CN102854750A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, method for producing lead frame, and method for producing printed wiring board - Google Patents
Photosensitive resin composition, photosensitive element, method for forming resist pattern, method for producing lead frame, and method for producing printed wiring board Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—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
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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
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- 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
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- 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
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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
-
- 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
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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
- H05K3/10—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
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention provides a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, a method for producing a lead frame, and a method for producing a printed wiring board. The photosensitive resin composition 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
The application is to be on June 10th, 2011 applying date of original application, application number is 201180004361.8, and denomination of invention is divided an application for " photosensitive polymer combination and the manufacture method of manufacture method, printed-wiring board (PWB) and printed-wiring board (PWB) of using manufacture method, the lead frame of its photosensitive element, resist figure ".
Technical field
The manufacture method of manufacture method, printed-wiring board (PWB) and printed-wiring board (PWB) that the present invention relates to photosensitive polymer combination and use manufacture method, the lead frame (lead frame) of its photosensitive element, resist figure.
Background technology
Manufacturing field at printed-wiring board (PWB); anticorrosive additive material as being used for etching, plating etc. is widely used photosensitive polymer combination, has at support membrane and form the layer (hereinafter referred to as " photo-sensitive resin ") that contains this photosensitive polymer combination and the photosensitive element (duplexer) that disposes the structure of diaphragm at photo-sensitive resin.
In the past, for printed-wiring board (PWB), used above-mentioned photosensitive element, made according to for example following order.That is, at first the photo-sensitive resin of photosensitive element being laminated to the circuit such as copper-clad laminated board forms with on the substrate.At this moment, make face (hereinafter referred to as " top " of photo-sensitive resin) and the circuit of opposition side of the face that contacts with support membrane (hereinafter referred to as " following " of photo-sensitive resin) of photo-sensitive resin form face driving fit with the formation circuit of substrate.Therefore, on photo-sensitive resin, dispose in the situation of diaphragm, when peelling off diaphragm, carry out this lamination operation.In addition, lamination carries out (normal pressure laminating) by the photo-sensitive resin heating is crimped on the formation of substrate circuit with substrate.
Then, by 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 by developing solution dissolution or dispersion.Then, implement etch processes or plating and form figure, peel off at last and remove cured portion.
Here, so-called etch processes is after the circuit formation that the formed resist that is not cured after developing covers is removed with the metal covering etching of substrate, to peel off the method for solidifying resist.
On the other hand, so-called plating is after the circuit that the formed resist that is not cured after the development covers forms metal covering with substrate and carries out the platings such as copper and scolding tin, remove the curing resist, the method for the metal covering that etching is covered by this resist.
But, as the method for above-mentioned graph exposure, used the method that mercury lamp is exposed by photomask as light source in the past.In addition, in recent years, as new exposure technique, proposed to be called DLP(Digital Light Processing, digit optical is processed), the numerical data of figure directly drawn on photo-sensitive resin, directly draws exposure method.Than the exposure method by 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 in recent years densification of printed-wiring board (PWB), also improved the requirement to high resolution and high adaptation for photosensitive polymer combination.Particularly in the making of base plate for packaging, requirement can form L/S(live width/line-spacing) be 10/10(unit: the μ m) photosensitive polymer combination of following resist figure.
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 inverted trapezoidal, or there is a crimping (full front of a Chinese gown draws I) of resist, then in the circuit that the etch processes by thereafter or plating form, the possibility that produces short circuit, broken string is arranged, therefore be undesirable, wish 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 filming of photo-sensitive resin is effective.But, when forming, printed-wiring board (PWB) needs in the situation of circuit thickness (copper is thick etc.) to a certain degree, the impact of lateral etch when having etching in the etch process, therefore the resist line of thin thread part easily comes off, and there is restriction in the densification of printed-wiring board (PWB) (taking into account circuit thick wide with circuit).In addition, in plating technic, with the photo-sensitive resin filming 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-resolution in order not carry out the filming of photo-sensitive resin, carried out various trials.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 to a certain degree stickability, if use the method, then can produce such as inferior problem: optical tool and photo-sensitive resin driving fit, be difficult to peel off optical tool and workability reduces, optical tool is polluted by photosensitive polymer combination, or the impact that encumbers owing to oxygen makes sensitivity.
Therefore, trial as improvement the method, 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 the method wastes time and energy for the coating that the photo-sensitive resin multiple stratification is carried out, and does not have effect for sensitivity.
In addition, in order to realize the densification of printed-wiring board (PWB), as manufacture method, half addition technique attracts attention.In this technique, by carrying out successively on the base material through formation very thin films conductor layers such as electroless plating cover, form resist figure, plating, peeling off resist and fast-etching (removing unnecessary very thin films conductor layer), form printed-wiring board (PWB).As the advantage of this technique, can enumerate: owing to almost there not being the impact 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 the resist figure of exploring degree and adaptation excellence, just can fully reduce short circuit, broken string between circuit.
In addition, if photosensitive polymer combination can form the resist of peel property excellence, then improved the formation efficient of resist figure by the splitting time that shortens resist, in addition, by the size reduction with the stripping film of resist, resist peel off residual tailing off, circuit-formed yield rate improves.
For such requirement, proposed to use the photosensitive polymer combination of specific binder polymer, Photoepolymerizationinitiater initiater etc. and sensitivity, exploring degree and resist peel property excellence 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 the 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, although 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 mentioned above, 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, by in the graph exposure of photomask, if increase exposure in order to show deep curing property, the live width with respect to photomask being arranged then, it is large that the surface element of figure tee section (top) becomes, 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 peel property all excellent photosensitive polymer combination and the manufacture method of manufacture method, printed-wiring board (PWB) and printed-wiring board (PWB) of using manufacture method, 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.
The 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 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.
Described acylphosphine oxide based compound is preferably the compound shown in following general formula (I) or the general formula (II).Thus, further improve the exploring degree, and then can access excellent resist shape.
[changing 1]
In the general formula (I), R
1, R
2And R
3The alkyl or aryl that represents independently of one another carbon number 1 ~ 20.In the formula (II), R
4, R
5And R
6The alkyl or aryl that represents independently of one another carbon number 1 ~ 20.
Described Hexaarylbiimidazole derivant is preferably 2,4,5-triarylimidazoles dipolymer.Thus, sensitivity and exploring degree further improve.
The 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 described supporter.
Third Way of the present invention is a kind of manufacture method of resist figure, and it has: in the photo-sensitive resin formation operation of substrate formation as the photo-sensitive resin of filming of above-mentioned photosensitive polymer combination; At least a portion of described photo-sensitive resin irradiation active ray is made the exposure process of its photocuring; And the uncured portion of described photo-sensitive resin removed from substrate and form the developing procedure of the resist figure that the solidfied material by described photo-sensitive resin consists of.
Cubic formula of the present invention is a kind of manufacture method of lead frame, and it comprises the substrate that the manufacture method by above-mentioned resist pattern is formed with the resist figure and carries out the operation that plating forms conductor fig.
The 5th mode of the present invention is a kind of manufacture method of printed-wiring board (PWB), and it comprises the substrate that the manufacture method by above-mentioned resist figure is formed with the resist figure and carries out the operation that plating forms conductor fig.
According to this manufacture method, can and effectively make the printed-wiring board (PWB) of the such densification of high-density packages substrate with good precision.
The 6th mode of the present invention is the printed-wiring board (PWB) of making by the manufacture method 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 the equal excellent photosensitive polymer combination and use its photosensitive element, the manufacture method of resist figure, the manufacture method of lead frame and the manufacture method of printed-wiring board (PWB) of peel property.
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 operation independently, even in the situation that can't clearly distinguish with other operation, as long as realized the desired effect of this operation, then is 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 was multiple situation in the material that meets each composition in the composition, as long as no especially in advance explanation, the meaning was the total amount that is present in this many kinds of substance in the composition.
＜photosensitive polymer combination＞
Photosensitive polymer combination of the present invention contains at least a, (B) following polymerizable compound at least a of (A) following binder polymer and (C) Photoepolymerizationinitiater initiater; 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 unsaturated link, and this Photoepolymerizationinitiater initiater contains acylphosphine oxide based compound and Hexaarylbiimidazole derivant.
By such formation, demonstrate sensitivity, exploring degree, adaptation, resist shape and solidify after the equal 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, described 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 described coming from, and can also further have as required other structural units such as the structural unit that comes from (methyl) alkyl acrylate, the structural unit that comes from styrene or styrene derivative and consists of.
