CN101675388B - Photosensitive resin composition, photosensitive element, method of forming resist pattern, and process for producing printed wiring board - Google Patents

Photosensitive resin composition, photosensitive element, method of forming resist pattern, and process for producing printed wiring board Download PDF

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Publication number
CN101675388B
CN101675388B CN2008800142486A CN200880014248A CN101675388B CN 101675388 B CN101675388 B CN 101675388B CN 2008800142486 A CN2008800142486 A CN 2008800142486A CN 200880014248 A CN200880014248 A CN 200880014248A CN 101675388 B CN101675388 B CN 101675388B
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photosensitive resin
resin composition
expression
epoxy resin
formula
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CN101675388A (en
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佐藤邦明
吉野利纯
大川昌也
日高敬浩
立木秀康
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Lishennoco Co ltd
Resonac Corp
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Hitachi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

A photosensitive resin composition comprising (A) an acid-modified vinyl-containing epoxy resin, (B) a photopolymerization initiator containing a compound having an oxime ester bond and (C) a sensitizer containing any of coumarin compounds of the following general formula (1).

Description

The formation method of photosensitive resin composition, photosensitive element, resist pattern and the manufacturing approach of printed circuit board (PCB)
Technical field
The present invention relates to the formation method of photosensitive resin composition, photosensitive element, resist pattern and the manufacturing approach of printed circuit board (PCB).
Background technology
Permanent mask resist is to adopt the method for serigraphy thermohardening type resist printing ink or ultraviolet hardening resist printing ink to make in the printed circuit board (PCB) manufacturing in the past.Be accompanied by the highly integrated of electronic equipment in recent years, in printed circuit board (PCB), require the height of wiring pattern and insulating pattern to become more meticulous.But, for the resist forming method that in the past utilized serigraphy since the time can ooze in printing spread and sink in, drip etc., be difficult to form high meticulous resist image.Therefore, developed the resist image forming method that utilizes photolithography in order to form high meticulous resist image.Be specially following method: the hot pressing of dry-film type photosensitivity resist is received on the base material; Perhaps coating of photosensitivity resist curtain or the spraying with liquid state is applied on the base material, behind minus mask irradiation ultraviolet radiation isoreactivity light, forms the resist image through developing.The situation of dry-film type photosensitivity resist to the base material thermo-compressed time, is involved in air easily and produces bubble, thereby causes that adaptation reduces, the resist image is mixed and disorderly, may reduce the resist performance.
On the other hand, liquid photosensitivity resist comprises solvent develop type and alkali developable, and the angle of collateral security operating environment, the environment of preserving our planet considers that alkali developable becomes main flow.Photosensitivity resist (photosensitive resin composition) as such alkali developable is known to the resist shown in following patent documentation 1 and 2.In addition, in order to improve thermotolerance, chemical reagent resistance, the electrology characteristic of filming, also taked further to carry out ultraviolet exposure and heated to promote cross-linking reaction to filming.
Yet,, do not use mask pattern and the what is called of directly describing the resist pattern is directly described exposure method and received concern as the formation method of resist pattern.Think that directly describing exposure method according to this can form high-resolution resist pattern with high productivity.And; The laser of oscillation wavelength 405nm, long-life and high output in recent years gallium nitride based blue laser light source becomes gradually and can practicably be used as light source; Through at the laser of directly describing to utilize in the exposure method such short wavelength, wait in expectation to form was difficult to the highdensity resist pattern made in the past.Proposed the method that digital light that application Texas Instruments (Texas Instruments) advocates is handled (DLP) system as such exposure method Ball semiconductor company (BallSemiconductor) of directly describing, the exposure device that is suitable for this method begun practicability.
And then, attempt through adopting such laser such as blue laser to propose several kinds (reference example such as patent documentations 3,4) so far as the photosensitive resin composition of directly describing exposure method formation resist pattern of active ray.
Patent documentation 1: japanese kokai publication sho 61-243869 communique
Patent documentation 2: japanese kokai publication hei 1-141904 communique
Patent documentation 3: TOHKEMY 2002-296764 communique
Patent documentation 4: TOHKEMY 2004-45596 communique
Summary of the invention
Even but the photosensitive resin composition of record in above-mentioned patent documentation 3 and 4, when adopting the situation directly describe exposure method etc., still there is further room for improvement in light sensitivity when using near the wavelength 405nm exposure light to form the resist pattern.
The present invention carries out in view of the problem that exists in the above-mentioned prior art, the photosensitive resin composition that light sensitivity was excellent when its purpose was to provide the exposure light that uses in wavelength 370nm～450nm scope to form the resist pattern, uses photosensitive element, the formation method of resist pattern and the manufacturing approach of printed circuit board (PCB) of said composition.
To achieve these goals; The invention provides a kind of photosensitive resin composition, contain (A) sour modification and contain vinyl epoxy resin, (B) and comprise the Photoepolymerizationinitiater initiater of compound and (C) comprise sensitizer by the coumarin compound of formula (1) expression with oxime ester bond.
[changing 1]
Z in the formula (1) 1The carbon number of the hydroxy alkyl of the alkyl thiol of the alkyl amino of the aryl of the alkyl of expression halogen atom, carbon number 1～20, the naphthenic base of carbon number 3～10, carbon number 6～14, amino, carbon number 1～10, the dialkyl amido of carbon number 1～20, sulfydryl, carbon number 1～10, allyl, carbon number 1～20, carboxyl, alkyl be the carbon number of 1～10 carboxyalkyl, alkyl be 1～10 acyl group, carbon number 1～20 alkoxy, carbon number 1～20 alkoxy carbonyl group or comprise the group of heterocycle, Z 2The hydroxy alkyl of the alkyl thiol of the alkyl amino of the aryl of the alkyl of expression halogen atom, carbon number 1～20, the naphthenic base of carbon number 3～10, carbon number 6～14, amino, carbon number 1～10, the dialkyl amido of carbon number 1～20, sulfydryl, carbon number 1～10, allyl, carbon number 1～20, the carbon number of alkyl be 1～10 acyl group, carbon number 1～20 alkoxy, comprise the group of heterocycle or by the group of formula (2) expression, s representes 0～4 integer.In addition, the Z in the formula (2) 1With the Z in s and the formula (1) 1Identical with the s definition.And, the Z in the formula (1) 1With the Z in s and the formula (2) 1With s can be identical separately also can be different.And then s is under the situation more than 2 in formula (1) or the formula (2), existing a plurality of Z 1Can be identical separately also can be different, any two link and to form ring also passable each other.
[changing 2]
Figure G2008800142486D00031
According to such photosensitive resin composition; Through also containing (C) when (A) sour modification contains vinyl epoxy resin and the Photoepolymerizationinitiater initiater that (B) comprises the compound with oxime ester bond and comprise sensitizer containing by the coumarin compound of above-mentioned general formula (1) expression; Can be with the light sensitivity of excellence and resolution, use the exposure light in wavelength 370nm～450nm scope to form the resist pattern, particularly form the resist pattern through the exposure method of directly describing that uses wavelength 405nm laser.
And then; According to photosensitive resin composition of the present invention with above-mentioned formation; Thermotolerance, humidity resistance, adaptation, mechanical property, the excellent high performance cured film of electrology characteristic can be formed, printed circuit board (PCB), high-density multi-layered plate and semiconductor package body etc. can be used to make aptly.
In addition, photosensitive resin composition of the present invention preferably further contains the compound that (D) has mercapto.
The compound that above-mentioned through containing (D) has mercapto can suppress photosensitive resin composition fully along with gelation takes place effluxion, can improve ageing stability.
In addition, above-mentioned compound with oxime ester bond preferably includes at least a by the compound of formula (3) or (4) expression in the photosensitive resin composition of the present invention.
[changing 3]
Figure G2008800142486D00041
R in the formula (3) 1Replacement or the unsubstituted alkanoyl of expression carbon number 2～12, two key be not with the replacement or the unsubstituted alkoxy carbonyl group of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6 or replace or unsubstituted carbobenzoxy R 2, R 3And R 4Represent independently of one another replacement or unsubstituted alkyl, replacement or unsubstituted cyclopentyl, replacement or unsubstituted cyclohexyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl, replacement or unsubstituted benzoyl, the carbon number 2～12 of halogen atom, carbon number 1～12 replacement or unsubstituted alkanoyl, carbon number 2～12 replacement or unsubstituted alkoxy carbonyl group or replace or unsubstituted carbobenzoxy; M1 representes 0～4 integer, and m2 and m3 represent 0～5 integer independently of one another.In addition, m1 is under the situation more than 2, existing a plurality of R 2Can be identical separately also can be different, m2 is under the situation more than 2, existing a plurality of R 3Can be identical separately also can be different, m3 is under the situation more than 2, existing a plurality of R 4Can be identical separately also can be different.
[changing 4]
R in the formula (4) 5The replacement of the replacement of the replacement of the replacement of expression replacement or unsubstituted phenyl, carbon number 1～6 or unsubstituted alkyl, replacement or unsubstituted phenyl, carbon number 1～20 or unsubstituted alkyl, carbon number 5～8 or unsubstituted naphthenic base, carbon number 2～20 or unsubstituted alkanoyl or replacement or unsubstituted benzoyl, R 6Replacement or the unsubstituted alkanoyl of expression carbon number 2～12, two key be not with the replacement or the unsubstituted alkoxy carbonyl group of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6 or replace or unsubstituted carbobenzoxy R 7The replacement of the replacement of the replacement of expression hydrogen atom, halogen atom, carbon number 1～12 or unsubstituted alkyl, replacement or unsubstituted cyclopentyl, replacement or unsubstituted cyclohexyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl, replacement or unsubstituted benzoyl, carbon number 2～12 or unsubstituted alkanoyl, carbon number 2～12 or unsubstituted alkoxy carbonyl group or replacement or unsubstituted carbobenzoxy, R 8, R 9And R 10Represent independently of one another replacement or unsubstituted alkyl, replacement or unsubstituted cyclopentyl, replacement or unsubstituted cyclohexyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl, replacement or unsubstituted benzoyl, the carbon number 2～12 of halogen atom, carbon number 1～12 replacement or unsubstituted alkanoyl, carbon number 2～12 replacement or unsubstituted alkoxy carbonyl group or replace or unsubstituted carbobenzoxy; M4 and m5 represent 0～3 integer independently of one another, and m6 representes 0～5 integer.In addition, m4 is under the situation more than 2, existing a plurality of R 8Can be identical separately also can be different, m5 is under the situation more than 2, existing a plurality of R 9Can be identical separately also can be different, m6 is under the situation more than 2, existing a plurality of R 10Can be identical separately also can be different.
