CN102597877A - Photosensitive resin composition, photosensitive element using same, method for forming resist pattern, method for producing lead frame, printed wiring board, and method for producing printed wiring board - Google Patents

Photosensitive resin composition, photosensitive element using same, method for forming resist pattern, method for producing lead frame, printed wiring board, and method for producing printed wiring board Download PDF

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Publication number
CN102597877A
CN102597877A CN2011800043618A CN201180004361A CN102597877A CN 102597877 A CN102597877 A CN 102597877A CN 2011800043618 A CN2011800043618 A CN 2011800043618A CN 201180004361 A CN201180004361 A CN 201180004361A CN 102597877 A CN102597877 A CN 102597877A
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methyl
resist
quality
photo
sensitive resin
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岩下健一
栉田昌孝
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating

Abstract

Disclosed is a photosensitive resin composition which is configured to contain: a binder polymer that has a constituent unit derived from a (meth)acrylic acid and a constituent unit derived from a benzyl (meth)acrylate or a benzyl (meth)acrylate derivative; a polymerizable compound that has at least one ethylenically unsaturated bond; and a photopolymerization initiator that contains an acylphosphine oxide compound and a hexaaryl biimidazole derivative.

Description

Photosensitive polymer combination and the manufacturing approach of manufacturing approach, printed-wiring board (PWB) and printed-wiring board (PWB) of using manufacturing approach, the lead frame of its photosensitive element, resist figure
Technical field
The manufacturing approach of manufacturing approach, printed-wiring board (PWB) and printed-wiring board (PWB) that the present invention relates to photosensitive polymer combination and use manufacturing approach, the lead frame (lead frame) of its photosensitive element, resist figure.
Background technology
Manufacturing field at printed-wiring board (PWB); As the anticorrosive additive material that is used for etching, plating etc., the photosensitive polymer combination that is widely used, have and forming the layer that contains this photosensitive polymer combination (below be called " photo-sensitive resin ") on the support membrane and on photo-sensitive resin, disposing the photosensitive element (duplexer) of the structure of diaphragm.
In the past, for printed-wiring board (PWB), used above-mentioned photosensitive element, below for example, made in proper order.That is, at first the photo-sensitive resin of photosensitive element being laminated to circuit such as copper-clad laminated board forms with on the substrate.At this moment, make the face " top " of photo-sensitive resin (below be called) of opposition side of the face that contacts with support membrane " following " of photo-sensitive resin (below be called) of photo-sensitive resin form face driving fit with the formation circuit of substrate with circuit.Therefore, on photo-sensitive resin, dispose under the situation of diaphragm, when peelling off diaphragm, carry out this lamination operation.In addition, lamination carries out (normal pressure laminating) through the photo-sensitive resin heating is crimped on the formation of substrate circuit with substrate.
Then, through mask film etc. photo-sensitive resin is carried out graph exposure.At this moment, before exposure or peel off support membrane any opportunity after the exposure.Then, unexposed of photo-sensitive resin removed through dissolves or dispersion.Then, implement the processing of etch processes or plating and form figure, peel off at last and remove cured portion.
Here, so-called etch processes be with the formed circuit that resist covered of not being cured in the back of developing form remove with the metal covering etching of substrate after, peel off the method for curing resist.
On the other hand; It is after on the formed circuit that resist covered of not being cured forms with the metal covering of substrate after the development, carrying out plating processing such as copper and scolding tin that so-called plating is handled; Remove the curing resist, etching is by the method for the metal covering of this resist covering.
But,, used the method that mercury lamp is made public through photomask as light source as the method for above-mentioned graph exposure in the past.In addition, in recent years, as new exposure technique, proposed to be called DLP (Digital Light Processing, digit optical handle), the numerical data of figure directly drawn on photo-sensitive resin, directly draws exposure method.Than the exposure method through photomask, it is good that this directly draws the exposure method bearing accuracy, and can access meticulous figure, therefore constantly is introduced into for the making of high-density packages substrate.
On the other hand, be accompanied by the densification of printed-wiring board (PWB) in recent years, also improved requirement high resolution and high adaptation for photosensitive polymer combination.Particularly in the making of base plate for packaging, it is 10/10 (unit: the photosensitive polymer combination of the resist figure μ m) that requirement can form L/S (live width/line-spacing).
In the high-density packages substrate, the narrow width between circuit, so resist shape excellence also is important.If the cross sectional shape of resist is trapezoidal or trapezoidal; Or there is a crimping (full front of a Chinese gown draws I) of resist; Then handling in the circuit that forms through thereafter etch processes or plating; The possibility that produces short circuit, broken string is arranged, and is undesirable therefore, hopes that the resist shape is rectangle and does not have crimping.
In addition, in order to improve the exploring degree of photo-sensitive resin, the filmization of photo-sensitive resin is effective.But;, printed-wiring board (PWB) needs when forming under the situation of circuit thickness (copper is thick etc.) to a certain degree; The influence of lateral etch when having etching in the etch process, so the resist line of thin thread part comes off the densification of printed-wiring board (PWB) (it is thick wide with circuit to take into account circuit) existence restriction easily.In addition, in plating technic, with the photoresist layer film time, be difficult to obtain required circuit thickness (copper is thick), there is restriction in the densification of printed-wiring board (PWB).
In recent years, do not realize high-resolutionization, carried out various trials in order not carry out the filmization of photo-sensitive resin.For example, before exposure, peel off support membrane and make the directly method of driving fit on photo-sensitive resin of optical tool (phototool).Usually; Photo-sensitive resin for driving fit on base material and keep stickability to a certain degree; If use this method; Then can produce like inferior problem: optical tool and photo-sensitive resin driving fit, be difficult to peel off optical tool and the reduction of operation property, optical tool is polluted by photosensitive polymer combination, or the influence that encumbers owing to oxygen reduces sensitivity.
Therefore; Trial as this method of improvement; In japanese kokai publication hei 1-221735 communique, japanese kokai publication hei 2-230149 communique, carry out following method: make photo-sensitive resin be two-layer more than, make the layer that directly contacts with optical tool for the Abherent resin bed.But this method wastes time and energy for the coating that the photo-sensitive resin multiple stratification is carried out, and does not have effect for the sensitivity reduction.
In addition, in order to realize the densification of printed-wiring board (PWB), as manufacturing approach, false add becomes technology to be gazed at.In this technology,, form printed-wiring board (PWB) through carrying out on base material through formation very thin films conductor layers such as electroless plating cover successively, form resist figure, plating, peeling off resist and fast-etching (removing unnecessary very thin films conductor layer).As the advantage of this technology, can enumerate: owing to almost there is not the influence of lateral etch, therefore can obtain good circuit, can realize the densification of printed-wiring board (PWB).
In addition, for photosensitive polymer combination, except above-mentioned sensitivity, the peel property of exploring degree, resist and adaptation excellence also are important.If photosensitive polymer combination can provide exploring degree and the excellent resist figure of adaptation, just can fully reduce short circuit, broken string between circuit.
In addition; If photosensitive polymer combination can form the excellent resist of peel property; Then improved the formation efficient of resist figure, in addition, reduced through size with the stripping film of resist through the splitting time that shortens resist; Resist peel off residual tailing off, circuit-formed yield rate improves.
To such requirement, specific binder polymer, Photoepolymerizationinitiater initiater etc. and the excellent photosensitive polymer combination of sensitivity, exploring degree and resist peel property have been proposed to use in the japanese kokai publication hei 11-327137 communique.
In addition; In TOHKEMY 2003-215799 communique, the TOHKEMY 2000-162767 communique, the photosensitive polymer combination that well uses polymerization inhibitors such as catechol, quinhydrones for the contrast (imaging) that makes exposed portion and unexposed portion is disclosed.
Summary of the invention
The technical matters that invention will solve
But, for the photosensitive polymer combination of putting down in writing in the japanese kokai publication hei 11-327137 communique, have good fissility, but have the inadequate situation in exploring degree aspect.
And then; For the photosensitive polymer combination of putting down in writing in TOHKEMY 2003-215799 communique and the TOHKEMY 2000-162767 communique; Though exploring degree and imaging aspect are good; If but the addition of polymerization inhibitor is too much, the situation that sensitivity descends and then adaptation reduces is arranged then.
As stated, photosensitive polymer combination does not in the past fully satisfy desired characteristic with regard to sensitivity, exploring degree, adaptation, resist shape with regard to the peel property after solidifying whole.
And then, through in the graph exposure of photomask,, the live width with respect to photomask being arranged then if increase exposure in order to show the deep curable, the surface element (top) of figure tee section becomes big, the problem that resolution reduces.
Therefore, technical matters of the present invention provide a kind of sensitivity, exploring degree, adaptation, resist shape and solidify after all excellent photosensitive polymer combination of peel property and the manufacturing approach of manufacturing approach, printed-wiring board (PWB) and printed-wiring board (PWB) of using manufacturing approach, the lead frame of its photosensitive element, resist figure.
The method that is used for the technical solution problem
The present invention comprises following mode.
First mode of the present invention is a kind of photosensitive polymer combination; It contains (A) binder polymer, (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater; Should (A) binder polymer have and come from (methyl) acrylic acid structural unit and come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant; Should have at least one ethene property unsaturated link by (B) polymerizable compound, should contain acylphosphine oxide based compound and Hexaarylbiimidazole derivant by (C) Photoepolymerizationinitiater initiater.
Peel property after the sensitivity of the photosensitive polymer combination of above-mentioned formation, exploring degree, adaptation, resist shape and the curing is all excellent.
