CN108027559A - Photosensitive polymer combination - Google Patents

Photosensitive polymer combination Download PDF

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Publication number
CN108027559A
CN108027559A CN201680052525.7A CN201680052525A CN108027559A CN 108027559 A CN108027559 A CN 108027559A CN 201680052525 A CN201680052525 A CN 201680052525A CN 108027559 A CN108027559 A CN 108027559A
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CN
China
Prior art keywords
mass
methyl
polymer combination
photosensitive polymer
component
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Granted
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CN201680052525.7A
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Chinese (zh)
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CN108027559B (en
Inventor
内藤也
内藤一也
山田有里
小坂隼也
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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Priority to CN202111430178.6A priority Critical patent/CN114296315A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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

Abstract

A kind of photosensitive polymer combination, it is characterized in that, compound and Photoepolymerizationinitiater initiater containing alkali solubility macromolecule, with olefinic double bond, the photo-sensitive resin formed on the copper-clad laminated board of copper foil for being laminated with 18 μ m thicks with the stacking of 25 μ m thicks by photosensitive resin combination, curing corrosion-resisting pattern is formed by the light irradiation and development treatment of the pattern-like of line/interval=50 μm/30 μm, after implementing the copper etching process of 55 seconds at 50 DEG C, the bottom width of copper wire pattern obtained from removing said curing corrosion-resisting pattern is more than 38 μm.

Description

Photosensitive polymer combination
Technical field
Technical field ＞ involved by the first embodiment of the ＜ present invention
The first embodiment of the present invention is related to photosensitive polymer combination.
Technical field ＞ involved by ＜ second embodiment of the present invention
Second embodiment of the present invention is related to photosensitive polymer combination etc..
Technical field ＞ involved by ＜ third embodiment of the present invention
Third embodiment of the present invention is related to photosensitive polymer combination etc..
Technical field ＞ involved by the 4th embodiment of the ＜ present invention
The 4th embodiment of the present invention is related to photosensitive polymer combination.
Background technology
Background technology ＞ involved by the first embodiment of the ＜ present invention
Printed circuit board (PCB) is usually manufactured by photoetching process.Photoetching process refers to, is formed on substrate by photosensitive resin group Compound formed layer, to the film carry out pattern exposure and development and form corrosion-resisting pattern, then by etching or plating at Reason forms conductive pattern, the corrosion-resisting pattern on substrate is then removed, so as to form the method for desired wiring pattern on substrate.
In the photoetching process, when forming photosensitive polymer combination layer on substrate, it is known to：After coating composition solution The method for removing solvent；The photosensitive element or even dry film that are laminated supporter and photosensitive polymer combination layer and are formed is against corrosion Oxidant layer is pressed on substrate, method for then peeling off foregoing supporter etc..
In the manufacture of printed circuit board (PCB), often using photosensitive element.As the wiring pattern using the photosensitive element Forming method and be suitable for its photosensitive polymer combination, exist many known example.
For example, respectively, Patent Document 1 discloses can be readily formed the thin copper film pattern with good cross sectional shape Method and this method in the photosensitive polymer combination that uses；
Patent Document 2 discloses the photoresist group containing the specific addition-polymerizable monomer with olefinic double bond Compound.
However, in recent years, due to the densification of printed circuit board (PCB), substrate is often by multiple stratification.In multilager base plate, in order to Make to turn between substrate stacked on top of one another and set through hole.Pass through photoetching process on the substrate with through hole used in multilager base plate When forming wiring pattern, the etchant resist (cap bore film) that is formed on the through hole requires will not be because of spray when developing, wash etc. Mist pressure and destroyed property (film of resistance to cap bore disruptiveness or even hole covering character).
On this point, Patent Document 3 discloses contain the small binder polymer of dispersion degree (Mw/Mn), photopolymerization Property compound and acridine compounds photosensitive polymer combination, illustrate can utilize said composition formed hole covering character it is excellent Etchant resist.
Background technology ＞ involved by ＜ second embodiment of the present invention
Printed circuit board (PCB) is usually manufactured by photoetching process.Photoetching process refers to, is formed and is included by photoresist on substrate The film for the layer that composition is formed, carries out film pattern exposure and development and forms corrosion-resisting pattern, then by etching or plating Cover processing and form conductive pattern, the corrosion-resisting pattern on substrate is then removed, so as to form desired wiring pattern on substrate Method.
In photoetching process, when forming photo-sensitive resin on substrate, it is known to：Solvent is removed after coating composition solution Method；The photosensitive element or even dry film photoresist that are laminated supporter and photo-sensitive resin and are formed are laminated to substrate On, method for then peeling off foregoing supporter etc..
In the manufacture of printed circuit board (PCB), often using photosensitive element.As the wiring pattern using the photosensitive element Forming method and be suitable for its photosensitive polymer combination, there are many known examples.
For example, respectively, Patent Document 1 discloses can be readily formed the thin copper film pattern with good cross sectional shape Method and this method in the photosensitive polymer combination that uses, Patent Document 4 discloses containing specifically having the olefinic double The photosensitive polymer combination of the addition-polymerizable monomer of key.
Background technology ＞ involved by ＜ third embodiment of the present invention
All the time, printed circuit board (PCB) is usually manufactured by photoetching process.In photoetching process, first, to being layered on substrate Photosensitive polymer combination layer carries out pattern exposure.Polymerizing curable (the feelings of minus occur for the exposure portion of photosensitive polymer combination Condition) or become soluble in developer solution (situation of eurymeric).Then, remove unexposed portion's (situation of minus) with developer solution or expose Light portion (situation of eurymeric), forms corrosion-resisting pattern on substrate.And then after implementing etching or plating formation conductive pattern, Corrosion-resisting pattern is removed from strippable substrate.By these processes, so as to form conductive pattern on substrate.
Usually using by the solution coating of photosensitive polymer combination to substrate and dry method or will in photoetching process The photonasty tree of dry film photoresist (the photoresist layered product that photosensitive polymer combination layer forms is laminated on supporter) Oil/fat composition is laminated to any one of method on substrate layer by layer.The latter is usually used in the manufacture of printed circuit board (PCB).
With the miniaturization of the routing space in printed circuit board (PCB) in recent years, various characteristics are required to dry film photoresist. With the miniaturization of routing space, the thickness of dry film photoresist also has the tendency of filming, but for the through hole on protective substrate And still require tough hole covering character.
In addition, when developing to corrosion-resisting pattern, due to remaining in the moisture between pattern, resist component is molten between pattern Go out, water residual short trouble occurs.In order to reduce water residual short trouble, it is necessary to improve the hydrophobicity for curing resist.
In order to improve the characteristic of resist, it is proposed that various photosensitive polymer combinations (patent document 5 and 6).
Background technology ＞ involved by the 4th embodiment of the ＜ present invention
Printed circuit board (PCB) is usually manufactured by photoetching process.Photoetching process refers to, is formed on substrate by photosensitive resin group The layer that compound is formed, carries out the film pattern exposure and development and forms corrosion-resisting pattern, then pass through etching or plating And after forming conductive pattern, the corrosion-resisting pattern on substrate is removed, so as to form the method for desired wiring pattern on substrate.
In photoetching process, when forming photo-sensitive resin on substrate, it is known to remove solvent after coating composition solution Method；After the photosensitive element or even dry film photoresist that stacking supporter and photo-sensitive resin are formed are laminated on substrate Method for peeling off foregoing supporter etc..
In the manufacture of printed circuit board (PCB), usually using photosensitive element.Use the shape of the wiring pattern of the photosensitive element It is known (patent document 1 and 2) into method and suitable for its photosensitive polymer combination.Having been recorded in patent document 1 has The conventional forming method of the thin copper film pattern of good cross sectional shape and its photosensitive polymer combination used.In patent document 2 Describe the photosensitive polymer combination for including the specific addition-polymerizable monomer with ethylenic unsaturated bond.
With the miniaturization of the routing space in printed circuit board (PCB) in recent years, the spies such as resolution ratio are required to dry film photoresist Property.For example, in order to improve the characteristic of corrosion-resisting pattern, it is proposed that various photosensitive polymer combinations (patent document 5 and 6).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-233769 publications
Patent document 2：International Publication No. 2009/022724
Patent document 3：Japanese Unexamined Patent Publication 2013-109321 publications
Patent document 4：Japanese Unexamined Patent Publication 2015-60120 publications
Patent document 5：International Publication No. 2015/098870
Patent document 6：Japanese Unexamined Patent Publication 2014-048340 publications
The content of the invention
Problems to be solved by the invention
The first embodiment of the ＜ present invention will solve the problems, such as ＞
In recent years, flowing water of the manufacture of circuit board usually by the way that substrate edge fixed-direction conveying side is handled successively Line carries out.Herein, when forming such as conductive pattern of line/intermittent pattern on substrate, there is the conveying direction relative to substrate, The situation of the parallel situation (line in MD directions) of the line of conductor, vertical situation (line in TD directions) and deflection.Use existing skill When the erosion resistant of art forms the conductive pattern of line/intermittent pattern by assembly line, the cloth of the line in MD directions and the line in TD directions Line width is different, produces the poor in length and breadth of so-called wiring width.In many cases, the line in MD directions is easier than the line in TD direction Liquid erosion is etched, therefore, tendency that wiring width attenuate more in the presence of etching quantitative change.In order to form fine lead by assembly line Body pattern, the wiring for preferably reducing this MD directions are poor with the wiring width of the wiring in TD directions.
However, with above patent document 1~3 for representative in the prior art, do not studied from this point of view, Erosion resistant poor in length and breadth for reducing wiring width still belongs to unknown.
The present invention first embodiment be in view of above-mentioned present situation and make.Therefore, first embodiment of the invention Purpose be to provide the material against corrosion poor in length and breadth for inhibiting wiring width when forming fine conductive pattern by assembly line Material.
＜ second embodiment of the present invention will solve the problems, such as ＞
In order to form corrosion-resisting pattern using photosensitive polymer combination, to pass through developing procedure.In the developing procedure, respectively Ground, the composition of exposure area is dissolved removal in the case of the composition of eurymeric, exposure region in the case of the composition of minus The composition in domain is dissolved removal, so as to form corrosion-resisting pattern.It is not the composition in unwanted region in the developing procedure All " dissolving " is in developer solution, but at least one part is scattered in developer solution with keeping insoluble state, so that from substrate Remove.Therefore, when repeating developing procedure every time, the amount increase of the unwanted material in developer solution, final bad dispersibility is not Solvent components form aggregation sometimes.Remained on this aggregation substrate to be developed after being attached to, occasionally result in short circuit Failure etc..
Therefore, from the finished product rate and then the viewpoint of the manufacture cost of reduction printed circuit board (PCB) improved in developing procedure Set out, the developer solution good dispersion of photosensitive polymer combination used in strong expectation.
In recent years, the miniaturization of printed circuit board (PCB), the requirement to become more meticulous grow to even greater heights.Therefore, for the printed circuit board (PCB) Formation in the photosensitive polymer combination that uses, also be required to form fine pattern.Herein, the pattern formed on substrate Minimum dimension depends on exposure wavelength, therefore, by using photonasty polymerization initiator corresponding with used exposure wavelength Do not have difficulty more in theory in itself so as to expose the pattern to form miniaturization.But with such as less than tens μm of size The fine pattern formed is exposed sometimes in the subsequent handlings such as developing procedure there is a phenomenon where being peeled off from substrate, as a result, print The miniaturization of printed circuit board is restricted.
Therefore, in order to form fine printed circuit board (PCB), it is necessary to the high photosensitive resin composition of the adaptation of fine pattern Thing.
However, the photosensitive polymer combination described in patent document 1 and 4 is dispersed closely sealed with fine pattern in development Property these two aspects can not meet current rigors, still have the leeway of improvement in this field.
Second embodiment of the present invention be in view of this present situation and make.
Therefore, the purpose of second embodiment of the present invention is to provide possesses the photosensitive materials such as resolution ratio with high level The performance and the novel photoactive material of develop dispersiveness and the excellent adhesion of fine pattern usually required that.
＜ third embodiment of the present invention will solve the problems, such as ＞
In patent document 5, from the developability of photosensitive polymer combination and resolution ratio, adaptation and the bending of corrosion-resisting pattern Property from the viewpoint of, on photosensitive polymer combination, have studied construction unit, styrene or α with (methyl) acrylic acid- The construction unit of methyl styrene and possess carbon number 1~12 hydroxy alkyl (methyl) hydroxyalkyl acrylates structure list The construction unit number of the binding agent macromolecule of member and inferior ethoxyl is 1~20 and the construction unit number of sub- propoxyl group is 0~7 The combination of bisphenol type two (methyl) acrylate monomer.
In patent document 6, from the viewpoint of the interval width and hole covering character of eurymeric corrosion-resisting pattern, as alkali solubility high score The content of the construction unit of styrene or styrene derivative in son, it is proposed that more than 30 mass %, also, gather as addition The weight average molecular weight of conjunction property monomer, it is proposed that more than 1100.
Patent document 5 and 6 is conceived to comprising the macromolecule of construction unit with special ratios with styrene and specific The photosensitive polymer combination of monomer, but the photosensitive polymer combination described in patent document 5 and 6 is from taking into account corrosion-resisting pattern Still there is room for improvement from the viewpoint of hole covering character and water residual short trouble inhibition.
Therefore, third embodiment of the present invention will solve the problems, such as to be, there is provided can take into account the cap bore of corrosion-resisting pattern Property and water residual short trouble inhibition photosensitive polymer combination.
The 4th embodiment of the ＜ present invention will solve the problems, such as ＞
In recent years, flowing water of the manufacture of circuit board usually by the way that substrate edge fixed-direction conveying side is handled successively Line carries out.At this time, the processing of the developer solution to substrate or etching solution is carried out by spraying.Based on photolithographic corrosion-resisting pattern In formation, it is important that the resist line width after development, which does not produce deviation,.But the formation of the corrosion-resisting pattern based on spray development Deviation in the real estate of developer solution is easily produced in the case where developing time is short, produces the above problem sometimes, therefore it is required that aobvious Shadow time lengthening.
Herein, developing time refers to, substrate stops the time for carrying out development treatment in developing trough, such as is determined as minimum 2 times time of developing time etc..Minimum developing time refers to, the unexposed portion to photo-sensitive resin is dissolved goes completely The minimum time needed for untill removing, according to the concentration of developer solution or temperature, the direction of spraying or spray amount, pressure, vibration Frequency etc. and change.
Herein, it is believed that the dissolving reaction of the resist based on development is substantially controlled and occurred by the diffusion of developer solution.Therefore, From promoting from the viewpoint of developing, it is necessary on one's own initiative based on spraying etc. to supplying developer solution on substrate.When the supply needs some Between, it is understood that in the case where developing time is short, the supply of developer solution can not be against corrosion fully throughout substrate whole face The deviation of agent line width substantially becomes larger.On the other hand, it is believed that in the case where developing time is grown, developer solution on substrate Supply becomes uniform, therefore the deviation of line width also diminishes.Accordingly, it is believed that use the slower sense of minimum developing time itself Photosensitive resin composition is effective from the viewpoint of the deviation for suppressing line width.
In patent document 5, from the developability of photosensitive polymer combination and resolution ratio, adaptation and the bending of corrosion-resisting pattern Property from the viewpoint of, on photosensitive polymer combination, have studied construction unit, styrene or α with (methyl) acrylic acid- The construction unit of methyl styrene and possess carbon number 1~12 hydroxy alkyl (methyl) hydroxyalkyl acrylates structure list The construction unit number of the binding agent macromolecule of member and inferior ethoxyl is 1~20 and the construction unit number of sub- propoxyl group is 0~7 The combination of bisphenol type two (methyl) acrylate monomer.
In patent document 6, from the viewpoint of the interval width and hole covering character of eurymeric corrosion-resisting pattern, as alkali solubility high score The content of the construction unit of styrene or styrene derivative in son, it is proposed that more than 30 mass %, also, gather as addition The weight average molecular weight of conjunction property monomer, it is proposed that more than 1100.
Patent document 5 and 6 is conceived to comprising the macromolecule of construction unit with special ratios with styrene and specific The photosensitive polymer combination of monomer, but the photosensitive polymer combination described in patent document 5 and 6 is from taking into account corrosion-resisting pattern Still there is room for improvement from the viewpoint of the extension of fine resolution and minimum developing time.
Therefore, the 4th embodiment of the invention will solve the problems, such as to be to provide good point that can take into account corrosion-resisting pattern The extended photosensitive polymer combination of resolution and minimum developing time.
The solution used to solve the problem
＜ is used for the means ＞ for solving first problem
The inventors of the present invention's discovery can realize above-mentioned purpose by following technological means, and complete the present invention first is real Apply mode.The first embodiment of the present invention is as shown below.