About (B) Photoepolymerizationinitiater initiater; Through containing the compound with oxime ester bond by above-mentioned general formula (3) or (4) expression, photosensitive resin composition can be with more excellent light sensitivity and resolution, use exposure light in wavelength 370nm～450nm scope to form resist pattern, the particularly exposure method of directly describing through use wavelength 405nm laser forms and comes the resist pattern.
In addition; In the photosensitive resin composition of the present invention, above-mentioned (A) sour modification contains vinyl epoxy resin and is preferably the resin that obtains with containing vinyl monocarboxylic acid (b) reaction from by at least a epoxy resin of selecting the phenolic resin varnish type epoxy resin of formula (5) expression, the group that constitutes by the bisphenol-type epoxy resin of formula (6) expression and by the salicylide type epoxy resin of formula (7) expression (a).
[changing 5]
Figure G2008800142486D00051
R in the formula (5) 11Expression hydrogen atom or methyl, Y 1Expression hydrogen atom or glycidyl (here, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70), n1 representes the integer more than 1.In addition, a plurality of R of existence 11And Y 1Can be identical separately also can be different.
[changing 6]
R in the formula (6) 12Expression hydrogen atom or methyl, Y 2Expression hydrogen atom or glycidyl (here, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70), n2 representes the integer more than 1.In addition, a plurality of R of existence 12And Y 2Can be identical separately also can be different.
[changing 7]
Y in the formula (7) 3Expression hydrogen atom or glycidyl (here, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70), n3 representes the integer more than 1.In addition, a plurality of R of existence 11And Y 3Can be identical separately also can be different.
Through using such (A) sour modification to contain vinyl epoxy resin, photosensitive resin composition can be with more excellent light sensitivity and resolution, use exposure light in wavelength 370nm～450nm scope to form the resist pattern, particularly directly describe exposure method formation resist pattern through what use wavelength 405nm laser.
In addition, the present invention provides a kind of photosensitive element, has support and photosensitive resin composition layer that the photosensitive resin composition by the invention described above that on this support, forms constitutes.
According to such photosensitive element; Through having the photosensitive resin composition layer that constitutes by above-mentioned photosensitive resin composition of the present invention, can be with the light sensitivity and the resolution of excellence, use the exposure light in wavelength 370nm～450nm scope to form the resist pattern, particularly form the resist pattern through the exposure method of directly describing that uses wavelength 405nm laser.
In addition, the present invention provides a kind of formation method of resist pattern, comprising: lamination operation, the photosensitive resin composition that will be made up of the photosensitive resin composition of the invention described above are long-pending layer by layer to substrate; Exposure process makes exposure portion carry out photocuring to above-mentioned photosensitive resin composition layer with image shape irradiation active ray; And developing procedure, the unexposed portion of removing above-mentioned photosensitive resin composition layer through development.
At this, above-mentioned exposure process is preferably through the laser of wavelength 405nm above-mentioned photosensitive resin composition layer directly to be described to make public and makes exposure portion carry out the operation of photocuring.
According to the formation method of such resist pattern,, can form the resist pattern of excellent in resolution effectively owing to adopted the photosensitive resin composition of the invention described above that light sensitivity is excellent when exposure method formation resist pattern is directly described in utilization.And the resist pattern that forms through such method becomes thermotolerance, humidity resistance, adaptation, mechanical property, the excellent high performance cured film of electrology characteristic.
The present invention further provides a kind of manufacturing approach of printed circuit board (PCB), and the circuit that the formation method of the resist pattern through the invention described above is formed with the resist pattern forms and carries out etching or plating with substrate.
According to the manufacturing approach of such printed circuit board (PCB), form the resist pattern owing to pass through the formation method of the resist pattern of the invention described above, can realize the densification that connects up.
In the time of can providing the exposure light that uses in wavelength 370nm～450nm scope to form the resist pattern according to the present invention, photosensitive resin composition that particularly light sensitivity is excellent when using directly the describing exposure method and form the resist pattern of wavelength 405nm laser, use photosensitive element, the formation method of resist pattern and the manufacturing approach of printed circuit board (PCB) of said composition.In addition; According to photosensitive resin composition of the present invention and photosensitive element; With the blue laser of wavelength 405nm as directly the describing can form in the exposure method and be difficult to the highdensity resist pattern made of light source in the past, and can obtain thermotolerance, humidity resistance (shear bond property), adaptation, mechanical property, the excellent high performance cured film of electrology characteristic.Thus, photosensitive resin composition of the present invention and photosensitive element can be used to make printed circuit board (PCB), high-density multi-layered plate and semiconductor package body etc. aptly.
Description of drawings
Fig. 1 is the schematic cross-section of a preferred implementation of expression photosensitive element of the present invention.
Symbol description
1 is that photosensitive element, 10 is that support, 14 is the photosensitive resin composition layer.
Embodiment
According to circumstances at length describe to preferred implementation of the present invention below with reference to accompanying drawing.To identical or be equal to part and give same-sign, omit the explanation of repetition in the accompanying drawing.In addition, (methyl) acrylic is meant acrylic and the methacrylic acid group corresponding with it among the present invention, and (methyl) acrylic ester is meant acrylic ester and the methacrylate corresponding with it.
Photosensitive resin composition of the present invention contains (A) sour modification and contains the Photoepolymerizationinitiater initiater that vinyl epoxy resin (below be sometimes referred to as " (A) composition "), (B) comprise the compound with oxime ester bond (below be sometimes referred to as " (B) composition ") and (C) comprise by the sensitizer of the coumarin compound of above-mentioned general formula (1) expression (below be sometimes referred to as " (C) composition "), preferably further contains the compound that (D) have mercapto (below be sometimes referred to as " (D) composition ").At length describe to each composition below.
Contain vinyl epoxy resin as (A) sour modification of using among the present invention and adopt, be preferably the resin that obtains with containing vinyl monocarboxylic acid (b) reaction from by at least a epoxy resin of selecting the phenolic resin varnish type epoxy resin of formula (5) expression, the group that constitutes by the bisphenol A type epoxy resin of formula (6) expression or bisphenol f type epoxy resin and by the salicylide type epoxy resin of formula (7) expression (a) by containing the resin that the vinyl monocarboxylic acid is crossed epoxy resin modification.
[changing 8]
Figure G2008800142486D00081
R in the formula (5) 11Expression hydrogen atom or methyl, Y 1Expression hydrogen atom or glycidyl (here, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70), n1 representes the integer more than 1.In addition, a plurality of R of existence 11And Y 1Can be identical separately also can be different.
[changing 9]
Figure G2008800142486D00091
R in the formula (6) 12Expression hydrogen atom or methyl, Y 2Expression hydrogen atom or glycidyl (here, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70), n2 representes the integer more than 1.In addition, a plurality of R of existence 12And Y 2Can be identical separately also can be different.
[changing 10]
Figure G2008800142486D00092
Y in the formula (7) 3Expression hydrogen atom or glycidyl (here, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70), n3 representes the integer more than 1.In addition, a plurality of R of existence 11And Y 3Can be identical separately also can be different.
(A) sour modification of using among the present invention contains vinyl epoxy resin except above-mentioned epoxy resin (a) with contain and can also adopt the resultant of reaction (below be called " resultant of reaction (A ') ") of vinyl monocarboxylic acid (b) that addition contains addition reaction product saturated or unsaturated group multi-anhydride (c) to this resultant of reaction (A ').At this; Infer when synthesizing the addition reaction product in initial reaction; Through the epoxy radicals of epoxy resin (a) and the addition reaction formation hydroxyl of the carboxyl that contains vinyl monocarboxylic acid (b); In ensuing reaction, the hydroxyl that is generated (also comprising the hydroxyl that exists originally in the epoxy resin (a)) with contain anhydride group saturated or unsaturated group multi-anhydride (c) and carry out the half ester reaction.
As enumerating phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin by the phenolic resin varnish type epoxy resin of above-mentioned general formula (5) expression.These phenolic resin varnish type epoxy resins utilize known method to obtain through making phenol novolac resin, cresols novolac resin and chloropropylene oxide reaction respectively.
In addition, in the compound by above-mentioned general formula (6) expression, Y 2Hydroxyl and the chloropropylene oxide of bisphenol A type epoxy resin or bisphenol f type epoxy resin that for example can be through making formula (8) expression for the bisphenol A type epoxy resin of glycidyl or bisphenol f type epoxy resin reacts and obtains.
[changing 11]
Figure G2008800142486D00101
R in the formula (8) 12Expression hydrogen atom or methyl, n2 representes the integer more than 1.In addition, a plurality of R of existence 12Can be identical separately also can be different.
In order to promote the reaction of hydroxyl and chloropropylene oxide,, in dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide (DMSO) isopolarity organic solvent, react preferably 50～120 ℃ of temperature of reaction and in the presence of alkali metal hydroxide.Therefore and not preferred if temperature of reaction is less than 50 ℃ then react slack-off, a large amount of subsidiary reactions can take place when surpassing 120 ℃ in temperature of reaction.