Said acylphosphine oxide based compound is preferably the compound shown in formula (I) or the general formula (II).Thus, further improve the exploring degree, and then can access excellent resist shape.
[changing 1]
Figure BDA0000157806130000041
In the general formula (I), R 1, R 2And R 3The alkyl or aryl of representing carbon number 1～20 independently of one another.In the formula (II), R 4, R 5And R 6The alkyl or aryl of representing carbon number 1～20 independently of one another.
Said Hexaarylbiimidazole derivant is preferably 2,4,5-triarylimidazoles dipolymer.Thus, sensitivity and exploring degree further improve.
Second mode of the present invention is a kind of photosensitive element, the photo-sensitive resin of filming that it possesses supporter and is formed at the above-mentioned photosensitive polymer combination of conduct on the said supporter.
Third Way of the present invention is a kind of manufacturing approach of resist figure, and it has: on substrate, form the photo-sensitive resin formation operation as the photo-sensitive resin of filming of above-mentioned photosensitive polymer combination; At least a portion of said photo-sensitive resin irradiation active ray is made the exposure process of its photocuring; And the uncured portion of said photo-sensitive resin removed from substrate and form the developing procedure of the resist figure that the solidfied material by said photo-sensitive resin constitutes.
Cubic formula of the present invention is a kind of manufacturing approach of lead frame, and it comprises the substrate that the manufacturing approach through above-mentioned resist pattern is formed with the resist figure and carries out plating and handle the operation that forms conductor fig.
The 5th mode of the present invention is a kind of manufacturing approach of printed-wiring board (PWB), and it comprises the substrate that the manufacturing approach through above-mentioned resist figure is formed with the resist figure and carries out plating and handle the operation that forms conductor fig.
According to this manufacturing approach, can and make the printed-wiring board (PWB) of the such densification of high-density packages substrate effectively with good precision.
The 6th mode of the present invention is the printed-wiring board (PWB) of making through the manufacturing approach of above-mentioned printed-wiring board (PWB).
The effect of invention
According to the present invention, sensitivity, exploring degree, adaptation, resist shape can be provided and solidify after all excellent photosensitive polymer combination of peel property and use its photosensitive element, the manufacturing approach of resist figure, the manufacturing approach of lead frame and the manufacturing approach of printed-wiring board (PWB).
Description of drawings
Fig. 1 is the pattern sectional view of an embodiment of expression photosensitive element of the present invention.
Embodiment
" operation " this term in this instructions is not only an operation independently, even under situation about can't clearly distinguish with other operation, as long as realized the desired effect of this operation, then be also contained in this term.
In addition, in this manual, represent to comprise respectively numerical value with record before and after "～" as minimum value and peaked scope with the numerical range of "～" expression.
And then, in this manual, when mentioning the amount of each composition in the composition, for there is multiple situation in the material that meets each composition in the composition, short of explanation in advance especially, the meaning is the total amount that is present in this multiple material in the composition.
< photosensitive polymer combination >
Photosensitive polymer combination of the present invention contains at least a and (C) Photoepolymerizationinitiater initiater of at least a, (B) following polymerizable compound of (A) following binder polymer; This binder polymer has and comes from (methyl) acrylic acid structural unit and come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant; This polymerizable compound has at least one ethene property unsaturated link, and this Photoepolymerizationinitiater initiater contains acylphosphine oxide based compound and Hexaarylbiimidazole derivant.
Through such formation, demonstrate sensitivity, exploring degree, adaptation, resist shape and solidify after all excellent characteristic of peel property.
(A) binder polymer
Come from (methyl) acrylic acid structural unit and come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant as long as the binder polymer among the present invention has, have no particular limits.In addition; Said binder polymer is except (methyl) acrylic acid structural unit and come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant of said coming from, and can also further have other structural units such as the structural unit that comes from (methyl) alkyl acrylate, the structural unit that comes from styrene or styrene derivative as required and constitutes.
As said (methyl) benzyl acrylate derivant, can enumerate the compound of the alkyl of the alkoxy that is substituted with carbon number 1～6 on the aromatic rings of benzyl for example, halogen, carbon number 1～6.Particularly, can enumerate (methyl) acrylic acid ethoxy benzylidene ester, (methyl) acrylic acid methoxy benzyl ester, (methyl) acrylic acid chloro benzyl ester, (methyl) acrylic acid methyl benzyl ester, (methyl) acrylic acid benzyl ethyl ester etc.
In addition, as (methyl) acrylic acid and other polymerizable monomer beyond (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant, for example can enumerate: styrene; Vinyltoluene, AMS etc. are at the substituted styrene derivative that can polymerization of alpha-position or aromatic ring; Acrylic amides such as diacetone acrylamide; Vinyl cyanide; The ester class of vinyl alcohols such as vinyl-n-butyl ether; (methyl) alkyl acrylate, (methyl) acrylic acid cycloalkyl ester, (methyl) acrylic acid chaff ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) IBOA, (methyl) acrylic acid diamantane ester, (methyl) acrylic acid two ring pentyl esters, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid-2; 2; 2-trifluoro ethyl ester, (methyl) acrylic acid-2; 2; 3; 3-tetrafluoro propyl ester, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid, maleic acid monoesters such as 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 and propiolic acid.These can use separately or with two or more combination in any.
For said (A) binder polymer, consider from the viewpoint that improves alkali-developable and peel property, preferably further contain the structural unit of (methyl) alkyl acrylate of at least a coming from.
As (methyl) alkyl acrylate, can enumerate the compound shown in the formula (IV).In the formula (IV), R 9Expression hydrogen atom or methyl, R 10The alkyl of expression carbon number 1～12.
[changing 2]
Figure BDA0000157806130000071
As the R in the above-mentioned general formula (IV) 10The alkyl of represented carbon number 1～12 can be enumerated methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their constitutional isomer.Consider that from the viewpoint of further raising peel property abovementioned alkyl is preferably the alkyl of carbon number 1～4.
As the object lesson of the compound shown in the above-mentioned general formula (IV), for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) 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 caproite, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate.These can use separately or with two or more combination in any.
In addition, for said adhesive composition, consider, also preferably further contain at least a in the structural unit that comes from the styrene or derivatives thereof from making the good viewpoint of exploring degree and adaptation.
The containing ratio that constitutes each structural unit of said binder polymer has no particular limits.
For example; As the containing ratio that comes from (methyl) acrylic acid structural unit; Be preferably the containing ratio that the acid number that makes binder polymer is 100mg KOH/g～250mg KOH/g; The acid number that more preferably makes binder polymer is the containing ratio of 120mg KOH/g～240mg KOH/g; Further be preferably the containing ratio that the acid number that makes binder polymer is 140mg KOH/g～230mg KOH/g, be preferably the containing ratio that the acid number that makes binder polymer is 150mg KOH/g～230mg KOH/g especially.
Acid number through binder polymer is more than the 100mg KOH/g, and it is elongated to suppress development time.In addition, be below the 250mg KOH/g through acid number, the anti-development fluidity (adaptation) of the solidfied material of photosensitive polymer combination improves.Here, under the situation of carrying out solvent develop, also preferred a small amount of preparation (methyl) acrylic acid etc. has the polymerizable monomer (monomer) of carboxyl.
In addition; (A) come from the containing ratio of the structural unit of (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant in the binder polymer; All-mass with the binder polymer molecule is that benchmark is preferably 5 quality %～65 quality %; More preferably 10 quality %～55 quality % further are preferably 20 quality %～50 quality %.
Through this containing ratio is that the exploring degree further improves more than the 5 quality %.In addition, be below the 65 quality % through this containing ratio, can suppress stripping film and become big, and it is elongated to suppress splitting time.
In addition; Contain at said binder polymer under the situation of the structural unit that comes from (methyl) alkyl acrylate; Its containing ratio is that benchmark is preferably 1 quality %～50 quality % with the all-mass of binder polymer molecule; More preferably 2 quality %～30 quality % further are preferably 3 quality %～20 quality %.
Through this content is more than the 1 quality %, can suppress stripping film and become big, and it is elongated to suppress splitting time.In addition, be that exploring degree and adaptation further improve below the 50 quality % through this content.
And then; Have in molecule at said binder polymer under the situation of the structural unit that comes from the styrene or derivatives thereof; Its containing ratio is that benchmark is preferably 5 quality %～65 quality % with the all-mass of binder polymer molecule; More preferably 10 quality %～60 quality % further are preferably 15 quality %～55 quality %, are preferably 20 quality %～50 quality % especially.
Through this containing ratio is that adaptation further improves below the 5 quality %.In addition, be below the 65 quality % through this containing ratio, can suppress stripping film and become big, and it is elongated to suppress splitting time.
The weight-average molecular weight of said binder polymer (Mw) is preferably 10000～100000, and more preferably 20000～80000, further be preferably 25000～60000.
If Mw is more than 10000, the excellent tendency of anti-development fluidity (adaptation) of the solidfied material of photosensitive polymer combination is arranged, if be below 100000, the excellent tendency of development time is arranged.
Here, the weight-average molecular weight of binder polymer is measured (typical curve through using normal polyethylene converts) through gel permeation chromatography (GPC).
The dispersion degree of said binder polymer (Mw/Mn) has no particular limits, and is preferably 1.0～3.0, and more preferably 1.5～2.5.
If dispersion degree is below 3.0, adaptation and exploring degree further improve.
In addition, said binder polymer can also have following characteristic group as required in its molecule, and this characteristic group has photonasty for the light with the wavelength in 350nm～440nm scope.