[1]
A kind of photosensitive polymer combination, it is characterised in that each component containing following (A)~(C),
(A) component：Alkali solubility macromolecule,
(B) component：Compound with olefinic double bond and
(C) component：Photoepolymerizationinitiater initiater
It is laminated on the copper-clad laminated board of copper foil for being laminated with 18 μ m thicks with 25 μ m thicks by photosensitive resin group The photo-sensitive resin that compound is formed, forms by the light irradiation and development treatment of the pattern-like of line/interval=50 μm/30 μm Cure corrosion-resisting pattern, after implementing the copper etching process of 55 seconds at 50 DEG C, remove copper wire obtained from said curing corrosion-resisting pattern The bottom width of pattern is more than 38 μm.
[2]
According to the photosensitive polymer combination described in [1], wherein, foregoing (A) component is containing for (methyl) acrylic acid units Proportional is more than 10 mass % and the copolymer of below 24 mass %.
[3]
According to the photosensitive polymer combination described in [1] or [2], wherein, foregoing (A) component is containing for styrene units Ratio is more than 32 mass % and the copolymer of below 60 mass %.
[4]
According to the photosensitive polymer combination any one of [1]~[3], wherein, foregoing (C) component contains acridine Compound.
[5]
According to the photosensitive polymer combination any one of [1]~[4], wherein, foregoing (B) component contains Ji Wusi Alcoholic compound.
[6]
According to the photosensitive polymer combination any one of [1]~[5], wherein, foregoing (B) component contains three hydroxyl first Base propane compounds.
[7]
According to the photosensitive polymer combination any one of [1]~[6], wherein, foregoing (B) component contains bisphenol-A Compound.
[8]
A kind of photosensitive polymer combination, it contains each component of following (A)~(C),
(A) component：Alkali solubility macromolecule,
(B) component：Compound with olefinic double bond and
(C) component：Photoepolymerizationinitiater initiater
Foregoing (A) component include the content ratio of (methyl) acrylic acid units for more than 10 mass % and 24 mass % with Under and styrene units content ratio be more than 32 mass % copolymer,
Foregoing (C) component includes acridine compounds.
[9]
According to the photosensitive polymer combination described in [8], wherein, foregoing (A) component includes (methyl) acrylic acid units Content ratio be more than 10 mass % and the content ratio of below 24 mass % and styrene units be it is more than 32 mass % and The copolymer of below 60 mass %.
[10]
According to the photosensitive polymer combination described in [8] or [9], wherein, foregoing (B) component contains pentaerythrite chemical combination Thing.
[11]
According to the photosensitive polymer combination any one of [8]~[10], wherein, foregoing (B) component contains three hydroxyls Methylpropane compound.
[12]
According to the photosensitive polymer combination any one of [8]~[11], wherein, foregoing (B) component contains bisphenol-A Compound.
[13]
A kind of photosensitive element, it is will to be formed as the photosensitive polymer combination any one of [1]~[12] Photo-sensitive resin is layered in obtained from supporter.
[14]
A kind of forming method of corrosion-resisting pattern, it is characterised in that including：
The photo-sensitive resin of photosensitive element described in [13] is layered in lamination process on conductor substrate,
The exposure process that is exposed to the photosensitive polymer combination layer of foregoing stacking and
The developing procedure in the unexposed portion after foregoing exposure is removed with developer solution.
[15]
The forming method of corrosion-resisting pattern according to [14], wherein, foregoing lamination process is by the sense of photosensitive element Photosensitive resin layer clips the process that wetting agent is stacked on conductor substrate.
[16]
A kind of manufacture method of circuit board, it is characterised in that including：
By lamination process of the photosensitive polymer combination layer stackup of the photosensitive element described in [13] on conductor substrate,
The exposure process that is exposed to the photosensitive polymer combination layer of foregoing stacking,
With developer solution remove the unexposed portion after foregoing exposure developing procedure,
To by it is foregoing development the conductor substrate formed with corrosion-resisting pattern be etched or the conductive pattern of plating formed work Sequence and
The stripping process that foregoing corrosion-resisting pattern is peeled off.
[17]
The manufacture method of circuit board according to [16], wherein, foregoing lamination process is by the photosensitive of photosensitive element Property resin bed clips the process that wetting agent is stacked on conductor substrate.
＜ is used for the means ＞ for solving Second Problem
The inventors of the present invention's discovery can realize above-mentioned purpose by following technological means, and complete the present invention second is real Apply mode.Second embodiment of the present invention is as shown below.
[1]
A kind of photosensitive polymer combination, it is characterised in that each component containing following (A)~(C),
(A) component：The alkali solubility macromolecule of acid equivalent 100~600,
(B) component：Compound with olefinic double bond and
(C) component：Photoepolymerizationinitiater initiater
Foregoing (A) component contains the copolymer for including 50 mass % above styrene units,
Foregoing (B) component contains the compound shown in the following general formula (I),
{ in formula, R is independently of one another hydrogen atom or the alkyl of carbon number 1~4, and n1, n2 and n3 are 0~30 independently of one another Integer, wherein, meet the conditions of n1+n2+n3 >=6.}
The content of compound shown in the logical formula (I) is 5 matter relative to the solid constituent of photosensitive resin combination More than % is measured, and foregoing (C) component contains acridine compounds.
[2]
According to the photosensitive polymer combination described in [1], wherein, n1, n2 and n3 in aforementioned formula (I) meet 20 >=n1 + n2+n3 ＞ 9.
[3]
According to the photosensitive polymer combination described in [1] or [2], wherein, all hydrogen atoms of R in aforementioned formula (I).
[4]
According to the photosensitive polymer combination any one of [1]~[3], wherein, foregoing (B) component also contains season penta Tetrol modified monomer.
[5]
A kind of photosensitive element, it is the sense that will be formed as the photosensitive polymer combination any one of [1]~[4] Photosensitive resin layer is layered in obtained from supporter.
[6]
A kind of forming method of corrosion-resisting pattern, it is characterised in that including：
The photo-sensitive resin of photosensitive element described in [5] is layered in lamination process on conductor substrate,
The exposure process that is exposed to the photo-sensitive resin of foregoing stacking and
The developing procedure in the unexposed portion after foregoing exposure is removed with developer solution.
[7]
A kind of manufacture method of circuit board, it is characterised in that including：
The photo-sensitive resin of photosensitive element described in [5] is layered in lamination process on conductor substrate,
The exposure process that is exposed to the photo-sensitive resin of foregoing stacking,
With developer solution remove the unexposed portion after foregoing exposure developing procedure,
To by it is foregoing development the conductor substrate formed with corrosion-resisting pattern be etched or the conductive pattern of plating formed work Sequence and
The stripping process that foregoing corrosion-resisting pattern is peeled off.
＜ is used to solve the problems, such as the 3rd means ＞
The inventors discovered that it can be solved the above problems by following technological means.Third embodiment of the present invention is such as It is as shown below.
[1]
A kind of photosensitive polymer combination, it is characterised in that include：
(A) alkali solubility macromolecule；
(B) compound containing ethylenic unsaturated bond；And
(C) Photoepolymerizationinitiater initiater；
Foregoing (A) alkali solubility macromolecule is used as benchmark using the all-mass for forming the high molecular monomer of foregoing (A) alkali solubility Comprising 10 mass %~24 mass % the construction unit of (methyl) acrylic acid and the styrene of 35 mass %~90 mass % Construction unit, also,
The weight average molecular weight of foregoing (B) compound containing ethylenic unsaturated bond is more than 1200.
[2]
According to the photosensitive polymer combination described in [1], wherein, foregoing (B) compound containing ethylenic unsaturated bond it is foregoing Weight average molecular weight is more than 1300.
[3]
According to the photosensitive polymer combination described in [1] or [2], wherein, foregoing (B) compound containing ethylenic unsaturated bond it In more than 40 mass % be the following general formula (II) shown in alkylene oxide modified bisphenol A type two (methyl) acrylate compounds,
In formula, R3And R4Hydrogen atom or methyl, A C are represented independently of one another2H4, B C3H6, n1、n2、n3And n4It is full Sufficient n1+n2+n3+n4The integer of=2~50 relation, the arrangement of the repetitive unit of-(A-O)-and-(B-O)-can be random Can be block, optionally any one of-(A-O)-and-(B-O)-is in double phenyl sides in the case of block }.
[4]
According to the photosensitive polymer combination described in [3], wherein, the n in aforementioned formula (II)1、n2、n3And n4Meet n1+ n2+n3+n4=30~50 relation.
[5]
According to the photosensitive polymer combination described in [3], wherein, the n in aforementioned formula (II)1、n2、n3And n4Meet n1+ n2+n3+n4=2~10 relation.
[6]
According to the photosensitive polymer combination described in [1] or [2], wherein, foregoing (B) compound containing ethylenic unsaturated bond bag Containing three (methyl) acrylate compounds shown in the following general formula (III),
In formula, R5、R6And R7Hydrogen atom or methyl are represented independently of one another, and X represents the alkylidene of carbon number 2~6, m2、m3With m4Independently of one another be 0~40 integer, m2+m3+m4For 1~40, and m2+m3+m4In the case of more than 2, multiple X are optional It is same to each other or different to each other }.
[7]
According to the photosensitive polymer combination described in [1] or [2], wherein, foregoing (B) compound containing ethylenic unsaturated bond bag Containing carbamate two (methyl) acrylate compounds shown in the following general formula (IV),
In formula, R8And R9Hydrogen atom or methyl are represented independently of one another, and Y represents the alkylidene of carbon number 2~6, and Z represents divalence Organic group, s and t independently of one another be 0~40 integer, and s+t >=1.
[8]
According to the photosensitive polymer combination any one of [1]~[7], wherein, foregoing (A) alkali solubility macromolecule is also Include the construction unit of (methyl) butyl acrylate.
[9]
According to the photosensitive polymer combination any one of [1]~[8], it is used for direct imaging exposure.
[10]
A kind of forming method of corrosion-resisting pattern, it includes：
The photo-sensitive resin formed as the photosensitive polymer combination any one of [1]~[9] is layered in branch Lamination process on support body；
The exposure process being exposed to the photo-sensitive resin；And
The developing procedure to develop to the photo-sensitive resin of the exposure.
[11]
A kind of manufacture method of circuit board, it includes：
The photo-sensitive resin formed as the photosensitive polymer combination any one of [1]~[9] is layered in base Lamination process on plate；
The exposure process being exposed to the photo-sensitive resin；
Develop to the photo-sensitive resin of the exposure, obtain the developing procedure of the substrate formed with corrosion-resisting pattern；
The substrate formed with corrosion-resisting pattern is etched or the conductive pattern formation process of plating；And
The stripping process that the corrosion-resisting pattern is peeled off.
＜ is used to solve the problems, such as the 4th means ＞
The inventors of the present invention's discovery can realize above-mentioned purpose by following technological means, and complete the present invention the 4th is real Apply mode.The 4th embodiment of the present invention is as shown below.
[1]
A kind of photosensitive polymer combination, it includes：
(A) alkali solubility macromolecule；
(B) compound containing ethylenic unsaturated bond；And
(C) Photoepolymerizationinitiater initiater；
Foregoing (A) alkali solubility macromolecule includes the content ratio of acid monomer units less than 25 mass % and aromatic monomer list The content ratio of member is the first copolymer of more than 30 mass %, also,
The weight average molecular weight of foregoing (B) compound containing ethylenic unsaturated bond is less than 900.
[2]
According to the photosensitive polymer combination described in [1], wherein, foregoing (C) Photoepolymerizationinitiater initiater includes acridine compounds.
[3]
According to the photosensitive polymer combination described in [1] or [2], wherein, foregoing (A) alkali solubility macromolecule includes aromatic series The content ratio of monomeric unit for the mass % of 45 mass %~90 the second copolymer.
[4]
According to the photosensitive polymer combination any one of [1]~[3], wherein, foregoing (B) contains ethylenic unsaturated bond Compound includes three (methyl) acrylate compounds shown in the following general formula (III),
In formula, R5、R6And R7Hydrogen atom or methyl are represented independently of one another, and X represents the alkylidene of carbon number 2~6, m2、m3With m4Independently of one another be 0~40 integer, m2+m3+m4For 0~40, and m2+m3+m4In the case of more than 2, multiple X are optional It is same to each other or different to each other }.
[5]
According to the photosensitive polymer combination any one of [1]~[4], wherein, foregoing (B) contains ethylenic unsaturated bond Compound includes alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in the following general formula (II),
In formula, R3And R4Hydrogen atom or methyl, A C are represented independently of one another2H4, B C3H6, n1、n2、n3And n4It is full Sufficient n1+n2+n3+n4The integer of=2~50 relation, the arrangement of the repetitive unit of-(A-O)-and-(B-O)-can be random Can be block, optionally any one of-(A-O)-and-(B-O)-is in double phenyl sides in the case of block }.
[6]
According to the photosensitive polymer combination any one of [1]~[5], wherein, as hindered phenol, also comprising following Compound shown in logical formula (V),
In formula, R51Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, clip divalent linker The straight chained alkyl of group, clip the branched alkyl of divalent linker, clip the cyclohexyl of divalent linker or clip divalence company Meet the aryl of group, and R52、R53And R54Represent independently of one another hydrogen or optionally substituted, straight chained alkyl, branched alkyl, Aryl, cyclohexyl, the straight chained alkyl for clipping divalent linker, the branched alkyl for clipping divalent linker, clip divalence company Connect the cyclohexyl of group or clip the aryl of divalent linker.}.
[7]
According to the photosensitive polymer combination any one of [1]~[6], it is used for direct imaging exposure.
[8]
A kind of photosensitive element, it is the sense that will be formed as the photosensitive polymer combination any one of [1]~[7] Photosensitive resin layer is layered in obtained from supporter.
[9]
A kind of forming method of corrosion-resisting pattern, it includes：
The lamination process photosensitive resin bed of photosensitive element described in [8] being layered on conductor substrate；
The exposure process being exposed to the photosensitive resin bed of stacking；And
The developing procedure to develop to the photosensitive resin bed of exposure.
[10]
A kind of manufacture method of circuit board, it includes：
The lamination process photosensitive resin bed of photosensitive element described in [8] being layered on conductor substrate；
The exposure process being exposed to the photosensitive resin bed of stacking；
Develop to the photosensitive resin bed of exposure, the development work of corrosion-resisting pattern is formed on foregoing conductor substrate Sequence；
Foregoing conductor substrate formed with foregoing corrosion-resisting pattern is etched or the conductive pattern formation process of plating；With And
The stripping process that foregoing corrosion-resisting pattern is peeled off.
The effect of invention
The effect ＞ of ＜ first embodiments
According to the first embodiment of the invention, there is provided inhibit cloth when forming fine conductive pattern by assembly line The erosion resistant poor in length and breadth of line width.
The effect ＞ of ＜ second embodiments
Second embodiment of the invention, there is provided possess the photosensitive materials such as sensitivity, resolution ratio with high level and lead to The performance and the excellent novel photoactive material of both development dispersiveness and the adaptation of fine pattern often required.
The effect ＞ of the 3rd embodiments of ＜
3rd embodiment according to the present invention, there is provided the hole covering character and water residual short trouble of corrosion-resisting pattern can be taken into account The photosensitive polymer combination of inhibition.
The effect ＞ of the 4th embodiments of ＜
4th embodiment according to the present invention, there is provided be able to ensure that the fine resolution of corrosion-resisting pattern and extend minimum aobvious The photosensitive polymer combination of shadow time and using its corrosion-resisting pattern or circuit board forming method.
Embodiment
＜ first embodiments ＞
Hereinafter, for mode (hereinafter referred to as " this first embodiment party of the first embodiment for implementing the present invention Formula ") it is specifically described.
＜ photosensitive polymer combinations ＞
In this first embodiment, photosensitive polymer combination contains each component of following (A)~(C),
(A) component：Alkali solubility macromolecule,
(B) component：Compound with olefinic double bond and
(C) component：Photoepolymerizationinitiater initiater.
[(A) component：Alkali solubility macromolecule]
Foregoing (A) is just not particularly limited as long as component is dissolved in aftermentioned developer solution.Preferably (methyl) acrylic acid and its The copolymer of its monomer.The dispersion degree of the copolymer represented by the ratio between the weight average molecular weight (aftermentioned) of copolymer and number-average molecular weight Preferably more than 1 and less than 6.
As (methyl) acrylic acid, such as (methyl) acrylic acid, penetenoic acid, unsaturated dicarboxylic acid anhydride, hydroxyl can be included Styrene etc..As above-mentioned unsaturated dicarboxylic acid anhydride, such as maleic anhydride, itaconic anhydride, fumaric acid, citraconic anhydride can be included Deng.Wherein, preferred (methyl) acrylic acid.