As can enumerate FAE-2500, EPPN-501H, EPPN-502H (above is Japanese chemical drug (strain) manufacturing, trade name) etc. particularly by the salicylide type epoxy resin of above-mentioned general formula (7) expression.
In addition; Can enumerate for example acrylic acid, acrylic acid dipolymer, methacrylic acid, β-furfuryl group acrylic acid, β-styrene acrylic, cinnamic acid, crotonic acid, alpha-cyano cinnamic acid etc. as containing vinyl monocarboxylic acid (b), half ester compound, the conduct that also can enumerate in addition as the resultant of reaction of hydroxy acryl acid ester and saturated or unsaturated dicarboxylic acid anhydride contain vinyl list glycidyl ether or contain vinyl list ethylene oxidic ester and the half ester compound of the resultant of reaction of saturated or unsaturated dicarboxylic acid anhydride.These half ester compounds through with etc. mol ratio make the hydroxy acryl acid ester, contain the vinyl monoglycidyl ether or contain vinyl list ethylene oxidic ester and saturated or unsaturated dicarboxylic acid anhydride reacts and obtains.These contain vinyl monocarboxylic acid (b) and can use a kind perhaps to make up use more than 2 kinds separately.
As the hydroxy acryl acid ester that uses in the above-mentioned half ester compound of an example that contains vinyl monocarboxylic acid (b) synthetic; Contain vinyl list glycidyl ether; Contain vinyl list glycidyl esters and can enumerate for example Hydroxyethyl Acrylate; Methacrylic acid hydroxyl ethyl ester; The acrylic acid hydroxy propyl ester; Methacrylic acid hydroxyl propyl ester; Acrylic acid hydroxyl butyl ester; Methacrylic acid hydroxyl butyl ester; The polyglycol mono acrylic ester; Polyethylene glycol monomethacrylate; Trimethylolpropane diacrylate; The trimethylolpropane dimethylacrylate; Pentaerythritol triacrylate; Pentaerythritol acrylate trimethyl; Dipentaerythritol five acrylic ester; Pentaerythrite pentamethyl acrylic ester; Glycidyl acrylate; GMA etc.
The synthetic middle saturated or unsaturated dicarboxylic acid anhydride that uses as above-mentioned half ester compound can be enumerated for example succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride etc.
Epoxy resin (a) and contain in the reaction of vinyl monocarboxylic acid (b) preferably with contain vinyl monocarboxylic acid (b) relatively epoxy radicals 1 equivalent of epoxy resin (a) be that the ratio of 0.6～1.05 equivalent reacts; Being that the ratio of 0.8～1.05 equivalent reacts to contain vinyl monocarboxylic acid (b) more preferably, is that the ratio of 0.9～1.0 equivalent reacts to contain vinyl monocarboxylic acid (b) especially preferably.
Epoxy resin (a) and contain vinyl monocarboxylic acid (b) and be preferably dissolved in organic solvent and react.Can enumerate for example ketone such as butanone, cyclohexanone as organic solvent; Toluene, xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, BC, propylene glycol monomethyl ether, DPG list ether, DPG diethyl ether, triethylene glycol list ether; Ester classes such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; Aliphatic hydrocarbon such as octane, decane, oil series solvents such as sherwood oil, petroleum naphtha, hydrotreated petroleum naphtha, solvent naphtha etc.
And then, in order to promote to react preferred use catalyzer.Catalyzer as using can be enumerated for example triethylamine, benzyl methylamine, methyl triethyl ammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine etc.Relative epoxy resin of catalyst consumption (a) and total 100 mass parts that contain vinyl monocarboxylic acid (b) are preferably 0.1～10 mass parts.
In addition, preferably use polymerization inhibitor for the polymerization in preventing to react.Can enumerate for example quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol etc. as polymerization inhibitor.Relative epoxy resin of the consumption of polymerization inhibitor (a) and total 100 mass parts that contain vinyl monocarboxylic acid (b) are preferably 0.01～1 mass parts.And temperature of reaction is preferably 60～150 ℃, and then is preferably 80～120 ℃.
In addition, as required can be with containing multi-anhydrides such as phenol system compound, trimellitic anhydride, PMA, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride and usefulness such as vinyl monocarboxylic acid (b) and p-hydroxyphenylethanol.
In addition, contain vinyl epoxy resin as (A) sour modification among the present invention and also preferably use the resin that above-mentioned resultant of reaction (A ') is obtained with containing saturated or unsaturated group multi-anhydride (c) reaction.
As containing saturated or unsaturated group multi-anhydride (c) can be enumerated for example succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride etc.
Resultant of reaction (A ') with contain in the reaction of saturated or unsaturated group multi-anhydride (c), through hydroxyl 1 equivalent reaction 0.1～1.0 equivalent in the relative response product (A ') contain saturated or unsaturated group multi-anhydride (c) can be regulated the acid number that sour modification contains vinyl epoxy resin (A).
(A) the sour modification acid number that contains vinyl epoxy resin is preferably 30～150mgKOH/g, more preferably 50～120mgKOH/g.If acid number less than 30mgKOH/g photosensitive resin composition the dissolubility of dilute alkaline soln is tended to reduce, the electrology characteristic of the cured film that obtains when surpassing 150mgKOH/g tends to reduce.
Resultant of reaction (A ') with contain temperature of reaction saturated or unsaturated group multi-anhydride (c) and be preferably 60～120 ℃.
In addition, as required, for example can also part also use the hydrogenation bisphenol A type epoxy resin as epoxy resin (a).And then containing vinyl epoxy resin as (A) sour modification can also part be resin with the styrene-maleic acid of the Hydroxyethyl Acrylate modifier of styrene-maleic anhydride copolymer or the Hydroxyethyl Acrylate modifier of styrene-maleic anhydride copolymer etc. also.
As for the content of (A) composition in the photosensitive resin composition, be that benchmark is preferably 10～60 quality % with the solid constituent total amount of photosensitive resin composition, more preferably 20～40 quality % are preferably 20～30 quality % especially.This content during less than 10 quality % thermotolerance tend to variation, curable tends to variation when surpassing 60 quality %.
Preferably use compound as the compound that comprises in (B) Photoepolymerizationinitiater initiater that uses among the present invention by formula (3) or (4) expression with oxime ester bond.
[changing 12]
Figure G2008800142486D00131
R in the above-mentioned general formula (3) 1Replacement or the unsubstituted alkanoyl of expression carbon number 2～12, two key be not with the replacement or the unsubstituted alkoxy carbonyl group of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6 or replace or unsubstituted carbobenzoxy.At this, alkanoyl has that this substituting group of substituent situation is preferably halogen atom or cyanic acid more than 1.Benzoyl has alkyl, halogen atom or the cyanic acid that this substituting group of substituent situation more than 1 is preferably carbon number 1～6.Carbobenzoxy has alkyl or the halogen atom that this substituting group of substituent situation more than 1 is preferably carbon number 1～6.
In addition, R in the above-mentioned general formula (3) 2, R 3And R 4Represent independently of one another replacement or unsubstituted alkyl, replacement or unsubstituted cyclopentyl, replacement or unsubstituted cyclohexyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl, replacement or unsubstituted benzoyl, the carbon number 2～12 of halogen atom, carbon number 1～12 replacement or unsubstituted alkanoyl, carbon number 2～12 replacement or unsubstituted alkoxy carbonyl group or replace or unsubstituted carbobenzoxy.At this, alkoxy carbonyl group has that this substituting group of substituent situation is preferably hydroxyl or alkoxy more than 1.
In addition, m1 representes 0～4 integer in the above-mentioned general formula (3), and m2 and m3 represent 0～5 integer independently of one another.In addition, m1 is a plurality of R that exist in the situation general formula (3) more than 2 2Can be identical separately also can be different, m2 is a plurality of R of existence in the situation general formula (3) 2 or more 3Can be identical separately also can be different, m3 is a plurality of R of existence in the situation general formula (3) 2 or more 4Can be identical separately also can be different.
[changing 13]
R in the above-mentioned general formula (4) 5The replacement of the replacement of the replacement of the replacement of expression replacement or unsubstituted phenyl, carbon number 1～6 or unsubstituted alkyl, replacement or unsubstituted phenyl, carbon number 1～20 or unsubstituted alkyl, carbon number 5～8 or unsubstituted naphthenic base, carbon number 2～20 or unsubstituted alkanoyl or replacement or unsubstituted benzoyl.At this, alkyl has that this substituting group of substituent situation is preferably hydroxyl or alkoxy more than 1.Benzoyl has the alkyl or phenyl that this substituting group of substituent situation more than 1 is preferably carbon number 1～6.
In addition, R in the above-mentioned general formula (4) 6Replacement or the unsubstituted alkanoyl of expression carbon number 2～12, two key be not with the replacement or the unsubstituted alkoxy carbonyl group of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6 or replace or unsubstituted carbobenzoxy.At this, alkanoyl has that this substituting group of substituent situation is preferably halogen atom or cyanic acid more than 1.Benzoyl has alkyl, halogen atom or the cyanic acid that this substituting group of substituent situation more than 1 is preferably carbon number 1～6.Carbobenzoxy has alkyl or the halogen atom that this substituting group of substituent situation more than 1 is preferably carbon number 1～6.
In addition, R in the above-mentioned general formula (4) 7The replacement of the replacement of the replacement of expression hydrogen atom, halogen atom, carbon number 1～12 or unsubstituted alkyl, replacement or unsubstituted cyclopentyl, replacement or unsubstituted cyclohexyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl, replacement or unsubstituted benzoyl, carbon number 2～12 or unsubstituted alkanoyl, carbon number 2～12 or unsubstituted alkoxy carbonyl group or replacement or unsubstituted carbobenzoxy, R 8, R 9And R 10Represent independently of one another replacement or unsubstituted alkyl, replacement or unsubstituted cyclopentyl, replacement or unsubstituted cyclohexyl, replacement or unsubstituted phenyl, replacement or unsubstituted benzyl, replacement or unsubstituted benzoyl, the carbon number 2～12 of halogen atom, carbon number 1～12 replacement or unsubstituted alkanoyl, carbon number 2～12 replacement or unsubstituted alkoxy carbonyl group or replace or unsubstituted carbobenzoxy.At this, alkoxy carbonyl group has that this substituting group of substituent situation is preferably hydroxyl or alkoxy more than 1.
