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CN102621810B - 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
CN102621810B
CN102621810B CN201210116487.0A CN201210116487A CN102621810B CN 102621810 B CN102621810 B CN 102621810B CN 201210116487 A CN201210116487 A CN 201210116487A CN 102621810 B CN102621810 B CN 102621810B
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resin composition
photosensitive resin
resist pattern
replacement
epoxy resin
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CN102621810A (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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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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  • 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

本发明涉及一种光敏性树脂组合物、光敏性元件、抗蚀剂图案的形成方法及印刷电路板的制造方法，所述光敏性树脂组合物含有(A)酸改性含乙烯基环氧树脂、(B)包含1，2-辛烷二酮-1-[4-(苯基硫代)苯基]-2-(O-苯甲酰基肟)的光聚合引发剂、以及(C)增敏剂。

The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed circuit board. The photosensitive resin composition contains (A) an acid-modified vinyl group-containing epoxy resin , (B) a photopolymerization initiator comprising 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), and (C) an increaser sensitizer.

Description

The formation method of photosensitive resin composition, photosensitive element, resist pattern and the manufacture method of printed circuit board (PCB)
The present invention is that application number is 2008800142486 (international application no is PCT/JP2008/058551), and the applying date is that on May 8th, 2008, denomination of invention are the divisional application of the patent application of " the formation method of photosensitive resin composition, photosensitive element, resist pattern and the manufacture method 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 manufacture method of printed circuit board (PCB).
Background technology
In printed circuit board (PCB) manufacture in the past, permanent mask resist is to adopt the method for serigraphy thermohardening type resist ink or ultraviolet hardening resist ink to make.Be accompanied by recent years the highly integrated of electronic equipment, in printed circuit board (PCB), require the high-precision refinement of wiring pattern and insulating pattern.But, for utilizing the resist forming method of serigraphy, spread and sink in owing to can oozing in when printing, drip etc. in the past, be difficult to form the resist image of fine.Therefore, developed in order to form the resist image of fine the resist image forming method that utilizes photolithography.Be specially following method: the hot pressing of dry-film type photosensitivity resist is received on base material, or liquid photosensitivity resist curtain coating or spraying are applied on base material, after minus mask irradiation ultraviolet radiation isoreactivity light, form resist image by development.The situation of dry-film type photosensitivity resist, when to base material thermo-compressed, is easily involved in air and produces bubble, thereby causes that adaptation reduces, resist image is mixed and disorderly, may reduce 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 film, also taked further film to be carried out ultraviolet exposure and heats to promote cross-linking reaction.
But, as the formation method of resist pattern, do not use mask pattern and the what is called of directly describing resist pattern is directly described exposure method and received concern.Think and directly describe exposure method and can form high-resolution resist pattern with high productivity according to this.And, the gallium nitride based blue laser light source laser of oscillation wavelength 405nm, long-life and high output becomes gradually and can practicably be used as light source in recent years, can form by utilizing such short wavelength's laser in directly describing exposure method, waiting in expectation the highdensity resist pattern that was in the past difficult to manufacture.As so method of directly describing exposure method Ball semiconductor company (Ball Semiconductor) and having proposed digital light processing (DLP) system that application Texas Instruments (Texas Instruments) advocates, the exposure device that is suitable for the method has started practical.
And then, attempt by adopting the laser such as such blue laser to propose so far several (reference example is as patent documentations 3,4) 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 recording in above-mentioned patent documentation 3 and 4, while adopting the situation etc. of directly describing exposure method, while using near exposure light wavelength 405nm to form resist pattern still there is further room for improvement in light sensitivity.
The present invention carries out in view of above-mentioned problems of the prior art, photosensitive element, the formation method of resist pattern and the manufacture method of printed circuit board (PCB) of the photosensitive resin composition of light sensitivity excellence, use said composition when its object is to provide the exposure light using within the scope of wavelength 370nm～450nm to form resist pattern.
To achieve these goals, the invention provides a kind of photosensitive resin composition, contain Photoepolymerizationinitiater initiater that (A) sour modification comprises the compound with oxime ester bond containing vinyl epoxy resin, (B) and (C) comprise the coumarin compound being represented by following general formula (1) sensitizer.
[changing 1]
Figure BDA0000154976290000021
Z in formula (1) 1acyl group, the alkoxy of carbon number 1～20, the alkoxy carbonyl group of carbon number 1～20 or the group that comprises heterocycle that the carboxyalkyl that the carbon number that represents hydroxy alkyl, carboxyl, the alkyl of alkyl thiol, allyl, the carbon number 1～20 of dialkyl amido, sulfydryl, the carbon number 1～10 of alkyl amino, the carbon number 1～20 of aryl, amino, the carbon number 1～10 of naphthenic base, the carbon number 6～14 of alkyl, the carbon number 3～10 of halogen atom, carbon number 1～20 is 1～10, the carbon number of alkyl are 1～10, Z 2acyl group, the alkoxy of carbon number 1～20, the group that comprises heterocycle that the carbon number that represents hydroxy alkyl, the alkyl of alkyl thiol, allyl, the carbon number 1～20 of dialkyl amido, sulfydryl, the carbon number 1～10 of alkyl amino, the carbon number 1～20 of aryl, amino, the carbon number 1～10 of naphthenic base, the carbon number 6～14 of alkyl, the carbon number 3～10 of halogen atom, carbon number 1～20 is 1～10 or the group being represented by following general formula (2), s represents 0～4 integer.In addition, the Z in formula (2) 1with the Z in s and formula (1) 1identical with s definition.And, the Z in formula (1) 1with the Z in s and formula (2) 1with s can be separately identical also can be different.And then in formula (1) or formula (2), s is in more than 2 situations, existing multiple Z 1can be separately identical also can be different, any two link and to form ring also passable mutually.
[changing 2]
Figure BDA0000154976290000031
According to such photosensitive resin composition, by contain (A) sour modification containing vinyl epoxy resin and (B) comprise the compound with oxime ester bond Photoepolymerizationinitiater initiater in also contain (C) and comprise the sensitizer of coumarin compound being represented by above-mentioned general formula (1), can form resist pattern with excellent light sensitivity and resolution, with the exposure light within the scope of wavelength 370nm～450nm, particularly form resist pattern by the exposure method of directly describing with wavelength 405nm laser.
And then, according to the photosensitive resin composition of the present invention with above-mentioned formation, can form the high performance cured film of thermotolerance, humidity resistance, adaptation, mechanical property, electrology characteristic excellence, can be aptly for the manufacture of printed circuit board (PCB), high-density multi-layered plate and semiconductor package body etc.
In addition, photosensitive resin composition of the present invention preferably further contains (D) and has the compound of mercapto.
The compound that above-mentioned by containing (D) has mercapto can suppress photosensitive resin composition fully along with the time is through gelation occurs, and can improve ageing stability.
In addition, in photosensitive resin composition of the present invention, the above-mentioned compound with oxime ester bond preferably includes at least one of the compound that represented by following general formula (3) or (4).
[changing 3]
Figure BDA0000154976290000041
R in formula (3) 1represent the replacement of carbon number 2～12 or unsubstituted alkanoyl, two key not with replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6, R 2, R 3and R 4represent independently of one another replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the replacement of 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; m1 represents 0～4 integer, and m2 and m3 represent 0～5 integer independently of one another.In addition, m1 is in more than 2 situations, existing multiple R 2can be separately identical also can be different, m2 is in more than 2 situations, existing multiple R 3can be separately identical also can be different, m3 is in more than 2 situations, existing multiple R 4can be separately identical also can be different.
[changing 4]
Figure BDA0000154976290000042
R in formula (4) 5replacement or unsubstituted alkanoyl or replacement or the unsubstituted benzoyl 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, R 6represent the replacement of carbon number 2～12 or unsubstituted alkanoyl, two key not with replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6, R 7replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy 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, R 8, R 9and R 10represent independently of one another replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the replacement of 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; m4 and m5 represent 0～3 integer independently of one another, and m6 represents 0～5 integer.In addition, m4 is in more than 2 situations, existing multiple R 8can be separately identical also can be different, m5 is in more than 2 situations, existing multiple R 9can be separately identical also can be different, m6 is in more than 2 situations, existing multiple R 10can be separately identical also can be different.
About (B) Photoepolymerizationinitiater initiater, by containing the compound with oxime ester bond being represented by above-mentioned general formula (3) or (4), photosensitive resin composition can form resist pattern, particularly be formed and carried out resist pattern by the exposure method of directly describing with wavelength 405nm laser with more excellent light sensitivity and resolution, with the exposure light within the scope of wavelength 370nm～450nm.
In addition, in photosensitive resin composition of the present invention, the group that above-mentioned (A) sour modification is preferably the phenolic resin varnish type epoxy resin from being represented by following general formula (5), the bisphenol-type epoxy resin being represented by following general formula (6) containing vinyl epoxy resin and the salicylide type epoxy resin that represented by following general formula (7) forms at least one epoxy resin (a) of selecting with containing that vinyl monocarboxylic acid (b) reacts the resin that obtains.