As the copolymerization ratios of (methyl) acrylic acid units in foregoing (A) component, relative to the total of whole monomeric units Quality, is preferably the mass % of the mass % of 10 mass %~24, more preferably 15 mass %~23.(methyl) acrylic acid units contain Proportional when being in the scope, the suppression from etching speed when forming conductive pattern is (wide by the bottom of above-mentioned conductor line pattern More than degree is maintained at certain) and the suppression poor in length and breadth of wiring width from the viewpoint of be preferable.
As other monomers, such as unsaturated aromatic compound can be included and (be also recited as " aromatic series list sometimes Body "), (methyl) alkyl acrylate, (methyl) acrylic acid aralkyl ester, conjugated diene compound, polar monomer, bridging property list Body etc..
As unsaturated aromatic compound, such as styrene, α-methylstyrene, vinyl naphthalene etc. can be included.Its In, optimization styrene.
(methyl) alkyl acrylate is the concept for including both chain-like alkyl ester and cyclic alkyl ester, specifically, example It is different that (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid can such as be included Propyl ester, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (first Base) decyl acrylate, (methyl) lauryl acrylate, (methyl) n-myristyl base ester, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate etc..
Respectively, as (methyl) acrylic acid aralkyl ester, such as (methyl) benzyl acrylate etc. can be included；
As conjugated diene compound, such as it can include, 1,3-butadiene, isoprene, 2,3- dimethyl -1,3- fourths Diene, 2- phenyl -1,3- butadiene, 1,3- pentadienes, 2- methyl-1,3-pentylenes, 1,3- hexadienes, 4,5- diethyl -1, 3- octadienes, 3- butyl -1,3- octadienes etc..
As polar monomer, such as can include：
(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, pentenol Deng hydroxyl monomer；
The emulsion stabilities such as methacrylic acid 2- amino ethyl esters；
The amide-containing monomers such as (methyl) acrylamide, N- methylols (methyl) acrylamide；
The cyano-containing monomers such as acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, alpha-cyano ethyl propylene acid esters；
(methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- epoxy cyclohexyls etc. contain epoxy based monomers；
Deng.
As cross-linkable monomer, such as trimethylolpropane trimethacrylate, divinylbenzene etc. can be included.
Copolymer as foregoing (A) component, particularly preferably (methyl) acrylic acid, styrene and other monomers.
It is excellent relative to the gross mass of whole monomeric units as the copolymerization ratios of the styrene units in foregoing (A) component Elect as more than 32 mass %, more preferably more than 35 mass %.In addition, being total to as the styrene units in foregoing (A) component Poly- ratio, is preferably below 60 mass %, more preferably below 55 mass % relative to the gross mass of whole monomeric units.Will Hydrophobicity is high, is difficult to the copolymerization ratios of the styrene compatible with developer solution and development ejected wash water when being set as above range, from cloth It is preferable from the viewpoint of the suppression poor in length and breadth of line width.
The weight average molecular weight of foregoing (A) component is (when (A) component includes a variety of copolymers, for the weight of mixture entirety Average molecular weight) it is preferably 5000~1000000, more preferably 10000~500000, more preferably 15000~100000. When the weight average molecular weight of (A) component is adjusted in the range of this, it is suitable for being made from developing time when forming corrosion-resisting pattern It is preferable from the viewpoint of the operating status of assembly line.
In this first embodiment, the content of (A) component in photosensitive polymer combination is with photosensitive polymer combination Solid constituent total amount it is excellent as benchmark (being same below in case of no particular description, on respectively containing component) Elect the matter of the mass %, more preferably 40 mass % of the mass % of 10 mass %~90, more preferably 20 mass %~80~60 as Measure %.The content is preferably more than 10 mass % from the viewpoint of alkali-developable is maintained, and on the other hand, is formed from by exposing Corrosion-resisting pattern to give full play to from the viewpoint of the performance as resist be preferably below 90 mass %.
The content ratio of (methyl) acrylic acid units for the mass % of 10 mass %~24 and styrene units content ratio Using the solid constituent total amount of photosensitive polymer combination as benchmark it is preferably 8% for the copolymer of the mass % of 32 mass %~60 More than, more preferably more than 10 mass %, particularly preferably more than the mass % of 13.5/99.19 × 100.(methyl) acrylic acid list The content ratio of member is the mass % of 10 mass %~24 and the content ratio of styrene units is the mass % of 32 mass %~60 Copolymer using the solid constituent total amount of photosensitive polymer combination as benchmark can be below 50 mass %, can be 40 matter Measure below %, can be below 30 mass %, can be below 27/99.19 × 100 mass %, can be below 20 mass %.
[(B) component：Compound with olefinic double bond]
(B) component has more than 1 olefinic double bond.Preferably using the compound with more than 2 olefinic double bonds.
As (B) compound with 2 olefinic double bonds, for example, preferably using bisphenol A compounds, particularly in bisphenol-A Each average 2 moles~15 mol of alkylene oxide of both ends difference addition obtained from polyalkylene glycol two (methyl) acrylate Deng.
In addition, as (B) compound with 3 olefinic double bonds, such as preferably using trimethylolpropane compound, spy It is not three (methyl) third of polyalkylene triol obtained from 3 moles~25 mol of alkylene oxide of being averaged to trimethylolpropane addition Olefin(e) acid ester etc..
And then as (B) compound with 4 olefinic double bonds, such as preferably using pentaerythrite compound, particularly Be averaged pentaerythrite addition four (methyl) acrylate of polyalcohol obtained from 4 moles~35 mol of alkylene oxide etc..
As their commercially available product, for example, can include " BPE-500 ", " A-TMPT-3EO ", " A-9300-1CL " etc. (with On be the manufacture of Xin Zhong villages Chemical Co., Ltd.)：
" ARONIX M-327 " etc. (Toagosei Co., Ltd's manufacture) etc..
The content of (B) component in the photosensitive polymer combination of this first embodiment is preferably the matter of 1 mass %~70 Measure the mass % of %, the more preferably mass % of 5 mass %~60, more preferably 10 mass %~50.The content is solid from suppression It is preferably more than 1 mass % to change from the viewpoint of the bad and delay of developing time, on the other hand, from suppressing cold flow and cure anti- It is preferably below 70 mass % from the viewpoint of the stripping delay of erosion agent.
As (B) component, preferably using the high-molecular weight compounds that molecular weight is more than 1000.The high-molecular weight compounds Molecular weight be more preferably more than 1300 and less than 3000.During containing this high-molecular weight compounds, from when forming conductive pattern Etching speed suppress and wiring width suppression poor in length and breadth from the viewpoint of be preferable.
It should be noted that ratio of this high-molecular weight compounds shared by (B) component is preferably set to 20 mass % Above, 20~50 mass % are more preferably set to.
Herein, as (B) component double bond concentration index, define DD values.DD values are monomers relative to Weight-average molecular The double key number of amount, every kind of monomer have distinctive value.
When the small monomer of DD values is used for photosensitive polymer combination, easily becomes soft there are the film after photocuring and incline To.
(B) when component is by a variety of form, by the weighting of the DD values of each compound containing ethylenic unsaturated bond and compounding ratio Average is considered as the DD values of said composition.
From the viewpoint of suppression poor in length and breadth, hole covering character from wiring width improve, the scope of the DD values of preferable composition For 0.10~0.13.More preferably 0.10~0.125.
[(C) component：Photoepolymerizationinitiater initiater]
(C) component is the component that the free radical that foregoing (B) component can be triggered to polymerize is produced by the irradiation of light.
As this (C) component, such as aromatic ketone compound, naphtoquinone compounds, benzoin ether compound, benzene can be included Acyloin com, benzil compound, six aryl united imidazoles, acridine compounds etc..
Among them, from the viewpoint of the resolution ratio of height and good hole covering character, preferably using acridine compounds.
The content of acridine compounds in the photosensitive polymer combination of this first embodiment is preferably 0.05 mass % Above, more preferably more than 0.1 mass %, more preferably 0.2 mass %, more preferably 0.3 mass %, more preferably 0.4 matter Measure %.
The content of acridine compounds in the photosensitive polymer combination of this first embodiment be preferably 2.0 mass % with Under, more preferably below 1.8 mass %, more preferably below 1.7 mass %, more preferably below 1.6 mass %.If above-mentioned Scope, then be capable of providing the erosion resistant poor in length and breadth for suppressing wiring width, be preferable.
As acridine compounds, such as acridine, 9- phenylacridines, 1,6- double (9- acridinyls) hexane, 1,7- can be included Double (9- acridinyls) octanes of double (9- acridinyls) heptane, 1,8-, double (9- acridinyls) nonanes of 1,9-, 1,10- are double (9- acridinyls) Double (9- acridinyls) hendecanes of decane, 1,11-, double (9- acridinyls) dodecanes of 1,12- etc..
As (C) component, preferably using acridine compounds and six aryl united imidazoles.
As above-mentioned six aryl united imidazole, such as 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole bases can be included Dimer, 2,2 ', 5- tri--(Chloro-O-Phenyl) -4- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl-imidazole base dimer, 2, 4- is double-(Chloro-O-Phenyl) -5- (3,4- Dimethoxyphenyls)-diphenyl-imidazole base dimer, 2,4,5- tri--(Chloro-O-Phenyl) - Diphenyl-imidazole base dimer, 2- (Chloro-O-Phenyl)-bis- -4,5- (3,4- Dimethoxyphenyls)-imidazole radicals dimer, 2,2 ' - Double-(2- fluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3- difluoromethyls Phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,4 difluorobenzene base) -4,4 ', 5, 5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,5- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxies Base phenyl)-imidazole radicals dimer, 2,2 '-bis--(2,6- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles Base dimer, 2,2 '-bis--(2,3,4- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2, 2 '-bis--(2,3,5- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-it is bis--(2,3, 6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,4,5- trifluoro-benzenes Base) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,4,6- trifluorophenyls) -4,4 ', 5, 5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,5- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- Methoxyphenyl)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,6- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxybenzenes Base)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,5,6- pentafluorophenyl groups) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-miaow Oxazolyl dimer etc..
The content of (C) component in the photosensitive polymer combination of this first embodiment is preferably the matter of 0.1 mass %~2 Measure the model of %, the more preferably mass % of the scope of the mass % of 0.2 mass %~1.8, more preferably 0.3 mass %~1.7 Enclose, the particularly preferably mass % of 0.4 mass %~1.6.It is good from obtaining when the content of (C) component is set as this scope Sensitivity and peel property from the viewpoint of be preferable.
From the viewpoint of sensitivity and the raising of resolution ratio, (C) component can further contain sensitizer.As this Sensitizer, such as N- aryl amino acids, organohalogen compound, other sensitizers can be included.
Respectively, as above-mentioned N- aryl amino acids, such as can to include N-phenylglycine, N- Methyl-N-phenyls sweet Propylhomoserin, N- ethyl, N-phenyl glycine etc.；
As organohalogen compound, such as amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, two can be included Phenyl methyl bromine, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3- dibromopropyls) ester, three Chloroacetamide, amyl iodide, isobutyl iodide, tri- chloro- 2,2- of 1,1,1- double (rubigan) ethane, chlorination triaizine compounds etc..
As above-mentioned other sensitizers, such as can include：2- ethyl hydrazine, octaethyl anthraquinone, 1,2 benzae thracene quinone, 2, 3- benzos anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl isophthalic acids, 4- The naphtoquinone compounds such as naphthoquinones, 2,3- dimethyl anthraquinone, 3- chloro-2-methyl anthraquinones；
Benzophenone, michaelis ketone [4,4 '-bis- (dimethylamino) benzophenone], 4,4 '-bis- (diethylamino) hexichol The aromatic ketone compound such as ketone；
The benzoin ether chemical combination such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethyl benzoin Thing；
Benzil dimethyl ketal, benzil diethyl ketal, 1- phenyl -1,2- pentanedione -2-O- benzoyls oxime, 1- The oxime ester compounds such as phenyl -1,2- pentanediones -2- (O- carbethoxyl groups) oxime；
Deng.
The content of the sensitizer of this first embodiment is from the fissility of the sensitivity of composition and resist cured film Viewpoint is set out the mass % of the mass % of preferably 0.01 mass %~5, more preferably 0.05 mass %~3, more preferably 0.1 The mass % of quality %~2.
It should be noted that in the photosensitive polymer combination of this first embodiment, acridine is used as (C) component Compound and positive aryl amino acid, when they are applied in combination in the range of above-mentioned use ratio, from formed conductive pattern when It is preferable from the viewpoint of etching speed suppression and the suppression poor in length and breadth of wiring width.
[other components]
The photosensitive polymer combination of this first embodiment can be with addition to (A)~(C) components of described above Contain other components.As this other components, for example, can include leuco dye, basic-dyeable fibre, plasticizer, antioxidant, Stabilizer, radical polymerization inhibitor, solvent etc..
[leuco dye]
Above-mentioned leuco dye can in order to assign suitable colour rendering and excellent peel property to resist cured film and With the photosensitive polymer combination for being mixed in this first embodiment.
As the concrete example of leuco dye, such as leuco crystal violet (three [4- (dimethylamino) phenyl] first can be included Alkane), double (to the dimethylaminophenyl) -6- dimethylaminos phthalides of 3,3-, 3- (4- diethylaminos phenyl) -3- (1- ethyls - 2 methyl indole -3- bases) phthalide, 3- (4- diethylamino -2- ethoxyl phenenyls) -3- (1- Ethyl-2-Methyl indoles -3- Base) -4- azepines phthalide, 1,3- dimethyl -6- diethylaminos fluorane, the chloro- 3- methyl -6- dimethylaminos fluoranes of 2-, 3- bis- Butylamino -6- methyl -7- anilino fluoranes, 3- diethylamino -6- methyl -7- anilino fluoranes, 3- diethylaminos -6- Methyl -7- diformazans are for phenylamino fluorane, 2- (2- chloroanilinos) -6- dibutylamino fluorans, 3,6- dimethoxys fluorane, 3,6- bis- N-butoxy fluorane, 1,2- benzo -6- diethylaminos fluorane, 1,2- benzo -6- dibutylamino fluorans, 1,2- benzos -6- Ethyl isoamylamino fluorane, 2- methyl -6- (N- is to toluene-N- ethylaminos) fluorane, 2- (N- benzyl-N-methyls) - 6- (N- is to toluene-N- ethylaminos) fluorane, 2- (3 '-trifluoromethylbenzene amido) -6- diethylaminos fluorane, the chloro- 6- rings of 3- Hexylamino fluorane, 2- methyl -6- Cyclohexylaminos fluorane, 3- methoxyl group -4- dodecyloxy styryl quinoline etc..They Among, preferred leuco crystal violet.
The content of leuco dye in the photosensitive polymer combination of this first embodiment be preferably 0.6 mass %~ 1.6 mass %, more preferably the mass % of 0.7 mass %~1.2.By the way that the use ratio of leuco dye is set as the scope, It can realize good colour rendering and good fissility.
[basic-dyeable fibre]
As above-mentioned basic-dyeable fibre, for example, can include Viride Nitens 1 [CAS number (similarly hereinafter)：633-03-4] (for example, Aizen Diamond Green GH, trade name, Baotugu Chemical Industrial Co., Ltd manufacture), malachite green oxalates [2437-29-8] (such as Aizen Malachite Green, trade name, Baotugu Chemical Industrial Co., Ltd's manufacture), brilliant green [633-03-4], pinkish red [632-99-5], crystal violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62- 9], methyl green [82-94-0], victoria blue B [2580-56-5], Blue 7 [2390-60-5] are (for example, Aizen Victoria Pure Blue BOH, trade name, Baotugu Chemical Industrial Co., Ltd manufacture), rhodamine B [81-88-9], sieve Red bright 6G [989-38-8], basic yellow 2 [2465-27-2], diamond green (Diamond Green) etc..Among them, it is preferably selected from More than a kind in Viride Nitens 1, malachite green oxalates, Blue 7 and diamond green, from form and aspect stability and expose contrast Viewpoint is set out, particularly preferred Viride Nitens 1.
The content of basic-dyeable fibre in the photosensitive polymer combination of this first embodiment be preferably 0.001 mass %~ The mass %'s of 3 mass %, the more preferably scope of the mass % of 0.01 mass %~2, more preferably 0.01 mass %~1.2 Scope.By being set to the use ratio of the scope, good colour rendering and high sensitivity can be taken into account.
[solvent]
The photosensitive polymer combination of this first embodiment can be above-mentioned (A)~(C) component and optionally employ its The mixture of its component, alternatively, photosensitive polymer combination tune that can be to add appropriate solvent in these components and be formed Form with liquid uses.
As solvent used herein, such as can include：
The ketone compounds such as methyl ethyl ketone (MEK)；
The alcohol such as ethanol, ethanol and isopropanol；
Deng.