As described (methyl) benzyl acrylate derivant, can enumerate the compound of the alkyl that replaces alkoxy that carbon number 1 ~ 6 is arranged, halogen, carbon number 1 ~ 6 on the aromatic rings of benzyl for example.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 other polymerizable monomer beyond (methyl) acrylic acid and (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant, for example can enumerate: styrene; Vinyltoluene, α-methyl styrene etc. are at the substituted styrene derivative that can polymerization of alpha-position or aromatic ring; The acrylamides such as diacetone acrylamide; Vinyl cyanide; The ester class of the 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) isobornyl acrylate, (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, the 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, maleic anhydride, monomethyl maleate, ethyl maleate, the maleic acid monoesters such as maleic acid list isopropyl ester, fumaric acid, cinnamic acid, the alpha-cyano cinnamic acid, itaconic acid, crotonic acid and propiolic acid.These can use separately or with two or more combination in any.
For described (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 following general formula (IV).In the following general formula (IV), R
9Expression hydrogen atom or methyl, R
10The alkyl of expression carbon number 1 ~ 12.
[changing 2]
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 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 described adhesive composition, consider from making the good viewpoint of exploring degree and adaptation, also preferably further contain at least a in the structural unit that comes from the styrene or derivatives thereof.
The containing ratio that consists of each structural unit of described 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, the acid number that more preferably makes binder polymer is the containing ratio of 140mg KOH/g ~ 230mg KOH/g, is particularly preferably the containing ratio that the acid number that makes binder polymer is 150mg KOH/g ~ 230mg KOH/g.
Acid number by binder polymer is more than the 100mg KOH/g, can suppress development time elongated.In addition, be below the 250mg KOH/g by acid number, the anti-development fluidity (adaptation) of the solidfied material of photosensitive polymer combination improves.Here, in the situation that carry 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, be preferably 5 quality % ~ 65 quality % take the all-mass of binder polymer molecule as benchmark, more preferably 10 quality % ~ 55 quality %, more preferably 20 quality % ~ 50 quality %.
Be that the exploring degree further improves more than the 5 quality % by this containing ratio.In addition, be below the 65 quality % by this containing ratio, can suppress stripping film and become large, and it is elongated to suppress splitting time.
In addition, contain at described binder polymer in the situation of the structural unit that comes from (methyl) alkyl acrylate, its containing ratio is preferably 1 quality % ~ 50 quality % take the all-mass of binder polymer molecule as benchmark, more preferably 2 quality % ~ 30 quality %, more preferably 3 quality % ~ 20 quality %.
Be more than the 1 quality % by this content, can suppress stripping film and become large, and it be elongated to suppress splitting time.In addition, be that exploring degree and adaptation further improve below the 50 quality % by this content.
And then, have in molecule at described binder polymer in the situation of the structural unit that comes from the styrene or derivatives thereof, its containing ratio is preferably 5 quality % ~ 65 quality % take the all-mass of binder polymer molecule as benchmark, 10 quality % ~ 60 quality % more preferably, more preferably 15 quality % ~ 55 quality % are particularly preferably 20 quality % ~ 50 quality %.
Be that adaptation further improves below the 5 quality % by this containing ratio.In addition, be below the 65 quality % by this containing ratio, can suppress stripping film and become large, and it is elongated to suppress splitting time.
The weight-average molecular weight of described binder polymer (Mw) is preferably 10000 ~ 100000, and more preferably 20000 ~ 80000, more 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 tendency of development time excellence is arranged.
Here, the weight-average molecular weight of binder polymer is measured (converting by the poly typical curve of Application standard) by gel permeation chromatography (GPC).
The dispersion degree of described 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, described 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 the structural unit of (methyl) alkyl acrylate that carbon number is 1 ~ 4 alkyl and the structural unit that comes from the styrene or derivatives thereof of 10 quality % ~ 60 quality %, acid number is 120mg KOH/g ~ 230mgKOH/g, and weight-average molecular weight is 20000 ~ 80000.
More 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 the structural unit of (methyl) alkyl acrylate that carbon number is 1 ~ 4 alkyl and the structural unit that comes from the styrene or derivatives thereof of 15 quality % ~ 55 quality %, acid number is 140mgKOH/g ~ 230mg KOH/g, and weight-average molecular weight is 25000 ~ 60000.
Binder polymer among the present invention can be by the usual way manufacturing.Particularly for example, can carry out the incompatible manufacturing of radical polymerization by 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 be used alone binder polymer, also two or more binder polymer combination in any can be used.
Binder polymer when being used in combination of two or more, for example can enumerate two or more (containing different monomeric units as the copolymer composition) binder polymer that is formed 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.In addition, can also use the polymkeric substance that multi-modal molecular-weight distributes that has of putting down in writing in the Japanese kokai publication hei 11-327137 communique.
The containing ratio of (A) binder polymer is preferably 20 quality % in the photosensitive polymer combination ~ 90 quality %, more preferably 30 quality % ~ 80 quality %, more preferably 40 quality ~ 65 quality % in the photosensitive polymer combination of the present invention.
If the containing ratio of binder polymer is more than the 20 quality %, the tendency of film shaped property excellence is arranged.In addition, if be below the 90 quality %, the tendency of sensitivity and exploring degree excellence is arranged.
In addition, the containing ratio of (A) binder polymer preferably is made as 30 mass parts ~ 70 mass parts at (A) binder polymer composition with (B) in total amount 100 mass parts of polymerizable compound composition in the described photosensitive polymer combination, more preferably be made as 35 mass parts ~ 65 mass parts, particularly preferably be made as 40 mass parts ~ 60 mass parts.
Be more than 30 mass parts by this containing ratio, the film formative further improves.In addition, by 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 unsaturated link.
The containing ratio of described polymerizable compound is preferably 3 quality % in the photosensitive polymer combination ~ 70 quality %, more preferably 10 quality % ~ 60 quality %, more preferably 25 quality % ~ 50 quality %.
If the containing ratio of polymerizable compound is more than the 3 quality %, the tendency of sensitivity and exploring degree excellence is arranged.In addition, if be below the 70 quality %, the tendency that has film to have excellent formability.
Described polymerizable compound has no particular limits so long as have at least one ethene unsaturated link and compound that can polymerization gets 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 following general formula (III).
[changing 3]
In the above-mentioned general formula (III), R
7And R
8Represent independently of one another hydrogen atom or methyl, X represents 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 adjacent plural X separately can be identical in the molecule, 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.By 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, by m+n=8 ~ 10, the peel property of resist further improves, and is preferred therefore.
If be that (A) binder polymer composition and (B) tendency that improves of the compatibility of polymerizable compound composition more than 2, are arranged (m+n).In addition, if (m+n) be below 10, have and suppress 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 described photosensitive polymer combination, for the compound shown in the above-mentioned general formula (III), if these two kinds of compound 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, are more preferred therefore.
For described photosensitive polymer combination, as the compound shown in the above-mentioned general formula (III), when the compound (IIIb) of the 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 described bisphenol-A system (methyl) acrylate compounds, can enumerate 2 particularly, two (4-((methyl) the acryloxy polyethoxies of 2-) phenyl) propane, 2, the poly-propoxyl group of two (4-((methyl) acryloxies of 2-) phenyl) propane, 2, the poly-butoxy of two (4-((methyl) acryloxies of 2-) phenyl) propane, 2, the poly-propoxyl group of two (4-((methyl) the acryloxy polyethoxies of 2-) phenyl) propane etc.Wherein, consider from the viewpoint of further raising resolution and peel property, preferred 2, two (4-((methyl) the acryloxy polyethoxies of 2-) phenyl) propane.
In these, for example with regard to 2, two (4-((methyl) the acryloxy dipropoxies of 2-) phenyl) propane, can be used as BPE-200(Xin Zhong village chemical industry (strain) manufacturing, ProductName) and be purchased, with regard to 2, two (the 4-(methacryloxy five ethoxys) phenyl of 2-) propane, can be used as BPE-500(Xin Zhong village chemical industry (strain) and make, ProductName) or FA-321M(Hitachi change into industry (strain) manufacturing, ProductName) and be purchased.
These bisphenol-As system (methyl) acrylate compounds are can be separately a kind of or with two or more combination in any uses.
In described photosensitive polymer combination, the containing ratio of described 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 %.Be this scope by described containing ratio, further improved the exploring degree of resist.