For the binder polymer among the present invention; Be preferably: in binder polymer, contain the structural unit that comes from (methyl) benzyl acrylate or derivatives thereof that comes from (methyl) acrylic acid structural unit, 5 quality %～65 quality %, the structural unit that comes from (methyl) alkyl acrylate of 1 quality %～50 quality % and the structural unit that comes from the styrene or derivatives thereof of 5 quality %～65 quality %; Acid number is 100mg KOH/g～250mg KOH/g, and weight-average molecular weight is 10000～100000.
More preferably: containing coming from of the structural unit that comes from (methyl) benzyl acrylate that comes from (methyl) acrylic acid structural unit, 10 quality %～55 quality %, 2 quality %～30 quality % has structural unit and the structural unit that comes from the styrene or derivatives thereof of 10 quality %～60 quality % that carbon number is (methyl) alkyl acrylate of 1～4 alkyl; Acid number is 120mg KOH/g～230mgKOH/g, and weight-average molecular weight is 20000～80000.
Further be preferably: containing coming from of the structural unit that comes from (methyl) benzyl acrylate that comes from (methyl) acrylic acid structural unit, 20 quality %～50 quality %, 3 quality %～20 quality % has structural unit and the structural unit that comes from the styrene or derivatives thereof of 15 quality %～55 quality % that carbon number is (methyl) alkyl acrylate of 1～4 alkyl; Acid number is 140mgKOH/g～230mg KOH/g, and weight-average molecular weight is 25000～60000.
Binder polymer among the present invention can pass through the usual way manufacturing.Particularly for example, can carry out the incompatible manufacturing of radical polymerization through other polymerizable monomers that make (methyl) acrylic acid, (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant and use as required.
For the binder polymer in the photosensitive polymer combination of the present invention, can use a kind of binder polymer separately, also can two or more binder polymer combination in any be used.
Binder polymer when two or more combinations are used; For example can enumerate two or more (the containing different monomeric units) binder polymer that forms by different copolymer compositions, the different two or more binder polymer of two or more binder polymers, dispersion degree that weight-average molecular weight is different as copolymer composition.In addition, can also use the polymkeric substance of putting down in writing in the japanese kokai publication hei 11-327137 communique that multi-modal molecular-weight distributes that has.
The containing ratio of (A) binder polymer is preferably the 20 quality %～90 quality % in the photosensitive polymer combination in the photosensitive polymer combination of the present invention, and more preferably 30 quality %～80 quality % further are preferably 40 quality～65 quality %.
If the containing ratio of binder polymer is more than the 20 quality %, the excellent tendency of film shaped property is arranged.In addition, if be below the 90 quality %, the excellent tendency of sensitivity and exploring degree is arranged.
In addition; The containing ratio of (A) binder polymer preferably is made as 30 mass parts～70 mass parts in the said photosensitive polymer combination in total amount 100 mass parts of (A) binder polymer composition and (B) polymerizable compound composition; More preferably be made as 35 mass parts～65 mass parts, especially preferably be made as 40 mass parts～60 mass parts.
Through this containing ratio is more than 30 mass parts, and film formation property further improves.In addition, through being below 70 mass parts, sensitivity and exploring degree further improve.
(B) polymerizable compound
Photosensitive polymer combination of the present invention contains at least a polymerizable compound with at least one ethene property unsaturated link.
The containing ratio of said polymerizable compound is preferably the 3 quality %～70 quality % in the photosensitive polymer combination, and more preferably 10 quality %～60 quality % further are preferably 25 quality %～50 quality %.
If the containing ratio of polymerizable compound is more than the 3 quality %, the excellent tendency of sensitivity and exploring degree is arranged.In addition, if be below the 70 quality %, the tendency that has film to have excellent formability.
Said polymerizable compound has no particular limits so long as have at least one ethene property unsaturated link and can polymeric compounds get final product.Wherein, from improve alkali-developable, exploring degree and solidify after the viewpoint of peel property consider, preferably contain at least a bisphenol A-type (methyl) acrylate compounds, more preferably contain the compound shown at least a formula (III).
[changing 3]
Figure BDA0000157806130000101
In the above-mentioned general formula (III), R 7And R 8Represent hydrogen atom or methyl independently of one another, X representes the alkylidene of carbon number 2～6 independently of one another.M and n represent to satisfy the integer of m+n=2～10.When X is two or more alkylidene ,-(X-O)-structural unit both can randomly exist, also can exist on block ground.
In the above-mentioned general formula (III), R 7And R 8All be preferably methyl.
In addition; The a plurality of X that are present in a part are the alkylidene (for example ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and hexylidene) of carbon number 2～6 independently of one another; Consider from the good viewpoint of exploring degree that makes the plating of anti-noble metal property and resist figure; X is preferably ethylidene, propylidene or isopropylidene, more preferably ethylidene.
M and n are 2 when above, and plural X adjacent in the molecule separately can be identical, also can be different.In addition, when X is two or more alkylidene ,-(X-O)-structural unit both can randomly exist, also can exist on block ground.
In addition, in the above-mentioned general formula (III), m and n are the integers that satisfies m+n=2～10.Through m+n=3～6, suppress by the swelling of the formed resist of photosensitive polymer combination that contains the compound shown in the above-mentioned general formula (III) for developer solution, so the raising of exploring degree, be preferred.In addition, through m+n=8～10, the peel property of resist further improves, and is preferred therefore.
If (m+n) be the tendency that more than 2, has the compatibility of (A) binder polymer composition and (B) polymerizable compound composition to improve.In addition, if (m+n) be below 10, have inhibition by the formed resist of photosensitive polymer combination that contains the compound shown in the above-mentioned general formula (III) for the swelling of developer solution, the tendency that adaptation further improves.
In said photosensitive polymer combination; For the compound shown in the above-mentioned general formula (III); If these two kinds of compounds combinations of the compound of the compound of m+n=3～6 and m+n=8～10 are used, then exploring degree and peel property improve with good balance, so are more preferred.
For said photosensitive polymer combination; As the compound shown in the above-mentioned general formula (III); When the compound (IIIb) of compound that contains m+n=3～6 (IIIa) and m+n=8～10, contain than (IIIa/IIIb) as it and to be preferably 1/10～1/1, more preferably 1/7～1/3.
In addition; As said bisphenol-A is (methyl) acrylate compounds; Can enumerate 2 particularly, 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, consider from the viewpoint of further raising resolution and peel property, preferred 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-.
In these, for example with regard to 2, two (4-((methyl) acryloxy dipropoxy) phenyl) propane of 2-; Can be used as BPE-200 (Xin Zhong village chemical industry (strain) make, ProductName) and be purchased, with regard to 2; Two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-; Can be used as BPE-500 (Xin Zhong village chemical industry (strain) make, ProductName) or FA-321M (Hitachi changes into industry (strain) manufacturing, ProductName) and be purchased.
These bisphenol-As system (methyl) acrylate compounds can be a kind of separately or with two or more combination in any uses.
In said photosensitive polymer combination; The containing ratio of said bisphenol-A system's (methyl) acrylate compounds (being preferably the compound shown in the general formula (III)) is preferably 30 quality %～100 quality % in the gross mass of (B) polymerizable compound composition, more preferably 50 quality %～90 quality %.Through said containing ratio is this scope, has further improved the exploring degree of resist.
In said photosensitive polymer combination; As (B) polymerizable compound composition; PAG two (methyl) acrylic ester that preferably further contains at least a molecule at least one side with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain more preferably further contains in the molecule two sides' with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain PAG two (methyl) acrylic ester.Thus, the pliability of the solidfied material of photosensitive polymer combination (cured film) improves.
In the molecule of said PAG two (methyl) acrylic ester, (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain can be separately continuously, the existence of block ground, also can randomly exist.In addition, in (gathering) oxygen isopropylidene chain, can be that the secondary carbon of isopropylidene combines with oxygen atom, also can be primary carbon combines with oxygen atom.
As said PAG two (methyl) acrylic ester, be preferably the compound shown in formula (V), general formula (VI) or the general formula (VII) especially.These can be a kind of separately or two or more combinations are used.
[changing 4]
Figure BDA0000157806130000121
In above-mentioned general formula (V), general formula (VI) and the general formula (VII), R representes hydrogen atom or methyl independently of one another, and 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 number independently of one another, the repetition sum n of oxygen propylidene 1, n 2+ n 3And n 4(mean value) is represented 1～30 number independently of one another.
In above-mentioned general formula (V), general formula (VI) and general formula (VII) in the compound shown in any, the repetition of oxygen ethylidene sum m 1+ m 2, m 3And m 4(mean value) is 1～30 number, is preferably 1～10 number, and more preferably 4～9 number is preferably 5～8 number especially.Through ading up to below 30 of this repeat number, exploring degree, adaptation and resist shape are further improved.
In addition, the repetition of oxygen propylidene sum n 1, n 2+ n 3And n 4(mean value) is 1～30 number, is preferably 5～20 number, and more preferably 8～16 number is preferably 10～14 number especially.Through ading up to below 30 of this repeat number, the exploring degree improves, and can suppress the generation of sludge (ス ラ Star ジ).
As the compound shown in the above-mentioned general formula (V), can enumerate R=methyl, m particularly 1+ m 2=6 (mean values), n 1The vinyl compound of=12 (mean values) (Hitachi changes into industry (strain) manufacturing, trade name FA-023M) etc.In addition, as the compound shown in the above-mentioned general formula (VI), can enumerate R=methyl, m particularly 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.And then, as the compound shown in the above-mentioned general formula (VII), can enumerate R=hydrogen, m particularly 4=1 (mean value), n 4The vinyl compound of=9 (mean values) (Xin Zhong village chemical industry (strain) is made, sample name NK ESTER HEMA-9P) etc.These can be a kind of separately or two or more combinations are used.