[changing 5]
Figure BDA0000154976290000051
R in formula (5) 11represent hydrogen atom or methyl, Y 1represent hydrogen atom or glycidyl (, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70) here, n1 represents more than 1 integer.In addition, multiple R of existence 11and Y 1can be separately identical also can be different.
[changing 6]
Figure BDA0000154976290000061
R in formula (6) 12represent hydrogen atom or methyl, Y 2represent hydrogen atom or glycidyl (, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70) here, n2 represents more than 1 integer.In addition, multiple R of existence 12and Y 2can be separately identical also can be different.
[changing 7]
Figure BDA0000154976290000062
Y in formula (7) 3represent hydrogen atom or glycidyl (, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70) here, n3 represents more than 1 integer.In addition, multiple R of existence 11and Y 3can be separately identical also can be different.
By using such (A) sour modification containing vinyl epoxy resin, photosensitive resin composition can form resist pattern, particularly form resist pattern by the exposure method of directly describing that uses wavelength 405nm laser with the exposure light within the scope of more excellent light sensitivity and resolution, use wavelength 370nm～450nm.
In addition, the invention provides a kind of photosensitive element, there is support and photosensitive resin composition layer that the photosensitive resin composition by the invention described above that forms forms on this support.
According to such photosensitive element, by thering is the photosensitive resin composition layer being formed by above-mentioned photosensitive resin composition of the present invention, can form resist pattern, particularly form resist pattern by the exposure method of directly describing that uses wavelength 405nm laser with the exposure light within the scope of excellent light sensitivity and resolution, use wavelength 370nm～450nm.
In addition, the invention provides a kind of formation method of resist pattern, comprising: lamination operation, the photosensitive resin composition being made up of the photosensitive resin composition of the invention described above is amassed on substrate layer by layer; Exposure process, irradiates active ray to above-mentioned photosensitive resin composition layer with image shape and makes exposure portion carry out photocuring; And developing procedure, the unexposed portion of removing above-mentioned photosensitive resin composition layer by development.
At this, above-mentioned exposure process is preferably by the laser of wavelength 405nm, above-mentioned photosensitive resin composition layer directly to be described to expose and makes exposure portion carry out the operation of photocuring.
According to the formation method of such resist pattern, owing to having adopted the photosensitive resin composition of the invention described above of light sensitivity excellence in the time that exposure method formation resist pattern is directly described in utilization, can effectively form the resist pattern of excellent in resolution.And the resist pattern forming by such method becomes the high performance cured film of thermotolerance, humidity resistance, adaptation, mechanical property, electrology characteristic excellence.
The present invention further provides a kind of manufacture method of printed circuit board (PCB), the circuit formation substrate that the formation method of the resist pattern by the invention described above is formed with to resist pattern carries out etching or plating.
According to the manufacture method of such printed circuit board (PCB), because the formation method of the resist pattern by the invention described above forms resist pattern, can realize the densification of wiring.
Can provide the exposure light using within the scope of wavelength 370nm～450nm to form resist pattern during according to the present invention, particularly when using directly the describing exposure method and form resist pattern of wavelength 405nm laser the photosensitive resin composition of light sensitivity excellence, use photosensitive element, the formation method of resist pattern and the manufacture method of printed circuit board (PCB) of said composition.In addition, according to photosensitive resin composition of the present invention and photosensitive element, the blue laser using wavelength 405nm as light source directly describe exposure method in can form and be difficult to the highdensity resist pattern manufactured in the past, and can obtain the high performance cured film of thermotolerance, humidity resistance (shear bond), adaptation, mechanical property, electrology characteristic excellence.Thus, photosensitive resin composition of the present invention and photosensitive element can be aptly for the manufacture of printed circuit board (PCB), high-density multi-layered plate and semiconductor package body etc.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section that represents a preferred implementation of photosensitive element of the present invention.
Symbol description
1 is that photosensitive element, 10 is that support, 14 is photosensitive resin composition layer.
Embodiment
According to circumstances at length describe for the preferred embodiment of the present invention with reference to accompanying drawing below.In accompanying drawing to identical or be equal to part give same-sign, the repetitive description thereof will be omitted.In addition, in the present invention, (methyl) acrylic refers to acrylic and the methacrylic acid group corresponding with it, and (methyl) acrylate refers to acrylate and the methacrylate corresponding with it.
Photosensitive resin composition of the present invention contain Photoepolymerizationinitiater initiater (being sometimes referred to as " (B) composition " below) that (A) sour modification comprises the compound with oxime ester bond containing vinyl epoxy resin (being sometimes referred to as " (A) composition " below), (B) and (C) comprise the coumarin compound being represented by above-mentioned general formula (1) sensitizer (being sometimes referred to as " (C) composition " below), preferably further contain the compound (being sometimes referred to as " (D) composition " below) that (D) has mercapto.At length describe for each composition below.
Adopt by the resin of epoxy resin modification being crossed containing vinyl monocarboxylic acid containing vinyl epoxy resin as (A) the sour modification using in the present invention, be preferably the phenolic resin varnish type epoxy resin from being represented by following general formula (5), the bisphenol A type epoxy resin being represented by following general formula (6) or bisphenol f type epoxy resin and group that the salicylide type epoxy resin that represented by following general formula (7) forms at least one epoxy resin (a) of selecting with containing that vinyl monocarboxylic acid (b) reacts the resin that obtains.
[changing 8]
Figure BDA0000154976290000081
R in formula (5) 11represent hydrogen atom or methyl, Y 1represent hydrogen atom or glycidyl (, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70) here, n1 represents more than 1 integer.In addition, multiple R of existence 11and Y 1can be separately identical also can be different.
[changing 9]
R in formula (6) 12represent hydrogen atom or methyl, Y 2represent hydrogen atom or glycidyl (, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70) here, n2 represents more than 1 integer.In addition, multiple R of existence 12and Y 2can be separately identical also can be different.
[changing 10]
Figure BDA0000154976290000092
Y in formula (7) 3represent hydrogen atom or glycidyl (, hydrogen atom/glycidyl (mol ratio) is 0/100～30/70) here, n3 represents more than 1 integer.In addition, multiple R of existence 11and Y 3can be separately identical also can be different.
(A) the sour modification using in the present invention containing vinyl epoxy resin except above-mentioned epoxy resin (a) with containing adopting the addition reaction product containing saturated or unsaturated group multi-anhydride (c) to this resultant of reaction (A ') addition the resultant of reaction of vinyl monocarboxylic acid (b) (being called " resultant of reaction (A ') " below).At this, when synthetic addition reaction product, be speculated as in initial reaction, form hydroxyl by the epoxy radicals of epoxy resin (a) and the addition reaction of the carboxyl containing vinyl monocarboxylic acid (b), in ensuing reaction, the hydroxyl that generates (also comprising the hydroxyl originally existing in epoxy resin (a)) with carry out half esterification containing anhydride group saturated or unsaturated group multi-anhydride (c).
Can enumerate phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin as the phenolic resin varnish type epoxy resin being represented by above-mentioned general formula (5).These phenolic resin varnish type epoxy resins utilize respectively known method by making phenol novolac resin, cresols novolac resin react and obtain with chloropropylene oxide.
In addition, in the compound being represented by above-mentioned general formula (6), Y 2for bisphenol A type epoxy resin or the bisphenol f type epoxy resin of glycidyl for example can be by making the bisphenol A type epoxy resin of following general formula (8) expression or the hydroxyl of bisphenol f type epoxy resin react to obtain with chloropropylene oxide.
[changing 11]
R in formula (8) 12represent hydrogen atom or methyl, n2 represents more than 1 integer.In addition, multiple R of existence 12can be separately identical also can be different.
In order to promote reacting of hydroxyl and chloropropylene oxide, preferably, 50～120 ℃ of temperature of reaction and under alkali metal hydroxide exists, in dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide (DMSO) isopolarity organic solvent, react.If temperature of reaction is less than 50 ℃, react slack-off, when exceeding 120 ℃, temperature of reaction can there is a large amount of subsidiary reactions, and therefore also not preferred.
Can enumerate particularly FAE-2500, EPPN-501H, EPPN-502H (being Japanese chemical drug (strain) manufacture, trade name above) etc. as the salicylide type epoxy resin being represented by above-mentioned general formula (7).
In addition, as enumerating such as acrylic acid, acrylic acid dipolymer, methacrylic acid, β-furfuryl group acrylic acid, β-styrene acrylic, cinnamic acid, crotonic acid, alpha-cyano cinnamic acid etc. containing vinyl monocarboxylic acid (b), also can enumerate in addition as half ester compounds of the resultant of reaction of hydroxy acryl acid ester and saturated or unsaturated dicarboxylic acid anhydride, as containing vinyl list glycidyl ether or contain half ester compounds of the resultant of reaction of vinyl list ethylene oxidic ester and saturated or unsaturated dicarboxylic acid anhydride.These half ester compounds are by making hydroxy acryl acid ester, reacting to obtain with saturated or unsaturated dicarboxylic acid anhydride containing vinyl monoglycidyl ether or containing vinyl list ethylene oxidic ester with equimolar ratio.These can use separately a kind or be used in combination two or more containing vinyl monocarboxylic acid (b).