In described photosensitive polymer combination, as (B) polymerizable compound composition, poly alkylene glycol two (methyl) acrylate that preferably further contains at least a molecule at least one party with (gathering) oxygen ethylidene chain and (gather) oxygen propylidene chain more preferably further contains in the molecule poly alkylene glycol two (methyl) acrylate of two sides with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.Thus, the pliability of the solidfied material of photosensitive polymer combination (cured film) improves.
In the molecule of described poly alkylene glycol two (methyl) acrylate, (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain separately continuous, block ground exist, and also can randomly exist.In addition, in (gathering) oxygen isopropylidene chain, can be that the secondary carbon of isopropylidene is combined with oxygen atom, also can be primary carbon is combined with oxygen atom.
As described poly alkylene glycol two (methyl) acrylate, be particularly preferably the compound shown in following general formula (V), general formula (VI) or the general formula (VII).These are can be separately a kind of or be used in combination of two or more.
[changing 4]
In above-mentioned general formula (V), general formula (VI) and the general formula (VII), R represents hydrogen atom or methyl independently of one another, and EO represents the oxygen ethylidene, and PO represents the oxygen propylidene.m
1, m
2, m
3And m
4The repeat number of the structural unit that expression is made of the oxygen ethylidene, n
1, n
2, n
3And n
4The repeat number of the structural unit that expression is made of the oxygen propylidene, the repetition sum m of oxygen ethylidene
1+ m
2, m
3And m
4(mean value) represents 1 ~ 30 number independently of one another, the repetition sum n of oxygen propylidene
1, n
2+ n
3And n
4(mean value) represents 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 one, 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 particularly preferably 5 ~ 8 number.By 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 particularly preferably 10 ~ 14 number.By ading up to below 30 of this repeat number, the exploring degree improves, and can suppress the generation of sludge (ス ラ ッ ジ).
As the compound shown in the above-mentioned general formula (V), can enumerate R=methyl, m particularly
1+ m
2=6(mean value), n
1=12(mean value) vinyl compound (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 value), n
2+ n
3=12(mean value) vinyl compound (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
4=9(mean value) vinyl compound (Xin Zhong village chemical industry (strain) is made, sample name NK ESTER HEMA-9P) etc.These are can be separately a kind of or be used in combination of two or more.
Containing ratio as described poly alkylene glycol two (methyl) acrylate 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 %.
Be more than the 5 quality % by described containing ratio, pliability improves.In addition, be below the 50 quality % by described containing ratio, resolution improves.
For the photosensitive polymer combination among the present invention, as (B) polymerizable compound, can further contain described bisphenol-A system's (methyl) acrylate compounds and poly alkylene glycol two (methyl) acrylate other polymerizable compounds in addition.
As other polymerizable compounds, can enumerate the poly-ethyleneoxy group acrylate of Nonylphenoxy, 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 the poly-ethyleneoxy group acrylate of Nonylphenoxy and phthalic acid based compound, select at least a.
As the poly-ethyleneoxy group acrylate of described Nonylphenoxy, can enumerate for example Nonylphenoxy triethylene oxygen base acrylate, Nonylphenoxy four ethyleneoxy group acrylate, Nonylphenoxy five ethyleneoxy group acrylate, Nonylphenoxy six ethyleneoxy group acrylate, Nonylphenoxy seven ethyleneoxy group acrylate, Nonylphenoxy eight ethyleneoxy group acrylate, Nonylphenoxy nine ethyleneoxy group acrylate, Nonylphenoxy ten ethyleneoxy group acrylate, Nonylphenoxy 11 ethyleneoxy group acrylate.
These are can be separately a kind of 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 and change into industry (strain) and make ProductName) and be purchased.
These are can be separately a kind of or be used in combination of two or more.
Further, as (methyl) acrylic acid multielement alcohol ester, can enumerate for example trimethylolpropane polyethoxy three (methyl) acrylate, trimethylolpropane gathers propoxyl group three (methyl) acrylate, trimethylolpropane gathers butoxy three (methyl) acrylate, the trimethylolpropane polyethoxy gathers propoxyl group three (methyl) acrylate, trimethylolethane polyethoxy three (methyl) acrylate, trimethylolethane gathers propoxyl group three (methyl) acrylate, trimethylolethane gathers butoxy three (methyl) acrylate, the trimethylolethane polyethoxy gathers propoxyl group three (methyl) acrylate, pentaerythrite polyethoxy three (methyl) acrylate, pentaerythrite gathers propoxyl group three (methyl) acrylate, pentaerythrite gathers butoxy three (methyl) acrylate, the pentaerythrite polyethoxy gathers propoxyl group three (methyl) acrylate, glyceryl polyethoxy three (methyl) acrylate, glyceryl gathers propoxyl group three (methyl) acrylate, glyceryl gathers butoxy three (methyl) acrylate, the glyceryl polyethoxy gathers propoxyl group three (methyl) acrylate.
These are can be separately a kind of or be used in combination of two or more.
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 %, more preferably 5 quality % ~ 20 quality %.
(C) Photoepolymerizationinitiater initiater
Described 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, by containing at least two kinds of compounds, sensitivity, exploring degree improve, and then the resist shape is also good.In addition, diminish with respect to the variation of the line width values of the resist figure of exposure, therefore process tolerance and broaden, well.
In described photosensitive polymer combination, the containing ratio of described Photoepolymerizationinitiater initiater is preferably 0.1 quality % ~ 20 quality % in the gross mass of photosensitive polymer combination, more preferably 1 quality % ~ 10 quality %, more 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 %, there be the film formability to become and better be inclined to.
As described (C-1) acylphosphine oxide based compound, be preferably the compound shown in following general formula (I) or the general formula (II).
[changing 5]
In the general formula (I), R
1, R
2And R
3The alkyl or aryl that represents independently of one another carbon number 1 ~ 20.In the general formula (II), R
4, R
5And R
6The alkyl or aryl that represents independently of one another carbon number 1 ~ 20.
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, a chain 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, a chain 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 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 particularly for example two (2,6-dimethoxy benzoyls)-2,4,4-trimethyl-amyl group phosphine oxide.Compound shown in described general formula (I) or the general formula (II) is can be separately a kind of or be used in combination of two or more.
Described (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 following general formula (VIII) or the general formula (IX).
[changing 6]
In the above-mentioned general formula (VIII), R
11, R
12And R
13Represent independently of one another the alkyl of carbon number 1 ~ 6 or the alkoxy of carbon number 1 ~ 4, 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]
In the above-mentioned general formula (IX), R
14, R
15And R
16Represent independently of one another the alkyl of carbon number 1 ~ 6 or the alkoxy of carbon number 1 ~ 4, 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 independently of one another the alkyl of carbon number 1 ~ 4, 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 and make trade name) and be purchased.
In addition, as the compound shown in the above-mentioned general formula (IX), consider from the viewpoint of more effectively improving sensitivity and resist shape, be preferably two (2,4,6-trimethylbenzoyl)-phenylphosphine oxide.For two (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, for example can be used as IRGACURE-819(BASF Japanese firm and 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 separately a kind of or be used in combination of two or more.
In described 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 described (C-2) Hexaarylbiimidazole derivant, consider from the viewpoint that improves sensitivity and adaptation, preferably contain at least a 2,4,5-triarylimidazoles dipolymer.Described 2,4, the structure of 5-triarylimidazoles dipolymer can be symmetrical also can be asymmetric.
As described 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 the 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.
In described photosensitive polymer combination, as the containing ratio of described (C-2) Hexaarylbiimidazole derivant, be preferably 30 quality % ~ 70 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater composition, more preferably 45 quality % ~ 65 quality %.
In described 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 from the viewpoint of sensitivity, exploring degree and adaptation, the described ratio (C-1/C-2) that contains is preferably 0.1 ~ 0.9, and more preferably 0.3 ~ 0.9, more preferably 0.5 ~ 0.8.
Described photosensitive polymer combination can further contain other Photoepolymerizationinitiater initiaters beyond described 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, the 2-methyl isophthalic acid-and the 4-(methyl mercapto) phenyl ］-aromatic ketone such as 2-morpholino-acetone-1 grade, the quinones such as alkyl-anthraquinone, the benzoin ether compounds such as benzoin alkylether, the benzoin compounds such as benzoin, alkyl benzene acyloin, the benzil derivants such as benzil dimethyl ketal, 9-phenylacridine, 1,7-(9,9 '-acridinyl) acridine derivatives such as heptane.
These are can be separately a kind of or be used in combination of two or more.