Containing ratio as said PAG two (methyl) acrylic ester among the present invention is preferably 5 quality %～50 quality % in the gross mass of (B) polymerizable compound composition, more preferably 5 quality %～15 quality %.
Through said containing ratio is more than the 5 quality %, and pliability improves.In addition, be below the 50 quality % through said containing ratio, resolution improves.
For the photosensitive polymer combination among the present invention,, can further contain said bisphenol-A system's (methyl) acrylate compounds and other polymerizable compounds beyond PAG two (methyl) acrylic ester as (B) polymerizable compound.
As other polymerizable compounds, can enumerate Nonylphenoxy and gather ethyleneoxy group acrylic ester, phthalic acid based compound, (methyl) acrylic acid multielement alcohol ester, (methyl) alkyl acrylate etc.Wherein, from improve exploring degree, adaptation, resist shape with good balance and solidify after the viewpoint of peel property consider, be preferably from Nonylphenoxy and gather select ethyleneoxy group acrylic ester and the phthalic acid based compound at least a.
Gather the ethyleneoxy group acrylic ester as said Nonylphenoxy, can enumerate for example Nonylphenoxy triethylene oxygen base acrylic ester, Nonylphenoxy four ethyleneoxy group acrylic ester, Nonylphenoxy five ethyleneoxy group acrylic ester, Nonylphenoxy six ethyleneoxy group acrylic ester, Nonylphenoxy seven ethyleneoxy group acrylic ester, Nonylphenoxy eight ethyleneoxy group acrylic ester, Nonylphenoxy nine ethyleneoxy group acrylic ester, Nonylphenoxy ten ethyleneoxy group acrylic ester, Nonylphenoxy 11 ethyleneoxy group acrylic ester.
These can be a kind of separately or two or more combination in any are used.
In addition; As the phthalic acid based compound; For example can enumerate γ-chloro-β-hydroxy propyl-Beta '-(methyl) acrylyl oxy-ethyl-phthalic ester, beta-hydroxyethyl-β '-(methyl) acrylyl oxy-ethyl-phthalic ester and β-hydroxy propyl-Beta '-(methyl) acrylyl oxy-ethyl-phthalic ester; Wherein, be preferably γ-chloro-β-hydroxy propyl-Beta '-(methyl) acrylyl oxy-ethyl-phthalic ester.For γ-chloro-β-hydroxy propyl-Beta '-methylacryoyloxyethyl-phthalic ester for, can be used as FA-MECH (Hitachi changes into industry (strain) and makes, ProductName) and be purchased.
These can be a kind of separately or two or more combinations are used.
Further; As (methyl) acrylic acid multielement alcohol ester, for example can enumerate trimethylolpropane polyethoxy three (methyl) acrylic ester, trimethylolpropane and gather propoxyl group three (methyl) acrylic ester, trimethylolpropane and gather butoxy three (methyl) acrylic ester, trimethylolpropane polyethoxy and gather propoxyl group three (methyl) acrylic ester, trimethylolethane polyethoxy three (methyl) acrylic ester, trimethylolethane and gather propoxyl group three (methyl) acrylic ester, trimethylolethane and gather butoxy three (methyl) acrylic ester, trimethylolethane polyethoxy and gather propoxyl group three (methyl) acrylic ester, pentaerythrite polyethoxy three (methyl) acrylic ester, pentaerythrite and gather propoxyl group three (methyl) acrylic ester, pentaerythrite and gather butoxy three (methyl) acrylic ester, pentaerythrite polyethoxy and gather propoxyl group three (methyl) acrylic ester, glyceryl polyethoxy three (methyl) acrylic ester, glyceryl and gather that propoxyl group three (methyl) acrylic ester, glyceryl gather butoxy three (methyl) acrylic ester, the glyceryl polyethoxy gathers propoxyl group three (methyl) acrylic ester.
These can be a kind of separately or two or more combinations are used.
For photosensitive polymer combination of the present invention; As (B) polymerizable compound, when containing other polymerizable compounds, for its containing ratio; From improve exploring degree, adaptation, resist shape with good balance and solidify after the viewpoint of peel property consider; Its containing ratio is preferably 1 quality %～30 quality % in the gross mass of (B) polymerizable compound composition, more preferably 3 quality %～25 quality % further are preferably 5 quality %～20 quality %.
(C) Photoepolymerizationinitiater initiater
Said photosensitive polymer combination comprises and contains at least a of (C-1) acylphosphine oxide based compound and (C-2) at least a Photoepolymerizationinitiater initiater of Hexaarylbiimidazole derivant.As Photoepolymerizationinitiater initiater, through containing at least two kinds of compounds, sensitivity, exploring degree improve, and then the resist shape is also good.In addition, diminish, therefore handle tolerance and broaden, well with respect to the variation of the line width values of the resist figure of exposure.
In said photosensitive polymer combination, the containing ratio of said Photoepolymerizationinitiater initiater is preferably 0.1 quality %～20 quality % in the gross mass of photosensitive polymer combination, and more preferably 1 quality %～10 quality % further are preferably 3 quality %～7 quality %.
If the containing ratio of Photoepolymerizationinitiater initiater is more than the 0.1 quality %, the tendency that can access sufficient sensitivity, exploring degree is arranged.In addition, if be below the 20 quality %, the tendency that has the film formability to improve.
As said (C-1) acylphosphine oxide based compound, be preferably the compound shown in formula (I) or the general formula (II).
[changing 5]
Figure BDA0000157806130000151
In the general formula (I), R 1, R 2And R 3The alkyl or aryl of representing carbon number 1～20 independently of one another.In the general formula (II), R 4, R 5And R 6The alkyl or aryl of representing carbon number 1～20 independently of one another.
R in the general formula (I) 1, R 2Or R 3When being 1～20 alkyl, this alkyl can be any one in straight chain shape, branched and the ring-type.In addition, the carbon number of this alkyl more preferably 5～10.In addition, the R in the general formula (II) 4, R 5Or R 6During for the alkyl of carbon number 1～20, this alkyl can be any one in straight chain shape, branched and the ring-type.In addition, the carbon number of this alkyl more preferably 5～10.
R in the general formula (I) 1, R 2Or R 3During for aryl, this aryl can have or not have substituting group.As this substituting group, can enumerate the for example alkyl of carbon number 1～6 and the alkoxy of carbon number 1～4.In addition, the R in the general formula (II) 4, R 5Or R 6During for aryl, this aryl can have or not have substituting group.As this substituting group, for example can enumerate the alkyl of carbon number 1～6 and the alkoxy of carbon number 1～4.
As the compound shown in the general formula (II), can enumerate for example two (2,6-dimethoxy benzoyl)-2,4 particularly, 4-trimethyl-amyl group phosphine oxide.Compound shown in said general formula (I) or the general formula (II) can be a kind of separately or two or more combinations is used.
Said (C-1) acylphosphine oxide based compound is preferably the compound shown in above-mentioned general formula (I) or the general formula (II), more preferably the compound shown in formula (VIII) or the general formula (IX).
[changing 6]
Figure BDA0000157806130000161
In the above-mentioned general formula (VIII), R 11, R 12And R 13Represent the alkyl of carbon number 1～6 or the alkoxy of carbon number 1～4 independently of one another, p1, p2 and p3 represent 0～5 integer independently of one another.P1, p2 or p3 are 2 when above, the R of a plurality of existence 11, R 12And R 13Can be the same or different separately.
As the alkyl of above-mentioned carbon number 1～6, can enumerate for example methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group, hexyl.As the alkoxy of above-mentioned carbon number 1～4, can enumerate for example methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, tert-butoxy.
R 11Be preferably the alkyl of carbon number 1～4, more preferably methyl.P1 is preferably 1～4 integer, and more preferably 3.In addition, p2 and p3 are preferably 0.
[changing 7]
Figure BDA0000157806130000171
In the above-mentioned general formula (IX), R 14, R 15And R 16Represent the alkyl of carbon number 1～6 or the alkoxy of carbon number 1～4 independently of one another, q1, q2 and q3 represent 0～5 integer independently of one another.Q1, q2 or q3 are 2 when above, the R of a plurality of existence 14, R 15And R 16Can be the same or different separately.
As the alkyl of above-mentioned carbon number 1～6, can enumerate for example methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group, hexyl.As the alkoxy of above-mentioned carbon number 1～4, can enumerate for example methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, tert-butoxy.
R 14And R 15Be preferably the alkyl of carbon number 1～4 independently of one another, more preferably methyl.Q1 and q2 are preferably 1～4 integer, and more preferably 3.In addition, q3 is preferably 0.
As the compound shown in the above-mentioned general formula (VIII), consider from the viewpoint of more effectively improving sensitivity and resist shape, be preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.For 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide for example can be used as DAROCUR-TPO (BASF Japanese firm make, trade name) and is purchased.
In addition,, consider, be preferably two (2,4, the 6-trimethylbenzoyl)-phenylphosphine oxide from the viewpoint of more effectively improving sensitivity and resist shape as the compound shown in the above-mentioned general formula (IX).For two (2,4, the 6-trimethylbenzoyl)-phenylphosphine oxide, for example can be used as IRGACURE-819 (BASF Japanese firm make, trade name) and be purchased.
Above-mentioned general formula (VIII) among the present invention or the compound shown in the general formula (IX) can be a kind of separately or two or more combinations are used.
In said photosensitive polymer combination, the containing ratio of these (C-1) acylphosphine oxide based compounds is preferably 20 quality %～60 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater, more preferably 30 quality %～45 quality %.