In addition, m4 and m5 represent 0～3 integer independently of one another in the above-mentioned general formula (4), and m6 representes 0～5 integer.In addition, m4 is under the situation more than 2, existing a plurality of R 8Can be identical separately also can be different, m5 is under the situation more than 2, existing a plurality of R 9Can be identical separately also can be different, m6 is under the situation more than 2, existing a plurality of R 10Can be identical separately also can be different.
In addition; More specifically can enumerate by 1 of following formula (9) expression as the compound that comprises in (B) Photoepolymerizationinitiater initiater that uses among the present invention with oxime ester bond; 2-octane diketone-1-[4-(phenyl sulfo-) phenyl]-2-(O-benzoyl oximes) (trade name: OXE-01, Ciba manufactured), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl group oxime) (trade name: OXE-02, Ciba manufactured), 1-phenyl-1,2-propane diketone-2-[O-(carbethoxyl group) oxime] (trade name: Quantacure-PDO, Japanese chemical drug society make etc.).
[changing 14]
Figure G2008800142486D00151
In addition, can be also with above-mentioned compound Photoepolymerizationinitiater initiater in addition in the photosensitive resin composition of the present invention with oxime ester bond as (B) composition.
Photoepolymerizationinitiater initiater as beyond the compound with oxime ester bond can be enumerated for example benzoin classes such as benzoin, benzoin methylether, benzoin iso-propylether, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2; 2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl acetone-1, N; Aromatic series ketones such as N-dimethylamino benzoylformaldoxime, anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-amino anthraquinones, ketal classes such as acetophenone dimethyl ketal, dibenzoyl dimethyl ketal; Benzophenone, methyldiphenyl ketone, 4; 4 '-dichloro benzophenone, 4-benzoyl-4 '-benzophenones such as dimethyl diphenyl sulfide, 9-phenylacridine, 1,7-two (9; 9 '-acridinyl) acridine derivatives such as heptane; 2,4,5-triarylimidazoles dipolymer or derivatives thereof, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide etc.These materials can use a kind or combination to use more than 2 kinds separately.
The content of (B) composition in the photosensitive resin composition is preferably 0.5～20 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 2～10 quality % are preferably 2～5 quality % especially.If this content is less than 0.5 quality % then the often stripping in development easily of exposure portion, the thermotolerance of the cured film that obtains when surpassing 20 quality % tends to reduce.
(C) sensitizer that uses in the photosensitive resin composition of the present invention comprises the coumarin compound by formula (1) expression.
[changing 15]
Figure G2008800142486D00161
Z in the above-mentioned general formula (1) 1The carbon number of the hydroxy alkyl of the alkyl thiol of the alkyl amino of the aryl of the alkyl of expression halogen atom, carbon number 1～20, the naphthenic base of carbon number 3～10, carbon number 6～14, amino, carbon number 1～10, the dialkyl amido of carbon number 1～20, sulfydryl, carbon number 1～10, allyl, carbon number 1～20, carboxyl, alkyl be the carbon number of 1～10 carboxyalkyl, alkyl be 1～10 acyl group, carbon number 1～20 alkoxy, carbon number 1～20 alkoxy carbonyl group or comprise the group of heterocycle, Z 2The hydroxy alkyl of the alkyl thiol of the alkyl amino of the aryl of the alkyl of expression halogen atom, carbon number 1～20, the naphthenic base of carbon number 3～10, carbon number 6～14, amino, carbon number 1～10, the dialkyl amido of carbon number 1～20, sulfydryl, carbon number 1～10, allyl, carbon number 1～20, the carbon number of alkyl be 1～10 acyl group, carbon number 1～20 alkoxy, comprise the group of heterocycle or by the group of formula (2) expression, s representes 0～4 integer.In addition, the Z in the formula (2) 1With the Z in s and the formula (1) 1Identical with the s definition.And, the Z in the formula (1) 1With the Z in s and the formula (2) 1With s can be identical separately also can be different.And then s is under the situation more than 2 in formula (1) or the formula (2), existing a plurality of Z 1Can be identical separately also can be different, any two link and to form ring also passable each other.
[changing 16]
Figure G2008800142486D00162
Coumarin compound by above-mentioned general formula (1) expression absorbs as near the light the 405nm of wavelength photoreceptor, excites the compound with oxime ester bond as (B) Photoepolymerizationinitiater initiater.Coumarin compound by above-mentioned general formula (1) expression is preferably the compound of maximum absorption wavelength in 370nm～450nm scope.
In addition, Z in by the coumarin compound of above-mentioned general formula (1) expression 2Be preferably group by above-mentioned general formula (2) expression.And then the coumarin compound of being represented by above-mentioned general formula (1) is preferably 7,7 '-two (diethylamino)-3-ketone-cumarins (greening company ((strain) body ど り chemistry) manufacturing, trade name: BC) by following formula (10) expression especially.Through using coumarin compound can further improve light sensitivity to 405nm light by following formula (10) expression, can be so that more exposure method formation resist pattern is directly described in high resolving power, utilization.
[changing 17]
Figure G2008800142486D00171
In addition, the sensitizer as (C) composition also can comprise by other sensitizers beyond the coumarin compound of above-mentioned general formula (1) expression.Can enumerate for example anthracene class, Coumarins, xanthene ketone, thioxanthene ketone, 4 such as pyrazolines, dialkoxy anthracene as other sensitizers, 4 '-two (dialkyl amido) benzophenone, oxazole class, Benzooxazole kind, thiazoles, triazole type, stilbene class, triazines, thiophene-based etc.These materials can use a kind or combination to use more than 2 kinds separately.
The content of (C) composition in photosensitive resin composition is preferably 0.01～5 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 0.1～2 quality % is preferably 0.2～1 quality % especially.In above-mentioned scope, can obtain good light sensitivity through this content.
Consider that from the angle that ageing stability is good photosensitive resin composition of the present invention preferably further contains the compound that (D) has mercapto.The compound that has mercapto as (D) is preferably the compound that effective performance hydrogen is supplied with the body function.As such compound preferably by the compound of formula (11) expression.
[changing 18]
Ar representes to have the aryl of substituent divalence or trivalent in the formula, and X representes oxygen atom, nitrogen-atoms or sulphur atom.
The concrete example that has the compound of mercapto as (D) for example can be enumerated by the mercaptobenzoxazole (MBO) of following formula (12) expression, by the mercaptobenzothiazoler (MBT) of following formula (13) expression, by mercaptobenzimidazole (MBI), ethyl mercaptan, benzenethiol, mercapto-phenol, sulfydryl toluene, 2-mercaptoethylmaine, mercaptoethanol, sulfydryl xylene, sulfo-xylenols, 2-mercaptoquinoline, TGA, alpha-mercapto propionic acid, 3-mercaptopropionic acid, mercapto succinic acid, thiosalicylic acid, sulfydryl cyclohexane, alpha-mercapto diphenyl methane, C-mercapto-tetrazole, mercaptonaphthalene, sulfydryl naphthols, 4-sulfydryl biphenyl, sulfydryl hypoxanthine, mercaptopyridine, 2-mercaptopyrimidine, purinethol, sulfo-coumarone, sulfo-tonka-bean thiophene ketone, the butane-2 of following formula (14) expression; 3-two mercaptan, sulfo-cyanuric acid, 2; 4; 6-tri-thiol s-triazine, 2-dibutylamino-4; 6-dimercapto s-triazine, 2-anilino--4,6-dimercapto s-triazine etc.
[changing 19]
[changing 20]
Figure G2008800142486D00183
[changing 21]
Figure G2008800142486D00184
The compound that these (D) have mercapto can use a kind perhaps to make up use more than 2 kinds separately.Among these compounds; Supply with the body function, further improve the light sensitivity of photosensitive resin composition and the angle of ageing stability and consider from effective performance hydrogen; The compound that preferably in molecule, has sulfydryl, preferred particularly mercaptobenzoxazole (MBO), mercaptobenzothiazoler (MBT), mercaptobenzimidazole (MBI).
The content of (D) composition in photosensitive resin composition of the present invention is preferably 0.1～5 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 0.3～3 quality % is preferably 0.5～1.5 quality % especially.The often gelation easily of the solution of this content photosensitive resin composition during less than 0.1 quality %, light sensitivity tends to reduce when surpassing 5 quality %.
Enumerate exemplary compounds, above-mentioned (B) composition of combination in the expression photosensitive resin composition of the present invention, (C) composition are inferred reaction mechanism with (D) composition and during irradiation ultraviolet radiation in reactions formula (I)～(V).Be considered to following mechanism: at first; Absorb the light of 405nm as the coumarin compound (Sens) by above-mentioned general formula (1) expression of (C) sensitizer; Become the excited state of singlet state, but it reports to the leadship after accomplishing a task between being apace, become the excited state (reaction equation (I)) of triplet.This sensitizer that is excited moves the compound (OXE-01) (reaction equation (II)) by above-mentioned formula (9) expression with oxime ester bond that will excite as (B) Photoepolymerizationinitiater initiater through energy.Subsequently, the Photoepolymerizationinitiater initiater that becomes the triplet excitation state will decompose and produce free radical (reaction equation (III)).Then, the free radical of generation and (D) that supply with body as hydrogen have mercapto by compound (MBO) reaction of above-mentioned formula (12) expression and carry out chain and move, become active high sulphur free radical (reaction equation (IV) and (V)).Infer that this sulphur free radical is the effective constituent that promotes photopolymerization reaction.