The content of the composition of (C) Photoepolymerizationinitiater initiater in the described photosensitive polymer combination, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of polymerizable compound composition be preferably 0.1 mass parts ~ 10 mass parts, 1 mass parts ~ 7 mass parts more preferably, more preferably 2 mass parts ~ 6 mass parts are particularly preferably 3 mass parts ~ 5 mass parts.
Content by described Photoepolymerizationinitiater initiater is more than 0.1 mass parts, and sensitivity, exploring degree and adaptation further improve.In addition, by being below 10 mass parts, can obtain more excellent resist shape.
Described photosensitive polymer combination is preferred: the containing ratio of described binder polymer is 20 quality % ~ 90 quality %, and the containing ratio of described polymerizable compound is 3 quality % ~ 70 quality %, and the containing ratio of described Photoepolymerizationinitiater initiater is 0.1 quality % ~ 20 quality %.
More preferably: the containing ratio of described binder polymer is 30 quality % ~ 80 quality %, and the containing ratio of described polymerizable compound is 10 quality % ~ 60 quality %, and the containing ratio of described Photoepolymerizationinitiater initiater is 1 quality % ~ 10 quality %.
Further preferably: the containing ratio of described binder polymer is 40 quality % ~ 65 quality %, and the containing ratio of described polymerizable compound is 25 quality % ~ 50 quality %, and the containing ratio of described Photoepolymerizationinitiater initiater is 3 quality % ~ 7 quality %.
Described 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 separately or be used in combination of two or more.
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 select at least a from the group that pyrazolines, anthracene class, Coumarins and triaryl amine form, wherein, more preferably contain from the group that pyrazolines, anthracene class and triaryl amine form, 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 by described (D) sensitizing coloring matter is more than 0.01 mass parts, and sensitivity and exploring degree further improve.In addition, by being below 10 mass parts, having suppressed the resist shape and become inverted trapezoidal, adaptation improves.
Described photosensitive polymer combination preferably further contains (E) amine compound.Thus, the sensitivity of photosensitive polymer combination is better.
As described (E) amine compound, [4-(dimethylamino) phenyl] methane, two of for example can enumerating two [4-(lignocaine) phenyl] methane, leuco crystal violet.These are can be separately a kind of or be used in combination of two or more.
When described 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, particularly preferably be made as 0.1 mass parts ~ 2 mass parts.
Content by described (E) amine compound is that sensitivity further improves more than 0.01 mass parts.In addition, by being below 10 mass parts, can suppressing (E) amine compound composition that film forms rear surplus and separate out as foreign matter.
For described photosensitive polymer combination, except mentioned component, can also contain other compositions as required.As other compositions, can enumerate plastifier, pigment, filling agent, defoamer, fire retardant, stabilizing agent, adaptation imparting agent, the levelling agents such as the dyestuffs such as optical polymerism compound (oxetane compound etc.) such as the ring-type ether that has at least one cationically polymerizable in the molecule, cationic polymerization initiators, peacock green, tribromo-benzene sulfone, light display toner, heat colour developing preventing agent, para toluene sulfonamide, peel off promoter, antioxidant, spices, developer, thermal cross-linking agent.
These are can be separately a kind of or be used in combination of two or more.
In addition, the content of these other compositions preferably is made as about 0.01 mass parts ~ 20 mass parts separately with respect to (A) binder polymer composition and (B) total amount 100 mass parts of polymerizable compound composition.
Described photosensitive polymer combination can contain at least a organic solvent.As described organic solvent, can use normally used organic solvent, be not particularly limited.Can enumerate particularly for example methyl alcohol, ethanol, acetone, MEK, methyl cellosolve, ethyl cellosolve, toluene, DMF, propylene glycol monomethyl ether and these mixed solvent.
For example, can with described (A) binder polymer, (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater be dissolved in the described organic solvent, the solution (hereinafter referred to as " coating fluid ") that forms solid constituent and be about 30 quality % ~ 60 quality % uses.
Here, so-called solid constituent, the meaning is to remove residual composition behind the volatile ingredient from described solution (photosensitive polymer combination).
Described coating fluid for example can be used for forming as described as follows photo-sensitive resin.By also dry on the surface of described coating fluid being coated the supporters such as support membrane described later, sheet metal, can form the photo-sensitive resin that come from described photosensitive polymer combination at supporter.
As sheet metal, can enumerate the 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 the polymer films such as tygon, polypropylene etc.
Described photosensitive polymer combination for example can be used for the manufacture method of resist figure described later aptly.Wherein, be applicable to form by plating the manufacture method of circuit.
＜photosensitive element＞
For photosensitive element 10 of the present invention; the fragmentary cross sectional view of the one that goes out an as shown in Figure 1 example constitutes the photo-sensitive resin of filming 4 that possesses supporter 2 and be formed at the described photosensitive polymer combination of conduct on the described supporter, possesses as required and other layers such as diaphragm 6 of arranging.
As described supporter, can use polyethylene terephthalate, polypropylene, tygon, polyester etc. to have the polymer film of thermotolerance and solvent resistance.
The thickness of described supporter (below be sometimes referred to as " support membrane ") is preferably 1 μ m ~ 100 μ m, more preferably 5 μ m ~ 50 μ m, more preferably 5 μ m ~ 30 μ m.Be that support membrane breaks in the time of can suppressing to peel off support membrane more than the 1 μ m by the thickness that makes supporter.In addition, by being below the 100 μ m, can suppressing the exploring degree and reduce.
Described 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 described 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 consist of the material heat fusing of diaphragm, by mixing, extrude, during the 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 the polypropylene screen that ALPHAN MA-410, E-200C, film company of SHIN-ETSU HANTOTAI that Oji Paper company makes make etc., the polyethylene terephthalate films such as the PS series such as PS-25 that Supreme Being people company makes etc.Here, diaphragm can be identical with described supporter.
The thickness of diaphragm is preferably 1 μ m ~ 100 μ m, 5 μ m ~ 50 μ m more preferably, and more preferably 5 μ m ~ 30 μ m are particularly preferably 15 μ m ~ 30 μ m.Thickness by 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, by being below the 100 μ m, improved throughput rate.
Described photosensitive element can for example be made as described below.Can make by the following method, it comprises: with (A) binder polymer, (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater be dissolved in the organic solvent, the step of the coating fluid about preparation solid constituent 30 quality % ~ 60 quality %, described coating fluid is coated on the supporter and forms the step of coating layer, and described coating layer is dry and form the step of photo-sensitive resin.
Described coating fluid for example can be undertaken by roll coater, unfilled corner wheel coating machine, intaglio plate coating machine, Kohler coater, die coater, these known methods of scraping strip coating machine to the coating on the supporter.
In addition, the drying of described coating layer is not particularly limited so long as can remove at least part of organic solvent from coating layer and get final product.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 described photosensitive element can suitably be selected according to purposes, is preferably 1 μ m ~ 100 μ m with dried thickness gauge, more preferably 1 μ m ~ 50 μ m, more preferably 5 μ m ~ 40 μ m.
Thickness by photo-sensitive resin is more than the 1 μ m, and industrial coating becomes easily, throughput rate improves.In addition, by being below the 100 μ m, adaptation and exploring degree improve.
For described photo-sensitive resin for ultraviolet ray transmissivity, be preferably 5% ~ 75% for the ultraviolet ray of wavelength 365nm, more preferably 10% ~ 65%, be particularly preferably 15% ~ 55%.
Be that adaptation further improves more than 5% by this transmitance.In addition, be below 75% by transmitance, the exploring degree further improves.Here, above-mentioned transmitance can be measured by the UV spectrometer.As the UV spectrometer, can enumerate the 228A type W rays spectrophotometer that the Hitachi makes.
Described photosensitive element can also further have the known middle layers such as cushion, adhesive linkage, light absorbing zone, gas barrier layer etc. as required.
The form of described photosensitive element is not particularly limited.For example can be sheet, perhaps can be the state that is wound into the roller shape at the volume core.
Be wound in the situation of roller shape, the mode outside preferably becoming according to support membrane is reeled.
As the volume core, can enumerate the plastics such as polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-styrene copolymer) 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.
Described photosensitive element is applicable to for example manufacture method of resist figure described later.Wherein, be fit to be applied to form by plating the manufacture method of circuit.
The manufacture method of＜resist figure＞
The manufacture method of resist figure of the present invention possesses: (i) form photo-sensitive resin as the photo-sensitive resin of filming of described photosensitive polymer combination at substrate 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 described photo-sensitive resin is removed and formed the developing procedure of the resist figure that is made of the solidfied material that comes from described photo-sensitive resin from substrate, can comprise other operation as required and consist of.