As said (C-2) Hexaarylbiimidazole derivant, from improving the viewpoint consideration of sensitivity and adaptation, preferably contain at least a 2,4,5-triarylimidazoles dipolymer.Said 2,4, the structure of 5-triarylimidazoles dipolymer can be symmetry also can be asymmetric.
As said 2,4,5-triarylimidazoles dipolymer; Can enumerate for example 2-(Chloro-O-Phenyl)-4; 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-two-(m-methoxyphenyl) imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer.Wherein, be preferably 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.
In said photosensitive polymer combination,, be preferably 30 quality %～70 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater composition, more preferably 45 quality %～65 quality % as the containing ratio of said (C-2) Hexaarylbiimidazole derivant.
In said photosensitive polymer combination, (C-1) the acylphosphine oxide based compound has no particular limits with respect to the ratio (C-1/C-2) that contains of (C-2) Hexaarylbiimidazole derivant.Consider that from the viewpoint of sensitivity, exploring degree and adaptation the said ratio (C-1/C-2) that contains is preferably 0.1～0.9, more preferably 0.3～0.9, further be preferably 0.5～0.8.
Said photosensitive polymer combination can further contain other Photoepolymerizationinitiater initiaters beyond said acylphosphine oxide based compound and the Hexaarylbiimidazole derivant.As other Photoepolymerizationinitiater initiaters, can enumerate 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-morpholino-acetone-1 grade; Quinones such as alkyl-anthraquinone, benzoin ether compounds such as benzoin alkylether, benzoin compounds such as benzoin, alkyl benzene acyloin; Benzil derivants such as benzil dimethyl ketal; 9-phenylacridine, 1, acridine derivatives such as 7-(9,9 '-acridinyl) heptane.
These can be a kind of separately or two or more combinations are used.
The content of the composition of (C) Photoepolymerizationinitiater initiater in the said photosensitive polymer combination; Be preferably 0.1 mass parts～10 mass parts with respect to (A) binder polymer composition and (B) total amount 100 mass parts of polymerizable compound composition; 1 mass parts～7 mass parts more preferably; Further be preferably 2 mass parts～6 mass parts, be preferably 3 mass parts～5 mass parts especially.
Content through said Photoepolymerizationinitiater initiater is more than 0.1 mass parts, and sensitivity, exploring degree and adaptation further improve.In addition, through being below 10 mass parts, can obtain more excellent resist shape.
Said photosensitive polymer combination is preferred: the containing ratio of said binder polymer is 20 quality %～90 quality %; The containing ratio of said polymerizable compound is 3 quality %～70 quality %, and the containing ratio of said Photoepolymerizationinitiater initiater is 0.1 quality %～20 quality %.
More preferably: the containing ratio of said binder polymer is 30 quality %～80 quality %, and the containing ratio of said polymerizable compound is 10 quality %～60 quality %, and the containing ratio of said Photoepolymerizationinitiater initiater is 1 quality %～10 quality %.
Further preferably: the containing ratio of said binder polymer is 40 quality %～65 quality %, and the containing ratio of said polymerizable compound is 25 quality %～50 quality %, and the containing ratio of said Photoepolymerizationinitiater initiater is 3 quality %～7 quality %.
Said photosensitive polymer combination preferably further contains (D) sensitizing coloring matter.Thus, the curing sensitivity of photosensitive polymer combination is better.
As (D) sensitizing coloring matter, can enumerate for example dialkyl amido benzophenone, pyrazolines, anthracene class, Coumarins, xanthene ketone, oxazole class, Benzooxazole kind, thiazoles, benzothiazoles, triazole type, Stilbene class, triazines, thiophene-based, naphthalimide class, triaryl amine.These can use separately or with two or more combinations.
Especially; When carrying out the exposure of photo-sensitive resin with the active ray of 390nm～420nm; Consider from the viewpoint of sensitivity and adaptation; (D) sensitizing coloring matter preferably contains from the group that pyrazolines, anthracene class, Coumarins and triaryl amine are formed, select at least a, wherein, more preferably contains from the group that pyrazolines, anthracene class and triaryl amine are formed, select at least a.
(D) content of sensitizing coloring matter is with respect to (A) binder polymer composition and (B) total amount 100 mass parts of polymerizable compound composition; Preferably be made as 0.01 mass parts～10 mass parts; More preferably be made as 0.05 mass parts～5 mass parts, further preferably be made as 0.1 mass parts～3 mass parts.
Content through said (D) sensitizing coloring matter is more than 0.01 mass parts, and sensitivity and exploring degree further improve.In addition, through being below 10 mass parts, having suppressed the resist shape and become trapezoidally, adaptation improves.
Said photosensitive polymer combination preferably further contains (E) amine compound.Thus, the sensitivity of photosensitive polymer combination is better.
As said (E) amine compound, can enumerate for example two [4-(dimethylamino) phenyl] methane, two [4-(lignocaine) phenyl] methane, leuco crystal violet.These can be a kind of separately or two or more combinations are used.
When said photosensitive polymer combination contains (E) amine compound; Its content is with respect to (A) binder polymer composition and (B) total amount 100 mass parts of polymerizable compound composition; Preferably be made as 0.01 mass parts～10 mass parts; More preferably be made as 0.05 mass parts～5 mass parts, especially preferably be made as 0.1 mass parts～2 mass parts.
Content through said (E) amine compound is that sensitivity further improves more than 0.01 mass parts.In addition, through being below 10 mass parts, can suppressing film and form superfluous (E) amine compound composition in back and separate out as foreign matter.
For said photosensitive polymer combination,, can also contain other compositions as required except mentioned component.As other compositions, can enumerate dyestuff, tribromo-benzene sulfone, light developer, heat colour developings such as the optical polymerism compound (oxetane compound etc.) that has the ring-type ether of at least one cationically polymerizable in the molecule for example, cationic polymerization initiators, peacock green and prevent plastifier, pigment, filling agent, foam-breaking agent, fire retardant, stabilizing agent, adaptation imparting agent, levelling agents such as agent, para toluene sulfonamide, peel off promoter, anti-oxidant, spices, developer, thermal cross-linking agent.
These can be a kind of separately or two or more combinations are used.
In addition, the content of these other compositions preferably is made as about 0.01 mass parts～20 mass parts with respect to (A) binder polymer composition and (B) total amount 100 mass parts of polymerizable compound composition separately.
Said photosensitive polymer combination can contain at least a organic solvent.As said organic solvent, can use normally used organic solvent, not special restriction.Can enumerate for example methyl alcohol, ethanol, acetone, MEK, methyl cellosolve, ethyl cellosolve, toluene, N particularly, dinethylformamide, propylene glycol monomethyl ether and these mixed solvent.
For example, can said (A) binder polymer, (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater be dissolved in the said organic solvent, form solid constituent and be solution about 30 quality %～60 quality % (below be called " coating fluid ") and use.
Here, so-called solid constituent, the meaning is from said solution (photosensitive polymer combination), to remove residual composition behind the volatile ingredient.
Said coating fluid for example can be used to be described below form photo-sensitive resin suchly.On the surface of supporters such as the support membrane through stating after said coating fluid is coated, sheet metal and dry, can on supporter, form the photo-sensitive resin that comes from said photosensitive polymer combination.
As sheet metal, can enumerate iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, preferably can enumerate copper, copper series alloy, iron-based alloy etc.
The thickness of formed photo-sensitive resin is according to its purposes and difference, but preferably counts about 1 μ m～100 μ m with dried thickness.Also can cover face (surface) photo-sensitive resin and the opposition side supporter opposite face with diaphragm.As diaphragm, can enumerate polymer films such as tygon, polypropylene etc.
The manufacturing approach of the resist figure that said photosensitive polymer combination is stated after for example can being used for aptly.Wherein, be applicable to the manufacturing approach of handling the formation circuit through plating.
< photosensitive element >
For photosensitive element 10 of the present invention; The fragmentary cross sectional view of an one of which example that goes out as shown in Figure 1 constitutes and possesses supporter 2 and the photo-sensitive resin of filming 4 that is formed at the said photosensitive polymer combination of conduct on the said supporter, possesses as required and other layers such as diaphragm 6 of being provided with.
As said supporter, can use polyethylene terephthalate, polypropylene, tygon, polyester etc. to have the polymer film of thermotolerance and solvent resistance.
The thickness of said supporter (below be sometimes referred to as " support membrane ") is preferably 1 μ m～100 μ m, and more preferably 5 μ m～50 μ m further are preferably 5 μ m～30 μ m.Through the thickness that makes supporter is that support membrane breaks in the time of can suppressing to peel off support membrane more than the 1 μ m.In addition, through being below the 100 μ m, can suppressing the exploring degree and reduce.
Said photosensitive element 10 can also further possess the diaphragm 6 of the face (surface) that covers photo-sensitive resin 4 and opposition sides supporter 2 opposite faces as required.
As said diaphragm, be preferably bonding force to photo-sensitive resin less than the diaphragm of support membrane to the bonding force of photo-sensitive resin, in addition, the few film of shrinkage cavity (fish eye) is preferred.
Here, so-called " shrinkage cavity " meaning is: will constitute the material heat fusing of diaphragm, through mixing, extrude, during manufacturing film such as biaxial stretch-formed, casting method, 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, can use polyethylene terephthalate, polypropylene, tygon, polyester etc. to have the polymer film of thermotolerance and solvent resistance as diaphragm.As commercially available diaphragm, can enumerate polyethylene terephthalate films such as PS series such as the polypropylene screen of the ALPHAN MA-410, E-200C, SHIN-ETSU HANTOTAI's film manufactured etc. of Oji Paper manufactured, the PS-25 of Supreme Being people's manufactured etc.Here, diaphragm can be identical with said supporter.