As the hydroxy acryl acid ester using in above-mentioned half ester compounds containing an example of vinyl monocarboxylic acid (b) synthetic, containing vinyl list glycidyl ether, can enumerate for example Hydroxyethyl Acrylate containing vinyl list glycidyl esters, methacrylic acid hydroxyl ethyl ester, acrylic acid hydroxy propyl ester, methacrylic acid hydroxyl propyl ester, acrylic acid hydroxyl butyl ester, methacrylic acid hydroxyl butyl ester, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, dipentaerythritol five acrylate, pentaerythrite pentamethyl acrylate, glycidyl acrylate, glycidyl methacrylate etc.
The synthetic middle saturated or unsaturated dicarboxylic acid anhydride using as above-mentioned half ester compounds can be enumerated such as 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) with containing preferably reacting take epoxy radicals 1 equivalent containing the relative epoxy resin of vinyl monocarboxylic acid (b) (a) as the ratio of 0.6～1.05 equivalent in the reaction of vinyl monocarboxylic acid (b), more preferably to react as the ratio of 0.8～1.05 equivalent containing vinyl monocarboxylic acid (b), particularly preferably to react as the ratio of 0.9～1.0 equivalent containing vinyl monocarboxylic acid (b).
Epoxy resin (a) and be preferably dissolved in organic solvent and react containing vinyl monocarboxylic acid (b).Can enumerate the such as ketone such as butanone, cyclohexanone as organic solvent, toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based, the glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, DPE, dipropylene glycol diethyl ether, triethylene glycol list ether, the ester classes such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, the aliphatic hydrocarbon such as octane, decane, the petroleum solvents such as sherwood oil, petroleum naphtha, hydrotreated petroleum naphtha, solvent naphtha etc.
And then, in order to promote to react preferred use catalyzer.Can enumerate such as triethylamine, benzyl methylamine, methyl triethyl ammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine etc. as the catalyzer using.The relative epoxy resin of consumption (a) of catalyzer and be preferably 0.1～10 mass parts containing total 100 mass parts of vinyl monocarboxylic acid (b).
In addition, in order to prevent that the polymerization in reaction from preferably being used polymerization inhibitor.Can enumerate such as quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, youngster's naphthol, pyrogallol etc. as polymerization inhibitor.The relative epoxy resin of consumption (a) of polymerization inhibitor and be preferably 0.01～1 mass parts containing total 100 mass parts of vinyl monocarboxylic acid (b).And temperature of reaction is preferably 60～150 ℃, and then be preferably 80～120 ℃.
In addition, can will also use containing multi-anhydrides such as phenol system compound, trimellitic anhydride, PMA, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride such as vinyl monocarboxylic acid (b) and p-hydroxyphenylethanols as required.
In addition, in the present invention as (A) sour modification containing vinyl epoxy resin also preferably use by above-mentioned resultant of reaction (A ') with containing that saturated or unsaturated group multi-anhydride (c) reacts the resin that obtains.
As enumerating such as succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride etc. containing saturated or unsaturated group multi-anhydride (c).
Resultant of reaction (A ') with containing in the reacting of saturated or unsaturated group multi-anhydride (c), can regulate the acid number of sour modification containing vinyl epoxy resin (A) by hydroxyl 1 equivalent reaction 0.1～1.0 equivalent in relative response product (A ') containing saturated or unsaturated group multi-anhydride (c).
(A) sour modification is preferably 30～150mgKOH/g, more preferably 50～120mgKOH/g containing the acid number of vinyl epoxy resin.If acid number is less than 30mgKOH/g, photosensitive resin composition tends to reduce to the dissolubility of dilute alkaline soln, and the electrology characteristic of the cured film obtaining while exceeding 150mgKOH/g tends to reduce.
Resultant of reaction (A ') and be preferably 60～120 ℃ containing temperature of reaction saturated or unsaturated group multi-anhydride (c).
In addition, as required, for example can also part also use hydrogenation bisphenol A type epoxy resin as epoxy resin (a).And then, can also part be also 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. as (A) sour modification containing vinyl epoxy resin.
As for the content of (A) composition in photosensitive resin composition, be preferably 10～60 quality % take the solid constituent total amount of photosensitive resin composition as benchmark, more preferably 20～40 quality %, are particularly preferably 20～30 quality %.When this content is less than 10 quality %, thermotolerance tends to variation, and while exceeding 60 quality %, curability tends to variation.
Preferably use the compound being represented by following general formula (3) or (4) as the compound with oxime ester bond comprising in (B) Photoepolymerizationinitiater initiater using in the present invention.
[changing 12]
Figure BDA0000154976290000131
R in above-mentioned general formula (3) 1represent the replacement of carbon number 2～12 or unsubstituted alkanoyl, two key not with replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6.At this, alkanoyl has 1 above this substituting group of substituent situation and is preferably halogen atom or cyano group.Benzoyl has 1 above this substituting group of substituent situation and is preferably alkyl, halogen atom or the cyano group of carbon number 1～6.Carbobenzoxy has 1 above this substituting group of substituent situation and is preferably alkyl or the halogen atom of carbon number 1～6.
In addition, R in above-mentioned general formula (3) 2, R 3and R 4represent independently of one another replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the replacement of 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.At this, alkoxy carbonyl group has 1 above this substituting group of substituent situation and is preferably hydroxyl or alkoxy.
In addition, in above-mentioned general formula (3), m1 represents 0～4 integer, and m2 and m3 represent 0～5 integer independently of one another.In addition, m1 is the multiple R that exist in more than 2 situation general formulas (3) 2can be separately identical also can be different, m2 is the multiple R that exist in more than 2 situation general formulas (3) 3can be separately identical also can be different, m3 is the multiple R that exist in more than 2 situation general formulas (3) 4can be separately identical also can be different.
[changing 13]
R in above-mentioned general formula (4) 5replacement or unsubstituted alkanoyl or replacement or the unsubstituted benzoyl 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.At this, alkyl has 1 above this substituting group of substituent situation and is preferably hydroxyl or alkoxy.Benzoyl has 1 above this substituting group of substituent situation and is preferably the alkyl or phenyl of carbon number 1～6.
In addition, R in above-mentioned general formula (4) 6represent the replacement of carbon number 2～12 or unsubstituted alkanoyl, two key not with replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the carbon number 4～6 of carbonyl conjugation or unsubstituted enoyl-, replacement or unsubstituted benzoyl, carbon number 2～6.At this, alkanoyl has 1 above this substituting group of substituent situation and is preferably halogen atom or cyano group.Benzoyl has 1 above this substituting group of substituent situation and is preferably alkyl, halogen atom or the cyano group of carbon number 1～6.Carbobenzoxy has 1 above this substituting group of substituent situation and is preferably alkyl or the halogen atom of carbon number 1～6.
In addition, R in above-mentioned general formula (4) 7replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy 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, R 8, R 9and R 10represent independently of one another replacement or unsubstituted alkoxy carbonyl group or replacement or the unsubstituted carbobenzoxy of the replacement of the replacement of 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.At this, alkoxy carbonyl group has 1 above this substituting group of substituent situation and is preferably hydroxyl or alkoxy.
In addition, in above-mentioned general formula (4), m4 and m5 represent 0～3 integer independently of one another, and m6 represents 0～5 integer.In addition, m4 is in more than 2 situations, existing multiple R 8can be separately identical also can be different, m5 is in more than 2 situations, existing multiple R 9can be separately identical also can be different, m6 is in more than 2 situations, existing multiple R 10can be separately identical also can be different.
In addition, more specifically can enumerate by 1 of following formula (9) expression as the compound with oxime ester bond comprising in (B) Photoepolymerizationinitiater initiater using in the present invention, 2-octane diketone-1-[4-(phenyl sulfo-) phenyl]-2-(O-benzoyl oximes) (trade name: OXE-01, Ciba company manufactures), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl group oxime) (trade name: OXE-02, Ciba company manufactures), 1-phenyl-1, 2-propane diketone-2-[O-(carbethoxyl group) oxime] (trade name: Quantacure-PDO, chemical drug society of Japan manufacture etc.).
[changing 14]
Figure BDA0000154976290000151
In addition, in photosensitive resin composition of the present invention, can be used together the Photoepolymerizationinitiater initiater beyond the above-mentioned compound with oxime ester bond as (B) composition.
Can enumerate for example benzoin as the Photoepolymerizationinitiater initiater having beyond the compound of oxime ester bond, benzoin methylether, the benzoin classes such as 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, the aromatic series ketones such as N-dimethylamino benzoylformaldoxime, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, the Anthraquinones such as 2-amino anthraquinones, acetophenone dimethyl ketal, the ketal classes such as dibenzoyl dimethyl ketal, benzophenone, methyldiphenyl ketone, 4,4 '-dichloro benzophenone, the benzophenones such as 4-benzoyl-4 '-dimethyl diphenyl sulfide, 9-phenylacridine, the acridine derivatives such as 1,7-bis-(9,9 '-acridinyl) heptane, 2,4,5-triarylimidazoles dipolymer or derivatives thereof, TMDPO etc.These materials can use separately a kind or be used in combination two or more.