(i) photo-sensitive resin forms operation
Form in the operation at photo-sensitive resin, at the photo-sensitive resin of filming of substrate formation as described photosensitive polymer combination.Be not particularly limited as described substrate, usually can use the circuit that possesses insulation course and be formed at the conductor layer on the insulation course to form with lower bolsters (die pad) (lead frame base material) such as substrate or alloy base materials.
As the method that forms photo-sensitive resin at substrate, for example, can in heating, be crimped on aforesaid substrate and carry out by remove behind the diaphragm photo-sensitive resin with photosensitive element from described photosensitive element.Thus, can access and comprise substrate, photo-sensitive resin and supporter and these duplexers that stacks 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 ℃, then in advance substrate is carried out thermal pretreatment optional, 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, by to being formed at least a portion irradiation active ray of the photo-sensitive resin on the substrate, the part photocuring that is shone by active ray and form sub-image.
At this moment, be in the situation of permeability to active ray at the supporter (support membrane) that is present on the photo-sensitive resin, can see through support membrane irradiation active ray, be in 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 graph that is called as wiring diagram (ART WORK).In addition, also can adopt the Imaging by LDI(Laser Direct, laser direct imaging) exposure method, DLP(Digital Light Processing, digit optical is processed) exposure method etc. directly draws exposure method active ray is the method that image shape ground shines.
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 the ultraviolet rays such as Solid State Laser, the semiconductor lasers such as gas laser, YAG laser such as argon laser, visible light.
(iii) developing procedure
In developing procedure, by the uncured portion of described photo-sensitive resin is removed the resist figure that the solidfied material that is formed by described photo-sensitive resin photocuring in substrate formation consists of from substrate.
In the situation that there is support membrane in 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.
In the situation that wet developing uses the developer solution corresponding with photosensitive polymer combination, develop by 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 from the viewpoint of carrying high-resolution, the high-pressure fog mode is the most suitable.Also the two or more combinations in these methods can be developed.
The formation of developer solution can suitably be selected according to the formation of described 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, the carbonic acid alkali such as the carbonate of lithium, sodium, potassium or ammonia or supercarbonate, the alkali metal phosphates such as potassium phosphate, sodium phosphate, the 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, defoamer, a small amount of being used in the alkaline aqueous solution and promote the organic solvent that develops etc.
The water system developer solution is the developer solution for being made 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, Tetramethylammonium hydroxide, 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 separately or be used in combination of two or more.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 on a small quantity surfactant, defoamer etc. in the water system developer solution.
Be developer solution as organic solvent, can enumerate the organic solvents such as 1,1,1-trichloroethanes, 1-METHYLPYRROLIDONE, DMF, 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 as required heating or 0.2J/cm about 60 ℃ ~ 250 ℃
2~ 10J/cm
2About exposure, thereby the resist figure is further solidified.
The manufacture method of＜lead frame＞
The manufacture method of lead frame of the present invention constitutes: comprise the substrate that the manufacture method by above-mentioned resist figure is formed with the resist figure and carry out the operation that plating forms conductor fig, comprise as required resist and remove other operations such as operation, etch processes operation.
As described substrate, can use the lower bolsters (lead frame base material) such as alloy base material.
In the present invention, can with being formed at resist figure on the supporter as mask, carry out plating to supporter.
As the method for plating, can be that electrolytic coating is processed, also can be that electroless plating covers processing, but preferred electroless plating cover processing.Cover processing as electroless plating, can enumerate scolding tin plating, the watts such as the plating such as the copper such as copper sulphate plating, cupric pyrophosphate plating, high evenly scolding tin (high-throw solder) plating and bathe the golden plating such as nickel plating, hard gold plating, soft golden plating such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid plating.
Behind the described plating, the resist figure on the supporter is removed.For example removing of resist figure can be peeled off by stronger alkaline aqueous solution by the alkaline aqueous solution of using than described developing procedure.As this alkaline aqueous solution, can example such as 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 may be used.
After removing the resist figure, can by further carry out etch processes, remove unwanted metal level and make lead frame.
The metal level that the method for etch processes can be removed as required and suitably selecting.For example, as etching solution, can enumerate copper chloride solution, ferric chloride solution, alkaline etching solution and hydrogen peroxide etching solution, in these, consider from the aspect that etching factor (etch factor) is good, preferably use ferric chloride solution.
The manufacture method of＜printed-wiring board (PWB)＞
The manufacture method of printed-wiring board (PWB) of the present invention constitutes: comprise the substrate that the manufacture method by described resist figure is formed with the resist figure and carry out the operation that plating forms conductor fig, comprise as required resist and remove other operations such as operation, etch processes operation.
In the present invention, can with being formed at resist figure on the substrate as mask, carry out plating to the conductor layer that is arranged on the substrate.
The method of the plating in the manufacture method of printed-wiring board (PWB), the method for removing of resist figure, etch processes are identical with the manufacture method of described lead frame.
According to the printed-wiring board (PWB) that the manufacture method 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, described printed-wiring board (PWB) also can carry out the manufacture method that etch processes forms the operation of conductor fig and makes by comprising the substrate that the manufacture method by described resist figure is formed with the resist figure.
In this manufacture method, can with being formed at resist figure on the substrate as mask, carry out etch processes to the conductor layer that is arranged on the substrate.
Japanese publication 2010-173083 number disclosed full content introduced this instructions by reference.
For whole documents, patented claim and the technical standard put down in writing in this instructions, each document, patented claim and technical standard by with reference to the situation with specifically and respectively record incorporated into degree ground, by with reference to incorporating this instructions into.
Embodiment
Specifically describe by the following examples the present invention, but the present invention is not limited by these embodiment.Here, as long as no special in advance statement, " part " and " % " is quality criteria.
＜synthesis 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 3:2) 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 3:2) 450g of methyl cellosolve 270g and toluene 180g, the limit is blown into the stirring of nitrogen limit in flask, be heated to 80 ℃.
After dripping mentioned solution a with 4 hours in the above-mentioned mixed liquor in the flask, while stirring 80 ℃ of insulations 2 hours.Then, after dripping mentioned solution b in the solution in 10 minutes clockwise flasks, the solution limit in the stirred flask of limit was 80 ℃ of insulations 3 hours.And then with 30 minutes the solution in the flask is warming up to 90 ℃, 90 ℃ of lower insulation coolings after 2 hours, 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 by gel permeation chromatography (GPC) and the typical curve of Application standard polystyrene converts and derives.The condition of GPC as shown below.
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
Change into industry (strain) manufacturing, trade name for Hitachi more than the Gelpack GL-R440()
Eluant: tetrahydrofuran
Measure temperature: 40 ℃
Flow: 2.05mL/ minute
Detecting device: the L-3300 of Hitachi type RI((strain) Hitachi makes)
(synthesizing of binder polymer (A-2) ~ (A-6))
In binder polymer (A-1) synthetic, as polymerizable monomer (monomer), except using the material shown in the following table 1 with the mass ratio shown in the identical table, with the solution that obtains binder polymer (A-1) similarly, obtain respectively the solution of binder polymer (A-2) ~ (A-6).
Table 1
＜embodiment 1 ~ 11 and comparative example 1 ~ 4 〉
[preparation of photosensitive polymer combination]
Use respectively C-1A shown below, C-1B, the C-2 of B-1 ~ B-4 shown below, conduct (C) Photoepolymerizationinitiater initiater of A-1 ~ A-6 obtained above as (A) binder polymer, conduct (B) polymerizable compound, as the composition shown below of other compositions, mix according to the use level shown in the following table 2 (cooperation umber), distinguish thus the photosensitive polymer combination of Preparation Example 1 ~ 11 and comparative example 1 ~ 4.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 (the 4-(methacryloxy five ethoxys) phenyl of 2-) propane [FA-321M(Hitachi changes into industry (strain) manufacturing, ProductName)]
B-2:2, two (4-((methyl) the acryloxy dipropoxies of 2-) phenyl) propane [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 value), n
1Compound=12(mean value) [FA-023M(Hitachi changes into industry (strain) manufacturing, ProductName)]
B-4: in above-mentioned general formula (VI), R=methyl, m
3=6(mean value), n
2+ n
3Compound=12(mean value) [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 (2,4,6-trimethylbenzoyl)-phenylphosphine oxide [IRGACURE-819(BASF Japanese firm makes, trade name)].