The thickness of diaphragm is preferably 1 μ m～100 μ m, and more preferably 5 μ m～50 μ m further are preferably 5 μ m～30 μ m, are preferably 15 μ m～30 μ m especially.Thickness through diaphragm is more than the 1 μ m, Yi Bian peeling off diaphragm, Yi Bian when being laminated to photo-sensitive resin and support membrane on the substrate, can suppressing diaphragm and break.In addition, through being below the 100 μ m, improved throughput rate.
Said photosensitive element can be for example by the manufacturing that is described below.Can be through following method manufacturing; It comprises: (A) binder polymer, (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater are dissolved in the organic solvent; The step of the coating fluid about preparation solid constituent 30 quality %～60 quality %; Said coating fluid is coated on the supporter and forms the step of coating layer, and said coating layer is dry and form the step of photo-sensitive resin.
The coating of said coating fluid on supporter for example can be carried out through roll coater, unfilled corner wheel coating machine, intaglio plate coating machine, Kohler coater, die coater, these known method of scraping strip coating machine.
In addition, the part organic solvent gets final product the drying of said coating layer so long as can remove at least from coating layer, not special restriction.For example preferably carry out about 5 minutes～30 minutes at 70 ℃～150 ℃.After the drying, the remaining organic solvent amount in the photo-sensitive resin, the viewpoint of organic solvent diffusion is considered from prevent subsequent handling, preferably is made as below the 2 quality %.
The thickness of the photo-sensitive resin in the said photosensitive element can suitably be selected according to purposes, is preferably 1 μ m～100 μ m in dried thickness, and more preferably 1 μ m～50 μ m further are preferably 5 μ m～40 μ m.
Thickness through photo-sensitive resin is more than the 1 μ m, and industrial coated becomes easily, throughput rate improves.In addition, through being below the 100 μ m, adaptation and exploring degree improve.
For said photo-sensitive resin as far as ultraviolet ray transmissivity, be preferably 5%～75% for the ultraviolet ray of wavelength 365nm, more preferably 10%～65%, be preferably 15%～55% especially.
Through this transmitance is that adaptation further improves more than 5%.In addition, be below 75% through transmitance, the exploring degree further improves.Here, above-mentioned transmitance can be measured through the UV spectrometer.As the UV spectrometer, can enumerate the 228A type W rays spectrophotometer that the Hitachi makes.
Said photosensitive element can also further have known middle layers such as cushion, adhesive linkage, light absorbing zone, gas barrier layer etc. as required.
The not special restriction of the form of said photosensitive element.For example can be sheet, perhaps can be the state that on the volume core, is wound into the roller shape.
Be wound under the situation of roller shape, the mode outside preferably becoming according to support membrane is reeled.
As the volume core, can enumerate polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin plastics such as (acrylonitrile-butadiene-styrene copolymers) etc.At the end face of the roller shape photosensitive element roller that obtains like this, consider from the position of protection end face, the end face dividing plate preferably is set, consider from the position on refractory limit, damp proof end face dividing plate preferably is set.In addition, as bundling method, preferably wrap in the little black sheet of moisture-penetrability (Black sheet) and pack.
Said photosensitive element is applicable to the manufacturing approach of the resist figure of stating after for example.Wherein, be fit to be applied to handle the manufacturing approach that forms circuit through plating.
< manufacturing approach of resist figure >
The manufacturing approach of resist figure of the present invention possesses: (i) on substrate, form photo-sensitive resin as the photo-sensitive resin of filming of said photosensitive polymer combination and form operation, (ii) at least a portion irradiation active ray of above-mentioned photo-sensitive resin made the exposure process of its photocuring the and (iii) uncured portion of said photo-sensitive resin is removed and formed the developing procedure of the resist figure that is made up of the solidfied material that comes from said photo-sensitive resin from substrate, can comprise other operation as required and constitute.
(i) photo-sensitive resin forms operation
Form in the operation at photo-sensitive resin, on substrate, form the photo-sensitive resin of filming as said photosensitive polymer combination.As the not special restriction of said substrate, can use the circuit that possesses insulation course and be formed at the conductor layer on the insulation course to form usually with lower bolsters such as substrate or alloy base material (die pad) (lead frame is used base material).
As the method that on substrate, forms photo-sensitive resin, for example, can in heating, be crimped on aforesaid substrate and carry out through remove behind the diaphragm photo-sensitive resin with photosensitive element from said photosensitive element.Thus, can access the duplexer that comprises that substrate, photo-sensitive resin and supporter and these stack gradually.
This photo-sensitive resin forms operation, considers from the position of adaptation and tracing ability, preferably under reduced pressure carries out.The heating of photo-sensitive resin and/or substrate is preferably carried out under 70 ℃～130 ℃ temperature during crimping.In addition, the preferred (1kgf/cm about 0.1MPa～1.0MPa of crimping 2～10kgf/cm 2About) pressure under carry out, but these conditions can suitably be selected as required.Here, if photo-sensitive resin is heated to 70 ℃～130 ℃, it is optional then in advance substrate to be carried out thermal pretreatment, but in order further to improve adaptation and tracing ability, also can carry out the thermal pretreatment of substrate.
(ii) exposure process
In exposure process,, formed sub-image by the part photocuring of active ray irradiation through to being formed at least a portion irradiation active ray of the photo-sensitive resin on the substrate.
At this moment; Supporter (support membrane) being present on the photo-sensitive resin is under the situation of permeability to active ray; Can see through support membrane irradiation active ray, be under the situation of light-proofness when support membrane, removes behind the support membrane photo-sensitive resin irradiation active ray.
As exposure method, can enumerate the method (mask exposure method) that active ray is the irradiation of image shape ground across the negative or positive mask pattern shape that is called as wiring diagram (ART WORK).In addition; Also can adopt (Laser Direct Imaging through LDI; Laser direct imaging) exposure method, DLP (Digital Light Processing, digit optical is handled) exposure method etc. are directly drawn the method that exposure method is active ray the irradiation of image shape ground.
As the light source of active ray, can use known light source, for example can use carbon arc lamp; The mercury vapour arc lamp; High-pressure sodium lamp, xenon lamp effectively radiates the light source of ultraviolet rays such as Solid State Laser, semiconductor lasers such as gas laser, YAG laser such as argon laser, visible light.
(iii) developing procedure
In developing procedure, through the uncured portion of said photo-sensitive resin is removed the resist figure that the solidfied material that formation is formed by said photo-sensitive resin photocuring on substrate constitutes from substrate.
Under the situation that has support membrane on the photo-sensitive resin, remove support membrane after, carry out the removing of unexposed portion (development) beyond the above-mentioned exposed portion.Wet developing and dry process development are arranged in developing method, and wet developing is widely used.
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 use impregnation method, revolve the submergence mode of covering (バ ト Le mode), spray pattern, scrub mode, beating (slapping), blade coating (scrapping), the method for shaking impregnating; Consider that from the viewpoint that improves the exploring degree high-pressure fog mode is the most suitable.Also can the two or more combinations in these methods be developed.
The formation of developer solution can suitably be selected according to the formation of said photosensitive polymer combination.For example can enumerating, alkaline aqueous solution, water system developer solution and organic solvent are developer solution.
When alkaline aqueous solution is used as developer solution, safety and stable, operability is good.Alkali as alkaline aqueous solution; Can use the alkali hydroxides such as oxyhydroxide of lithium, sodium or potassium, carbonic acid alkali such as the carbonate of lithium, sodium, potassium or ammonia or supercarbonate, alkali metal phosphates such as potassium phosphate, sodium phosphate; Alkali metal pyrophosphate 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, a spot ofly be used to promote organic solvent that develops etc.
The water system developer solution is the developer solution for being made up of water or alkaline aqueous solution and more than one organic solvent for example.Here; As the alkali of alkaline aqueous solution, except foregoing material, can also enumerate for example borax, sodium silicate, TMAH, monoethanolamine, ethylenediamine, diethylene triamine, 2-amino-2-methylol-1; Ammediol, 1,3-diamino-propanol-2 and morpholine etc.
The pH of water system developer solution preferably is made as in the scope that can fully develop as far as possible little, preferably is made as pH8～12, more preferably is made as pH9～10.
As the organic solvent that is used for the water system developer solution, can enumerate acetone, ethyl acetate, have alkoxyethanol, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, TC and the diethylene glycol single-butyl ether etc. of the alkoxy of carbon number 1～4.These can use separately or with two or more combinations.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, can enumerate 1,1,1-trichloroethanes, N-Methyl pyrrolidone, N, organic solvents such as dinethylformamide, cyclohexanone, methyl isobutyl ketone and gamma-butyrolacton.On fire for preventing, preferably the scope with 1～20 quality % is added water in these organic solvents.
In the present invention, in developing procedure, remove unexposed portion after, can also carry out heating or the 0.2J/cm about 60 ℃～250 ℃ as required 2～10J/cm 2About exposure, thereby the resist figure is further solidified.
< manufacturing approach of lead frame >
The manufacturing approach of lead frame of the present invention constitutes: comprise the substrate that the manufacturing approach through above-mentioned resist figure is formed with the resist figure and carry out plating and handle the operation that forms conductor fig, comprise resist as required and remove other operations such as operation, etch processes operation.
As said substrate, can use lower bolsters (lead frame is used base material) such as alloy base material.
In the present invention, can supporter be carried out plating handle being formed at resist figure on the supporter as mask.