The content of (B) composition in photosensitive resin composition, is preferably 0.5～20 quality % using the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 2～10 quality %, are particularly preferably 2～5 quality %.If this content is less than 0.5 quality %, exposure portion is easily stripping in development often, and the thermotolerance of the cured film obtaining while exceeding 20 quality % tends to reduce.
(C) sensitizer using in photosensitive resin composition of the present invention comprises the coumarin compound being represented by following general formula (1).
[changing 15]
Figure BDA0000154976290000161
Z in above-mentioned general formula (1) 1acyl group, the alkoxy of carbon number 1～20, the alkoxy carbonyl group of carbon number 1～20 or the group that comprises heterocycle that the carboxyalkyl that the carbon number that represents hydroxy alkyl, carboxyl, the alkyl of alkyl thiol, allyl, the carbon number 1～20 of dialkyl amido, sulfydryl, the carbon number 1～10 of alkyl amino, the carbon number 1～20 of aryl, amino, the carbon number 1～10 of naphthenic base, the carbon number 6～14 of alkyl, the carbon number 3～10 of halogen atom, carbon number 1～20 is 1～10, the carbon number of alkyl are 1～10, Z 2acyl group, the alkoxy of carbon number 1～20, the group that comprises heterocycle that the carbon number that represents hydroxy alkyl, the alkyl of alkyl thiol, allyl, the carbon number 1～20 of dialkyl amido, sulfydryl, the carbon number 1～10 of alkyl amino, the carbon number 1～20 of aryl, amino, the carbon number 1～10 of naphthenic base, the carbon number 6～14 of alkyl, the carbon number 3～10 of halogen atom, carbon number 1～20 is 1～10 or the group being represented by following general formula (2), s represents 0～4 integer.In addition, the Z in formula (2) 1with the Z in s and formula (1) 1identical with s definition.And, the Z in formula (1) 1with the Z in s and formula (2) 1with s can be separately identical also can be different.And then in formula (1) or formula (2), s is in more than 2 situations, existing multiple Z 1can be separately identical also can be different, any two link and to form ring also passable mutually.
[changing 16]
Figure BDA0000154976290000162
The coumarin compound being represented by above-mentioned general formula (1) absorbs as near the light 405nm of wavelength photoreceptor, excites the compound with oxime ester bond as (B) Photoepolymerizationinitiater initiater.The coumarin compound being represented by above-mentioned general formula (1) is preferably the compound of maximum absorption wavelength within the scope of 370nm～450nm.
In addition, Z in the coumarin compound being represented by above-mentioned general formula (1) 2be preferably the group being represented by above-mentioned general formula (2).And then, the coumarin compound being represented by above-mentioned general formula (1) is particularly preferably 7,7 '-bis-(the diethylamino)-3-ketone-cumarins (green chemical company ((strain) body ど り chemistry) manufacture, trade name: BC) that represented by following formula (10).By using the coumarin compound being represented by following formula (10) can further improve the light sensitivity to 405nm light, can be so that more exposure method formation resist pattern is directly described in high resolving power, utilization.
[changing 17]
Figure BDA0000154976290000171
In addition, also can comprise other sensitizers beyond the coumarin compound being represented by above-mentioned general formula (1) as the sensitizer of (C) composition.Can enumerate such as anthracene class, Coumarins, xanthene ketone, the thioxanthene ketone, 4 such as pyrazolines, dialkoxy anthracene as other sensitizers, 4 '-bis-(dialkyl amido) benzophenone, oxazole class, Benzooxazole kind, thiazoles, triazole type, stilbene class, triazines, thiophene-based etc.These materials can use separately a kind or be used in combination two or more.
The content of (C) composition in photosensitive resin composition, is preferably 0.01～5 quality % using the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 0.1～2 quality %, is particularly preferably 0.2～1 quality %.In above-mentioned scope, can obtain good light sensitivity by this content.
Consider from the good angle of ageing stability, photosensitive resin composition of the present invention preferably further contains (D) and has the compound of mercapto.The compound that has a mercapto as (D) is preferably effective performance hydrogen supplies with the compound of body function.The compound preferably being represented by following general formula (11) as such compound.
[changing 18]
Figure BDA0000154976290000181
In formula, Ar represents to have the aryl of substituent divalence or trivalent, and X represents oxygen atom, nitrogen-atoms or sulphur atom.
The concrete example as (D) with the compound of mercapto can be enumerated the mercaptobenzoxazole (MBO) for example being represented by following formula (12), the mercaptobenzothiazoler (MBT) being represented by following formula (13), the mercaptobenzimidazole (MBI) being represented by following formula (14), ethyl mercaptan, benzenethiol, mercapto-phenol, sulfydryl toluene, 2-MEA, mercaptoethanol, sulfydryl dimethylbenzene, sulfo-xylenols, 2-mercaptoquinoline, mercaptoacetic acid, 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, butane-2, 3-bis-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]
Figure BDA0000154976290000182
[changing 20]
[changing 21]
Figure BDA0000154976290000184
The compound that these (D) have a mercapto can use separately a kind or be used in combination two or more.Among these compounds, supply with body function, further improve the light sensitivity of photosensitive resin composition and the angle of ageing stability and consider from effective performance hydrogen, preferably in molecule, there is the compound of sulfydryl, particularly preferred 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 % using the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 0.3～3 quality %, is particularly preferably 0.5～1.5 quality %.Often easily gelation of the solution of photosensitive resin composition when this content is less than 0.1 quality %, while exceeding 5 quality %, light sensitivity tends to reduce.
Enumerate exemplary compounds, in following reaction equation (I)～(V), represent to combine in photosensitive resin composition of the present invention above-mentioned (B) composition, (C) composition and (D) infer reaction mechanism when composition and irradiation ultraviolet radiation.Be considered to following mechanism: first, absorb the light of 405nm as the coumarin compound (Sens) being represented by above-mentioned general formula (1) of (C) sensitizer, become the excited state of singlet state, but it is reported to the leadship after accomplishing a task between being rapidly, become the excited state (reaction equation (I)) of triplet.This sensitizer being excited moves the compound (OXE-01) (reaction equation (II)) being represented by above-mentioned formula (9) with oxime ester bond that will excite as (B) Photoepolymerizationinitiater initiater by energy.Subsequently, the Photoepolymerizationinitiater initiater that becomes triplet excitation state will decompose and produce free radical (reaction equation (III)).Then, the free radical generating with supply with the compound (MBO) being represented by above-mentioned formula (12) that (D) of body have mercapto as hydrogen and react and carry out chain and move, become the Thiyl Radical that activity is high (reaction equation (IV) and (V)).Infer that this Thiyl Radical is the effective constituent that promotes photopolymerization reaction.
[changing 22]
Figure BDA0000154976290000191
[changing 23]
3(Sens) *+ 1(OXE-01)→ 1(Sens)+ 3(OXE-01) * (II)
[changing 24]
Figure BDA0000154976290000201
[changing 25]
Figure BDA0000154976290000202
[changing 26]
Figure BDA0000154976290000203
In addition, consider from the angle that can improve resistance to sudden heating and shear bond, photosensitive resin composition of the present invention preferably contains (E) elastic body.
Can enumerate such as 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 contributes to thermotolerance and intensity conventionally, and the latter contributes to flexibility and obdurability.
Can enumerate styrene-butadiene-styrene block copolymer, SIS, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene segmented copolymer etc. as styrene series elastomer.
Except styrene, can also use the styrene derivatives such as α-methyl styrene, 3-methyl styrene, 4-propylstyrene, 4-cyclohexyl benzene ethene as the composition that forms styrene series elastomer.Can enumerate particularly tower and exhale 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 is exhaled Te Ke (タ Off テ Star Network) (above for Asahi Chemical Industry's industry (strain) is manufactured), elastic body AR (peace Longhua becomes company to manufacture), Ku Ledun (Network レ イ ト Application) G, in card, exhale Le Kesi (crossing リ Off レ Star Network ス) (above for shell Japanese firm manufactures), JSR-TR, TSR-SIS, Da Yina synthetic fibre (ダ イ Na ロ Application) (being Japanese synthetic rubber (strain) manufacture above), electrification (デ Application カ) STR (electrochemical industry (strain) manufacture), storehouse is because of Plutarch (Network イ Application タ Star Network) (Japanese ZEON company manufacture), TPE-SB series (Sumitomo Chemical (strain) manufacture), draw bar synthetic fibre (ラ バ ロ Application) (Mitsubishi Chemical's (strain) manufacture), Sai Pudun (セ プ ト Application), sea Bradley (Ha イ Block ラ mono-) (above for Kuraray company manufactures), this rice is exhaled Le Kesi (ス ミ Off レ Star Network ス) (SUMITOMO CHEMICAL Bei Kulaite company (Sumitomo ベ mono-Network ラ イ ト (strain)) manufacture), thunder oersted agate (レ オ ス ト マ mono-), A Ku replaces agate (ア Network テ イ マ mono-) (above for Li Yan vinyl industrial group (reason is ground the industry of PVC ニ Le) manufactures) etc.