C-2A:2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-the tetraphenyl diimidazole [B-CIM(Hampford company makes, 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(Osaka organic chemistry industrial group makes, trade name): peacock green
Table 2
The preparation of＜photosensitive element＞
Photosensitive polymer combination obtained above is evenly coated respectively the polyethylene terephthalate film that thickness is 16 μ m, and (Supreme Being people's (strain) makes, ProductName " HTF-01 ") on, hot wind convection type dryer with 70 ℃ and 110 ℃ is dry, has formed the photo-sensitive resin that dried thickness is 25 μ m.
Make at this photo-sensitive resin diaphragm (TAMAPOLY(strain) of fitting; ProductName " NF-15 "), photosensitive element P1 ~ P11 and the P1c ~ P4c of polyethylene terephthalate film (support membrane), photo-sensitive resin and diaphragm have been obtained respectively stacking gradually.
The making of＜duplexer＞
The two sides is laminated with Copper Foil, and (thickness: glass epoxide material 35 μ m) is copper-clad laminated board (substrate, Hitachi changes into industrial group and makes, trade name " MLC-E-679 ") (MEC A/S makes with surface roughening treating fluid " MEC etch BOND CZ-8100 ", trade name) carries out surface treatment, after washing, pickling and the washing, dry with air stream.Surface-treated copper-clad laminated board is heated to 80 ℃, when peeling off diaphragm, so that the mode difference lamination photosensitive element obtained above on photo-sensitive resin contact copper surface.Thus, obtained respectively stacking gradually the duplexer of copper-clad laminated board, photo-sensitive resin, support membrane.Resulting duplexer is used as test film in test shown below.
Here, lamination uses 120 ℃ hot-rolling to carry out with the roller speed of the crimping pressure of 0.4MPa, 1.0m/ minute.
＜estimate＞
(luminous sensitivity determination test)
On the support membrane of test film obtained above, 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, make with the exposure machine with high-pressure sodium lamp (ORC(ォ one Network) company, trade name " EXM-1201 "), think 70mJ/cm
2The irradiation energy amount photo-sensitive resin is exposed.
Then, peel off support membrane, 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), remove unexposed portion, carry out development treatment.
After the development treatment, the hop count of the stage metraster by measuring the photocuring film that forms on the substrate is estimated the luminous sensitivity of photosensitive polymer combination.Luminous sensitivity represents with the hop count of stage metraster, and the hop count of this stage metraster is higher, represents that then luminous sensitivity is higher.The results are shown in table 3.
(determination test of exploring degree and adaptation)
In order to check exploring degree and adaptation, to be 2/2 ~ 30/30(unit with the live width/line-spacing that has of negative film as the adaptation evaluation: the glass chromium type optical tool driving fit of line pattern μ m) be on the support membrane of test film obtained above, use has the exposure machine of high-pressure sodium lamp, and the photo-sensitive resin take the remaining hop count of 41 sections stage metraster as 14 sections energy fluence to above-mentioned duplexer exposes.After the exposure, carry out the development treatment identical with above-mentioned luminous sensitivity determination test.
After the development treatment, be completely removed and line part (exposure section) does not produce in the resist figure of distortion, damaged and formation the live width by minimum/line-spacing value evaluation exploring degree adaptation in gap (unexposed section).Less exploring degree and the adaptation of then meaning of this numerical value is all better.The results are shown in table 3.
(evaluation of resist shape)
In the evaluation of above-mentioned exploring degree adaptation, with the electron scanning type microscope S-500A of Hitachi resulting resist shape (cross sectional shape of resist figure) is observed.
In the situation that resist is shaped as in the situation of trapezoidal or inverted trapezoidal, the crimping that has resist or crackle, in the circuit that the etch processes by thereafter or plating form, the tendency of easy generation short circuit, broken string is arranged.Therefore, wish that the resist shape is rectangle (rectangle) and crimping or the crackle that does not have resist.The results are 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 Line-width precision of resist)
For estimating the Line-width precision of resist, to be 10/10(unit with the live width/line-spacing that has of negative film as the evaluation of exploring degree: the glass chromium type optical tool driving fit of line pattern μ m) be on the support membrane of test film obtained above, use has the exposure machine of high-pressure sodium lamp, and the energy fluence take the remaining hop count of 41 sections stage metraster as 14 sections and 17 sections exposes to the photo-sensitive resin of above-mentioned duplexer.After the exposure, carry out the development treatment identical with 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 represents then that more near 10 μ m values Line-width precision is higher.The results are shown in table 3.
(evaluation of peel property)
Test film is cut into the tetragonal size of 40mm * 50mm, and the photo-sensitive resin take the remaining hop count of 41 sections stage metraster as 14 sections energy fluence to above-mentioned duplexer carries out blanket exposure.After the exposure, carry out the development treatment identical with 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 on one side, by the resist surface of each test film of visualization.
To begin to peel off fully to cured film from substrate time of removing as splitting time from stirring.
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 less, means that then peel property is better.The results are 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 less than 30mm.
Table 3
Be 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 Line-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 (95)
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 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, described (A) binder polymer further contains the structural unit that comes from (methyl) alkyl acrylate.
3. photosensitive polymer combination according to claim 2, wherein, described (methyl) alkyl acrylate is the compound shown in the following general formula (IV),
In the above-mentioned general formula (IV), R
9Expression hydrogen atom or methyl, R
10The alkyl of expression carbon number 1 ~ 12.
4. photosensitive polymer combination according to claim 1, wherein, described (A) binder polymer further contains the structural unit that comes from the styrene or derivatives thereof.
5. photosensitive polymer combination according to claim 2, wherein, described (A) binder polymer further contains the structural unit that comes from the styrene or derivatives thereof.
6. photosensitive polymer combination according to claim 1, wherein, described coming from (methyl) benzyl acrylate or the containing ratio of the structural unit of (methyl) benzyl acrylate derivant take the all-mass of binder polymer molecule as benchmark as 5 quality % ~ 65 quality %.
7. photosensitive polymer combination according to claim 2, wherein, described coming from (methyl) benzyl acrylate or the containing ratio of the structural unit of (methyl) benzyl acrylate derivant take the all-mass of binder polymer molecule as benchmark as 5 quality % ~ 65 quality %.
8. photosensitive polymer combination according to claim 1, wherein, described coming from (methyl) benzyl acrylate or the containing ratio of the structural unit of (methyl) benzyl acrylate derivant take the all-mass of binder polymer molecule as benchmark as 10 quality % ~ 55 quality %.
9. photosensitive polymer combination according to claim 2, wherein, described coming from (methyl) benzyl acrylate or the containing ratio of the structural unit of (methyl) benzyl acrylate derivant take the all-mass of binder polymer molecule as benchmark as 10 quality % ~ 55 quality %.
10. photosensitive polymer combination according to claim 1, wherein, described coming from (methyl) benzyl acrylate or the containing ratio of the structural unit of (methyl) benzyl acrylate derivant take the all-mass of binder polymer molecule as benchmark as 20 quality % ~ 50 quality %.
11. photosensitive polymer combination according to claim 2, wherein, described coming from (methyl) benzyl acrylate or the containing ratio of the structural unit of (methyl) benzyl acrylate derivant take the all-mass of binder polymer molecule as benchmark as 20 quality % ~ 50 quality %.
12. photosensitive polymer combination according to claim 2, wherein, described coming from (methyl) alkyl acrylate structural unit containing ratio take the all-mass of binder polymer molecule as benchmark as 1 quality % ~ 50 quality %.
13. photosensitive polymer combination according to claim 3, wherein, described coming from (methyl) alkyl acrylate structural unit containing ratio take the all-mass of binder polymer molecule as benchmark as 1 quality % ~ 50 quality %.
14. photosensitive polymer combination according to claim 2, wherein, described coming from (methyl) alkyl acrylate structural unit containing ratio take the all-mass of binder polymer molecule as benchmark as 2 quality % ~ 30 quality %.
15. photosensitive polymer combination according to claim 3, wherein, described coming from (methyl) alkyl acrylate structural unit containing ratio take the all-mass of binder polymer molecule as benchmark as 2 quality % ~ 30 quality %.
16. photosensitive polymer combination according to claim 2, wherein, described coming from (methyl) alkyl acrylate structural unit containing ratio take the all-mass of binder polymer molecule as benchmark as 3 quality % ~ 20 quality %.
17. photosensitive polymer combination according to claim 3, wherein, described coming from (methyl) alkyl acrylate structural unit containing ratio take the all-mass of binder polymer molecule as benchmark as 3 quality % ~ 20 quality %.