As the use ratio of solvent, it is preferably set to make viscosity of the photosensitive polymer combination seasoning liquid at 25 DEG C be Ratio as 500~4000mPasec.
＜ photosensitive elements ＞
In this first embodiment, photosensitive element is the photo-sensitive resin formed by above-mentioned photosensitive polymer combination It is layered in the layered product (photoresist layered product) formed on supporter.As needed, can also be in photosensitive resin Layer has protective layer with the surface of supporter opposite side.
[supporter]
As supporter, the preferably transparent base through the light from exposure light source radiation.As this supporter, such as can Include pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, poly- It is vinylidene chloride film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, polystyrene film, poly- Acrylonitrile film, styrol copolymer film, polyamide film, cellulose derivative film etc..As these films, according to need Will, the film of drawn can also be used.
The mist degree of supporter is preferably less than 5.
It is favourable in terms of image formative and economy during the thinner thickness of supporter, but need to maintain intensity.Consider Both, can be preferably used 10 μm~30 μm of supporter.
[photosensitive polymer combination layer]
When the photosensitive polymer combination used in the formation of photosensitive polymer combination layer contains solvent, preferably photosensitive Solvent has been removed in property resin composition layer, but dissolvent residual is also not related.
The thickness of photosensitive polymer combination layer is preferably 5 μm~100 μm, more preferably 7 μm~60 μm.The thickness is got over Thin, resolution ratio more improves, and the thickness is thicker, and film-strength more improves.Therefore, the thickness of said composition layer can be according to purposes upper Suitably adjusted in the range of stating.
[protective layer]
The key property of protective layer is to be sufficiently smaller than supporter and photonasty with the closing force of photosensitive polymer combination layer The closing force of resin composition layer, can be easily peeled off.As protective layer, for example, can be preferably used polyethylene film, Polypropylene film etc., in addition it is possible to use excellent thin of fissility for example disclosed in Japanese Unexamined Patent Application 59-202457 publications Film.
The thickness of protective layer is preferably 10 μm~100 μm, more preferably 10 μm~50 μm.
[manufacture method of photosensitive element]
Photosensitive element can by stack gradually supporter and photo-sensitive resin and protective layer as needed and Manufacture.As the laminating method of supporter, photo-sensitive resin and protective layer, known method can be used.
For example, photosensitive polymer combination is prepared into photosensitive resin combination seasoning liquid, first, applied using rod Machine or roll coater are coated on supporter and make its drying, on supporter formed formed by photosensitive polymer combination it is photosensitive Property resin composition layer.Then, protective layer is laminated on the photosensitive polymer combination layer formed as needed, so as to Manufacture photosensitive element.
The forming method ＞ of ＜ corrosion-resisting patterns
Photosensitive element as described above can be used, corrosion-resisting pattern is formed on substrate.
The forming method of corrosion-resisting pattern preferably includes following process successively：
The photo-sensitive resin of photosensitive element is layered in lamination process on conductor substrate,
The exposure process that is exposed to the photosensitive polymer combination layer of foregoing stacking and
The developing procedure in the unexposed portion after foregoing exposure is removed with developer solution.
In addition, lamination process is preferably that the photo-sensitive resin of photosensitive element is clipped wetting agent to be stacked in conductor substrate On process.As wetting agent, more than a kind in pure water, deionized water and electrolysis water and copper chelator are preferably comprised (more than a kind in the group for being selected from being made of imidazolium compounds, triazole compounds, pyridine compounds and pyrazole compound is changed Compound).
In the forming method of the corrosion-resisting pattern of this first embodiment, first, it is laminated in process, using laminating machine in substrate Upper formation photosensitive polymer combination layer.Specifically, in the case that photosensitive element has protective layer, protective layer is being peeled off Afterwards, photosensitive polymer combination layer is heated into crimping on the surface of the substrate to be laminated using laminating machine.
As substrate, using metallic plate or the insulative substrate with metal epithelium.As the material of metal, such as can arrange Enumerate copper, stainless steel (SUS), glass, tin indium oxide (ITO) etc..These substrates, which can also have, to be used to tackle multilager base plate Through hole.
Herein, photosensitive polymer combination layer can only be laminated to the single side of substrate surface, can also be laminated as needed It is two-sided in substrate.Heating-up temperature at this time is preferably set to 40 DEG C~160 DEG C.From obtained corrosion-resisting pattern is further improved to base From the viewpoint of the adaptation of plate, preferably heating crimping is carried out more than 2 times.When crimp for more than 2 times, can use possess The sandwich of substrate and photosensitive polymer combination layer, can also be repeated several times and pass through roller by the second order segmentation laminating machine of bigeminy roller To be crimped.
Then, in exposure process, photosensitive polymer combination layer is exposed using exposure machine.The exposure can not shell Carry out from supporter, can also be carried out as needed after supporter is peeled off across the supporter.
By carrying out the exposure with pattern-like, after aftermentioned developing procedure, it can obtain that there is the anti-of desired pattern Lose film (corrosion-resisting pattern).The exposure of pattern-like can be by across appointing in the method and maskless exposure that photomask is exposed One method carries out.When photomask is exposed, light exposure is determined by light illumination and time for exposure.Light exposure can make Measured with quantometer.
In maskless exposure, without using photomask, it is exposed on substrate with direct drawing apparatus.As light source, make With the semiconductor laser of wavelength 350nm~410nm, ultrahigh pressure mercury lamp etc..In maskless exposure, depicting pattern by computer come Control, light exposure are determined by the illumination of exposure light source and the translational speed of substrate.
Then, in developing procedure, the unexposed portion of photosensitive polymer combination layer is removed with developer solution.After exposure, feeling On photosensitive resin composition layer there are supporter in the case of, for developing procedure after preferably removing it.
In developing procedure, using the developer solution formed by aqueous alkali, unexposed portion is developed and is removed, obtains resist pattern Picture.As aqueous alkali, such as preferably using Na2CO3、K2CO3Deng aqueous solution.Aqueous alkali is according to photosensitive resin composition The characteristic of nitride layer selects, preferably using the Na of the concentration of the mass % of 0.2 mass %~22CO3Aqueous solution.In the aqueous alkali Surfactant, defoamer, a small amount of organic solvent etc. for promoting development can be mixed into.
The temperature of developer solution in developing procedure is preferably maintained at steady temperature in the range of 20 DEG C~40 DEG C.
Corrosion-resisting pattern is obtained by above-mentioned operation.According to circumstances, 100 DEG C~300 DEG C of heater can further be carried out Sequence.It is suitable from the viewpoint of chemical proofing is further improved to implement the heating process.Heating can use hot wind, The heating furnace of the suitable mode such as infrared ray, far infrared.
The forming method ＞ of ＜ circuit boards
The forming method of the circuit board of this first embodiment preferably includes following process successively：
By lamination process of the photosensitive polymer combination layer stackup of photosensitive element on conductor substrate,
The exposure process that is exposed to the photosensitive polymer combination layer of foregoing stacking,
With developer solution remove the unexposed portion after foregoing exposure developing procedure,
To by it is foregoing development the conductor substrate formed with corrosion-resisting pattern be etched or the conductive pattern of plating formed work Sequence and
The stripping process that foregoing corrosion-resisting pattern is peeled off.
In addition, lamination process is preferably that the photo-sensitive resin of photosensitive element is clipped wetting agent to be stacked in conductor substrate On process.As wetting agent, more than a kind in pure water, deionized water and electrolysis water and copper chelator are preferably comprised (more than a kind in the group for being selected from being made of imidazolium compounds, triazole compounds, pyridine compounds and pyrazole compound is changed Compound).
, can be on the substrate formed with corrosion-resisting pattern, to being exposed by developing procedure in conductive pattern formation process Substrate surface (such as copper face) form conductive pattern using known etching method or plating method.
In above-mentioned stripping process, the substrate formed with conductive pattern is set to be contacted with appropriate stripper, so that by resist pattern Case, which is peeled off, to be removed.By the process, desired circuit board is obtained.
The stripper used in stripping process is preferably aqueous alkali.As the aqueous alkali, such as preferably using 2 matter Measure the NaOH aqueous solutions or KOH aqueous solutions of the mass % of %~5.In stripper, a small amount of water-soluble solvent, such as alcohol can be added Deng.The temperature of stripper in stripping process is preferably set to 40 DEG C~70 DEG C.
Formed generally, based on the conductive pattern of etching, regardless of etching speed, the defeated of such as etching line can be adjusted Send speed etc. and reach the etching period of desired wiring width to adjust.But etching speed it is too fast when, conveying speed also becomes It is too fast, cause the problems such as etching period can not be set in practicality sometimes.
Moreover, in recent years, the manufacture of circuit board is usually by the way that substrate edge fixed-direction conveying side is handled successively Assembly line carry out, there is the conveying direction relative to substrate, it is the parallel situation (line in MD directions) of the line of conductor, vertical The situation of situation (line in TD directions) and deflection.When particularly etching speed is fast, poor in length and breadth there are wiring width becomes brighter Aobvious tendency.
The inventors of the present invention have made intensive studies, it turns out that, form the photosensitive polymer combination for curing corrosion-resisting pattern In the case of with specific physical property, using the teaching of the invention it is possible to provide inhibit wiring width when forming fine conductive pattern by assembly line Poor erosion resistant in length and breadth.
That is, the photosensitive polymer combination of this first embodiment has following feature：It is being laminated with the copper of 18 μ m thicks The photo-sensitive resin formed on the copper-clad laminated board of paper tinsel with the stacking of 25 μ m thicks by photosensitive resin combination, passes through The pattern-like of line/interval=50 μm/30 μm light irradiation and development treatment and form curing corrosion-resisting pattern, implement 55 at 50 DEG C After the copper etching process of second, the bottom width of copper wire pattern obtained from removing said curing corrosion-resisting pattern is (excellent for more than 38 μm Elect 38 μm~50 μm, more preferably 40 μm~45 μm as).
Swelling/contraction occurs in each operation of development, washing step and etching work procedure for corrosion-resisting pattern, particularly washes Swelling/contraction in process is big.Thinking swelling/contraction of the corrosion-resisting pattern makes the reduction of the adaptation of wiring and corrosion-resisting pattern.Recognize For by the corrosion-resisting pattern that the photosensitive polymer combination of this first embodiment is formed in development, washing step, etching work procedure Swelling/contraction is small in any process, is difficult in corrosion-resisting pattern with the interface etching connected up, can suppress wiring width It is poor in length and breadth.
In this first embodiment, by characteristic when being conceived to using specific analysis method (specific etching condition) (bottom width of conductor line width for certain more than) distinguishes specific photosensitive polymer combination as performance invention effect Means.
It should be noted that the adjustment of the bottom width of this conductor line width can be by suitably setting photoresist group The composition of compound is adjusted.
In addition, by the forming method of the circuit board of as described above first embodiment and the conductive pattern that is formed (wiring) can make the poor in length and breadth minimum of the wiring width of conductive pattern.The poor in length and breadth of wiring width is by the conductor lines in TD directions The difference of the wiring width (MD) of wiring width (TD) and the conductor lines in MD directions, TD-MD are come the amount that represents.
By the forming method of the conductive pattern of this first embodiment and the wiring width in the conductive pattern that is formed Poor absolute value is preferably 0 μm~5 μm, more preferably 0 μm~3 μm in length and breadth.
The forming method of photosensitive polymer combination, photosensitive element and circuit board in this first embodiment can be with It is well suited for such as printed circuit board (PCB), lead frame, the base material with relief pattern, the manufacture semiconductor package body.
It should be noted that the assay method on above-mentioned various parameters, in case of no particular description, according to rear The assay method in embodiment is stated to measure.
＜ second embodiments ＞
Hereinafter, mode (hereinafter referred to as " this second implementation for implementing second embodiment of the present invention is illustrated Mode ").
＜ photosensitive polymer combinations ＞
In this second embodiment, photosensitive polymer combination contains each component of following (A)~(C),
(A) component：The alkali solubility macromolecule of acid equivalent 100~600,
(B) component：Compound with olefinic double bond and
(C) component：Photoepolymerizationinitiater initiater.
[(A) component：Alkali solubility macromolecule]
The acid equivalent of foregoing (A) component is 100~600 (being preferably 200~500, more preferably 250~450), contains bag Copolymer containing 50 mass % above styrene units.Herein, in this specification, styrene units refer to substituted or unsubstituted Styrene.It should be noted that as substituent, it is not particularly limited, such as alkyl, halogen group, hydroxyl etc. can be included.
(A) component is the copolymer of other monomers such as styrene derivative and preferred acid monomers.
As acid monomers, such as (methyl) acrylic acid, penetenoic acid, unsaturated dicarboxylic acid anhydride, hydroxy styrenes can be included Deng.As unsaturated dicarboxylic acid anhydride, such as maleic anhydride, itaconic anhydride, fumaric acid, citraconic anhydride etc. can be included.Wherein, it is excellent Select (methyl) acrylic acid.
As other monomers, for example, can include unsaturated aromatic compound (being also denoted as sometimes " aromatic monomer "), (methyl) alkyl acrylate, (methyl) acrylic acid aralkyl ester, conjugated diene compound, polar monomer, cross-linkable monomer etc..
As unsaturated aromatic compound, such as vinyl naphthalene etc. can be included.
(methyl) alkyl acrylate is the concept for including both chain-like alkyl ester and cyclic alkyl ester, specifically, example It is different that (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid can such as be included Propyl ester, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (first Base) decyl acrylate, (methyl) lauryl acrylate, (methyl) n-myristyl base ester, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate etc..
Respectively, as (methyl) acrylic acid aralkyl ester, such as (methyl) benzyl acrylate etc. can be included；
As conjugated diene compound, such as 1,3-butadiene, isoprene, 2,3- dimethyl -1,3- fourths can be included Diene, 2- phenyl -1,3- butadiene, 1,3- pentadienes, 2- methyl-1,3-pentylenes, 1,3- hexadienes, 4,5- diethyl -1, 3- octadienes, 3- butyl -1,3- octadienes etc..
As polar monomer, such as can include：
(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, pentenol Deng hydroxyl monomer；
The emulsion stabilities such as methacrylic acid 2- amino ethyl esters；
The amide-containing monomers such as (methyl) acrylamide, N- methylols (methyl) acrylamide；
The cyano-containing monomers such as acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, alpha-cyano ethyl propylene acid esters；
(methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- epoxy cyclohexyls etc. contain epoxy based monomers；
Deng.
As cross-linkable monomer, such as trimethylolpropane trimethacrylate, divinylbenzene etc. can be included.
Foregoing (A) component is particularly preferably the copolymer of (methyl) acrylic acid, styrene and other monomers.
(A) component contains the copolymer 1 for including 50 mass % above styrene units.Styrene list in the copolymer 1 The amount of member is preferably the mass % of the mass % of 50 mass %~80, more preferably 51 mass %~70.
(A) component in this second embodiment can be only made of copolymer 1, or copolymer 1 gathers with other The mixture of compound.(A) content of the copolymer 1 in component is preferably the mass % of 5 mass %~90, more preferably 10 mass % ~80 mass %, more preferably the mass % of 20 mass %~70.
As other polymer, for the acid monomers of described above and the copolymer of other monomers and copolymer 1 is not belonging to Material (copolymer 2) is suitable.
(A) weight average molecular weight of component (when (A) component includes a variety of copolymers, is divided equally again for the mixture is overall Son amount) it is preferably 5000~1000000, more preferably 10000~500000, more preferably 15000~100000.Will (A) when the weight average molecular weight of component is adjusted within the range, it is suitable for being used from developing time when forming corrosion-resisting pattern Assembly line operating status from the viewpoint of be preferable.By the ratio between the weight average molecular weight of (A) component and number-average molecular weight table The dispersion degree of the copolymer shown is preferably more than 1 and less than 6.
In this second embodiment, the content of (A) component in photosensitive polymer combination is with photosensitive polymer combination Solid constituent total amount it is excellent as benchmark (being same below in case of no particular description, on respectively containing component) Elect the matter of the mass %, more preferably 40 mass % of the mass % of 10 mass %~90, more preferably 20 mass %~80~60 as Measure %.The content is preferably more than 10 mass % from the viewpoint of alkali-developable is maintained, and on the other hand, is formed from by exposing Corrosion-resisting pattern to give full play to from the viewpoint of the performance as resist be preferably below 90 mass %.
[(B) component：Compound with olefinic double bond]
(B) component is just not particularly limited as long as there is more than 1 olefinic double bond.Wherein, in this second embodiment (B) component include the following general formula (I) shown in compound as the compound (B1) that must contain.