[changing 22]
Figure G2008800142486D00191
[changing 23]
3(Sens) *+ 1(OXE-01)→ 1(Sens)+ 3(OXE-01) *(II)
[changing 24]
Figure G2008800142486D00201
[changing 25]
Figure G2008800142486D00202
[changing 26]
Figure G2008800142486D00203
In addition, consider that from the angle that can improve resistance to sudden heating and shear bond property photosensitive resin composition of the present invention preferably contains (E) elastic body.
Can enumerate for example styrene series elastomer, ethylene series elastic body, polyurethane series elastic body, polyester based elastomers, polyamide-based elastic body, acrylic elastomer and silicon-type elastic body etc. as (E) elastic body.These (E) elastic bodys are made up of hard segment and soft chain segment, and the former helps thermotolerance and intensity usually, and the latter helps flexibility and obdurability.
Can enumerate styrene-butadiene-styrene block copolymer, SIS, styrene-ethylene-butylene-styrene segmented copolymer, styrene-ethylene-propylene-styrene segmented copolymer etc. as styrene series elastomer.
Composition as constituting styrene series elastomer can also use styrene derivatives such as AMS, 3-methyl styrene, 4-propylstyrene, 4-cyclohexyl benzene ethene except styrene.Can enumerate tower particularly exhales Pu Lian (タ Off プ レ Application), Chinese herbaceous peony Pu Lian (ソ Le プ レ Application) T, A Sapulian (ア サ プ レ Application) T, tower to exhale Te Ke (タ Off テ Star Network) (above is Asahi Chemical Industry's industry (strain) manufacturing); Elastic body AR (the peace Longhua becomes manufactured); Exhale Le Kesi (リ Off レ Star Network ス excessively) (above is that shell Japanese firm makes) in Ku Ledun (Network レ イ ト Application) G, the card; JSR-TR, TSR-SIS, Da Yina synthetic fibre (ダ イ Na ロ Application) (above is Japanese synthetic rubber (strain) manufacturing); Electrification (デ Application カ) STR (electrochemical industry (strain) is made); The storehouse is because of Plutarch (Network イ Application タ Star Network) (Japanese ZEON manufactured); TPE-SB series (Sumitomo Chemical (strain) manufacturing) is drawn crust synthetic fibre (ラ バ ロ Application) (Mitsubishi Chemical's (strain) manufacturing), Sai Pudun (セ プ ト Application), extra large Bradley (Ha イ Block ラ one) (above is the Kuraray manufactured); This meter exhaled Le Kesi (ス ミ Off レ Star Network ス) (SUMITOMO CHEMICAL Bei Kulaite company (Sumitomo ベ one Network ラ イ ト (strain)) manufacturing), and thunder oersted agate (レ オ ス ト マ one), A Ku replace agate (ア Network テ イ マ one) (above is that reason is ground vinyl industrial group (reason is ground the industry of PVC ニ Le) manufacturing) etc.
The ethylene series elastic body is the multipolymer of the alpha-olefin of carbon numbers 2～20 such as ethene, propylene, 1-butylene, 1-hexene, 4-methylpentene, can enumerate for example ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) etc.In addition; Can enumerate bicyclopentadiene, 1 as the ethylene series elastic body, the non-conjugated diene of carbon numbers such as 4-hexadiene, cyclo-octadiene, methene norbornene, ethylidene norbornene, butadiene, isoprene 2～20 and the multipolymer of alpha-olefin and epoxidized polybutadiene etc.In addition, can enumerate for the hycar copolymerization the carboxy-modified NBR behind the methacrylic acid etc. as the ethylene series elastic body.And then, can enumerate ethylene-, ethylene-alpha-olefin-nonconjugated diene copolymers rubber, propylene-alpha-olefin copolymers rubber, 1-butene-alpha-olefin copolymers rubber etc. as the ethylene series elastic body.
Can enumerate the special agate (ミ ラ ス ト マ) (manufacturing of Mitsui petrochemistry society) of Mi Lasi particularly as the ethylene series elastic body; EXACT (exxon chemical manufactured); ENGAGE (Dow Chemical Company's manufacturing); Hydrogenation SBR styrene butadiene rubbers " DYNABON HSBR " (Japanese synthetic rubber society make); Hycar " NBR series " (Japanese synthetic rubber society make); " XER series " (Japanese synthetic rubber society make) with two terminal carboxyl group modification hycars of crosslinking points; With " BF-1000 " of the epoxidized polybutadiene behind the polybutadiene part epoxidation (Japanese Cao Da society make) etc.
The polyurethane series elastic body comprises the hard segment that is made up of low molecule (short chain) two pure and mild diisocyanate and the structural unit of the soft chain segment that is made up of macromolecule (long-chain) two pure and mild diisocyanate.Can enumerate polypropylene glycol, polytetramethylene glycol, gather (1 as macromolecule (long-chain) glycol; The 4-butylene adipate), gather (ethylidene-1; The 4-butylene adipate), polycaprolactone, gather (1,6-hexylidene carbonic ester), gather (1,6-hexylidene-Ya neopentyl adipate) etc.The number-average molecular weight of macromolecule (long-chain) glycol is preferably 500～10000.Can enumerate monoethylene glycol, propylene glycol, 1,4-butylene glycol, bisphenol-A etc. as low molecule (short chain) glycol.The number-average molecular weight of short-chain diol is preferably 48～500.Can enumerate PANDEX T-2185, T-2983N (above make for big Japanese ink chemical industry society), blue (the シ ラ Network ト ラ Application) E790 of hila Al Kut etc. as the elastomeric concrete example of polyurethane series.
Can enumerate the elastic body that makes dicarboxylic acid or derivatives thereof and the polycondensation of diol compound or derivatives thereof and obtain as the polyester based elastomers.Aromatic dicarboxylic acid after the hydrogen atom that can enumerate aromatic dicarboxylic acid such as terephthalic acid (TPA), m-phthalic acid, naphthalene dicarboxylic acids and their aromatic proton as the concrete example of dicarboxylic acid is replaced by methyl, ethyl, phenyl etc.; The aliphatic dicarboxylic acid of carbon numbers 2～20 such as hexane diacid, decanedioic acid, dodecanedioic acid, and ester ring type dicarboxylic acid such as cyclohexane dicarboxylic acid etc.These compounds can use a kind or combination to use more than 2 kinds separately.Concrete example as glycol can be enumerated monoethylene glycol, 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol, 1,10-decanediol, 1, aliphatic diol such as 4-cyclohexane diol and ester ring type glycol or by the dihydric phenol of formula (15) expression.These compounds can use a kind or combination to use more than 2 kinds separately.
[changing 27]
Figure G2008800142486D00221
Y in the formula (15) 11The alkylidene of expression singly-bound, carbon number 1～10, the cycloalkylidene of carbon number 4～8 ,-O-,-S-or-SO 2-, R 21And R 22The alkyl of expression halogen atom or carbon number 1～12, p and q represent 0～4 integer, r representes 0 or 1.
Concrete example as the dihydric phenol of being represented by above-mentioned general formula (15) can be enumerated bisphenol-A, two (4-hydroxy phenyl) methane, two (4-hydroxy-3-methyl phenyl) propane, resorcinol etc.These compounds can use a kind or combination to use more than 2 kinds separately.
In addition, can use with aromatic polyester (for example polybutylene terephthalate) part as the hard segment composition, with the segmented copolymer of aliphatic polyester (for example polytetramethylene glycol) part as the soft chain segment composition.There is the multipolymer of various grade in difference according to the kind of hard segment and soft chain segment, ratio, molecular weight.Can enumerate Hai Teleier (Ha イ ト レ Le) (Du Pont-Dong Li (strain) manufacturing), Pei Erpulian (ペ Le プ レ Application) (Japan's weaving (strain) is made), Ai Sipeier (エ ス ペ Le) (Hitachi changes into industry (strain) manufacturing) etc. as concrete example.
Polyamide-based elastic body roughly is divided into 2 types: adopt polyamide as hard phase, employing polyethers or polyester polyether block amide type and the polyether ester block acid amide type as soft phase.Use polyamide 6,11,12 etc. as polyamide, use polyethylene oxide, polypropyleneoxide, polytetramethylene glycol etc. as polyethers.Can enumerate UBE polyamide elastomer (the emerging product of space portion (strain) manufacturing) particularly as polyamide-based elastic body; Wear A Mide (ダ イ ア ミ De) (Daicel Xiu Ersi company (ダ イ セ Le ヒ ユ Le ス (strain)) manufacturing); PEBAX (make in east beautiful (strain)); Gu Lilun (グ リ ロ Application) ELY (Ai Mansi Japanese firm (エ system ス ジ ヤ パ Application (strain)) manufacturing); Nao handkerchief Mead (ノ パ ミ Star De) (Mitsubishi Chemical's (strain) manufacturing); Ancient sharp Eva kusz (グ リ ラ Star Network ス) (big Japanese ink (strain) is made) etc.
Acrylic elastomer is major component with the acrylic ester, adopts ethyl acrylate, butyl acrylate, acrylic acid methoxyl ethyl ester, acrylic acid ethoxy ethyl ester etc.In addition, adopt GMA, allyl glycidyl ether etc. as the crosslinking points monomer.And then, also can copolymerized acrylonitrile or ethene.Can enumerate vinyl cyanide-butyl acrylate copolymer, vinyl cyanide-butyl acrylate-ethyl acrylate copolymer, vinyl cyanide-butyl acrylate-glycidyl methacrylate copolymer etc. particularly as acrylic elastomer.
As the silicon-type elastic body, be to be major component with the organopolysiloxane, be divided into dimethyl silicone polymer system, PSI system, gather diphenyl siloxane system.Also exist by partially modified elastic bodys such as vinyl, alkoxys.As the elastomeric concrete example of silicon-type can enumerate KE series (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), SE series, CY is serial, SH is serial (above be eastern beautiful DOW CORNING organosilicon manufactured) etc.