18. photosensitive polymer combination according to claim 4, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 5 quality % ~ 65 quality %.
19. photosensitive polymer combination according to claim 5, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 5 quality % ~ 65 quality %.
20. photosensitive polymer combination according to claim 4, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 10 quality % ~ 60 quality %.
21. photosensitive polymer combination according to claim 5, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 10 quality % ~ 60 quality %.
22. photosensitive polymer combination according to claim 4, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 15 quality % ~ 55 quality %.
23. photosensitive polymer combination according to claim 5, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 15 quality % ~ 55 quality %.
24. photosensitive polymer combination according to claim 4, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 20 quality % ~ 50 quality %.
25. photosensitive polymer combination according to claim 5, wherein, the containing ratio of the described structural unit that comes from the styrene or derivatives thereof take the all-mass of binder polymer molecule as benchmark as 20 quality % ~ 50 quality %.
26. photosensitive polymer combination according to claim 1, wherein, the weight-average molecular weight of described binder polymer (Mw) is 10000 ~ 100000.
27. photosensitive polymer combination according to claim 2, wherein, the weight-average molecular weight of described binder polymer (Mw) is 10000 ~ 100000.
28. photosensitive polymer combination according to claim 1, wherein, the weight-average molecular weight of described binder polymer (Mw) is 20000 ~ 80000.
29. photosensitive polymer combination according to claim 2, wherein, the weight-average molecular weight of described binder polymer (Mw) is 20000 ~ 80000.
30. photosensitive polymer combination according to claim 1, wherein, the weight-average molecular weight of described binder polymer (Mw) is 25000 ~ 60000.
31. photosensitive polymer combination according to claim 2, wherein, the weight-average molecular weight of described binder polymer (Mw) is 25000 ~ 60000.
32. photosensitive polymer combination according to claim 1, wherein, described (B) composition contains bisphenol A-type (methyl) acrylate compounds.
33. photosensitive polymer combination according to claim 2, wherein, described (B) composition contains bisphenol A-type (methyl) acrylate compounds.
34. photosensitive polymer combination according to claim 32, wherein, described bisphenol A-type (methyl) acrylate compounds is the compound shown in the following general formula (III),
In the above-mentioned general formula (III), R
7And R
8Represent independently of one another hydrogen atom or methyl, X represents the alkylidene of carbon number 2 ~ 6 independently of one another, and 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 block ground exist.
35. photosensitive polymer combination according to claim 33, wherein, described bisphenol A-type (methyl) acrylate compounds is the compound shown in the following general formula (III),
In the above-mentioned general formula (III), R
7And R
8Represent independently of one another hydrogen atom or methyl, X represents the alkylidene of carbon number 2 ~ 6 independently of one another, and 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 block ground exist.
36. photosensitive polymer combination according to claim 34, wherein, described X is ethylidene, propylidene or isopropylidene.
37. photosensitive polymer combination according to claim 35, wherein, described X is ethylidene, propylidene or isopropylidene.
38. photosensitive polymer combination according to claim 34, wherein, the compound shown in the described general formula (III) comprises the compound of m+n=3 ~ 6 and the compound of m+n=8 ~ 10.
39. photosensitive polymer combination according to claim 35, wherein, the compound shown in the described general formula (III) comprises the compound of m+n=3 ~ 6 and the compound of m+n=8 ~ 10.
40. described photosensitive polymer combination according to claim 38, wherein, the compound (IIIb) of the compound of described m+n=3 ~ 6 (IIIa) and m+n=8 ~ 10 to contain than (IIIa/IIIb) be 1/10 ~ 1/1.
41. described photosensitive polymer combination according to claim 39, wherein, the compound (IIIb) of the compound of described m+n=3 ~ 6 (IIIa) and m+n=8 ~ 10 to contain than (IIIa/IIIb) be 1/10 ~ 1/1.
42. described photosensitive polymer combination according to claim 38, wherein, the compound (IIIb) of the compound of described m+n=3 ~ 6 (IIIa) and m+n=8 ~ 10 to contain than (IIIa/IIIb) be 1/7 ~ 1/3.
43. described photosensitive polymer combination according to claim 39, wherein, the compound (IIIb) of the compound of described m+n=3 ~ 6 (IIIa) and m+n=8 ~ 10 to contain than (IIIa/IIIb) be 1/7 ~ 1/3.
44. photosensitive polymer combination according to claim 1, wherein, described (B) composition comprises two (4-((methyl) the acryloxy polyethoxies of 2,2-) phenyl) propane.
45. photosensitive polymer combination according to claim 2, wherein, described (B) composition comprises two (4-((methyl) the acryloxy polyethoxies of 2,2-) phenyl) propane.
46. photosensitive polymer combination according to claim 1, wherein, described (B) composition contains in the molecule poly alkylene glycol two (methyl) acrylate of at least one party with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
47. photosensitive polymer combination according to claim 2, wherein, described (B) composition contains in the molecule poly alkylene glycol two (methyl) acrylate of at least one party with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
48. photosensitive polymer combination according to claim 1, wherein, described (B) composition contains in the molecule poly alkylene glycol two (methyl) acrylate of two sides with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
49. photosensitive polymer combination according to claim 2, wherein, described (B) composition contains in the molecule poly alkylene glycol two (methyl) acrylate of two sides with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
50. described photosensitive polymer combination according to claim 48, wherein, described poly alkylene glycol two (methyl) acrylate is the compound shown in following general formula (V), general formula (VI) or the general formula (VII),
In above-mentioned general formula (V), general formula (VI) and the general formula (VII), R represents hydrogen atom or methyl independently of one another, and EO represents the oxygen ethylidene, and PO represents oxygen propylidene, m
1, m
2, m
3And m
4The repeat number of the structural unit that expression is made of the oxygen ethylidene, n
1, n
2, n
3And n
4The repeat number of the structural unit that expression is made of the oxygen propylidene, the repetition sum m of oxygen ethylidene
1+ m
2, m
3And m
4Represent independently of one another 1 ~ 30 number, the repetition sum n of oxygen propylidene
1, n
2+ n
3And n
4Represent independently of one another 1 ~ 30 number.
51. described photosensitive polymer combination according to claim 49, wherein, described poly alkylene glycol two (methyl) acrylate is the compound shown in following general formula (V), general formula (VI) or the general formula (VII),
In above-mentioned general formula (V), general formula (VI) and the general formula (VII), R represents hydrogen atom or methyl independently of one another, and EO represents the oxygen ethylidene, and PO represents oxygen propylidene, m
1, m
2, m
3And m
4The repeat number of the structural unit that expression is made of the oxygen ethylidene, n
1, n
2, n
3And n
4The repeat number of the structural unit that expression is made of the oxygen propylidene, the repetition sum m of oxygen ethylidene
1+ m
2, m
3And m
4Represent independently of one another 1 ~ 30 number, the repetition sum n of oxygen propylidene
1, n
2+ n
3And n
4Represent independently of one another 1 ~ 30 number.
52. photosensitive polymer combination according to claim 1, wherein, described acylphosphine oxide based compound is the compound shown in following general formula (I) or the general formula (II),
In the general formula (I), R
1, R
2And R
3The alkyl or aryl that represents independently of one another carbon number 1 ~ 20, in the formula (II), R
4, R
5And R
6The alkyl or aryl that represents independently of one another carbon number 1 ~ 20.
53. photosensitive polymer combination according to claim 2, wherein, described acylphosphine oxide based compound is the compound shown in following general formula (I) or the general formula (II),
In the general formula (I), R
1, R
2And R
3The alkyl or aryl that represents independently of one another carbon number 1 ~ 20, in the formula (II), R
4, R
5And R
6The alkyl or aryl that represents independently of one another carbon number 1 ~ 20.
54. 2 described photosensitive polymer combinations according to claim 5, wherein, the compound shown in described general formula (I) or the general formula (II) is the compound shown in following general formula (VIII) or the general formula (IX),
In the above-mentioned general formula (VIII), R
11, R
12And R
13Represent independently of one another the alkyl of carbon number 1 ~ 6 or the alkoxy of carbon number 1 ~ 4, p1, p2 and p3 represent 0 ~ 5 integer independently of one another, and 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,
In the above-mentioned general formula (IX), R
14, R
15And R
16Represent independently of one another the alkyl of carbon number 1 ~ 6 or the alkoxy of carbon number 1 ~ 4, q1, q2 and q3 represent 0 ~ 5 integer independently of one another, and 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.