As the method that plating is handled, can be that electrolytic coating is handled, also can be that electroless plating covers processing, but preferred electroless plating cover processing.Cover processing as electroless plating, can enumerate for example golden plating such as nickel plating such as scolding tin plating such as copper such as copper sulphate plating, cupric pyrophosphate plating plating, high evenly scolding tin (high-throw solder) plating, watt bath (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid plating, hard gold plating, soft golden plating.
After said plating was handled, the resist figure on the supporter was removed.For example removing of resist figure can be peeled off through the stronger alkaline aqueous solution of alkaline aqueous solution that uses than said developing procedure.As this alkaline WS, can use for example 1 quality %～10 quality % sodium hydrate aqueous solutions, 1 quality %～10 quality % potassium hydroxide aqueous solutions etc.
Wherein, preferably use 1 quality %～10 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solutions, more preferably use 1 quality %～5 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solutions.
As the mode of peeling off of resist figure, can enumerate impregnation method, spray pattern etc., these can use separately, also can and use.
After removing the resist figure, can remove unwanted metal level and make lead frame through further carrying out etch processes.
The metal level that the method for etch processes can be removed as required and suitably selecting.For example,, can enumerate copper chloride solution, ferric chloride solution, alkaline etching solution and hydrogen peroxide etching solution, in these, consider, preferably use ferric chloride solution from the aspect that etching factor (etch factor) is good as etching solution.
< manufacturing approach of printed-wiring board (PWB) >
The manufacturing approach of printed-wiring board (PWB) of the present invention constitutes: comprise the substrate that the manufacturing approach through said resist figure is formed with the resist figure and carry out plating and handle the operation that forms conductor fig, comprise resist as required and remove other operations such as operation, etch processes operation.
In the present invention, can be with being formed at resist figure on the substrate as mask, carry out plating and handle being arranged at conductor layer on the substrate.
Method, the method for removing of resist figure, etch processes that plating in the manufacturing approach of printed-wiring board (PWB) is handled are identical with the manufacturing approach of said lead frame.
According to the printed-wiring board (PWB) that the manufacturing approach of printed-wiring board (PWB) of the present invention is made, can be multilayer printed circuit board, in addition, can also have the minor diameter through hole.
In addition, said printed-wiring board (PWB) also can carry out the manufacturing approach that etch processes forms the operation of conductor fig and makes through comprising the substrate that the manufacturing approach through said resist figure is formed with the resist figure.
In this manufacturing approach, can carry out etch processes to the conductor layer that is arranged on the substrate with being formed at resist figure on the substrate as mask.
Japanese publication 2010-173083 number disclosed full content introduced this instructions through reference.
For whole documents, patented claim and the technical standard put down in writing in this instructions, each document, patented claim and technical standard through with reference to the situation with specifically and respectively record incorporated into degree ground, through with reference to incorporating this instructions into.
Embodiment
Below through embodiment the present invention is described particularly, but the present invention is not limited by these embodiment.Here, short of special prior statement, " part " and " % " is quality criteria.
< synthetic example >
(synthesizing of binder polymer (A-1))
Will be as methacrylic acid 150g, benzyl methacrylate 125g, methyl methacrylate 25g and the styrene 200g (mass ratio 30/25/5/40) of polymerizable monomer (monomer), 9.0g mixes with azoisobutyronitrile, preparation solution a.
Azoisobutyronitrile 1.2g is dissolved among mixed liquor (mass ratio 3: the 2) 100g of methyl cellosolve 60g and toluene 40g preparation solution b.
In the flask that possesses stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, drop into mixed liquor (mass ratio 3: the 2) 450g of methyl cellosolve 270g and toluene 180g, the limit is blown into the stirring of nitrogen limit in flask, heat temperature raising to 80 ℃.
After dripping above-mentioned solution a in 4 hours above-mentioned mixed liquors in flask, while stirring 80 ℃ of insulations 2 hours.Then, after dripping above-mentioned solution b in the solution in 10 fens clockwise flasks, the solution limit in the stirred flask of limit was 80 ℃ of insulations 3 hours.And then the solution in the flask is warming up to 90 ℃ with 30 minutes, 90 ℃ of insulation coolings after 2 hours down, obtain the solution 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 196mg KOH/g.Here, weight-average molecular weight is measured through gel permeation chromatography (GPC) and is used the typical curve of polystyrene standard to convert and derive.The condition of GPC is as shown in following.
The GPC condition
Pump: the L-6000 of Hitachi type (manufacturing of (strain) Hitachi)
Chromatographic column: amount to following three
Gelpack?GL-R420
Gelpack?GL-R430
Gelpack GL-R440 (above 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 (manufacturing of (strain) Hitachi)
(synthesizing of binder polymer (A-2)～(A-6))
In binder polymer (A-1) synthetic; As polymerizable monomer (monomer); Except using with the mass ratio shown in the identical table the material shown in the below table 1, with the solution that obtains binder polymer (A-1) likewise, obtain the solution of binder polymer (A-2)～(A-6) respectively.
Table 1
Figure BDA0000157806130000281
< embodiment 1～11 and comparative example 1～4 >
[preparation of photosensitive polymer combination]
Use the C-1A shown in the B-1～B-4 shown in the above-mentioned A-1～A-6 that obtains as (A) binder polymer, conduct (B) polymerizable compound following, conduct (C) Photoepolymerizationinitiater initiater following, C-1B, C-2 respectively, as the composition shown in other compositions following; Mix according to the use level shown in the below table 2 (cooperation umber), prepare the photosensitive polymer combination of embodiment 1～11 and comparative example 1～4 thus respectively.Here, the use level (cooperation umber) of (A) binder polymer shown in the table 2 is the quality (solid constituent amount) of nonvolatile component.
(B) optical polymerism compound
B-1:2, two (4-(methacryloxy five ethoxys) phenyl) propane of 2-[FA-321M (Hitachi changes into industry (strain) manufacturing, ProductName)]
B-2:2, two (4-((methyl) acryloxy dipropoxy) phenyl) propane of 2-[BPE-200 (Xin Zhong village chemical industry (strain) is made, ProductName)]
B-3: in above-mentioned general formula (V), R=methyl, m 1+ m 2=6 (mean values), n 1The compound of=12 (mean values) [FA-023M (Hitachi changes into industry (strain) manufacturing, ProductName)]
B-4: in above-mentioned general formula (VI), R=methyl, m 3=6 (mean values), n 2+ n 3The compound of=12 (mean values) [FA-024M (Hitachi changes into industry (strain) manufacturing, ProductName)]
(C) Photoepolymerizationinitiater initiater
C-1A:2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCUR-TPO (BASF Japanese firm makes, trade name)]
C-1B: two (2,4, the 6-trimethylbenzoyl)-phenylphosphine oxide [IRGACURE-819 (BASF Japanese firm makes, trade name)].
C-2A:2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole [B-CIM (Hampford manufactured, trade name)]
(D) sensitizing coloring matter
D-1:4,4 '-two (lignocaine) benzophenone
(E) amine compound
E-1: leuco crystal violet [LCV (hillside plot chemical company makes, trade name)]
Dyestuff
MKG (organic chemistry industrial group in Osaka makes, trade name): peacock green
Table 2
Figure BDA0000157806130000301
< preparation of photosensitive element >
The above-mentioned photosensitive polymer combination that obtains is evenly coated the polyethylene terephthalate film that thickness is 16 μ m respectively, and (Supreme Being people's (strain) makes; ProductName " HTF-01 ") on; Hot air convection formula dryer with 70 ℃ and 110 ℃ is dry, has formed the photo-sensitive resin that dried thickness is 25 μ m.
On this photo-sensitive resin, fitting, (TAMAPOLY (strain) makes diaphragm; ProductName " NF-15 "), the photosensitive element P1～P11 and the P1c～P4c of polyethylene terephthalate film (support membrane), photo-sensitive resin and diaphragm have been obtained stacking gradually respectively.
< making of duplexer >
Copper Foil is arranged (thickness: glass epoxide material 35 μ m) is a copper-clad laminated board (substrate the two sides is range upon range of; Hitachi changes into industrial group and makes; Trade name " MLC-E-679 ") (MEC A/S makes with surface roughening treating fluid " MEC etchBOND CZ-8100 "; Trade name) carry out surface treatment, after washing, pickling and the washing, dry with airflow.Surface-treated copper-clad laminated board is heated to 80 ℃, when peeling off diaphragm, so that photo-sensitive resin contacts the surperficial mode of the copper above-mentioned photosensitive element that obtains of lamination respectively.Thus, obtained stacking gradually the duplexer of copper-clad laminated board, photo-sensitive resin, support membrane respectively.Be used as test film in the test of resulting duplexer shown in following.
Here, lamination uses 120 ℃ hot-rolling to carry out with the roller speed of the crimping pressure of 0.4MPa, 1.0m/ minute.
< evaluation >
(luminous sensitivity determination test)
On the support membrane of the above-mentioned test film that obtains; Placement is as the optical tool (photo tool) of 41 sections stage metraster with concentration range 0.00～2.00, concentration stage 0.05, table (tablet) big or small 20mm * 187mm, big or small 3mm * 12mm of being of each stage of negative mask; With having exposure machine (ORC (the オ one Network) manufactured of high-pressure sodium lamp; Trade name " EXM-1201 "), think 70mJ/cm 2The irradiation energy amount photo-sensitive resin is made public.
Then, peel off support membrane,, remove unexposed portion, carry out development treatment with 1 quality % aqueous sodium carbonate of 30 ℃ of the time spray development of the twice of minimum development time (removing the minimum time of unexposed portion).
After the development treatment, the hop count of the stage metraster through measuring the photocuring film that forms on the substrate is estimated the luminous sensitivity of photosensitive polymer combination.Luminous sensitivity representes that with the hop count of stage metraster the hop count of this stage metraster is high more, representes that then luminous sensitivity is high more.The result is shown in table 3.