Ethylene series elastic body is the multipolymer of the alpha-olefin of the carbon numbers 2～20 such as ethene, propylene, 1-butylene, 1-hexene, 4-methylpentene, can enumerate such as ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) etc.In addition, can enumerate the non-conjugated diene of carbon number 2～20 and multipolymer and the epoxidized polybutadienes etc. of alpha-olefin such as bicyclopentadiene, Isosorbide-5-Nitrae-hexadiene, cyclo-octadiene, methene norbornene, ethylidene norbornene, butadiene, isoprene as ethylene series elastic body.In addition, can enumerate for hycar copolymerization the carboxy-modified NBR after methacrylic acid etc. as ethylene series elastic body.And then, can enumerate ethylene-α-olefincopolymerrubber, ethylene-alpha-olefin-nonconjugated diene copolymers rubber, propylene-alpha-olefin copolymers rubber, 1-butene-alpha-olefin copolymers rubber etc. as ethylene series elastic body.
Can enumerate particularly the special agate (ミ ラ ス ト マ) of meter La Si (manufacture of Mitsui petrochemistry society) as ethylene series elastic body, EXACT (manufacture of exxon chemical company), ENGAGE (Dow Chemical Company's manufacture), hydrogenation styrene butadiene rubbers " DYNABON HSBR " (Japanese synthetic rubber society manufacture), hycar " NBR series " (Japanese synthetic rubber society manufacture), there is " XER series " (Japanese synthetic rubber society manufacture) of two terminal carboxyl group modification hycars of crosslinking points, by " BF-1000 " of the epoxidized polybutadiene after polybutadiene part epoxidation (Japanese Cao Da society manufacture) etc.
Polyurethane series elastic body comprises the structural unit of the hard segment being made up of low molecule (short chain) glycol and diisocyanate and the soft chain segment being made up of macromolecule (long-chain) glycol and diisocyanate.Can enumerate polypropylene glycol, polytetramethylene glycol, poly-(1 as macromolecule (long-chain) glycol, 4-butylene adipate), poly-(ethylidene-1,4-butylene adipate), polycaprolactone, poly-(1,6-hexylidene carbonic ester), poly-(1,6-hexylidene-Ya neopentyl adipate) etc.The number-average molecular weight of macromolecule (long-chain) glycol is preferably 500～10000.Can enumerate ethylene glycol, propylene glycol, BDO, 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 for large Japanese ink chemical industry society manufactures), hila Al Kut orchid (シ ラ Network ト ラ Application) E790 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 polyester based elastomers.Aromatic dicarboxylic acid after the hydrogen atom that can enumerate the aromatic dicarboxylic acids 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 the carbon numbers 2～20 such as hexane diacid, decanedioic acid, dodecanedioic acid, and the ester ring type dicarboxylic acid such as cyclohexane dicarboxylic acid etc.These compounds can use separately a kind or be used in combination two or more.Can enumerate ethylene glycol, 1,3-PD, BDO, 1 as the concrete example of glycol, 6-hexanediol, 1, the aliphatic diols such as 10-decanediol, Isosorbide-5-Nitrae-cyclohexane diol and ester ring type glycol or the dihydric phenol being represented by following general formula (15).These compounds can use separately a kind or be used in combination two or more.
[changing 27]
Y in formula (15) 11represent alkylidene, the carbon number 4～8 of singly-bound, carbon number 1～10 cycloalkylidene ,-O-,-S-or-SO 2-, R 21and R 22the alkyl that represents halogen atom or carbon number 1～12, p and q represent 0～4 integer, r represents 0 or 1.
Concrete example as the dihydric phenol 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 separately a kind or be used in combination two or more.
In addition, can use the segmented copolymer for example, take aromatic polyester (polybutylene terephthalate) part as hard segment composition, for example, take aliphatic polyester (polytetramethylene glycol) part as soft chain segment composition.There is the multipolymer of various grade according to the difference of 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) manufacture), Pei Erpulian (ペ Le プ レ Application) (Japan's weaving (strain) is manufactured), Ai Sipeier (エ ス ペ Le) (Hitachi changes into industry (strain) manufacture) etc. as concrete example.
Polyamide-based elastic body is roughly divided into 2 classes: employing polyamide is polyether block amide type and the polyether ester block amides type as soft phase as hard phase, employing polyethers or polyester.Use polyamide 6,11,12 etc. as polyamide, use polyethylene oxide, polypropyleneoxide, polytetramethylene glycol etc. as polyethers.Can enumerate particularly UBE polyamide elastomer (the emerging product of space portion (strain) manufacture) as polyamide-based elastic body, wear A meter De (ダ イ ア ミ De) (Daicel Xiu Ersi company (ダ イ セ Le ヒ ユ Le ス (strain)) manufacture), PEBAX (manufacture in east beautiful (strain)), Gu Lilun (グ リ ロ Application) ELY (Ai Mansi Japanese firm (エ system ス ジ ヤ パ Application (strain)) manufacture), Nao handkerchief Mead (ノ パ ミ Star De) (Mitsubishi Chemical's (strain) manufacture), ancient sharp Eva kusz (グ リ ラ Star Network ス) (large Japanese ink (strain) is manufactured) etc.
Acrylic elastomer, take acrylate as major component, adopts ethyl acrylate, butyl acrylate, acrylic acid methoxyl ethyl ester, acrylic acid ethoxy ethyl ester etc.In addition, adopt glycidyl methacrylate, allyl glycidyl ether etc. as crosslinking points monomer.And then, also can copolymerized acrylonitrile or ethene.Can enumerate particularly vinyl cyanide-butyl acrylate copolymer, vinyl cyanide-butyl acrylate-ethyl acrylate copolymer, vinyl cyanide-butyl acrylate-glycidyl methacrylate copolymer etc. as acrylic elastomer.
As silicon-type elastic body, be take organopolysiloxane as major component, be divided into dimethyl silicone polymer system, PSI system, polydiphenylsiloxane system.Also there is the elastic body partially modified by vinyl, alkoxy etc.Can enumerate KE series (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), SE series, CY series, SH series (above for eastern beautiful DOW CORNING organosilicon company manufactures) etc. as the elastomeric concrete example of silicon-type.
The epoxy resin that in addition, can also use modified rubber to cross except above-mentioned thermoplastic elastomer.The epoxy resin that modified rubber is crossed for example obtains by part or all 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 to modification with the carboxyl acid modified type butadiene-propylene of two ends nitrile rubber, terminal amino group modified organic silicon rubber etc.In these elastic bodys aspect shear bond preferably two terminal carboxyl group modification hycars, as have hydroxyl polyester based elastomers Ai Sipeier (エ ス ペ Le) (Japan change into industry (strain) manufacture, Ai Sipeier 1612,1620).
In photosensitive resin composition of the present invention, use (E) elastomeric situation, its content relatively (A) composition 100 mass parts 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 time.
In photosensitive resin composition of the present invention, preferably further contain (F) thinning agent.For example can be with an organic solvent and/or photopolymerization monomer as (F) thinning agent.Can enumerate the such as ketone such as butanone, cyclohexanone as organic solvent, toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based, the glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, DPE, dipropylene glycol diethyl ether, triethylene glycol list ether, the ester classes such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, the aliphatic hydrocarbon such as octane, decane, the petroleum solvents such as sherwood oil, petroleum naphtha, hydrotreated petroleum naphtha, solvent naphtha etc.
In addition, for example can enumerate (methyl) 2-Hydroxy ethyl acrylate as photopolymerization monomer, (methyl) acrylic acid hydroxyl alkane ester classes such as (methyl) 2-hydroxypropyl acrylate, ethylene glycol, methoxyl tetraethylene glycol, the list of the glycol such as polyglycol or two (methyl) esters of acrylic acid, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic amides such as N-methylol (methyl) acrylamide, N, aminoalkyl (methyl) esters of acrylic acids such as N-dimethyl aminoethyl (methyl) acrylate, hexanediol, trimethylolpropane, pentaerythrite, two trimethylolpropanes, dipentaerythritol, polynary (methyl) esters of acrylic acid of the polyvalent alcohols such as trihydroxy ethyl chlorinated isocyanurates or their oxirane or propylene oxide adduct, phenoxy group ethyl (methyl) acrylate, (methyl) esters of acrylic acid of the ethylene oxide propylene oxide addition product of the phenols such as polyethoxy two (methyl) acrylate of bisphenol-A, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, (methyl) esters of acrylic acid of the glycidol ethers such as triglycidyl group chlorinated isocyanurates, and melamine (methyl) acrylate etc.
These (F) thinning agents can use separately a kind or be used in combination two or more.
Content as the organic solvent of (F) thinning agent can suitablely be adjusted, 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 % using the solid constituent total amount of photosensitive resin composition as benchmark, more preferably 10～70 quality %, are particularly preferably 15～40 quality %.When this content is less than 5 quality %, light sensitivity is low, and exposure portion is easily stripping in development often; While exceeding 80 quality %, thermotolerance tends to reduce.
In addition, consider from can further improving stable on heating angle, in photosensitive resin composition of the present invention, can contain (G) hardening agent.