55. 3 described photosensitive polymer combinations according to claim 5, wherein, the compound shown in described general formula (I) or the general formula (II) is the compound shown in following general formula (VIII) or the general formula (IX),
In the above-mentioned general formula (VIII), R
11, R
12And R
13Represent independently of one another the alkyl of carbon number 1 ~ 6 or the alkoxy of carbon number 1 ~ 4, p1, p2 and p3 represent 0 ~ 5 integer independently of one another, and 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,
In the above-mentioned general formula (IX), R
14, R
15And R
16Represent independently of one another the alkyl of carbon number 1 ~ 6 or the alkoxy of carbon number 1 ~ 4, q1, q2 and q3 represent 0 ~ 5 integer independently of one another, and 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.
56. 4 described photosensitive polymer combinations according to claim 5, wherein, described R
11Alkyl for carbon number 1 ~ 4.
57. 5 described photosensitive polymer combinations according to claim 5, wherein, described R
11Alkyl for carbon number 1 ~ 4.
58. 4 described photosensitive polymer combinations according to claim 5, wherein, described R
11Be methyl.
59. 5 described photosensitive polymer combinations according to claim 5, wherein, described R
11Be methyl.
60. 4 described photosensitive polymer combinations according to claim 5, wherein, described p1 is 3.
61. 5 described photosensitive polymer combinations according to claim 5, wherein, described p1 is 3.
62. 4 described photosensitive polymer combinations according to claim 5, wherein, described p2 and p3 are 0.
63. 5 described photosensitive polymer combinations according to claim 5, wherein, described p2 and p3 are 0.
64. 4 described photosensitive polymer combinations according to claim 5, wherein, described R
14And R
15Independent separately is the alkyl of carbon number 1 ~ 4.
65. 5 described photosensitive polymer combinations according to claim 5, wherein, described R
14And R
15Independent separately is the alkyl of carbon number 1 ~ 4.
66. 4 described photosensitive polymer combinations according to claim 5, wherein, described R
14And R
15Be methyl.
67. 5 described photosensitive polymer combinations according to claim 5, wherein, described R
14And R
15Be methyl.
68. 4 described photosensitive polymer combinations according to claim 5, wherein, described q1 and q2 are 3.
69. 5 described photosensitive polymer combinations according to claim 5, wherein, described q1 and q2 are 3.
70. 4 described photosensitive polymer combinations according to claim 5, wherein, described q3 is 0.
71. 5 described photosensitive polymer combinations according to claim 5, wherein, described q3 is 0.
72. photosensitive polymer combination according to claim 1, wherein, described acylphosphine oxide based compound is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
73. photosensitive polymer combination according to claim 2, wherein, described acylphosphine oxide based compound is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
74. photosensitive polymer combination according to claim 1, wherein, described acylphosphine oxide based compound is two (2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
75. photosensitive polymer combination according to claim 2, wherein, described acylphosphine oxide based compound is two (2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
76. photosensitive polymer combination according to claim 1, wherein, the containing ratio of described acylphosphine oxide based compound is 20 quality % ~ 60 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater.
77. photosensitive polymer combination according to claim 2, wherein, the containing ratio of described acylphosphine oxide based compound is 20 quality % ~ 60 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater.
78. photosensitive polymer combination according to claim 1, wherein, the containing ratio of described acylphosphine oxide based compound is 30 quality % ~ 45 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater.
79. photosensitive polymer combination according to claim 2, wherein, the containing ratio of described acylphosphine oxide based compound is 30 quality % ~ 45 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater.
80. photosensitive polymer combination according to claim 1, wherein, described Hexaarylbiimidazole derivant is 2,4,5-triarylimidazoles dipolymer.
81. photosensitive polymer combination according to claim 2, wherein, described Hexaarylbiimidazole derivant is 2,4,5-triarylimidazoles dipolymer.
82. photosensitive polymer combination according to claim 1, wherein, the containing ratio of described Hexaarylbiimidazole derivant is 30 quality % ~ 70 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater composition.
83. photosensitive polymer combination according to claim 2, wherein, the containing ratio of described Hexaarylbiimidazole derivant is 30 quality % ~ 70 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater composition.
84. photosensitive polymer combination according to claim 1, wherein, the containing ratio of described Hexaarylbiimidazole derivant is 45 quality % ~ 65 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater composition.
85. photosensitive polymer combination according to claim 2, wherein, the containing ratio of described Hexaarylbiimidazole derivant is 45 quality % ~ 65 quality % with respect to the total amount of (C) Photoepolymerizationinitiater initiater composition.
86. photosensitive polymer combination according to claim 1, wherein, described (C-1) acylphosphine oxide based compound is 0.1 ~ 0.9 with respect to the ratio (C-1/C-2) that contains of described (C-2) Hexaarylbiimidazole derivant.
87. photosensitive polymer combination according to claim 2, wherein, described (C-1) acylphosphine oxide based compound is 0.1 ~ 0.9 with respect to the ratio (C-1/C-2) that contains of described (C-2) Hexaarylbiimidazole derivant.
88. photosensitive polymer combination according to claim 1, wherein, described (C-1) acylphosphine oxide based compound is 0.3 ~ 0.9 with respect to the ratio (C-1/C-2) that contains of described (C-2) Hexaarylbiimidazole derivant.
89. photosensitive polymer combination according to claim 2, wherein, described (C-1) acylphosphine oxide based compound is 0.3 ~ 0.9 with respect to the ratio (C-1/C-2) that contains of described (C-2) Hexaarylbiimidazole derivant.
90. photosensitive polymer combination according to claim 1, wherein, described (C-1) acylphosphine oxide based compound is 0.5 ~ 0.8 with respect to the ratio (C-1/C-2) that contains of described (C-2) Hexaarylbiimidazole derivant.
91. photosensitive polymer combination according to claim 2, wherein, described (C-1) acylphosphine oxide based compound is 0.5 ~ 0.8 with respect to the ratio (C-1/C-2) that contains of described (C-2) Hexaarylbiimidazole derivant.
92. a photosensitive element, it possesses supporter and is formed at the photo-sensitive resin of filming as the described photosensitive polymer combination of any one in the claim 1 ~ 91 on the described supporter.
93. the manufacture method of a resist figure, it has: in the photo-sensitive resin formation operation of substrate formation as the photo-sensitive resin of filming of the described photosensitive polymer combination of any one in the claim 1 ~ 91; At least a portion of described photo-sensitive resin irradiation active ray is made the exposure process of its photocuring; And the uncured portion of described photo-sensitive resin removed from substrate and form the developing procedure of the resist figure that the solidfied material by described photo-sensitive resin consists of.
94. the manufacture method of a lead frame, it comprises the substrate that the manufacture method by the described resist figure of claim 93 is formed with the resist figure and carries out the operation that plating forms conductor fig.
95. the manufacture method of a printed-wiring board (PWB), it comprises the substrate that the manufacture method by the described resist figure of claim 93 is formed with the resist figure and carries out the operation that plating forms conductor fig.
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| CN2011800043618A Pending CN102597877A (en) | 2010-07-30 | 2011-06-10 | 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 |
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| 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 |
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| US20080255297A1 (en) * | 2007-04-12 | 2008-10-16 | Chisso Corporation | Ink-jet ink |
| CN101401039A (en) * | 2006-03-08 | 2009-04-01 | 富士胶片株式会社 | Photosensitive composition, photosensitive film, method for permanent pattern formation using said photosensitive composition, and printed board |
| US20090170009A1 (en) * | 2007-12-27 | 2009-07-02 | Fujifilm Corporation | Holographic recording composition and holographic recording medium |
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| JP2005084537A (en) * | 2003-09-10 | 2005-03-31 | Asahi Kasei Electronics Co Ltd | Photosensitive resin composition for sandblasting and its use |
| JP4360242B2 (en) * | 2004-03-24 | 2009-11-11 | Ｊｓｒ株式会社 | Negative radiation sensitive resin composition |
| 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 |
| CN101558356B (en) * | 2006-12-19 | 2013-09-25 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
| WO2008078483A1 (en) * | 2006-12-27 | 2008-07-03 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
| WO2008114635A1 (en) * | 2007-03-20 | 2008-09-25 | Jsr Corporation | Radiation-sensitive resin composition |
| 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 |
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| US20080255297A1 (en) * | 2007-04-12 | 2008-10-16 | Chisso Corporation | Ink-jet ink |
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