{ in formula, R is independently of one another hydrogen atom or the alkyl of carbon number 1~4, and n1, n2 and n3 are 0~30 independently of one another Integer, wherein, meet the conditions of n1+n2+n3 >=6.}
In formula (I), as R, preferably hydrogen atom or methyl, more preferably hydrogen atom independently of one another.N1, n2 and n3 that This is preferably independently 1~30 integer, more preferably 3~21 integer.
In formula (I), from the viewpoint of development dispersiveness is improved, the value of n1+n2+n3 be preferably greater than 9 and for less than 20, more Preferably more than 15 and less than 20.
In formula (I), from the viewpoint of development dispersiveness is improved, preferably at least 1 R is hydrogen atom, more preferably whole R is Hydrogen atom.
And then in formula (I), from the viewpoint of development dispersiveness and adaptation is taken into account, it is therefore particularly preferred that whole R are Hydrogen atom, and the value of n1+n2+n3 is more than 15 and less than 20.
Compound shown in formula (I) is synthesized using known method, for example, can be for trimethylolpropane addition Addition product obtained from ethylene oxide more than 6 equivalents, further 3 moles of (methyl) acrylic acid of addition or progress ester exchange, from And obtain.
As the preferable concrete example of the compound shown in formula (I), ethylene oxide (EO) can be included and be modified trihydroxy methyl Propane three (methyl) acrylate (EO additions total moles are 6~20) etc..
(B) component in this second embodiment can be only made of compound (B1), or compound (B1) with The mixture of other (B) components.
When (B) component of this second embodiment is mixture, the content of the compound (B1) in mixture is with the mixing The gross mass of thing is preferably more than 10 mass % as benchmark, the mass % of more preferably 10 mass %~50, more preferably The mass % of 15 mass %~35.
The content of compound (B1) in the photosensitive polymer combination of this second embodiment is with photosensitive resin composition The solid constituent total amount of thing is preferably more than 5 mass % as benchmark, the mass % of more preferably 5.5 mass %~30, further The mass % of preferably 6 mass %~20.
Herein, by the alkali solubility macromolecule comprising the styrene units with specific acid equivalent and with specified quantitative, preceding (B1) component and acridine are stated, so as to fulfill the photoresist that the adaptation both of which of development dispersiveness and fine pattern is excellent The mechanism of composition is still uncertain, but speculate styrene units and acridine component interaction (being stacked based on pi-electron) and The interaction (being based on hydrogen bond) of acid monomers and foregoing (B1) component obtains good embodiment, compatibility improves on the whole, this has Beneficial to above-mentioned characteristic.
In this second embodiment, from the viewpoint of development dispersiveness, (B) component preferably contains with together with compound (B1) There is pentaerythrite modified monomer (hereinafter referred to as " compound (B2) ".).As compound (B2), using excellent to pentaerythrite addition Select 4 moles~35 moles, more preferably 8 moles~28 moles average, further preferred 12 moles~20 mol of alkylene oxide and obtain Polyalcohol four (methyl) acrylate.
(B) content of the compound in component (B2) using the gross mass of (B) component as benchmark be preferably 10 mass %~ 40 mass %, more preferably the mass % of 15 mass %~30.
The content of compound (B2) in the photosensitive polymer combination of this second embodiment be preferably 1 mass % with The mass % of the mass %, more preferably 5 mass % of upper, more preferably 1 mass %~20~15.
(B) component can also include the compound with olefinic double bond in addition to compound (B1) and (B2).
(B) component can also include following component：
Bisphenol A compounds, for example the both ends of bisphenol-A respectively each average 2 moles~15 mol of alkylene oxide of addition and obtain Two (methyl) acrylate of polyalkylene glycol etc.；
Compound (not including B1) with 3 olefinic double bonds, for example average to trimethylolpropane addition 3 moles~25 Three (methyl) acrylate of polyalkylene triol obtained from mol of alkylene oxide etc..
The content of (B) component in the photosensitive polymer combination of this second embodiment is preferably the matter of 1 mass %~70 Measure the mass % of %, the more preferably mass % of 5 mass %~60, more preferably 10 mass %~50.Its content is solid from suppression It is preferably more than 1 mass % to change from the viewpoint of bad and developing time postpones, and on the other hand, is gathered from suppressing to produce in developer solution It is preferably below 70 mass % from the viewpoint of collection thing.
[(C) component：Photoepolymerizationinitiater initiater]
(C) component is the component that the free radical that foregoing (B) component can be triggered to polymerize is produced by the irradiation of light.
In this second embodiment, as (B) Photoepolymerizationinitiater initiater, acridine compounds can be used.And then can also group Close using acridine compounds and other Photoepolymerizationinitiater initiaters.Acridine based compound is preferred for improving the sense of this second embodiment The sensitivity of photosensitive resin composition and resolution ratio.
As acridine compounds, such as 1,7- double (9,9 '-acridinyl) heptane, 9- phenylacridines, 9- methyl can be included Acridine, 9- ethyls acridine, 9- chloroethyls acridine, 9- methoxyacridines, 9- ethyoxyls acridine, 9- (4- aminomethyl phenyls) acridine, 9- (4- ethylphenyls) acridine, 9- (4- n-propyls phenyl) acridine, 9- (4- n-butylphenyls) acridine, 9- (4- tert-butyl-phenyls) a word used for translation Pyridine, 9- (4- methoxyphenyls) acridine, 9- (4- ethoxyl phenenyls) acridine, 9- (4- acetylphenyls) acridine, 9- (4- dimethyl Aminophenyl) acridine, 9- (4- chlorphenyls) acridine, 9- (4- bromophenyls) acridine, 9- (3- aminomethyl phenyls) acridine, 9- (the tertiary fourths of 3- Base phenyl) acridine, 9- (3- acetylphenyls) acridine, 9- (3- dimethylaminophenyls) acridine, 9- (3- diethylamino benzene Base) acridine, 9- (3- chlorphenyls) acridine, 9- (3- bromophenyls) acridine, 9- (2- pyridine radicals) acridine, 9- (3- pyridine radicals) acridine, 9- (4- pyridine radicals) acridine etc..
As other Photoepolymerizationinitiater initiaters, such as can include：
2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole bases dimer, 2,2 ', 5- tri--(Chloro-O-Phenyl) -4- (3,4- diformazans Phenyl) -4 ', 5 '-diphenyl-imidazole base dimer, 2,4- pairs-(Chloro-O-Phenyl) -5- (3,4- Dimethoxyphenyls)-two Phenylimidazole base dimer, 2,4,5- tri--(Chloro-O-Phenyl)-diphenyl-imidazole base dimer, 2- (Chloro-O-Phenyl)-bis- -4,5- (3,4- Dimethoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2- fluorophenyls) -4,4 ', 5,5 '-four-(3- methoxybenzenes Base)-imidazole radicals dimer, 2,2 '-bis--(2,3- difluoromethyls phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles Base dimer, 2,2 '-bis--(2,4 difluorobenzene base) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2, 2 '-bis--(2,5- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,6- bis- Fluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3,4- trifluorophenyls) -4, 4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3,5- trifluorophenyls) -4,4 ', 5,5 '-four - (3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3,6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxybenzenes Base)-imidazole radicals dimer, 2,2 '-bis--(2,4,5- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals Dimer, 2,2 '-bis--(2,4,6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2, 2 '-bis--(2,3,4,5- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-it is bis--(2, 3,4,6- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,5,6- Pentafluorophenyl group) the six aryl united imidazoles such as -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer；
2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, two (methoxyphenyl) imidazoles of 2- (Chloro-O-Phenyl) -4,5- Dimer, 2- (o-fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazole dimerization 2,4, the 5- triarylimidazoles dimers such as body, 2- (p-methoxyphenyl) -4,5- diphenyl-imidazole dimers (wherein, do not include Belong to the material of above-mentioned six aryl united imidazole.)；
Benzophenone, N, N '-tetramethyl -4,4 '-dimethylamino benzophenone (michaelis ketone), N, N '-tetraethyl -4, 4 '-diaminobenzophenone, 4- methoxyl groups -4 '-dimethylamino benzophenone, 2- benzyl -2- dimethylamino -1- (4- Quinoline phenyl)-butanone -1,2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyls-grade aromatic ketone of acetone -1；
2- ethyl hydrazine, phenanthrenequione, 2- tert-butyl groups anthraquinone, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3- benzos anthraquinone, 2- Phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 2-methylanthraquinone, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl isophthalic acids, 4- naphthalenes The naphtoquinone compounds such as quinone, 2,3- dimethyl anthraquinones；
The benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether；
The benzil derivatives such as benzil methyl ketal；
N-phenylglycine derivative, coumarin series compounds, 4,4 '-bis- (diethylamino) benzophenone etc..
The content of acridine compounds in the photosensitive polymer combination of this second embodiment is preferably 0.001 mass % The scope of the mass % of~2 mass %, more preferably the mass % of 0.01 mass %~1.5, more preferably 0.1 mass %~1 It is interior.
The content of (C) component in the photosensitive polymer combination of this second embodiment (includes (C) of acridine compounds The content of component entirety) it is preferably the mass % of the mass % of 0.1 mass %~2, more preferably 0.2 mass %~1.8, further excellent Elect the mass % of the mass % of 0.3 mass %~1.7, particularly preferably 0.4 mass %~1.6 as.
From the viewpoint of sensitivity and resolution ratio is improved, (C) component can further contain sensitizer.As this quick Agent, such as N- aryl amino acids, organohalogen compound, other sensitizers can be included.
Respectively, as above-mentioned N- aryl amino acids, such as can to include N-phenylglycine, N- Methyl-N-phenyls sweet Propylhomoserin, N- ethyl, N-phenyl glycine etc.；
As organohalogen compound, such as amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, two can be included Phenyl methyl bromine, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3- dibromopropyls) ester, three Chloroacetamide, amyl iodide, isobutyl iodide, tri- chloro- 2,2- of 1,1,1- double (rubigan) ethane, chlorination triaizine compounds etc..
As above-mentioned other sensitizers, such as can include：
2- ethyl hydrazine, octaethyl anthraquinone, 1,2 benzae thracene quinone, 2,3- benzos anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl Anthraquinone, 1- chloroanthraquinones, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl-1,4-naphthaquinones, 2,3- dimethyl anthraquinone, 3- chloro-2-methyl anthracenes The naphtoquinone compounds such as quinone；
Benzophenone, michaelis ketone [4,4 '-bis- (dimethylamino) benzophenone], 4,4 '-bis- (diethylamino) hexichol The aromatic ketone compound such as ketone；
The benzoin ether chemical combination such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethyl benzoin Thing；
Benzil dimethyl ketal, benzil diethyl ketal, 1- phenyl -1,2- pentanedione -2-O- benzoyls oxime, 1- The oxime ester compounds such as phenyl -1,2- pentanediones -2- (O- carbethoxyl groups) oxime；
Deng.
From the viewpoint of from the fissility of the sensitivity of composition and resist cured film, this second embodiment it is photosensitive Property resin combination in the content of sensitizer be preferably the matter of the mass % of 0.01 mass %~5, more preferably 0.05 mass %~3 Measure %, more preferably the mass % of 0.1 mass %~2.
[other components]
The photosensitive polymer combination of this second embodiment may be used also on the basis of (A)~(C) components of described above To contain other components.As other components, such as coloring material, halogen compounds, stabilizer, solvent etc. can be included.
Respectively, as coloring material, leuco dye and other coloring materials can be included；
As stabilizer, such as radical polymerization inhibitor, benzotriazole cpd, carboxyl benzotriazole can be included Compound etc..
＜ leuco dyes ＞
As leuco dye, such as three (4- dimethylaminophenyls) methane [leuco crystal violet], double (4- bis- can be included Methylamino phenyl) phenylmethane [leucogentian violet] etc..Especially from the viewpoint of good contrast, preferably using Leuco crystal violet.
The content of leuco dye in photosensitive polymer combination is preferably the mass % of 0.1 mass %~10.Procrypsis is contaminated When the content of material is adjusted to more than 0.1 mass %, it is from the viewpoint of the contrast for obtaining exposed portion and unexposed portion Preferably, on the other hand, it is preferred from the viewpoint of storage stability is maintained when its content is adjusted to below 10 mass % 's.
The other coloring material ＞ of ＜
As other coloring materials, such as magenta, phthalocyanine green, alkaline bright yellow (Auramine Base), substandard goods can be included Red (paramagenta), crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (hodogaya chemical industry strain formula Commercial firm manufacture Aizen (registration mark) MALACHITE GREEN), alkali blue 20, diamond green (hodogaya chemical industry strain formula meeting Society manufacture Aizen (registration mark) DIAMOND GREEN GH) etc..
The content of other coloring materials in photosensitive polymer combination is preferably the mass % of 0.001 mass %~1.By its It is preferable from the viewpoint of treatability is improved, on the other hand, by its content when content is adjusted to more than 0.001 mass % It is preferable from the viewpoint of storage stability is maintained when being adjusted to below 1 mass %.
＜ halogen compounds ＞
From the viewpoint of adaptation and contrast, leuco dye and following is applied in combination in photosensitive polymer combination Halogen compounds is preferable mode.
As halogen compounds, such as amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, diphenyl can be included Methyl bromide, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3- dibromopropyls) ester, three chloroethenes Acid amides, amyl iodide, isobutyl iodide, tri- chloro- 2,2- of 1,1,1- double (rubigan) ethane, chlorination triaizine compounds etc..It is especially excellent Select trisbromomethyl phenyl sulfone.When the content of halogen compounds in photosensitive polymer combination is 0.01 mass %~3 mass %, It is preferable from the viewpoint of the storage stability of form and aspect for maintaining photosensitive layer.
＜ radical polymerization inhibitors, benzotriazole cpd and carboxyl benzotriazole compound ＞
As radical polymerization inhibitor, such as p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tertiary fourth can be included Base catechol, stannous chloride, 2,6- di-t-butyls-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2, 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso phenylhydroxylamine aluminium salt, diphenyl nitrosamine etc..
As benzotriazole cpd, such as 1,2,3- benzotriazole, 1- chloro- 1 can be included, it is 2,3- benzotriazole, double (N-2- ethylhexyls) aminomethylene-l, 2,3 triazole, double (N-2- ethylhexyls) aminomethylene -1,2,3- toluene Base triazole, double (N-2- hydroxyethyls) aminomethylene-l, 2,3 triazoles etc..
As carboxyl benzotriazole compound, such as 4- carboxyls -1,2 can be included, 3- benzotriazole, 5- carboxyls -1,2, 3- benzotriazole, N- (bis- -2- ethylhexyls of N, N-) aminomethylene carboxyl benzotriazole, N- (bis- -2- hydroxyethyls of N, N-) Aminomethylene carboxyl benzotriazole, N- (bis- -2- ethylhexyls of N, N-) aminoethylene carboxyl benzotriazole etc..
Radical polymerization inhibitor, benzotriazole cpd and carboxyl benzotriazole chemical combination in photosensitive polymer combination The total content of thing is preferably the mass % of the mass % of 0.01 mass %~3, more preferably 0.05 mass %~1.Its content is adjusted For more than 0.01 mass % when, to photosensitive polymer combination assign storage stability from the viewpoint of be it is preferable, it is another Aspect, is preferred from the viewpoint of sensitivity, the decoloration of suppression dyestuff is maintained when its content is adjusted to below 3 mass % 's.
＜ plasticizer ＞
Photosensitive polymer combination can also contain plasticizer as needed.As plasticizer, such as benzene two can be included The Phthalates such as formic acid diethylester, o-toluene sulfonic acid acid amides, p-methyl benzenesulfonic acid acid amides, tributyl citrate, citric acid three It is ethyl ester, CitroflexA-2, three n-propyl of acetyl citrate, acetyl tributyl citrate, polyethylene glycol, poly- Propane diols, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether etc..
The content of plasticizer in photosensitive polymer combination is preferably the mass % of 1 mass %~50, more preferably 1 matter Measure the mass % of %~30.When its content is adjusted to more than 1 mass %, from suppress developing time delay, to cured film assign It is preferable from the viewpoint of flexibility, on the other hand, when its content is adjusted to below 50 mass %, cures deficiency from suppression Be preferable from the viewpoint of Fusion Edges.
＜ solvents ＞
Photosensitive polymer combination can also include solvent.As solvent, such as can include with methyl ethyl ketone (MEK) as generation The ketone of table；Using methanol, ethanol and isopropanol as alcohol of representative etc..Solvent is preferably to be coated on the photonasty tree in support film The viscosity of the solution of oil/fat composition is added to photosensitive resin composition at 25 DEG C for the mode of 500mPas~4000mPas In thing.
＜ photosensitive elements ＞
In this second embodiment, photosensitive element is the photoresist that will be formed by above-mentioned photosensitive polymer combination Layer stackup layered product obtained from supporter (photoresist layered product).Photosensitive element can also felt as needed Photosensitive resin layer has protective layer with the surface of supporter opposite side.