Preferably himself utilize the compound that is cured such as heat or ultraviolet ray or utilize heat or carboxyl or hydroxyl that ultraviolet etc. and (A) the sour modification as light-cured resin composition in photosensitive resin composition contain vinyl epoxy resin react and curing compound as hardening agent (G).By using such (G) hardening agent can improve thermotolerance, adaptation, chemical reagent resistance of the cured film finally obtaining 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 hetero ring type epoxy resin, the di-first phenol-type epoxy resins etc. such as such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, hydrogenation bisphenol A type epoxy resin, brominated bisphenol-A type epoxy resin, phenolic resin varnish type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin or triglycidyl group chlorinated isocyanurates as epoxy compound.Can enumerate such as 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 separately a kind or be used in combination two or more.
The content of (G) hardening agent in photosensitive resin composition, is preferably 2～50 quality % using the solid constituent total amount of photosensitive resin composition as benchmark, and more preferably 10～40 quality %, are particularly preferably 15～30 quality %.If this content is less than 2 quality %, the thermotolerance of final cured coating film tends to reduce, and while exceeding 50 quality %, developability tends to reduce.
In order further to improve each characteristic such as thermotolerance, adaptation, chemical reagent resistance of cured film, in photosensitive resin composition of the present invention, preferably contain epoxy curing agent.
Concrete example as such epoxy curing agent can be enumerated for example glyoxal ethyline, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-phenylimidazole, the imdazole derivatives such as 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, acetoguanamine, the guanidine amines such as benzoguanamine, diaminodiphenyl-methane, m-phenylene diamine, m-xylene diamine, diamino diphenyl sulfone, dicyandiamide, urea, urea derivative, melamine, the polynary amine such as polynary hydrazine, their acylate and/or epoxy adduct, the amine complex of boron trifluoride, ethyl diamido s-triazine, 2,4-diamido s-triazine, the pyrrolotriazine derivatives classes such as 2,4-diamido-6-xylyl s-triazine, trimethylamine, triethanolamine, N, N-dimethyl octylame, N-benzyl dimethylamine, pyridine, N-methylmorpholine, six (N-methyl) melamine, 2,4,6-tri-(dimethylamino phenol), tetramethyl guanidine, the tertiary amines such as m-aminophenol, polyvinylphenol, polyvinylphenol bromide, phenol novolaks, the oxidoreductases such as alkylphenol novolaks, tributylphosphine, triphenylphosphine, the organic phosphine classes such as three-2-cyano ethyl phosphine, three normal-butyls (2,5-dihydroxy phenyl) phosphonium bromide, the phosphonium salt classes such as six decyl tributyl phosphonium chlorides, benzyltrimethylammonium chloride, the quaternary ammonium salts such as 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 separately a kind or be used in combination two or more.Use its content of situation of epoxy curing agent to be preferably 0.01～20 quality % using the solid constituent total amount of photosensitive resin composition as benchmark, more preferably 0.1～10 quality %.
In order further to improve each characteristics such as adaptation, hardness of film, in photosensitive resin composition of the present invention, can also contain as required barium sulphate, barium titanate, silicon dioxide, talcum, burn till the known inorganic fillers such as porcelain earth, magnesium carbonate, aluminium oxide, aluminium hydroxide, mica.These materials can use separately a kind or be used in combination two or more.Wherein, consider preferred silicon dioxide and barium sulphate from the angle of the hardness that can improve printing and cured film.And, use its content of situation of inorganic filler to be preferably 2～80 quality % using the solid constituent total amount of photosensitive resin composition as benchmark, more preferably 5～50 quality %, are particularly preferably 10～40 quality %.
In photosensitive resin composition of the present invention, can use as required that phthalocyanine blue, phthalocyanine green, iodine are green, the known colorant such as two azophosphines, crystal violet, titanium dioxide, carbon black, naphthalene are black, the polymerization inhibitors such as quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, youngster's naphthol, pyrogallol, the tackifier such as bentonitic clay, polynite, silicon-type, fluorine system, vinylite are defoamer, the known usual various adjuvants such as silane coupling agent.And then, can use the fire retardants such as the 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 by utilize roller mill, ball mill etc. by above-mentioned each gradation composition equably mixing, be obtained by mixing.
The field of electronic materials such as interlayer dielectric, semiconductor-sealing-purpose solder resist in solder resist, the high-density multi-layered plate of photosensitive resin composition of the present invention in printed circuit board (PCB) can effectively be made the excellent permanent mask resist such as imaging, thermotolerance, adaptation, mechanical property, chemical reagent resistance, electrology characteristic.
Then, describe for the photosensitive element that has used above-mentioned photosensitive resin composition of the present invention.Fig. 1 is the schematic cross-section that represents a preferred implementation of photosensitive element of the present invention.Photosensitive element 1 shown in Fig. 1 is made up of support 10 and the photosensitive resin composition layer 14 being arranged on support 10.The layer of photosensitive resin composition layer 14 for being formed by above-mentioned photosensitive resin composition of the present invention.In addition, photosensitive element 1 of the present invention, also can be with on diaphragm coating photosensitive resin composition layer 14 and face F1 support 10 opposition sides.
Photosensitive resin composition layer 14 is preferably dissolved into photosensitive resin composition of the present invention after the solution that forms solid constituent 30～70 quality % degree in above-mentioned solvent or mixed solvent this solution coat to support 10 and forms.
The thickness of photosensitive resin composition layer 14 is according to purposes and difference, is preferably 10～100 μ m, more preferably 20～60 μ m by heating and/or blowing hot blast except the dried thickness of desolventizing.
The support 10 having as photosensitive element 1 can be enumerated such as polyethylene terephthalate, polypropylene, tygon, polyester etc. and 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.
As above by support 10 and photosensitive resin composition layer 14 this two layers of photosensitive elements forming 1 or for example can directly be stored by these three layers of photosensitive elements forming of support 10, photosensitive resin composition layer 14 and diaphragm, or can clip diaphragm and be wound on spool and take care of with roller shape.
Then, describe for the formation method of resist pattern of the present invention.The formation method of resist pattern of the present invention is the method that comprises following operation: lamination operation, the photosensitive resin composition being made up of the photosensitive resin composition of the invention described above is amassed on substrate layer by layer; Exposure process, irradiates active ray to above-mentioned photosensitive resin composition layer with image shape and makes exposure portion carry out photocuring; And developing procedure, the unexposed portion of removing above-mentioned photosensitive resin composition layer by development.
Photosensitive resin composition layer for example can carry out as follows to the lamination on substrate (copper-surfaced laminated board etc.): utilizes silk screen print method, spray-on process, rolling method, curtain to be coated with the methods such as method, static covering with paint method and on substrate, is coated with photosensitive resin composition with the thickness of 10～200 μ m, then at 60～110 ℃ of dry coatings.
In addition, also can use above-mentioned photosensitive element of the present invention to lamination photosensitive resin composition layer on substrate.Can enumerate as lamination method now, if photosensitive element has diaphragm, remove after diaphragm, heat photosensitive resin composition layers on one side with 0.1MPa～1MPa degree (1kgf/cm 70～130 ℃ of degree on one side 2～10kgf/cm 2degree) pressure carry out method of 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 is not particularly limited.
For by lamination, the photosensitive resin composition layer on substrate makes exposure portion carry out photocuring by minus or eurymeric mask pattern with image shape irradiation active ray like this.Now, use the situation support of photosensitive element lamination photosensitive resin composition layer can be present on photosensitive resin composition layer, this support is that transparent situation can be irradiated active ray by support to active ray, and support is being removed after support photosensitive resin composition layer irradiation active ray the situation of active ray demonstration light-proofness.
Adopt such as carbon arc lamp, mercury vapour arc lamp, high-pressure sodium lamp, xenon lamp etc. of known light source in the past effectively to radiate the light source of ultraviolet ray, visible ray etc. 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 by laser the purposes of exposure method imaging.Therefore, in the formation method of resist pattern of the present invention, above-mentioned exposure process is preferably directly described exposure method by laser and is carried out.
Directly describe by laser the situation that exposure method exposes, above-mentioned exposure process is preferably by the laser of wavelength 405nm, photosensitive resin composition layer directly to be described to expose and makes exposure portion carry out the operation of photocuring.In addition, as the laser that also can use wavelength 355nm by the laser of directly describing the situation that exposure method exposes.
In addition, in exposure process, exposure is preferably 10～1000mJ/cm 2.
After forming exposure portion, remove the photosensitive resin composition layer (unexposed portion) beyond exposure portion by development, form resist pattern.As the method for removing of so unexposed portion, on photosensitive resin composition layer, existing the situation of support to enumerate utilizes automatic stripping device etc. to remove support, again by utilizing the wet development of the developer solutions such as alkaline aqueous solution, water system developer solution, organic solvent, or method that unexposed portion develops etc. is removed in dry process development etc.Can enumerate the lean solution of for example 0.1 quality %～5 quality % sodium carbonate, lean solution, the lean solution of 0.1 quality %～5 quality % NaOH etc. of 0.1～5 quality % sal tartari as the alkaline aqueous solution using in wet development.The pH of alkaline aqueous solution is preferably 9～11 scope, and its temperature is adjusted according to the developability of photosensitive resin composition layer.In addition, also can in alkaline aqueous solution, sneak into surfactant, defoamer, organic solvent etc.Can enumerate such as impregnation method, spray pattern, scrub, scrape etc. as the mode of above-mentioned development.