The epoxy resin that in addition, except above-mentioned thermoplastic elastomer, can also use modified rubber to cross.The epoxy resin that modified rubber is crossed for example obtains through with two terminal carboxyl acid modified type butadiene-acrylonitrile rubber, terminal amino group modified organic silicon rubber etc. a part of or whole epoxy radicals of above-mentioned bisphenol f type epoxy resin, bisphenol A type epoxy resin, salicylide type epoxy resin, phenol novolak type epoxy resin or cresols phenolic resin varnish type epoxy resin being carried out modification.In these elastic bodys aspect shear bond property preferred two terminal carboxyl group modification hycars, as the Ai Sipeier (エ ス ペ Le) with polyester based elastomers of hydroxyl (Japan change into industry (strain) is made, Ai Sipeier 1612,1620).
In photosensitive resin composition of the present invention, use (E) elastomeric situation, its content (A) composition 100 mass parts relatively is preferably 2～30 mass parts, more preferably 4～20 mass parts.Content can further reduce the elastic modulus of cured film at high-temperature area in the scope of 2～30 mass parts the time.
Preferably further contain (F) thinning agent in the photosensitive resin composition of the present invention.For example can be with an organic solvent and/or photopolymerization monomer as (F) thinning agent.Can enumerate for example ketone such as butanone, cyclohexanone as organic solvent; Toluene, xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, BC, propylene glycol monomethyl ether, DPG list ether, DPG diethyl ether, triethylene glycol list ether; Ester classes such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; Aliphatic hydrocarbon such as octane, decane, oil series solvents such as sherwood oil, petroleum naphtha, hydrotreated petroleum naphtha, solvent naphtha etc.
In addition; For example can enumerate (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-(methyl) acrylic acid hydroxyl alkane ester classes such as 2-hydroxy propyl ester as photopolymerization monomer; List or two (methyl) esters of acrylic acid of glycol such as monoethylene glycol, methoxyl tetraethylene glycol, polyglycol; N; (methyl) acrylic amides such as N-dimethyl (methyl) acrylic amide, N-methylol (methyl) acrylic amide; N; Aminoalkyl (methyl) esters of acrylic acids such as N-dimethyl aminoethyl (methyl) acrylic ester, polynary (methyl) esters of acrylic acid of polyvalent alcohol such as hexanediol, trimethylolpropane, pentaerythrite, two trimethylolpropanes, dipentaerythritol, trihydroxy ethyl chlorinated isocyanurates or their oxirane or propylene oxide adduct, (methyl) esters of acrylic acid of the oxirane propylene oxide adduct of phenols such as polyethoxy two (methyl) acrylic ester of phenoxy group ethyl (methyl) acrylic ester, bisphenol-A; (methyl) esters of acrylic acid of glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group chlorinated isocyanurates, and melamine (methyl) acrylic ester etc.
These (F) thinning agents can use a kind or combination to use more than 2 kinds separately.
As the adjustment that can suit of the content of the organic solvent of (F) thinning agent, to regulate the viscosity of photosensitive resin composition.
In addition, as the content of the photopolymerization monomer of (F) thinning agent, be preferably 5～80 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, more preferably 10～70 quality % are preferably 15～40 quality % especially.This content during less than 5 quality % light sensitivity low, exposure portion is stripping in development easily often; Thermotolerance tends to reduce when surpassing 80 quality %.
In addition, consider, can contain (G) hardening agent in the photosensitive resin composition of the present invention from can further improving stable on heating angle.
As hardening agent (G) preferably himself utilize compound that heat or ultraviolet ray etc. are cured, or the carboxyl or the hydroxyl that utilize heat or ultraviolet ray etc. and (A) sour modification in the photosensitive resin composition to contain vinyl epoxy resin as the light-cured resin composition react and the compound that solidifies.Through using such (G) hardening agent can improve thermotolerance, adaptation, chemical reagent resistance of the cured film that finally obtains etc.
About (G) hardening agent, for example can enumerate epoxy compound, melamine compound, carbamide compound 、 oxazoline compound, block type isocyanate compound etc. as heat-curable compounds.Can enumerate for example hetero ring type epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenation bisphenol A type epoxy resin, bromo bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin or triglycidyl group chlorinated isocyanurates, di-cresols type epoxy resin etc. as epoxy compound.Can enumerate for example triamido triazine, hexa methoxy melamine, six butoxy melamines etc. as melamine compound.Can enumerate dimethylolurea etc. as carbamide compound.These (G) hardening agent can use a kind or combination to use more than 2 kinds separately.
The content of (G) hardening agent in photosensitive resin composition is preferably 2～50 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 10～40 quality % are preferably 15～30 quality % especially.If this content less than 2 quality % the thermotolerance of final cured coating film tend to reduce, the development property tends to reduce when surpassing 50 quality %.
For each characteristics such as the thermotolerance that further improves cured film, adaptation, chemical reagent resistances, in photosensitive resin composition of the present invention, preferably contain epoxy curing agent.
Can enumerate for example glyoxal ethyline, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methyl-imdazole derivatives such as 5-hydroxymethyl imidazoles, guanamines classes such as acetoguanamine, benzoguanamine, polynary amines such as diaminodiphenyl-methane, m-phenylene diamine, m-xylene diamine, diamino diphenyl sulfone, dicyandiamide, urea, urea derivative, melamine, polynary hydrazine as the concrete example of such epoxy curing agent; Their acylate and/or epoxy adduct; The amine complex of boron trifluoride, ethyl diamido s-triazine, 2,4-diamido s-triazine, 2; 4-diamido-pyrrolotriazine derivatives classes such as 6-xylyl s-triazine; Trimethylamine, triethanolamine, N, N-dimethyl octylame, N-benzyl dimethylamine, pyridine, N-methylmorpholine, six (N-methyl) melamine, 2,4; Tertiary amines such as 6-three (dimethylamino phenol), TMG, m-aminophenol; Polyphenyl phenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolaks, alkylphenol novolaks, organic phosphine classes such as tributylphosphine, triphenylphosphine, three-2-cyano ethyl phosphine, three normal-butyls (2; Phosphonium salt classes such as 5-dihydroxy phenyl) phosphonium bromide, six decyl tributyl phosphonium chlorides; Quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride, above-mentioned multi-anhydride, diphenyl tetrafluoro boric acid salt compounded of iodine, triphenyl hexafluoro-antimonic acid sulfonium, 2; 4,6-triphenyl hexafluorophosphoric acid sulfo-pyralium salt etc.
These epoxy curing agents can use a kind or combination to use more than 2 kinds separately.Its content of situation of use epoxy curing agent is preferably 0.01～20 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, more preferably 0.1～10 quality %.
In order further to improve each characteristic such as adaptation, hardness of film, can also contain barium sulphate, barium titanate, silicon dioxide, talcum in the photosensitive resin composition of the present invention as required, burn till known inorganic fillers such as porcelain earth, magnesium carbonate, aluminium oxide, hydrate of aluminium, mica.These materials can use a kind or combination to use more than 2 kinds separately.Wherein, consider preferred silicon dioxide and barium sulphate from the angle of the hardness that can improve printing and cured film.And its content of situation of use inorganic filler is preferably 2～80 quality % with the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 5～50 quality % are preferably 10～40 quality % especially.
Known colorant such as can use as required in the photosensitive resin composition of the present invention that phthalocyanine blue, phthalocyanine green, iodine are green, two azophosphines, crystal violet, titanium dioxide, carbon black, naphthalene are black; Polymerization inhibitors such as quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; Tackifier such as bentonitic clay, polynite; Silicon-type, fluorine system, vinylite are foam-breaking agent, known habitual various adjuvants such as silane coupling agent.And then, can use the fire retardant such as phosphate compounds, aromatic condensation phosphate, Halogen condensed phosphoric acid esters of brominated epoxy compound, sour modification brominated epoxy compound, antimonial and phosphorus series compound.
Photosensitive resin composition of the present invention can roller mill, ball mill etc. be mixing equably with each above-mentioned gradation composition through utilizing, mixing obtains.
Field of electronic materials such as the solder resist of photosensitive resin composition of the present invention in printed circuit board (PCB), the interlayer dielectric in the high-density multi-layered plate, semiconductor-sealing-purpose solder resist can effectively be used as excellent permanent mask resist such as imaging, thermotolerance, adaptation, mechanical property, chemical reagent resistance, electrology characteristic.
Then, describe to the photosensitive element that has used above-mentioned photosensitive resin composition of the present invention.Fig. 1 is the schematic cross-section of a preferred implementation of expression photosensitive element of the present invention.Photosensitive element 1 shown in Figure 1 is made up of support 10 and the photosensitive resin composition layer 14 that is arranged on the support 10.The layer of photosensitive resin composition layer 14 for constituting by above-mentioned photosensitive resin composition of the present invention.In addition, photosensitive element 1 of the present invention also can be with diaphragm be covered on the photosensitive resin composition layer 14 and face F1 support 10 opposition sides.
Photosensitive resin composition layer 14 preferably is dissolved into photosensitive resin composition of the present invention behind the solution that forms solid constituent 30～70 quality % degree in above-mentioned solvent or the mixed solvent this solution coat to support 10 and form.
The thickness of photosensitive resin composition layer 14 is according to purposes and difference, through heating and/or blow hot blast and remove the dried thickness that desolvates and be preferably 10～100 μ m, and 20～60 μ m more preferably.
The support 10 that has as photosensitive element 1 for example can be enumerated, and polyethylene terephthalate, polypropylene, tygon, polyester etc. have polymer film of thermotolerance and solvent resistance etc.
The thickness of support 10 is preferably 5～100 μ m, more preferably 10～30 μ m.
Aforesaid by support 10 with photosensitive resin composition layer 14 this two layers of photosensitive element that constitutes 1 or for example can directly store by these three layers of photosensitive elements that constitutes of support 10, photosensitive resin composition layer 14 and diaphragm, perhaps can clip diaphragm and be wound on the spool with the roller shape and take care of.