[supporter]
As supporter, the preferably transparent base through the light from exposure light source radiation.As supporter, such as can enumerate Go out pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, poly- inclined two Vinyl chloride film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, polystyrene film, polypropylene Nitrile film, styrol copolymer film, polyamide film, cellulose derivative film etc..As these films, as needed, The film of drawn can also be used.
The mist degree of supporter is preferably less than 5.
It is favourable in terms of image formative and economy during the thinner thickness of supporter, but need to maintain intensity.Consider Both, can be preferably used 10 μm~30 μm of supporter.
[photo-sensitive resin]
When the photosensitive polymer combination used in the formation of photo-sensitive resin includes solvent, solvent is preferably from photonasty It is removed in resin bed, but photo-sensitive resin can also be residued in.
The thickness of photo-sensitive resin is preferably 5 μm~100 μm, more preferably 7 μm~60 μm.The thickness is thinner, differentiates Rate more improves, and the thickness is thicker, and film-strength more improves.Therefore, the thickness of photo-sensitive resin can according to purposes 5 μm~ Suitably selected in the range of 100 μm.
[protective layer]
The key property of protective layer is to be sufficiently smaller than supporter and photo-sensitive resin with the closing force of photo-sensitive resin Closing force, can be easily peeled off., not only can be preferably using such as polyethylene film, polypropylene film as protective layer Deng, but also the excellent film of the fissility for example disclosed in Japanese Unexamined Patent Application 59-202457 publications can be used.
The thickness of protective layer is preferably 10 μm~100 μm, more preferably 10 μm~50 μm.
[manufacture method of photosensitive element]
Photosensitive element can by stack gradually supporter and photo-sensitive resin and protective layer as needed and Manufacture.As the laminating method of supporter, photo-sensitive resin and protective layer, known method can be used.
For example, adding solvent in photosensitive polymer combination and mixing, seasoning liquid is prepared, and then use bar coater or roller Painting machine is coated on supporter and makes its drying, and the photoresist formed by photosensitive polymer combination is formed on supporter Layer.Then, protective layer is laminated on the photo-sensitive resin formed as needed, so as to manufacture photosensitive element.
The forming method ＞ of ＜ corrosion-resisting patterns
Photosensitive element as described above can be used, corrosion-resisting pattern is formed on substrate.
The forming method of corrosion-resisting pattern preferably includes following process successively：
The photo-sensitive resin of photosensitive element is layered in lamination process on conductor substrate,
The exposure process that is exposed to the photo-sensitive resin of foregoing stacking and
The developing procedure in the unexposed portion after foregoing exposure is removed with developer solution.
Lamination process is preferably that the photo-sensitive resin of photosensitive element is clipped wetting agent to be stacked on conductor substrate Process.As wetting agent, more than a kind in pure water, deionized water and electrolysis water and copper chelator (example are preferably comprised More than a kind chemical combination such as in the group being made of imidazolium compounds, triazole compounds, pyridine compounds and pyrazole compound Thing).
In the forming method of the corrosion-resisting pattern of this second embodiment, first, in process is laminated, using laminating machine in base Photo-sensitive resin is formed on plate.Specifically, when photosensitive element has protective layer, laminating machine is used after protective layer is peeled off Photo-sensitive resin heating is crimped on substrate surface to be laminated.
As substrate, using metallic plate or the insulative substrate with metal epithelium.As the material of metal, such as can arrange Enumerate copper, stainless steel (SUS), glass, tin indium oxide (ITO) etc..These substrates, which can also have, to be used to tackle multilager base plate Through hole.
Photo-sensitive resin can only be laminated to the single side of substrate surface, and it is two-sided can also to be laminated to substrate as needed. Heating-up temperature during lamination is preferably 40 DEG C~160 DEG C.From further improving adaptation of the obtained corrosion-resisting pattern to substrate From the viewpoint of, preferably heating crimping is carried out more than 2 times.When crimp for more than 2 times, it can use and possess the two of bigeminy roller Substrate, can also be repeated several times by roller to be crimped by stage laminating machine with the sandwich of photo-sensitive resin.
Then, in exposure process, photo-sensitive resin is exposed using exposure machine.Exposure can not peel off supporter Ground is carried out across the supporter, can also be carried out as needed after supporter is peeled off.
By carrying out the exposure with pattern-like, after aftermentioned developing procedure, it can obtain that there is the anti-of desired pattern Lose film (corrosion-resisting pattern).The exposure of pattern-like can be by across appointing in the method and maskless exposure that photomask is exposed One method carries out.When photomask is exposed, light exposure is determined by light illumination and time for exposure.Light exposure can make Measured with quantometer.
In maskless exposure, without using photomask, it is exposed on substrate with direct drawing apparatus.As light source, make With the semiconductor laser of wavelength 350nm~410nm, ultrahigh pressure mercury lamp etc..In maskless exposure, depicting pattern by computer come Control, light exposure are determined by the illumination of exposure light source and the translational speed of substrate.
Then, in developing procedure, the unexposed portion of photo-sensitive resin is removed with developer solution.After exposure, in photonasty tree When there is supporter in lipid layer, for developing procedure after preferably removing it.
In developing procedure, using the developer solution formed by aqueous alkali, unexposed portion is developed and is removed, obtains resist pattern Picture.As aqueous alkali, such as preferably using Na2CO3、K2CO3Deng aqueous solution.Aqueous alkali is according to photo-sensitive resin Characteristic selects, preferably using the Na of the concentration of the mass % of 0.2 mass %~22CO3Aqueous solution.It can also be mixed into aqueous alkali Surfactant, defoamer, a small amount of organic solvent etc. for promoting development.
The temperature of developer solution in developing procedure is preferably maintained at steady temperature in the range of 20 DEG C~40 DEG C.
Corrosion-resisting pattern is obtained by above-mentioned operation.According to circumstances, 100 DEG C~300 DEG C of heater can further be carried out Sequence.The implementation of the heating process is suitable from the viewpoint of chemical proofing is further improved.Heating can use heat The heating furnace of the suitable mode such as wind, infrared ray, far infrared.
The forming method ＞ of ＜ circuit boards
The forming method of the circuit board of this second embodiment preferably includes following process successively：
The photo-sensitive resin of photosensitive element is layered in lamination process on conductor substrate,
The exposure process that is exposed to the photo-sensitive resin of foregoing stacking,
With developer solution remove the unexposed portion after foregoing exposure developing procedure,
To by it is foregoing development the conductor substrate formed with corrosion-resisting pattern be etched or the conductive pattern of plating formed work Sequence and
The stripping process that foregoing corrosion-resisting pattern is peeled off.
Lamination process is preferably that the photo-sensitive resin of photosensitive element is clipped wetting agent to be stacked on conductor substrate Process.As wetting agent, more than a kind in pure water, deionized water and electrolysis water and copper chelator (example are preferably comprised More than a kind chemical combination such as in the group being made of imidazolium compounds, triazole compounds, pyridine compounds and pyrazole compound Thing).
, can be on the substrate formed with corrosion-resisting pattern, to being exposed by developing procedure in conductive pattern formation process Substrate surface (such as copper face) form conductive pattern using known etching method or plating method.
In stripping process, the substrate formed with conductive pattern is set to be contacted with appropriate stripper, so that corrosion-resisting pattern be shelled Leave away and remove.By the process, desired circuit board is obtained.
The stripper used in stripping process is preferably aqueous alkali.As the aqueous alkali, such as preferably using 2 matter Measure the NaOH aqueous solutions or KOH aqueous solutions of the mass % of %~5.A small amount of water-soluble solvent, such as can also be added in stripper Alcohol etc..The temperature of stripper in stripping process is preferably 40 DEG C~70 DEG C.
The forming method of photosensitive polymer combination, photosensitive element and circuit board in this second embodiment can be with It is well suited for such as printed circuit board (PCB), lead frame, the base material with relief pattern, the manufacture semiconductor package body.
It should be noted that the assay method on above-mentioned various parameters, in case of no particular description, according to rear The assay method in embodiment is stated to measure.
The 3rd embodiment ＞ of ＜
Hereinafter, the mode (hereinafter also referred to as " reality of sheet the 3rd for implementing third embodiment of the present invention is illustrated Apply mode ").
＜ photosensitive polymer combinations ＞
In this 3rd embodiment, photosensitive polymer combination includes (A) alkali solubility macromolecule, (B) containing olefinic unsaturation Key compound and (C) Photoepolymerizationinitiater initiater.According to expectation, photosensitive polymer combination can also further include (D) additive Etc other components.
It should be noted that " (methyl) acrylic acid " refers to acrylic or methacrylic acid in this specification, " (methyl) third Enoyl- " refers to acryloyl group or methylacryloyl, and " (methyl) acrylate " refers to " acrylate " or " methyl-prop Olefin(e) acid ester ".
(A) alkali solubility macromolecule
(A) alkali solubility macromolecule is the macromolecule for dissolving in alkaloid substance.In this 3rd embodiment, from taking into account corrosion-resisting pattern Hole covering character and water residual short trouble inhibition from the viewpoint of, it is preferred that (A) alkali solubility macromolecule is to form (A) alkali The gross mass of the monomer of soluble macromolecular includes the structure list of (methyl) acrylic acid of the mass % of 10 mass %~24 as benchmark The construction unit of the styrene of member and the mass % of 35 mass %~90.
Using the gross mass of the composition high molecular monomer of (A) alkali solubility as benchmark, (methyl) in (A) alkali solubility macromolecule The content of the construction unit of acrylic acid is preferably below 24 mass % from the viewpoint of water residual short trouble is suppressed, from ensuring It is preferably more than 10 mass % from the viewpoint of alkali-developable and alkali fissility.The upper limit value of its content is more preferably 23 matter % or 22.5 mass % is measured, lower limit is more preferably 11 mass %, 15 mass %, 18 mass % or 20 mass %.Water residual is short Road failure with cure resist hydrophobicity have it is very strong associate, can by improving the hydrophobicity i.e. water contact angle of resist Suppress water residual short trouble.
It is related to the content of the construction unit of (methyl) acrylic acid in (A) alkali solubility macromolecule, (A) alkali solubility macromolecule Acid equivalent (when (A) component includes a variety of copolymers, for the acid equivalent of mixture entirety) from the resistance to of photo-sensitive resin It is preferably more than 100 from the viewpoint of the development resistance of developability and corrosion-resisting pattern, resolution ratio and adaptation, from photosensitive Property resin bed developability and fissility from the viewpoint of be preferably less than 900.(A) the high molecular acid equivalent of alkali solubility is more preferably For 250~600, more preferably 350~500.Acid equivalent refers to, the linear polymer of the carboxyl wherein with 1 equivalent Quality.
Using the gross mass of the composition high molecular monomer of (A) alkali solubility as benchmark, the styrene in (A) alkali solubility macromolecule Construction unit content from the viewpoint of developability be preferably below 90 mass %, from resolution ratio and water residual short trouble It is preferably more than 35 mass % from the viewpoint of inhibition.The upper limit value of its content is from developability and prevents what splitting time from postponing Viewpoint is set out more preferably 85 mass %, 80 mass %, 70 mass % or 60 mass %, and lower limit is remained from resolution ratio and water 36 mass %, 38 mass %, 40 mass % or 42 mass % are more preferably from the viewpoint of short trouble inhibition.
From the viewpoint of the hole covering character for improving corrosion-resisting pattern, it is preferred that (A) alkali solubility macromolecule further includes The construction unit of (methyl) butyl acrylate.The construction unit of (methyl) butyl acrylate can also be included to be derived from and is selected from by (first Base) n-butyl acrylate, (methyl) isobutyl acrylate and at least one kind of weight in the group of (methyl) tert-butyl acrylate composition Multiple unit.
From the viewpoint of hole covering character and water residual short trouble inhibition is taken into account, (the first in (A) alkali solubility macromolecule Base) butyl acrylate construction unit content using form the gross mass of the high molecular monomer of (A) alkali solubility as benchmark, preferably In the range of the mass % of the mass % of 0.1 mass %~5, more preferably 0.3 mass %~1.
(A) as long as alkali solubility macromolecule includes 10 using the gross mass for forming the high molecular monomer of (A) alkali solubility as benchmark The structure list of the styrene of the mass % of the construction unit of (methyl) acrylic acid of the mass % of quality %~24 and 35 mass %~90 Member, then can be a kind of independent copolymer, or the mixture of the mixture of a variety of copolymers and/or a variety of homopolymers.
(A) alkali solubility macromolecule can include poly- (methyl) acrylic acid, poly- (methyl) butyl acrylate, polystyrene, make More than a kind and/or more than a kind of aftermentioned second comonomer comprising (methyl) acrylic acid and/or styrene and aftermentioned first monomer Copolymer composition copolymerization obtained from copolymer etc..
First monomer is the monomer (not including (methyl) acrylic acid) containing carboxyl in molecule.As the first monomer, such as Fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and maleic acid half ester etc. can be included.
Second comonomer is nonacid and has the monomer of at least one polymerism unsaturated group in the molecule (not including benzene Ethene).As second comonomer, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid can be included N-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid The tert-butyl ester, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) cyclohexyl acrylate, (first Base) vinyl alcohol such as 2-EHA, (methyl) benzyl acrylate, vinyl acetate esters；(methyl) acrylonitrile；Energy Styrene derivative of polymerization etc..
Among them, from the viewpoint of the hole covering character for improving corrosion-resisting pattern, preferably (methyl) n-butyl acrylate, (first Base) isobutyl acrylate or (methyl) tert-butyl acrylate, the more preferably positive fourth of (methyl) acrylic acid from the viewpoint of hole covering character Ester, in addition, the styrene derivative that can preferably polymerize from the viewpoint of raising resolution ratio and water residual short trouble inhibition.
As the styrene derivative that can polymerize, such as methyl styrene, vinyltoluene, tert-butoxy benzene can be included Ethene, acetoxy-styrene, 4- vinyl benzoic acids, styrene dimer, styrene trimer etc..
Alkali solubility macromolecule is preferably as follows synthesis：Mixed and with solvent such as acetone, methyl ethyl ketone, first to by above-mentioned monomer Suitable radical polymerization initiator such as benzoyl peroxide is added in the solution that alcohol, ethanol, normal propyl alcohol or isopropanol form Formyl, azo isobutyronitrile, carry out heating stirring, so as to be synthesized.Also sometimes while a part for mixture is added drop-wise to instead Answer in liquid while being synthesized.Also further add solvent after the completion of reaction sometimes, adjust to desired concentration.As synthesis Means, in addition to polymerisation in solution, can also use polymerisation in bulk, suspension polymerisation or emulsion polymerization.
(A) the high molecular weight average molecular weight of alkali solubility is (overall for the mixture when (A) component includes a variety of copolymers Weight average molecular weight) be preferably 5000~500000.(A) alkali solubility high molecular weight average molecular weight is from maintaining dry film photoresist Thickness uniformly, obtain being preferably more than 5000 from the viewpoint of the tolerance for developer solution, from maintaining the aobvious of dry film photoresist It is preferably less than 500000 from the viewpoint of shadow.(A) the high molecular weight average molecular weight of alkali solubility be more preferably 10000~ 200000th, it is more preferably 20000~100000.(A) the high molecular dispersion degree of alkali solubility is preferably 1.0~6.0.
In this 3rd embodiment, the high molecular content of (A) alkali solubility in photosensitive polymer combination is with photonasty tree The solid constituent total amount of oil/fat composition (is same below in case of no particular description, for respectively containing component as benchmark Sample) it is preferably the mass %, more preferably 40 mass % of the mass % of 10 mass %~90, more preferably 20 mass %~80 In the range of~60 mass %.(A) viewpoint of the high molecular content of alkali solubility from the alkali-developable for maintaining photo-sensitive resin goes out Hair is preferably more than 10 mass %, from the viewpoint that the performance for being used as erosion resistant is given full play to by exposing the corrosion-resisting pattern formed Set out preferably below 90 mass %.
(B) compound containing ethylenic unsaturated bond
(B) compound containing ethylenic unsaturated bond is by its structure with ethylenically unsaturated group and with polymerism Compound.Ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group from the viewpoint of addition polymerization.
In this 3rd embodiment, when (A) alkali solubility macromolecule and (B) compound containing ethylenic unsaturated bond is applied in combination, From the viewpoint of the hole covering character for ensuring corrosion-resisting pattern, the weight average molecular weight of (B) compound containing ethylenic unsaturated bond is preferably More than 1200.It is unsaturated containing olefinic at (B) on the weight average molecular weight of (B) compound containing ethylenic unsaturated bond in this specification When key compound is individually a kind of, it is meant that the weight derived by a kind of structural formula of independent compound containing ethylenic unsaturated bond Average molecular weight, when (B) compound containing ethylenic unsaturated bond is by a variety of form, it is meant that each compound containing ethylenic unsaturated bond Weight average molecular weight with compounding ratio weighted average.
