substrate, thereby on said substrate, form the developing procedure of the resist pattern that the solidfied material by said photosensitive polymer combination constitutes.
10. the formation method of resist pattern according to claim 9, the wavelength of said active ray is 390～410nm.
11. the manufacturing approach of a printed-wiring board (PWB) comprises the operation of the substrate that has formed resist pattern according to claim 9 or 10 described methods being carried out etching or plating.
CN2010800171698A 2009-04-30 2010-04-26 Photosensitive resin composition, photosensitive element utilizing the composition, method for formation of resist pattern, and process for production of printed circuit board Expired - Fee Related CN102395924B (en)

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