Then, the formation method to resist pattern of the present invention describes.The formation method of resist pattern of the present invention is the method that comprises following operation: lamination operation, the photosensitive resin composition that will be made up of the photosensitive resin composition of the invention described above are long-pending layer by layer to substrate; Exposure process makes exposure portion carry out photocuring to above-mentioned photosensitive resin composition layer with image shape irradiation active ray; And developing procedure, the unexposed portion of removing above-mentioned photosensitive resin composition layer through development.
Lamination on the photosensitive resin composition course substrate (copper-surfaced laminated board etc.) for example can be carried out as follows: utilize silk screen print method, spray-on process, rolling method, curtain to be coated with methods such as method, static covering with paint method and on substrate, be coated with photosensitive resin composition with the thickness of 10～200 μ m, again at 60～110 ℃ of dry coatings.
In addition, also can use above-mentioned photosensitive element of the present invention lamination photosensitive resin composition layer on substrate.Lamination method as this moment can be enumerated, if photosensitive element has diaphragm after removing diaphragm, on one side at 70～130 ℃ of degree heating photosensitive resin composition layers on one side with 0.1MPa～1MPa degree (1kgf/cm 2～10kgf/cm 2Degree) pressure carries out the method for crimping etc.This lamination operation can under reduced pressure be carried out.The surface of the substrate of lamination photosensitive resin composition layer is generally metal covering, but not special restriction.
To being made exposure portion carry out photocuring through minus or eurymeric mask pattern with image shape irradiation active ray by the photosensitive resin composition layer of lamination on substrate like this.At this moment; Use the situation support of photosensitive element lamination photosensitive resin composition layer can be present on the photosensitive resin composition layer; This support is that transparent situation can be through support irradiation active ray to active ray, and support then shines active ray to the photosensitive resin composition layer to the situation of active ray demonstration light-proofness after removing support.
For example carbon arc lamp, mercury vapour arc lamp, high-pressure sodium lamp, xenon lamp etc. radiate the light source of ultraviolet ray, visible light etc. effectively to adopt known in the past light source as the light source of active ray.
In addition, photosensitive resin composition layer of the present invention and photosensitive element are suitable for directly describing through laser the purposes of exposure method imaging.Therefore, above-mentioned exposure process is preferably directly described exposure method through laser and is carried out in the formation method of resist pattern of the present invention.
Directly describe the situation that exposure method makes public through laser, above-mentioned exposure process is preferably through the laser of wavelength 405nm the photosensitive resin composition layer directly to be described to make public and makes exposure portion carry out the operation of photocuring.In addition, as the laser that also can use wavelength 355nm through the laser of directly describing the situation that exposure method makes public.
In addition, exposure is preferably 10～1000mJ/cm in exposure process 2
Remove the photosensitive resin composition layer (unexposed portion) beyond the exposure portion through development after forming exposure portion, form the resist pattern.As unexposed the such method of removing; On the photosensitive resin composition layer, existing the situation of support to enumerate utilizes automatic stripping device etc. to remove support; Through utilizing the wet development of developer solutions such as alkaline aqueous solution, water system developer solution, organic solvent, perhaps unexposed method of developing etc. removed in dry process development etc. again.Can enumerate the lean solution of 0.1 quality %～5 quality % sodium carbonate for example, the lean solution of 0.1～5 quality % sal tartari, lean solution of 0.1 quality %～5 quality % NaOH etc. as the alkaline aqueous solution that uses in the wet development.The pH of alkaline aqueous solution is preferably 9～11 scope, and its temperature is adjusted according to the development property of photosensitive resin composition layer.In addition, also can in alkaline aqueous solution, sneak into surfactant, foam-breaking agent, organic solvent etc.For example can enumerate impregnation method, spray pattern, scrub, scrape etc. as the mode of above-mentioned development.
Then, through post-exposure (ultraviolet exposure) and/or back heating exposure portion is fully solidified as the processing after developing and obtain cured film.Post-exposure is preferably with 1～5J/cm 2Exposure carry out.The back heating was preferably carried out 30 minutes～12 hours at 100～200 ℃.
The circuit that in the manufacturing approach of printed circuit board (PCB) of the present invention, the formation method of the resist pattern through the invention described above is formed with the resist pattern forms and carries out etching or plating with substrate.At this, the resist pattern that is made up of the photosensitive resin composition of the invention described above can effectively be used as excellent permanent mask resist such as imaging, thermotolerance, adaptation, mechanical property, chemical reagent resistance, electrology characteristic.
Embodiment
Based on embodiment and comparative example the present invention is described more specifically below, but the present invention is not limited to following embodiment.
[synthetic example 1]
(Dongdu changes into (strain) manufacturing, bisphenol f type epoxy resin, Y in general formula (6) to add YDF2001 2=glycidyl, R 12The compound of=hydrogen atom) 475 mass parts, acrylic acid 72 mass parts, quinhydrones 0.5 mass parts, carbitol acetate 120 mass parts are 90 ℃ of heated and stirred and the solubilizing reaction potpourri.Then, the solution that obtains is cooled to 60 ℃, adds benzyltrimethylammonium chloride 2 mass parts to it, be heated to 100 ℃ react to the solid constituent acid number be 1mgKOH/g.And then, add maleic anhydride 98 mass parts and carbitol acetate 85 mass parts, be heated to about 6 hours of 80 ℃ of reactions.Subsequently, be cooled to room temperature, using carbitol acetate to be diluted to solid component concentration is 60 quality %, obtains the carboxyl acid modified Bisphenol F type epoxy acrylate (below be called " epoxy resin A1 ") as (A) composition.
[synthetic example 2]
(Dongdu changes into (strain) manufacturing, cresols phenolic resin varnish type epoxy resin, Y in general formula (5) to add YDCN704 1=glycidyl, R 11The compound of=methyl) 220 mass parts, acrylic acid 72 mass parts, quinhydrones 1.0 mass parts, carbitol acetate 180 mass parts are 90 ℃ of heated and stirred and the solubilizing reaction potpourri.Then, the solution that obtains is cooled to 60 ℃, adds benzyltrimethylammonium chloride 1 mass parts to it, be heated to 100 ℃ react to the solid constituent acid number be 1mgKOH/g.And then, add tetrabydrophthalic anhydride 152 mass parts and carbitol acetate 100 mass parts, be heated to about 6 hours of 80 ℃ of reactions.Subsequently, be cooled to room temperature, using carbitol acetate to be diluted to solid component concentration is 60 quality %, obtains the carboxyl acid modified cresols phenolic varnish type epoxy acrylate (below be called " epoxy resin A2 ") as (A) composition.
(embodiment 1～5 and comparative example 1～4)
Form according to the cooperation shown in the below table 1 that (unit: mass parts) carry out mixingly behind the complexing compositions with three-roll grinder, adding carbitol acetate to solid component concentration is 70 quality %, obtains photosensitive resin composition.In addition, the use level of each composition in the below table 1 is represented the use level of solid constituent.
[table 1]
Figure G2008800142486D00301
In addition, the details of each composition in the table 1 is described below.
Bisphenol f type epoxy resin (trade name: YSLV-80XY-F, Dongdu change into society make), DPHA (trade name: block that inferior rad (カ ヤ ラ Star De) DPHA, Japanese chemical drug society make, dipentaerythritol acrylate),
OXE-01 (trade name, Ciba manufactured, by 1 of above-mentioned formula (9) expression, 2-octane diketone-1-[4-(phenyl sulfo-) phenyl]-2-(O-benzoyl oximes)),
IC907 (trade name: Irgacure 907, Ciba manufactured, by the compound of following formula (16) expression),
Cumarin (BC) (trade name: BC, greening learn manufactured, by 7,7 '-two (diethylamino)-3-ketone-cumarins, the maximum absorption wavelength of above-mentioned formula (10) expression: 449nm),
Cumarin (C-314T) (trade name: C-314T, A Ku Louth (ア Network ロ ス) manufactured, by compound, the maximum absorption wavelength of following formula (17) expression: 435nm),
DETX (trade name: Ka Yakua (カ ヤ キ ユ ア) DETX-S, the manufacturing of Japanese chemical drug society, diethyl thioxanthone, maximum absorption wavelength: 383nm),
C152 (trade name: Coumarin 152, A Ku Louth manufactured, by compound, the maximum absorption wavelength of following formula (18) expression: 394nm),
C153 (trade name: Coumarin 153, A Ku Louth manufactured, by compound, the maximum absorption wavelength of following formula (19) expression: 423nm),
MBO (by the mercaptobenzoxazole of above-mentioned formula (12) expression),
MBT (by the mercaptobenzothiazoler of above-mentioned formula (13) expression),
MBI (by the mercaptobenzimidazole of above-mentioned formula (14) expression),
EAB (trade name, the manufacturing of hodogaya chemical society, diethylamino benzophenone, maximum absorption wavelength: 365nm).
[changing 28]
Figure G2008800142486D00311
[changing 29]
Figure G2008800142486D00321
[changing 30]
Figure G2008800142486D00322
[changing 31]
< estimating the making of substrate >
Using 120 purpose terylene Netcoms to cross silk screen print method is that about 20 μ m are applied on the copper-surfaced laminated board with the photosensitive resin composition of embodiment 1～5 and comparative example 1～4 with dried thickness, through the heated air circulation type dryer 80 ℃ of dryings 30 minutes.Thus, obtain the evaluation substrate that on copper-surfaced laminated board lamination has the photosensitive resin composition layer that is made up of photosensitive resin composition.The evaluation substrate that use obtains carries out the evaluation of each characteristic through the method shown in following.Sum up its result and be illustrated in the table 2.