(B) viewpoint of the weight average molecular weight of the compound containing ethylenic unsaturated bond from the hole covering character for further improving corrosion-resisting pattern Set out more preferably more than 1300, more preferably more than 1400, also, from the resolution ratio of corrosion-resisting pattern and the sight of fissility Point sets out more preferably less than 5000, more preferably less than 4000, particularly preferably less than 3000.
(B) compound containing ethylenic unsaturated bond can be included and is selected from by following (b1)~(b5) composition group at least 1 Kind：
(b1) ethylene glycol two (methyl) acrylate compounds shown in the following general formula (I)：
In formula, R1And R2Hydrogen atom or methyl, and m are represented independently of one another1To meet 2~40 number.}；
(b2) alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in the following general formula (II)：
In formula, R3And R4Hydrogen atom or methyl, A C are represented independently of one another2H4, B C3H6, n1、n2、n3And n4It is full Sufficient n1+n2+n3+n4The integer of=2~50 relation, the arrangement of the repetitive unit of-(A-O)-and-(B-O)-can be random Can be block, optionally any one of-(A-O)-and-(B-O)-is in double phenyl sides in the case of block.}；
(b3) three (methyl) acrylate compounds shown in the following general formula (III)：
In formula, R5~R7Hydrogen atom or methyl are represented independently of one another, and X represents the alkylidene of carbon number 2~6, m2、m3And m4 Independently of one another be 0~40 integer, m2+m3+m4For 1~40, and m2+m3+m4In the case of more than 2, multiple X optionally that This is identical or different }；
(b4) carbamate two (methyl) acrylate compounds shown in the following general formula (IV)：
In formula, R8And R9Hydrogen atom or methyl are represented independently of one another, and Y represents the alkylidene of carbon number 2~6, and Z represents divalence Organic group, and s and t independently of one another be 0~40 integer, and s+t >=1；And
(b5) remove above-mentioned (b1)~(b4) outside addition-polymerizable monomer.
From the viewpoint of the splitting time and the size of stripping film for adjusting corrosion-resisting pattern, (B) contains ethylenic unsaturated bond Compound preferably comprises (b1) ethylene glycol two (methyl) acrylate compounds shown in logical formula (I).
In logical formula (I), m1It is preferably more than 2 from the viewpoint of splitting time and stripping chip size, from resolution ratio, resistance to plating It is preferably less than 40 from the viewpoint of the property covered and elching resistant.m1More preferably 4~20, it is more preferably 6~12.
As the concrete example of ethylene glycol two (methyl) acrylate compounds shown in logical formula (I), preferably m1=4 tetrem Glycol two (methyl) acrylate, m1=9 nine ethylene glycol, two (methyl) acrylate or m1=14 two (first of polyethylene glycol Base) acrylate.
From the viewpoint of resolution ratio and hole covering character, (B) compound containing ethylenic unsaturated bond preferably comprises (b2) general formula (II) alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in.B in logical formula (II) can be- CH2CH2CH2- or-CH (CH3)CH2-。
The hydrogen atom on aromatic rings in logical formula (II) can be substituted by hetero atom and/or substituent.
As hetero atom, such as halogen atom etc. can be included, also, be used as substituent, carbon number 1~20 can be included Alkyl, the cycloalkyl of carbon number 3~10, the aryl of carbon number 6~18, phenacyl, amino, the alkyl amino of carbon number 1~10, carbon The dialkyl amido of number 2~20, nitro, cyano group, carbonyl, sulfydryl, the alkyl thiol of carbon number 1~10, aryl, hydroxyl, carbon number 1~ Acyl group that 20 hydroxy alkyl, carboxyl, the carboxyalkyl that the carbon number of alkyl is 1~10, the carbon number of alkyl are 1~10, carbon number 1~ 20 alkoxy, the alkoxy carbonyl of carbon number 1~20, the alkyl-carbonyl of carbon number 2~10, the alkenyl of carbon number 2~10, carbon number 2~ 10 N- alkyl-carbamoyls or the aryl etc. substituted containing heterocyclic group or with these substituents.These substituents can be with shape Into fused rings, alternatively, the hydrogen atom in these substituents can be substituted by hetero atoms such as halogen atoms.Fragrance in logical formula (II) When ring has multiple substituents, multiple substituents can be identical or different.
R in logical formula (II)3And R4It is independently of one another hydrogen atom or methyl, is formed from by photosensitive polymer combination Photo-sensitive resin just expose after ensure contrast from the viewpoint of, preferably R3And R4One of or both be hydrogen atom, more It is preferred that R3And R4Both are hydrogen atom.
From the viewpoint of hole covering character, it is preferred that (b2) two (first of alkylene oxide modified bisphenol A type shown in logical formula (II) Base) on acrylate compounds addition have the alkylene oxide of longer chain.More specifically, lead in formula (II), n1、n2、n3And n4It is preferred that Meet n1+n2+n3+n4=4~50 relation, more preferably meets n1+n2+n3+n4=10~50 relation, further preferably meets n1+n2+n3+n4=20~50 relation, particularly preferably meets n1+n2+n3+n4=30~50 relation.
From the viewpoint of hole covering character, more than the 40 mass % in (B) compound containing ethylenic unsaturated bond are preferably (b2) Alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in logical formula (II), more preferably lead to the n in formula (II)1、 n2、n3And n4Meet n1+n2+n3+n4Alkylene oxide modified bisphenol A type two (methyl) acrylate chemical combination of=30~50 relation Thing.50 mass %, further preferred more than 55 mass % more preferably in (B) compound containing ethylenic unsaturated bond, most preferably 60 Quality % is (b2) alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in logical formula (II).
As (b2) alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in logical formula (II) preferred tool Body example, can include and addition is distinguished at the both ends of bisphenol-A be averaged two (methyl) of polyethylene glycol that the ethylene oxide of 1 unit forms Acrylate, distinguish at the both ends of bisphenol-A addition and be averaged two (methyl) propylene of polyethylene glycol that the ethylene oxide of 2 units forms Acid esters, distinguish at the both ends of bisphenol-A addition and be averaged two (methyl) acrylic acid of polyethylene glycol that the ethylene oxide of 5 units forms Ester, distinguish at the both ends of bisphenol-A addition be averaged 7 units the polyethylene glycol that forms of ethylene oxide two (methyl) acrylate, It is averaged the polyalkylene glycol that the ethylene oxide of 6 units and the propylene oxide of average 2 units form in the both ends addition of bisphenol-A Two (methyl) acrylate, distinguish at the both ends of bisphenol-A addition and be averaged the polyalkylene glycol that the ethylene oxide of 15 units forms Two (methyl) acrylate, bisphenol-A both ends difference addition be averaged 15 units ethylene oxide and be averaged 2 units epoxy Two (methyl) acrylate for the polyalkylene glycol that propane forms etc..
In logical formula (II), from the viewpoint of resolution ratio and water residual short trouble inhibition, n1、n2、n3And n4It is also preferred that Meet n1+n2+n3+n4=2~10 relation, also particularly preferably meets n1+n2+n3+n4=2~4 relation.
From the viewpoint of hole covering character and water residual the taking into account of short trouble inhibition, it is therefore particularly preferred that (B) contains olefinic Unsaturated bond compound contains in logical formula (II) and meets n at the same time1+n2+n3+n4R in=30~50 compound, logical formula (II)3With R4One of or both for hydrogen atom compound and logical formula (II) in meet n1+n2+n3+n4=2~10 compound.
From the viewpoint of resolution ratio and hole covering character, (B) compound containing ethylenic unsaturated bond preferably comprises (b3) general formula (III) three (methyl) acrylate compounds shown in.X in logical formula (III) can be the alkylidene of carbon number 2~6, such as- CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2- etc..
From the viewpoint of hole covering character, (b3) three (methyl) acrylate compounds shown in logical formula (III) preferably have The alkylene oxide moiety of longer chain.More specifically, lead in formula (III), m2+m3+m4Preferably 10~40,20~40 are more preferably.
As (b3) three (methyl) acrylate compounds shown in logical formula (III) preferred concrete example, ring can be included Oxidative ethane (EO) is modified trimethylolpropane tris (methyl) acrylate, and (EO is averaged addition molal quantity：10~40), propylene oxide (PO) (PO is averaged addition molal quantity for modified trimethylolpropane tris (methyl) acrylate：10~40) etc..
From the viewpoint of hole covering character, (B) compound containing ethylenic unsaturated bond preferably comprises (b4) lead to shown in formula (IV) Carbamate two (methyl) acrylate compounds.
In logical formula (IV), Z represents divalent organic group, such as can be the alkylidene of carbon number 1~10, carbon number 2~10 Epoxy alkyl, optionally divalence ester ring type group of carbon number 3~10 with substituent etc..
In logical formula (IV), Y represents the alkylidene of carbon number 2~6, such as can be-CH2CH2-、-CH2CH2CH2-、-CH (CH3)CH2- etc..
From the viewpoint of hole covering character is further improved, it is also preferred that in logical formula (IV)-(Y-O)s- partly and- (Y-O)t- part is independently of one another by-(C2H5O)-(C3H6O)9- replace.
As (b4) carbamate two (methyl) acrylate compounds shown in logical formula (IV) preferred concrete example, can Include in β (methyl) acrylic monomers with hydroxyl and isophorone diisocyanate, 2,6- toluene diisocynates The addition reactions of diisocyanate cpd such as ester, 2,4 toluene diisocyanate and 1,6- hexamethylene diisocyanates, Three ((methyl) acryloxy tetraethylene glycol isocyanates) hexa-methylene isocyanuric acid esters, two (first of EO modified urethanes Base) acrylate and EO, PO modified urethane two (methyl) acrylate.It should be noted that EO represents epoxy second Alkane, the compound that EO is modified have the block structure of Oxyranyle.In addition, PO represents propylene oxide, the compound that PO is modified Block structure with propylene oxide base.As EO modified urethanes two (methyl) acrylate, such as can include new Trade name " UA-11 " of middle village's chemical industry Co., Ltd. manufacture etc..In addition, as two (first of EO, PO modified urethane Base) acrylate, such as the trade name " UA-13 " of chemical industry Co., Ltd. of Xin Zhong villages manufacture can be included etc..They can be with It is used alone or in combination of two or more.
(B) compound containing ethylenic unsaturated bond can include and remove (b1)~(b4) addition-polymerizable monomer outside component makees For (b5) component.
As (b5) component, following material can be included：
Except (b3) three (methyl) acrylate outside component, such as trimethylolpropane tris (methyl) acrylate, second Oxygen nitro three (methyl) acrylate, ethoxylation isocyanuric acid three (methyl) acrylate, pentaerythrite three (methyl) Acrylate etc.；
Four (methyl) acrylate, such as two trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) Acrylate, dipentaerythritol four (methyl) acrylate, four (methyl) acrylate of pentaerythrite (more) alkoxy etc.；
Five (methyl) acrylate, such as dipentaerythritol five (methyl) acrylate etc.；
Six (methyl) acrylate, for example, dipentaerythritol six (methyl) acrylate, in 6 ends of dipentaerythritol Addition amounts to six (methyl) acrylate, the 6 terminal additions total in dipentaerythritol that 1~24 moles of ethylene oxide forms Six (methyl) acrylate that 1~10 mole of 6-caprolactone forms etc.；
Acrylate compounds with 1 (methyl) acryloyl group；
Make polyalcohol and compound obtained from alpha, beta-unsaturated carboxylic acid reaction；
Make containing glycidyl compound and compound obtained from alpha, beta-unsaturated carboxylic acid reaction；And
Phthalic acid based compound, such as γ-chloro- 2- hydroxy propyl-Betas '-(methyl) acryloyl-oxyethyl-O-phthalic Acid esters and beta-hydroxy alkyl-β '-(methyl) acryloxyalkyl-phthalic acid ester etc..
In this 3rd embodiment, from the viewpoint of the hole covering character of corrosion-resisting pattern and adaptation, photosensitive resin composition The total content of whole (B) compound containing ethylenic unsaturated bond in thing is preferably the mass % of 1 mass %~70, more preferably 2 matter In the range of measuring the mass % of the mass % of %~60, more preferably 4 mass %~50.
(C) Photoepolymerizationinitiater initiater
(C) Photoepolymerizationinitiater initiater is to make the compound that monomer polymerize using light.Photosensitive polymer combination, which includes, to be made The known compound in the art for Photoepolymerizationinitiater initiater.
The content of (C) Photoepolymerizationinitiater initiater in photosensitive polymer combination is preferably 0.01~20 mass %, more preferably In the range of the mass % of the mass % of 0.05 mass %~10, more preferably 0.1 mass %~7.(C) Photoepolymerizationinitiater initiater Content be preferably more than 0.01 mass % from the viewpoint of sufficient sensitivity is obtained, from light is made fully through to resist Bottom surface, obtain preferably below 20 mass % from the viewpoint of good high-resolution.
As (C) Photoepolymerizationinitiater initiater, quinones, aromatic ketones, acetophenones, acylphosphine oxide class, benzene can be included Acyloin or benzoin ethers, dialkyl group ketal class, thioxanthene ketone class, dialkylaminobenzoic acid esters class, oxime esters, acridine etc., And then six aryl bisglyoxalines, pyrazoline compounds, N- aryl amino acids or its ester compounds (such as the sweet ammonia of N- phenyl can be included Acid), organohalogen compound etc..They can be used alone or two or more is applied in combination.Among them, acridine is special Exposed suitable for direct imaging.
As acridine, such as double (9- acridinyls) hexanes of acridine, 9- phenylacridines, 1,6-, the double (9- of 1,7- can be included Acridinyl) heptane, double (9- acridinyls) octanes of 1,8-, double (9- acridinyls) nonanes of 1,9-, double (9- acridinyls) decane of 1,10-, The acridine derivatives such as double (9- acridinyls) hendecanes of 1,11-, double (9- acridinyls) dodecanes of 1,12-.Exposed from for direct imaging From the viewpoint of the adaptability of light, the content of the acridine in photosensitive polymer combination is preferably the matter of 0.1 mass %~5 In the range of measuring the mass % of %, the more preferably mass % of 0.3 mass %~3, more preferably 0.5 mass %~2.
As aromatic ketones, such as benzophenone, michaelis ketone [4,4 '-bis- (dimethylamino) hexichol first can be included Ketone], 4,4 '-bis- (diethylamino) benzophenone, 4- methoxyl groups -4 '-dimethylamino benzophenone.They can individually make With a kind or two or more is applied in combination.Among them, from the viewpoint of adaptation, preferably 4,4 '-bis- (diethylaminos) two Benzophenone.And then from the viewpoint of transmissivity, the content of the aromatic ketones in photosensitive polymer combination is preferably 0.01 In the range of the mass % of the mass % of quality %~0.5, more preferably 0.02 mass %~0.3.
As the example of six aryl bisglyoxalines, 2- (Chloro-O-Phenyl) -4,5- diphenyl bisglyoxaline, 2,2 ', 5- can be included Three-(Chloro-O-Phenyl) -4- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl bisglyoxaline, 2,4- pairs-(Chloro-O-Phenyl) -5- (3, 4- Dimethoxyphenyls)-diphenyl bisglyoxaline, 2,4,5- tri--(Chloro-O-Phenyl)-diphenyl bisglyoxaline, 2- (Chloro-O-Phenyl)- Double -4,5- (3,4- Dimethoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2- fluorophenyls) -4,4 ', 5,5 '-four-(3- methoxybenzenes Base)-bisglyoxaline, 2,2 '-bis--(2,3- difluoromethyls phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2, 2 '-bis--(2,4 difluorobenzene base) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2,2 '-bis--(2,5- difluorobenzenes Base) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2,6- difluorophenyls) -4,4 ', 5,5 '-four - (3- methoxyphenyls)-bisglyoxaline, 2,2 '-bis--(2,3,4- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-connection Imidazoles, 2,2 '-bis--(2,3,5- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline, 2,2 '-it is bis--(2, 3,6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2,4,5- trifluorophenyls) -4, 4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxalines, 2,2 '-bis--(2,4,6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- first Phenyl)-bisglyoxaline, 2,2 '-bis--(2,3,4,5- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-connection miaow Azoles, 2,2 '-bis--(2,3,4,6- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline and 2,2 '-bis- - (2,3,4,5,6- pentafluorophenyl group) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-bisglyoxaline etc., they can be used alone Or two or more is applied in combination.From the viewpoint of high sensitivity, resolution ratio and adaptation, preferably 2- (Chloro-O-Phenyl) -4,5- bis- Phenylimidazole dimer.