Then, make exposure portion fully solidify and obtain cured film as the processing after developing by post-exposure (ultraviolet exposure) and/or rear heating.Post-exposure is preferably with 1～5J/cm 2exposure carry out.Rear heating is preferably carried out 30 minutes～12 hours at 100～200 ℃.
The circuit that in the manufacture method of printed circuit board (PCB) of the present invention, the formation method of the resist pattern by the invention described above is formed with to resist pattern forms and carries out etching or plating with substrate.At this, the resist pattern being made up of the photosensitive resin composition of the invention described above can effectively be made the excellent permanent mask resist such as imaging, thermotolerance, adaptation, mechanical property, chemical reagent resistance, electrology characteristic.
Embodiment
Be described more specifically the present invention based on embodiment and comparative example below, but the present invention is not limited to the following examples.
[synthesis example 1]
(Dongdu changes into (strain) manufacture, 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, add thermal agitation and solubilizing reaction potpourri at 90 ℃.Then, the solution obtaining is cooled to 60 ℃, adds benzyltrimethylammonium chloride 2 mass parts to it, be heated to 100 ℃ react to solid constituent acid number be 1mgKOH/g.And then, add maleic anhydride 98 mass parts and carbitol acetate 85 mass parts, be heated to 80 ℃ of reactions approximately 6 hours.Subsequently, be cooled to room temperature, being diluted to solid component concentration with carbitol acetate is 60 quality %, obtains the carboxyl acid modified Bisphenol F type epoxy acrylate (being called " epoxy resin A1 " below) as (A) composition.
[synthesis example 2]
(Dongdu changes into (strain) manufacture, 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, add thermal agitation and solubilizing reaction potpourri at 90 ℃.Then, the solution obtaining is cooled to 60 ℃, adds benzyltrimethylammonium chloride 1 mass parts to it, be heated to 100 ℃ react to solid constituent acid number be 1mgKOH/g.And then, add tetrabydrophthalic anhydride 152 mass parts and carbitol acetate 100 mass parts, be heated to 80 ℃ of reactions approximately 6 hours.Subsequently, be cooled to room temperature, being diluted to solid component concentration with carbitol acetate is 60 quality %, obtains the carboxyl acid modified cresols phenolic varnish type epoxy acrylate (being called " epoxy resin A2 " below) as (A) composition.
(embodiment 1～5 and comparative example 1～4)
Mixing according to carrying out with three-roll grinder after the mix proportion shown in following table 1 (unit: mass parts) complexing compositions, adding carbitol acetate to solid component concentration is 70 quality %, obtains photosensitive resin composition.In addition, the use level of the each composition in following table 1 represents the use level of solid constituent.
[table 1]
Figure BDA0000154976290000301
In addition, the details of the each composition in table 1 is as described below.
Bisphenol f type epoxy resin (trade name: YSLV-80XY-F, Dongdu change into society and manufactures),
DPHA (trade name: block that sub-rad (カ ヤ ラ Star De) DPHA, Japanese chemical drug society manufacture, dipentaerythritol acrylate),
OXE-01 (trade name, Ciba company manufacture, represented by above-mentioned formula (9) 1,2-octane diketone-1-[4-(phenyl sulfo-) phenyl]-2-(O-benzoyl oximes)),
IC907 (compound that trade name: Irgacure 907, Ciba company manufacture, represented by following formula (16)),
Cumarin (BC) (7,7 '-bis-(diethylamino)-3-ketone-cumarins, maximum absorption wavelength: 449nm that trade name: BC, green chemical company manufacture, represented by above-mentioned formula (10)),
Cumarin (C-314T) (compound, maximum absorption wavelength that trade name: C-314T, A Ku Louth (ア Network ロ ス) company manufacture, represented by following formula (17): 435nm),
DETX (trade name: Ka Yakua (カ ヤ キ ユ ア) DETX-S, the manufacture of Japanese chemical drug society, diethyl thioxanthone, maximum absorption wavelength: 383nm),
C152 (compound, maximum absorption wavelength that trade name: Coumarin 152, A Ku Louth company manufacture, represented by following formula (18): 394nm),
C153 (compound, maximum absorption wavelength that trade name: Coumarin 153, A Ku Louth company manufacture, represented by following formula (19): 423nm),
MBO (mercaptobenzoxazole being represented by above-mentioned formula (12)),
MBT (mercaptobenzothiazoler being represented by above-mentioned formula (13)),
MBI (mercaptobenzimidazole being represented by above-mentioned formula (14)),
EAB (trade name, the manufacture of hodogaya chemical society, diethylamino benzophenone, maximum absorption wavelength: 365nm).
[changing 28]
Figure BDA0000154976290000311
[changing 29]
Figure BDA0000154976290000321
[changing 30]
Figure BDA0000154976290000322
[changing 31]
Figure BDA0000154976290000323
< evaluates the making > of substrate
Use 120 object terylene Netcoms to cross silk screen print method the photosensitive resin composition of embodiment 1～5 and comparative example 1～4 is applied on copper-surfaced laminated board take dried thickness as approximately 20 μ m, be dried 30 minutes by hot air circulation type drying machine at 80 ℃.Thus, obtain on copper-surfaced laminated board lamination and have the evaluation substrate of the photosensitive resin composition layer being formed by photosensitive resin composition.The evaluation substrate that use obtains carries out the evaluation of each characteristic by the method below.Sum up its result and be illustrated in table 2.
(light sensitivity)
On the photosensitive resin composition layer of evaluating substrate, place minus mask (41 sections of stage metraster of Stouffer), and then placement is thereon as Korean and Japanese light splitting Co., Ltd.'s manufacture light splitting optical filter (trade name: HG0405) of the band pass filter of the light of point optical wavelength 405 ± 30nm, uses the parallel exposing machine (trade name: EXM-1201, the manufacture of Losec (オ mono-Network) manufacturing company) take 5kW short-arc lamp as light source to irradiate exposure 100mJ/cm under this state 2ultraviolet ray.In addition, use ultraviolet integrating quantometer (trade name: UIT-150-A, Ushio Electric Inc manufacture, also can be used as illuminometer) and measure the illumination through the light of band pass filter as " UVD-S405 " (trade name, wavelength photoreceptor region: 320nm～470nm, Absolute Calibration wavelength: 405nm) of light-receiving device, illumination × time shutter is as exposure.Subsequently, with the aqueous sodium carbonate (30 ℃) of 1 quality % at 60 seconds, 1.8kgf/cm 2pressure under carry out spray development, dissolve and remove unexposed portion.Remove after unexposed portion, the hop count of the stage metraster by being determined at the photocuring film forming on copper-surfaced laminated board is evaluated the light sensitivity of photosensitive resin composition.Light sensitivity represents by the hop count of stage metraster, and the hop count of this stage metraster is higher means that light sensitivity is higher.
(developability)
On the photosensitive resin composition layer of evaluating substrate, placing path mask (PVC ア マ ス Network) opening size is the mask of 100 μ m, and then placement is thereon as Korean and Japanese light splitting Co., Ltd.'s manufacture light splitting optical filter (trade name: HG0405) of the band pass filter of the light of point optical wavelength 405 ± 30nm, uses the parallel exposing machine (trade name: EXM-1201, the manufacture of Losec manufacturing company) take 5kW short-arc lamp as light source to irradiate exposure 100mJ/cm under this state 2ultraviolet ray.In addition, use ultraviolet integrating quantometer (trade name: UIT-150-A, Ushio Electric Inc manufacture, also can be used as illuminometer) and measure the illumination through the light of band pass filter as " UVD-S405 " (trade name, wavelength photoreceptor region: 320nm～470nm, Absolute Calibration wavelength: 405nm) of light-receiving device, using 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, carries out the evaluation of developability according to following benchmark.
A: obtain passage opening portions more than opening size 80 μ m situation,
B: obtain opening size 60 μ m above and be less than the passage opening portion of 80 μ m situation,
C: the opening size of passage opening portion is less than the situation of 60 μ m.
The making > of < breadboard
On the photosensitive resin composition layer of evaluating substrate, place Korean and Japanese light splitting Co., Ltd.'s manufacture light splitting optical filter (trade name: HG0405) of the band pass filter of the light of conduct point optical wavelength 405 ± 30nm, under this state, use parallel exposing machine (trade name: EXM-1201, Losec manufacturing company manufacture) the irradiation exposure 100mJ/cm take 5kW short-arc lamp as light source 2ultraviolet ray.In addition, use ultraviolet integrating quantometer (trade name: UIT-150-A, Ushio Electric Inc manufacture, also can be used as illuminometer) and measure the illumination through the light of band pass filter as " UVD-S405 " (trade name, wavelength photoreceptor region: 320nm～470nm, Absolute Calibration wavelength: 405nm) of light-receiving device, using 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, dissolve and remove unexposed portion.Then,, 150 ℃ of heating 1 hour, make the breadboard of the cured film with photosensitive resin composition layer.The breadboard that use obtains carries out the evaluation of each characteristic by the method below.Sum up its result and be illustrated in table 2.