(determination test of exploring degree and adaptation)
In order to check exploring degree and adaptation; To use the live width/line-spacing that has of negative film as the adaptation evaluation is that 2/2～30/30 (unit: the glass chromium type optical tool driving fit of line pattern μ m) is on the support membrane of the above-mentioned test film that obtains; Use has the exposure machine of high-pressure sodium lamp, is that 14 sections energy fluence makes public to the photo-sensitive resin of above-mentioned duplexer with the remaining hop count of 41 sections stage metraster.After the exposure, carry out and the identical development treatment of above-mentioned luminous sensitivity determination test.
After the development treatment, removed fully and line part (exposure portion) does not produce in the resist figure of distortion, damaged and formation, through live width/line-spacing value evaluation exploring degree adaptation of minimum in gap (unexposed portion).More little exploring degree and the adaptation of then meaning of this numerical value is all good more.The result is shown in table 3.
(evaluation of resist shape)
In the evaluation of above-mentioned exploring degree adaptation, resulting resist shape (cross sectional shape of resist figure) is observed with the electron scanning type microscope S-500A of Hitachi.
Be shaped as trapezoidal or fall under the trapezoidal situation, exist under the situation of crimping or crackle of resist at resist,, the tendency of the short circuit of being easy to generate, broken string is arranged handling in the circuit that forms through thereafter etch processes or plating.Therefore, hope that the resist shape is rectangle (rectangle) and crimping or the crackle that does not have resist.The result is shown in table 3.
Here, so-called " crackle ", the meaning is to chap, chap in line part (exposed portion) generation of resist figure, perhaps follows its online part to produce damaged, fracture.
(evaluation of the live width precision of resist)
For estimating the live width precision of resist; To use the live width/line-spacing that has of negative film as the evaluation of exploring degree is that 10/10 (unit: the glass chromium type optical tool driving fit of line pattern μ m) is on the support membrane of the above-mentioned test film that obtains; Use has the exposure machine of high-pressure sodium lamp, is that the energy fluence of 14 sections and 17 sections makes public to the photo-sensitive resin of above-mentioned duplexer with the remaining hop count of 41 sections stage metraster.After the exposure, carry out and the identical development treatment of above-mentioned luminous sensitivity determination test.
For resulting resist figure, measure the line width values of resist topmost with the electron scanning type microscope S-500A of Hitachi.Here, line width values near 10 μ m values, representes that then the live width precision is high more more.The result is shown in table 3.
(evaluation of peel property)
Test film is cut into the tetragonal size of 40mm * 50mm, is that 14 sections energy fluence carries out blanket exposure to the photo-sensitive resin of above-mentioned duplexer with the remaining hop count of 41 sections stage metraster.After the exposure, carry out and the identical development treatment of above-mentioned luminous sensitivity determination test.
With each test film of the peel property evaluation usefulness that obtains like this, in 50 ℃ 3 quality % sodium hydrate aqueous solutions, with stirrer stir on one side and flood resist surface through visualization each test film on one side.
To begin to peel off fully time of removing as splitting time from stirring to cured film from substrate.
In addition, the size of the stripping film after visualization is peeled off is estimated according to following metewand.Splitting time is shorter, the stripping film size is more little, means that then peel property is good more.The result is shown in Fig. 3.
～metewand～
L: stripping film is of a size of sheet.
M: it is above and square less than 40mm that stripping film is of a size of 30mm.
S: the stripping film size is square littler than 30mm.
Table 3
Figure BDA0000157806130000331
Can clearly be seen that by table 3, by sensitivity, exploring degree, adaptation, the resist shape of the photosensitive element of the photosensitive polymer combination of embodiment 1～11 preparation and the peel property after solidifying all excellent.
In addition, the line width values when the remaining hop count of 41 sections stage metraster is 14 sections is near 10 μ m, even exposure is increased to 17 sections, the variable quantity of line width values is also little.
On the other hand, all poor by the live width precision or the peel property of the exploring degree of the photosensitive element of the photosensitive polymer combination of comparative example 1～2 preparation, adaptation, resist shape, resist.
In addition, low by the luminous sensitivity of the photosensitive element of the photosensitive polymer combination of comparative example 3～4 preparation, can not form figure.
Industrial applicibility
Photosensitive polymer combination of the present invention is suitable for the material as the resist figure that is formed for making printed-wiring board (PWB).Especially; The sensitivity of above-mentioned photosensitive polymer combination, exploring degree, adaptation, resist shape and solidify after peel property all excellent, therefore also can be suitable for use in and be formed for making the resist figure of wiring board that high-density packages substrate etc. has the circuit of graph thinning densification.
Symbol description
2 supporters
4 photo-sensitive resins
6 diaphragms
10 photosensitive elements

Claims (8)

1. photosensitive polymer combination; It contains (A) binder polymer, (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater; Should (A) binder polymer have and come from (methyl) acrylic acid structural unit and come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant; Should have at least one ethene property unsaturated link by (B) polymerizable compound, should contain acylphosphine oxide based compound and Hexaarylbiimidazole derivant by (C) Photoepolymerizationinitiater initiater.
2. photosensitive polymer combination according to claim 1, wherein, said acylphosphine oxide based compound is the compound shown in formula (I) or the general formula (II),
Figure FDA0000157806120000011
In the general formula (I), R 1, R 2And R 3The alkyl or aryl of representing carbon number 1～20 independently of one another, in the formula (II), R 4, R 5And R 6The alkyl or aryl of representing carbon number 1～20 independently of one another.
3. photosensitive polymer combination according to claim 1 and 2, wherein, said Hexaarylbiimidazole derivant is 2,4,5-triarylimidazoles dipolymer.
4. photosensitive element, it possesses supporter and is formed at the photo-sensitive resin of filming as any described photosensitive polymer combination in the claim 1～3 on the said supporter.
5. the manufacturing approach of a resist figure, it has: the photo-sensitive resin that on substrate, forms as the photo-sensitive resin of filming of any described photosensitive polymer combination in the claim 1～3 forms operation; At least a portion of said photo-sensitive resin irradiation active ray is made the exposure process of its photocuring; And the uncured portion of said photo-sensitive resin removed from substrate and form the developing procedure of the resist figure that the solidfied material by said photo-sensitive resin constitutes.
6. the manufacturing approach of a lead frame, it comprises the substrate that the manufacturing approach through the described resist figure of claim 5 is formed with the resist figure and carries out plating and handle the operation that forms conductor fig.
7. the manufacturing approach of a printed-wiring board (PWB), it comprises the substrate that the manufacturing approach through the described resist figure of claim 5 is formed with the resist figure and carries out plating and handle the operation that forms conductor fig.
8. the printed-wiring board (PWB) of making through the manufacturing approach of the described printed-wiring board (PWB) of claim 7.
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US9110371B2 (en) * 2012-05-31 2015-08-18 Hitachi Chemical Company, Ltd Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for producing wiring board
JP2013249452A (en) * 2012-06-04 2013-12-12 Hitachi Chemical Co Ltd Liquid curable resin composition, image display device, and method for manufacturing image display device
EP4151410A1 (en) * 2021-09-17 2023-03-22 Arkema France Photosensitive composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002059433A (en) * 2000-08-22 2002-02-26 Showa Highpolymer Co Ltd Method for forming decorative sheet
JP2005084537A (en) * 2003-09-10 2005-03-31 Asahi Kasei Electronics Co Ltd Photosensitive resin composition for sandblasting and its use
CN1934497A (en) * 2004-03-24 2007-03-21 捷时雅株式会社 Negative radiation-sensitive resin composition
CN101558356A (en) * 2006-12-19 2009-10-14 日立化成工业株式会社 Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board
CN101568883A (en) * 2006-12-27 2009-10-28 日立化成工业株式会社 Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007032215A1 (en) * 2005-09-12 2007-03-22 Fujifilm Corporation Photosensitive composition, pattern-forming material, photosensitive laminate, apparatus for formation of pattern, and method for formation of pattern
JP4711862B2 (en) * 2006-03-08 2011-06-29 富士フイルム株式会社 Photosensitive composition, photosensitive film, permanent pattern forming method, and printed circuit board
JP5093226B2 (en) * 2007-03-20 2012-12-12 Ｊｓｒ株式会社 Radiation sensitive resin composition
KR20080092839A (en) * 2007-04-12 2008-10-16 칫소가부시키가이샤 Ink-jet ink
JP4879157B2 (en) * 2007-12-27 2012-02-22 富士フイルム株式会社 Holographic recording compound, holographic recording composition, and holographic recording medium
WO2010002129A2 (en) * 2008-07-01 2010-01-07 주식회사 엘지화학 Photosensitive resin composition containing a plurality of photoinitiators, and transparent thin film layer and liquid crystal display using the same
WO2010013623A1 (en) * 2008-07-31 2010-02-04 日立化成工業株式会社 Photosensitive element, method for forming resist pattern using the same, and method for manufacturing printed wiring board

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002059433A (en) * 2000-08-22 2002-02-26 Showa Highpolymer Co Ltd Method for forming decorative sheet
JP2005084537A (en) * 2003-09-10 2005-03-31 Asahi Kasei Electronics Co Ltd Photosensitive resin composition for sandblasting and its use
CN1934497A (en) * 2004-03-24 2007-03-21 捷时雅株式会社 Negative radiation-sensitive resin composition
CN101558356A (en) * 2006-12-19 2009-10-14 日立化成工业株式会社 Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board
CN101568883A (en) * 2006-12-27 2009-10-28 日立化成工业株式会社 Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board

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