(light sensitivity)
On the photosensitive resin composition layer of estimating substrate, place minus mask (41 sections stage metraster of Stouffer); And then place Korean and Japanese beam split Co., Ltd. as the band pass filter of the light that divides optical wavelength 405 ± 30nm above that and make beam split optical filter (trade name: HG0405), under this state, uses with the 5kW short-arc lamp and shine exposure 100mJ/cm as the directional light exposure machine (trade name: EXM-1201, Ao Ke (オ one Network) making institute manufactured) of light source 2Ultraviolet ray.In addition; Use ultraviolet integrating quantometer (trade name: UIT-150-A, Ushio Electric Inc make, also can be used as illuminometer) and (trade name, wavelength photoreceptor zone: 320nm～470nm, absolute tuning wavelength: 405nm) measure the illumination of the light that sees through band pass filter, illumination * time shutter is as exposure as " UVD-S405 " of light-receiving device.Subsequently, with the aqueous sodium carbonate (30 ℃) of 1 quality % at 60 seconds, 1.8kgf/cm 2Pressure under carry out spray development, unexposed portion is removed in dissolving.After removing unexposed portion, the hop count of the stage metraster through being determined at the photocuring film that forms on the copper-surfaced laminated board is estimated the light sensitivity of photosensitive resin composition.Light sensitivity is represented that by the hop count of stage metraster the high more light sensitivity that means of the hop count of this stage metraster is high more.
(development property)
On the photosensitive resin composition layer of estimating substrate, placing path mask (PVC ア マ ス Network) opening size is the mask of 100 μ m; And then place Korean and Japanese beam split Co., Ltd. as the band pass filter of the light that divides optical wavelength 405 ± 30nm above that and make beam split optical filter (trade name: HG0405), under this state, uses with the 5kW short-arc lamp and shine exposure 100mJ/cm as the directional light exposure machine (institute's manufactured is made in trade name: EXM-1201, restraint difficult to understand) of light source 2Ultraviolet ray.In addition; Use ultraviolet integrating quantometer (trade name: UIT-150-A, Ushio Electric Inc make, also can be used as illuminometer) and as " UVD-S405 " of light-receiving device (trade name, wavelength photoreceptor zone: 320nm～470nm, absolute tuning wavelength: 405nm) measure the illumination of the light that sees through band pass filter, with illumination * time shutter as exposure.Subsequently, under the pressure of 60 seconds, 0.18MPa, carry out spray development with 1% aqueous sodium carbonate (30 ℃).Subsequently, the passage opening portion that visualization forms is according to the evaluation of following benchmark development property.
A: obtain the above passage opening portion of opening size 80 μ m situation,
B: obtain opening size 60 μ m above and less than the situation of the passage opening portion of 80 μ m,
C: the opening size of passage opening portion is less than the situation of 60 μ m.
< making of breadboard >
Make beam split optical filter (trade name: HG0405), under this state, uses with the 5kW short-arc lamp and shine exposure 100mJ/cm estimating the Korean and Japanese beam split Co., Ltd. of placing on the photosensitive resin composition layer of substrate as the band pass filter of the light that divides optical wavelength 405 ± 30nm as the directional light exposure machine (institute's manufactured is made in trade name: EXM-1201, restraint difficult to understand) of light source 2Ultraviolet ray.In addition; Use ultraviolet integrating quantometer (trade name: UIT-150-A, Ushio Electric Inc make, also can be used as illuminometer) and as " UVD-S405 " of light-receiving device (trade name, wavelength photoreceptor zone: 320nm～470nm, absolute tuning wavelength: 405nm) measure the illumination of the light that sees through band pass filter, with illumination * time shutter as exposure.Subsequently, with the aqueous sodium carbonate (30 ℃) of 1 quality % at 60 seconds, 1.8kgf/cm 2Pressure under carry out spray development, unexposed portion is removed in dissolving.Then, 150 ℃ of heating 1 hour, make the breadboard of cured film with photosensitive resin composition layer.The breadboard that use obtains carries out the evaluation of each characteristic through the method shown in following.Sum up its result and be illustrated in the table 2.
(adaptation)
Breadboard is carried out disbonded test through the method based on JIS K5400.That is, the cured film of breadboard is made the gridiron pattern of 100 1mm, after pasting the cellophane adhesive tape on the gridiron pattern, peeling off.The tessellated state of peeling off after observation is peeled off carries out the evaluation of adaptation according to following benchmark.
A: tessellatedly do not peel off more than 90/100,
B: tessellatedly do not peel off more than 50/100 and less than 90/100,
C: tessellatedly do not peel off less than 50/100.
(solvent resistance)
Room temperature was flooded 30 minutes with breadboard in isopropyl alcohol after, whether the outward appearance of Visual Confirmation cured film had unusually.Subsequently, the cellophane adhesive tape is pasted the disbonded test of drawing on carrying out on the cured film, confirm whether cured film is peeled off from the copper-surfaced laminated board.Carry out the evaluation of solvent resistance according to following benchmark from its result.
A: the outward appearance of cured film is not unusual, and in disbonded test, do not peel off,
B: the outward appearance of cured film exists unusual, perhaps in disbonded test, peels off.
(solder heat resistance property)
Behind the cured film surface coated rosin series flux of breadboard, in 260 ℃ solder bath, flooded for 10 seconds.It as 1 circulation, is repeated the outward appearance of visualization cured film after 6 circulations, carry out the evaluation of solder heat resistance property according to following benchmark.
A: the outward appearance of cured film not unusual (peel off, swell), there is not the infiltration of scolder yet,
B: there be unusual (peel off, swell) in the outward appearance of cured film, perhaps has the infiltration of scolder.
< the ageing stability evaluation is with the modulation of solution and the evaluation of ageing stability >
In the composition shown in the table 1, remove as the bisphenol f type epoxy resin of hardening agent and as the epoxy resin A1 and the A2 of optical polymerism compound, add carbitol acetate viscosity is adjusted to 50Pas, obtain the ageing stability evaluation and use solution.Place the solution that obtains in room temperature (25 ℃), measure the time of not flowing or gelation takes place until solution.Its result is illustrated in the table 2.
[table 2]
Can know from the result shown in the table 2,, compare with the photosensitive resin composition of comparative example 1～4 and to be identified the light sensitivity excellence according to the photosensitive resin composition of embodiment 1～5.In addition, comparative example 1 and 2 photosensitive resin composition are because insufficient to the light sensitivity of light at the 405nm wavelength, and photocuring is carried out in the fails overexposure, can not form images.
The possibility of utilizing on the industry
As stated, in the time of can providing the exposure light that uses in wavelength 370nm～450nm scope to form the resist pattern according to the present invention, photosensitive resin composition that particularly light sensitivity is excellent when using directly the describing exposure method and form the resist pattern of wavelength 405nm laser, use photosensitive element, the formation method of resist pattern and the manufacturing approach of printed circuit board (PCB) of said composition.In addition; According to photosensitive resin composition of the present invention and photosensitive element; With the blue laser of wavelength 405nm as directly the describing can form in the exposure method and be difficult to the highdensity resist pattern made of light source in the past, and can obtain thermotolerance, humidity resistance (shear bond property), adaptation, mechanical property, the excellent high performance cured film of electrology characteristic.Thus, photosensitive resin composition of the present invention and photosensitive element can be used to make printed circuit board (PCB), high-density multi-layered plate and semiconductor package body etc. aptly.

Claims (6)

1. photosensitive resin composition, contain:
(A1) the sour modification that is obtained with containing vinyl monocarboxylic acid (b) reaction by the epoxy resin (a) as the bisphenol-type epoxy resin of formula (6) expression contains vinyl epoxy resin;
(A2) the sour modification that is obtained with containing vinyl monocarboxylic acid (b) reaction by the epoxy resin (a) as the phenolic resin varnish type epoxy resin of formula (5) expression contains vinyl epoxy resin;
(B) comprise by 1 of following formula (9) expression, the Photoepolymerizationinitiater initiater of 2-octane diketone-1-[4-(phenyl sulfo-) phenyl]-2-(O-benzoyl oximes);
(C) sensitizer, said sensitizer comprise by 7,7 '-two (diethylamino)-3-ketone-cumarins of following formula (10) expression or the compound of being represented by following formula (17);
(G) as the bisphenol f type epoxy resin of hardening agent,
Figure FSB00000781911000011
R in the formula (5) 11Expression hydrogen atom or methyl, Y 1Expression hydrogen atom or glycidyl, the mol ratio of hydrogen atom/glycidyl is 0/100～30/70 here, n1 representes the integer more than 1; Existing in addition a plurality of R 11And Y 1Can be identical separately also can be different;
Figure FSB00000781911000012
R in the formula (6) 12Expression hydrogen atom or methyl, Y 2Expression hydrogen atom or glycidyl, here, the mol ratio of hydrogen atom/glycidyl is 0/100～30/70, n2 representes the integer more than 1; In addition, existing a plurality of R 12And Y 2Can be identical separately also can be different;
Figure FSB00000781911000021
2. photosensitive resin composition according to claim 1 further contains the compound that (D) has mercapto.
3. photosensitive element, the photosensitive resin composition layer that forms by claim 1 or 2 described photosensitive resin compositions that has support and on this support, form.
4. the formation method of a resist pattern comprises:
The lamination operation will be long-pending layer by layer to substrate by the photosensitive resin composition that claim 1 or 2 described photosensitive resin compositions form;
Exposure process makes exposure portion carry out photocuring to said photosensitive resin composition layer with image shape irradiation active ray;
Developing procedure, the unexposed portion of removing said photosensitive resin composition layer through development.
5. the formation method of resist pattern according to claim 4, said exposure process makes exposure portion carry out the operation of photocuring for through the laser of wavelength 405nm said photosensitive resin composition layer directly being described to make public.
6. the manufacturing approach of a printed circuit board (PCB), the circuit that the formation method through claim 4 or 5 described resist patterns is formed with the resist pattern forms and carries out etching or plating with substrate.
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