(adaptation)
Breadboard is carried out to disbonded test by the method based on JIS K5400.That is, the cured film of breadboard is made to the gridiron pattern of 100 1mm, peel off paste cellophane adhesive tape on gridiron pattern after.The tessellated state of peeling off after observation is peeled off, carries out the evaluation of adaptation according to benchmark below.
A: tessellatedly more than 90/100 do not peel off,
B: tessellated more than 50/100 and be less than 90/100 do not peel off,
C: be tessellatedly less than 50/100 and do not peel off.
(solvent resistance)
Breadboard is flooded in isopropyl alcohol after 30 minutes in room temperature, whether the outward appearance of Visual Confirmation cured film has extremely.Subsequently, cellophane tape-stripping, to the disbonded test of drawing on carrying out in cured film, is confirmed to whether cured film is peeled off from copper-surfaced laminated board.Carry out the evaluation of solvent resistance according to benchmark below from its result.
A: the outward appearance of cured film is not abnormal, and do not peel off in disbonded test,
B: the outward appearance of cured film exists abnormal, or peels off in disbonded test.
(solder heat resistance)
After the cured film surface-coated rosin series flux of breadboard, in the solder bath of 260 ℃, flooded for 10 seconds.Set it as 1 circulation, repeat the outward appearance of visualization cured film after 6 circulations, carry out the evaluation of solder heat resistance according to benchmark below.
A: the outward appearance of cured film not abnormal (peel off, swell), there is no the infiltration of scolder yet,
B: the outward appearance of cured film exists abnormal (peel off, swell), or there is the infiltration of scolder.
The modulation of solution and the evaluation > of ageing stability for the evaluation of < ageing stability
In the composition shown in table 1, remove as the bisphenol f type epoxy resin of hardening agent and as epoxy resin A1 and the A2 of optical polymerism compound, add carbitol acetate that viscosity is adjusted to 50Pas, obtain ageing stability evaluation solution.Place the solution obtaining in room temperature (25 ℃), measure until solution does not flow or the time of generation gelation.Its result is illustrated in table 2.
[table 2]
Figure BDA0000154976290000351
From the result shown in table 2, according to the photosensitive resin composition of embodiment 1～5, be identified light sensitivity excellence compared with the photosensitive resin composition of comparative example 1～4.In addition, the photosensitive resin composition of comparative example 1 and 2, due to insufficient to the light sensitivity of light at 405nm wavelength, could not carry out photocuring by exposure, can not imaging.
The possibility of utilizing in industry
As mentioned above, can provide the exposure light using within the scope of wavelength 370nm～450nm to form resist pattern according to the present invention time, particularly when using directly the describing exposure method and form resist pattern of wavelength 405nm laser the photosensitive resin composition of light sensitivity excellence, use photosensitive element, the formation method of resist pattern and the manufacture method of printed circuit board (PCB) of said composition.In addition, according to photosensitive resin composition of the present invention and photosensitive element, the blue laser using wavelength 405nm as light source directly describe exposure method in can form and be difficult to the highdensity resist pattern manufactured in the past, and can obtain the high performance cured film of thermotolerance, humidity resistance (shear bond), adaptation, mechanical property, electrology characteristic excellence.Thus, photosensitive resin composition of the present invention and photosensitive element can be aptly for the manufacture of printed circuit board (PCB), high-density multi-layered plate and semiconductor package body etc.

Claims (6)

1.一种光敏性树脂组合物，含有(A)酸改性含乙烯基环氧树脂、(B)包含由下述式(9)表示的1，2-辛烷二酮-1-[4-(苯基硫代)苯基]-2-(O-苯甲酰基肟)的光聚合引发剂、以及(C)增敏剂；所述(C)增敏剂包含由下述式(10)表示的7，7’-二(二乙基氨基)-3-酮-香豆素或由下述式(17)表示的化合物，所述(A)酸改性含乙烯基环氧树脂为从由下述通式(5)表示的酚醛清漆型环氧树脂以及由下述通式(6)表示的双酚型环氧树脂构成的组中选择的至少一种环氧树脂(a)与含乙烯基单羧酸(b)反应而得到的树脂，1. A photosensitive resin composition comprising (A) an acid-modified vinyl group-containing epoxy resin, (B) 1,2-octanedione-1-[4] represented by the following formula (9) -(phenylthio) phenyl]-2-(O-benzoyl oxime) photopolymerization initiator, and (C) sensitizer; Described (C) sensitizer comprises by following formula (10 ) represented by 7,7'-di(diethylamino)-3-keto-coumarin or a compound represented by the following formula (17), the (A) acid-modified vinyl-containing epoxy resin is At least one epoxy resin (a) selected from the group consisting of a novolak epoxy resin represented by the following general formula (5) and a bisphenol epoxy resin represented by the following general formula (6) and A resin obtained by the reaction of vinyl-containing monocarboxylic acid (b),
Figure FDA0000407701820000011
Figure FDA0000407701820000011
 式(5)中R11表示氢原子或甲基，Y1表示氢原子或缩水甘油基，Y1中，氢原子／缩水甘油基的摩尔比为0／100～30／70，n1表示1以上的整数；另外，所存在的多个R11和Y1各自相同或不同；In formula (5), R 11 represents a hydrogen atom or a methyl group, Y 1 represents a hydrogen atom or a glycidyl group, and in Y 1 , the molar ratio of a hydrogen atom/glycidyl group is 0/100 to 30/70, and n1 represents 1 or more An integer; In addition, a plurality of R 11 and Y 1 that exist are each the same or different;
Figure FDA0000407701820000012
Figure FDA0000407701820000012
 式(6)中R12表示氢原子或甲基，Y2表示氢原子或缩水甘油基，Y2中，氢原子／缩水甘油基的摩尔比为0／100～30／70，n2表示1以上的整数；另外，所存在的多个R12和Y2各自相同或不同；In formula (6), R12 represents a hydrogen atom or a methyl group, Y2 represents a hydrogen atom or a glycidyl group, and in Y2 , the molar ratio of a hydrogen atom/glycidyl group is 0/100 to 30/70, and n2 represents 1 or more An integer; In addition, a plurality of R 12 and Y 2 that exist are each the same or different;
Figure FDA0000407701820000021
Figure FDA0000407701820000021
 2.根据权利要求1所述的光敏性树脂组合物，进一步含有(D)具有硫醇基的化合物。2. The photosensitive resin composition according to claim 1, further comprising (D) a compound having a thiol group. 3.一种光敏性元件，具有支持体以及在该支持体上形成的由权利要求1或2所述的光敏性树脂组合物形成的光敏性树脂组合物层。3. A photosensitive element comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 or 2 formed on the support. 4.一种抗蚀剂图案的形成方法，包括：4. A method for forming a resist pattern, comprising: 层积工序，将由权利要求1或2所述的光敏性树脂组合物形成的光敏性树脂组合物层层积到基板上；Lamination process, laminating the photosensitive resin composition layer formed by the photosensitive resin composition described in claim 1 or 2 on the substrate; 曝光工序，对所述光敏性树脂组合物层以图像状照射活性光线使曝光部进行光固化；an exposure step, irradiating the photosensitive resin composition layer with active light in an image form to light-cure the exposed part; 显影工序，通过显影除去所述光敏性树脂组合物层的未曝光部。In the development step, the unexposed portion of the photosensitive resin composition layer is removed by development. 5.根据权利要求4所述的抗蚀剂图案的形成方法，所述曝光工序为通过波长405nm的激光对所述光敏性树脂组合物层进行直接描绘曝光而使曝光部进行光固化的工序。5 . The method for forming a resist pattern according to claim 4 , wherein the exposing step is a step of exposing the photosensitive resin composition layer by direct drawing with a laser beam having a wavelength of 405 nm to photocure the exposed portion. 5 . 6.一种印刷电路板的制造方法，对通过权利要求4或5所述的抗蚀剂图案的形成方法形成有抗蚀剂图案的电路形成用基板进行蚀刻或镀覆。6 . A method of manufacturing a printed wiring board, comprising etching or plating a circuit-forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 4 or 5 .
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JP5864524B2 (en) * 2013-12-26 2016-02-17 太陽ホールディングス株式会社 Photocurable resin composition
JP6748419B2 (en) * 2014-11-19 2020-09-02 三洋化成工業株式会社 Photosensitive resin composition
KR102329943B1 (en) * 2016-03-16 2021-11-22 동우 화인켐 주식회사 Negative photosensitive resin composition and photo-cured pattern prepared from the same
KR101910734B1 (en) * 2017-03-28 2018-10-22 동우 화인켐 주식회사 Colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter

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TW200910007A (en) 2009-03-01
TWI398728B (en) 2013-06-11
KR20100009548A (en) 2010-01-27
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CN101675388B (en) 2012-07-18
JP4985767B2 (en) 2012-07-25

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