In this 3rd embodiment, from the viewpoint of the peel property and/or sensitivity for improving photo-sensitive resin, sense The content of six aryl united imidazoles in photosensitive resin composition is preferably the mass % of 0.05 mass %~7, more preferably In the range of the mass % of the mass % of 0.1 mass %~6, more preferably 1 mass %~4.
As N- aryl amino acids, for example, can include N-phenylglycine, N- Methyl-N-phenyls glycine, N- ethyls- N-phenylglycine etc..Wherein, particularly preferred N-phenylglycine.From the viewpoint of peel property and/or sensitivity is improved, Relative to the solid constituent total amount of photosensitive polymer combination, the content of the N- aryl amino acids in photosensitive polymer combination is excellent Elect the mass % of 0.05 mass %~5, more preferably 0.1~2 mass % as.
As organohalogen compound, such as amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, two can be included Phenyl methyl bromine, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3- dibromopropyls) ester, three Chloroacetamide, amyl iodide, isobutyl iodide, 1, double (rubigan) ethane of 1,1- tri- chloro- 2,2- and chlorination triaizine compounds, its In, particularly preferably use trisbromomethyl phenyl sulfone.From the viewpoint of peel property and/or sensitivity is improved, relative to photosensitive The solid constituent total amount of property resin combination, the content of the organohalogen compound in photosensitive polymer combination is preferably 0.05 The mass % of the mass % of quality %~5, more preferably 0.1 mass %~3.
As other photosensitizers, such as 2- ethyl hydrazine, octaethyl anthraquinone, 1,2- benzos anthraquinone, 2,3- benzene can be included And anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl-1,4-naphthaquinones, The quinones such as 2,3- dimethyl anthraquinone and 3- chloro-2-methyl anthraquinones, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl The benzoin ethers such as benzoin and ethyl benzoin, benzil dimethyl ketal, benzil diethyl ketal and 1- phenyl- The oxime esters such as 1,2- pentanediones -2-O- benzoyls oxime and 1- phenyl -1,2- pentanediones -2- (O- carbethoxyl groups) oxime.From carrying From the viewpoint of high peel property and/or sensitivity, relative to the solid constituent total amount of photosensitive polymer combination, photonasty tree The content of photosensitizer in oil/fat composition is preferably the mass % of the mass % of 0.05 mass %~5, more preferably 0.1 mass %~3.
In addition, in this 3rd embodiment, photosensitive polymer combination is it is also preferred that contain pyrazoline compounds as photosensitive Agent.As pyrazoline compounds, preferably 1- phenyl -3- (4- tert-butyl-styrenes base) -5- (4- tbutyl-phenyls)-pyrazoles Quinoline, 1- (4- (benzoxazoles -2- bases) phenyl) -3- (4- tert-butyl-styrenes base) -5- (4- tbutyl-phenyls)-pyrazoline, (4- is tertiary pungent by 1- phenyl -3- (4- xenyls) -5- (4- tbutyl-phenyls)-pyrazolines and 1- phenyl -3- (4- xenyls) -5- Base-phenyl)-pyrazoline.
(D) additive
Photosensitive polymer combination can include colour-changing agent, dyestuff, plasticizer, antioxidant, stabilizer etc. according to expectation Additive.It is, for example, possible to use enumerated in Japanese Unexamined Patent Publication 2013-156369 publications and International Publication No. 2009/093706 Additive.
As colour-changing agent, leuco dye, fluoran dyes etc. can be exemplified.The use of colour-changing agent is developed the color based on exposed portion Visual aspect it is preferred.In addition, the reading such as check machine be used for expose telltale mark in the case of, exposure portion with it is unexposed Readily identified position when the contrast in portion is big, is favourable.
As leuco dye, three (4- dimethylaminophenyls) methane [leuco crystal violet], double (4- dimethyl can be included Aminophenyl) phenylmethane [leucogentian violet] etc..Especially, it is excellent as leuco dye from the viewpoint of contrast is good Choosing uses leuco crystal violet.The content of leuco dye in photosensitive polymer combination is preferably the mass % of 0.1 mass %~10. Its content is preferably more than 0.1 mass % from the viewpoint of the contrast of exposed portion and unexposed portion, is preserved from maintenance It is preferably below 10 mass % from the viewpoint of stability.
As basic-dyeable fibre, for example, can include Viride Nitens 1 [CAS number (similarly hereinafter)：633-03-4] (for example, Aizen Diamond Green GH, trade name, Baotugu Chemical Industrial Co., Ltd manufacture), malachite green oxalates [2437-29-8] (such as Aizen Malachite Green, trade name, Baotugu Chemical Industrial Co., Ltd's manufacture), brilliant green [633-03-4], Pinkish red [632-99-5], crystal violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], victoria blue B [2580-56-5], Blue 7 [2390-60-5] are (for example, Aizen Victoria Pure Blue BOH, trade name, Baotugu Chemical Industrial Co., Ltd manufacture), rhodamine B [81-88-9], rhodamine 6G [989-38- 8], basic yellow 2 [2465-27-2] etc..Wherein, preferably Viride Nitens 1, malachite green oxalates and Blue 7, from improving form and aspect Particularly preferred Viride Nitens 1 from the viewpoint of stability and exposure contrast.
In this 3rd embodiment, the content of the basic-dyeable fibre in photosensitive polymer combination is preferably 0.001 mass % The scope of the mass % of~3 mass %, more preferably the mass % of 0.01 mass %~2, more preferably 0.01 mass %~1 It is interior.The content of dyestuff is preferably more than 0.001 mass % from the viewpoint of good coloring is obtained, from maintenance photonasty tree It is preferably below 3 mass % from the viewpoint of the sensitivity of lipid layer.
In this 3rd embodiment, in order to which the content suppressed by the construction unit of (methyl) acrylic acid is 10 mass %~24 The delay of corrosion-resisting pattern stripping caused by the alkali solubility macromolecule of quality %, shortening splitting time, preferably in photoresist group Contain the toluenesulfonic acid acid amides such as o-toluene sulfonic acid acid amides, p-methyl benzenesulfonic acid acid amides in compound as plasticizer.Photoresist group The content of toluenesulfonic acid acid amides in compound is preferably the mass % of the mass % of 0.1 mass %~5, more preferably 1 mass %~4 In the range of.
As other plasticizer, such as polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene ether, polyoxy can be included Ethene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene list ethylether, polyoxy The diol-lipids such as propylene list ethylether, polyoxyethylene polyoxypropylene list ethylether；The phthalic acid esters such as diethyl phthalate Class；Tributyl citrate, triethyl citrate, CitroflexA-2, three n-propyl of acetyl citrate and acetyl group Tri-n-butyl citrate；Propane diols that addition propylene oxide forms is distinguished in the both sides of bisphenol-A, is added respectively in the both sides of bisphenol-A Ethylene glycol formed into ethylene oxide etc..
From the viewpoint of the heat endurance of photosensitive polymer combination or storage stability, photosensitive polymer combination is excellent Choosing includes to be selected from is used as stabilizer by least one of group of following material composition：Radical polymerization inhibitor, such as to first Epoxide phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, stannous chloride, 2,6- di-t-butyls-paracresol, 2,2 '-Asia Methyl double (4- methyl-6-tert-butylphenols), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), diphenyl nitrosamine, Triethylene glycol-bis- (the 3-3- tert-butyl group -5- methyl -4- hydroxy-phenylpropionic acids ester) and nitroso phenylhydroxylamine aluminium salt etc.；Benzo Triazole type, such as 1,2,3- benzotriazole, 1- chloro- 1,2,3- benzotriazole, double (N-2- ethylhexyls) aminomethylenes -1,2, 3- benzotriazole, double (N-2- ethylhexyls) aminomethylene -1,2,3- tolyl-triazoles, 1- (2- di-n-octyl amino first Base)-benzotriazole and double (N-2- hydroxyethyls) aminomethylene-l, 2,3 triazoles etc.；Carboxyl benzotriazole class example Such as, 4- carboxyls -1,2,3- benzotriazole, 5- carboxyls -1,2,3- benzotriazole, 6- carboxyls -1,2,3- benzotriazole, 1- (2- bis- N-butylamino methyl) -5- carboxyl benzotriazoles and the 1 of 1- (2- di-n-butyls amino methyl) -6- carboxyl benzotriazoles：1 is mixed Compound, N- (bis- -2- ethylhexyls of N, N-) aminomethylene carboxyl benzotriazole, N- (bis- -2- hydroxyethyls of N, N-) amino are sub- Methyl carboxyl benzotriazole and N- (bis- -2- ethylhexyls of N, N-) aminoethylene carboxyl benzotriazole etc.；It is and sweet with shrinking The oxirane compounds of oil base, such as neopentylglycol diglycidyl ether (for example, Kyoeisha Chemical Co., Ltd.'s manufacture Epolight1500NP), nine ethylene glycol diglycidylethers (such as Kyoeisha Chemical Co., Ltd. manufacture Epolight400E), 2 moles of addition product diglycidyl ethers of bisphenol-A-propylene oxide are (for example, Kyoeisha Chemical Co., Ltd.'s system The Epolight3002 made), hydrogenated bisphenol A diglycidyl ether (for example, Kyoeisha Chemical Co., Ltd. manufacture Epolight4000), 1,6- hexane diols diglycidyl ether is (for example, what Kyoeisha Chemical Co., Ltd. manufactured Epolight1600) etc..
In this 3rd embodiment, the total content of whole stabilizers in photosensitive polymer combination is preferably 0.001 matter Measure the mass %'s of the mass %, more preferably 0.05 mass % of the mass % of %~3, more preferably 0.01 mass %~1~0.7 In the range of.The total content of stabilizer is preferably from the viewpoint of good storage stability is assigned to photosensitive polymer combination More than 0.001 mass %, is preferably below 3 mass % from the viewpoint of the sensitivity for maintaining photo-sensitive resin.
The additive of described above can be used alone or two or more is applied in combination.
＜ photosensitive polymer combination seasoning liquids ＞
In this 3rd embodiment, by adding solvent in photosensitive polymer combination, so as to form photonasty Resin combination seasoning liquid.As suitable solvent, ketone, such as acetone, methyl ethyl ketone (MEK) etc. can be included；And alcohols, Such as methanol, ethanol, isopropanol etc..It is preferred that with the viscosity of photosensitive polymer combination seasoning liquid at 25 DEG C be 500mPa seconds Solvent is made an addition to photosensitive polymer combination by the mode of~4000mPa seconds.
＜ photoresist layered products ＞
In this 3rd embodiment, using the teaching of the invention it is possible to provide there is supporter and be layered on supporter and by above-mentioned photoresist The photoresist layered product for the photo-sensitive resin that composition is formed.Photoresist layered product can also felt according to expectation Photosensitive resin layer has protective layer with support side opposite side.
As supporter, it is not particularly limited, preferably the transparent supporting body through the light from exposure light source radiation.It is used as this Kind supporter, such as pet film, polyvinyl alcohol film, polyvinyl chloride film, chloroethene can be included Alkene copolymer film, polyvinylidene chloride film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, Polystyrene film, polyacrylonitrile film, styrol copolymer film, polyamide film and cellulose derivative film.These Film can also be stretched as needed.Mist degree is preferably 0.01%~5.0%, more preferably 0.01%~2.5%, into one Step is preferably 0.01%~1.0%.On the thickness of film, film is thinner, more has in terms of image formative and economy Profit, but due to need maintain intensity, preferably 10 μm~30 μm.
In addition, the key property of the protective layer used in photoresist layered product is, compared to supporter and photonasty The closing force of the closing force of resin bed, protective layer and photo-sensitive resin is smaller, can be easily peeled off.As protective layer, example Such as preferred polyethylene film, polypropylene film.It is, for example, possible to use described in Japanese Unexamined Patent Application 59-202457 publications The excellent film of fissility.The thickness of protective layer is preferably 10 μm~100 μm, more preferably 10 μm~50 μm.
In this 3rd embodiment, the thickness of the photo-sensitive resin in photoresist layered product is preferably 5 μm~100 μm, more preferably 7 μm~60 μm.The thickness of photo-sensitive resin is smaller, and the resolution ratio of corrosion-resisting pattern more improves, on the other hand, The thickness of photo-sensitive resin is bigger, cures film strength and more improves, therefore can be selected according to purposes.
As being stacked gradually supporter, photo-sensitive resin and according to desired protective layer and make photoresist The method of layered product, can use known method.
For example, preparing above-mentioned photosensitive polymer combination seasoning liquid, then support is coated on using bar coater or roll coater On body and make its drying, the photo-sensitive resin formed by photosensitive polymer combination seasoning liquid is laminated on supporter.And then Protective layer is laminated on photo-sensitive resin according to expectation, so as to make photoresist layered product.
＜ corrosion-resisting pattern forming methods ＞
The forming method of corrosion-resisting pattern preferably includes successively：It is laminated in supporter and is formed by above-mentioned photosensitive polymer combination Photo-sensitive resin lamination process, the exposure process that is exposed to photo-sensitive resin and the photonasty tree to exposure The developing procedure that lipid layer is developed.In this 3rd embodiment, by the one of the specific method for forming corrosion-resisting pattern be illustrated in Under.
First, in process is laminated, photo-sensitive resin is formed on substrate using laminating machine.Specifically, photonasty When laminated resin body has protective layer, photo-sensitive resin heating is crimped on substrate surface with laminating machine after protective layer is peeled off To be laminated.As the material of substrate, such as copper, stainless steel (SUS), glass, tin indium oxide (ITO) etc. can be enumerated.
In this 3rd embodiment, photo-sensitive resin can only be laminated to the single side of substrate surface, or layer as needed It is pressed on two-sided.Heating-up temperature during lamination is usually 40 DEG C~160 DEG C.In addition, by the way that heating crimping when being laminated is carried out 2 times More than, it is possible to increase adaptation of the obtained corrosion-resisting pattern to substrate.During heating crimping, the second order for possessing bigeminy roller can be used Segmentation laminating machine, or substrate is repeated several times with the sandwich of photo-sensitive resin by roller to be crimped.
Then, in exposure process, photo-sensitive resin is exposed with active light using exposure machine.Exposure can root Carried out according to expectation after supporter is peeled off.When being exposed through photomask, light exposure is determined by light illumination and time for exposure, It can be measured using quantometer.In exposure process, direct imaging exposure can also be carried out.In direct imaging exposure, without using It is exposed on substrate using direct drawing apparatus photomask.As light source, partly leading for wavelength 350nm~410nm is used Volumetric laser or ultrahigh pressure mercury lamp.Depicting pattern with computer to control when, light exposure is by the illumination of exposure light source and the shifting of substrate Dynamic speed determines.
Then, in developing procedure, removed using developing apparatus developer solution in the photo-sensitive resin after exposure not Exposure portion or exposure portion.After exposure, in the case of there is supporter on photo-sensitive resin, remove it.Then, using by alkali The developer solution that aqueous solution is formed, unexposed portion or exposure portion development are removed, obtain resist pattern picture.
As aqueous alkali, preferably Na2CO3、K2CO3Deng aqueous solution.Aqueous alkali is according to the characteristic of photo-sensitive resin To select, usually using the Na of the concentration of the mass % of 0.2 mass %~22CO3Aqueous solution.In aqueous alkali, it can also be mixed with Surfactant, defoamer, a small amount of organic solvent etc. for promoting development.The temperature of developer solution in developing procedure preferably exists Kept constant in the range of 20 DEG C~40 DEG C.
By above-mentioned operation, corrosion-resisting pattern can be obtained, can also according to it is expected further at 100 DEG C~300 DEG C into Row heating process.By implementing the heating process, the chemical proofing of corrosion-resisting pattern can be improved., can be with heating process Use the heating furnace using hot wind, infrared ray or far infrared mode.
The photosensitive polymer combination of this 3rd embodiment can be suitably used to form the circuit of printed base plate.It is logical Often, the circuit forming method as printed base plate, uses the method for residues and semi-additive process (SAP).
The method of residues is only removed inverter circuit part by etching and forms the side of circuit from being configured at substrate entire conductor Method.
SAP is to be formed in the inverter circuit part that is configured in the entire conductor Seed Layer of substrate after resist by plating only The method for forming circuit part.
The manufacture method ＞ of ＜ conductive patterns
The manufacture method of conductive pattern preferably includes successively：On the substrates such as metallic plate, metal epithelium insulation board stacking by The lamination process for the photo-sensitive resin that above-mentioned photosensitive polymer combination is formed；The exposure being exposed to photo-sensitive resin Process；The unexposed portion of the photo-sensitive resin of exposure or exposure portion are removed with developer solution, so as to obtain formed with resist pattern The developing procedure of the substrate of case；And the substrate formed with corrosion-resisting pattern is etched or the conductive pattern of plating formed work Sequence.
In this 3rd embodiment, the manufacture method of conductive pattern is carried out as follows：Metallic plate or metal are used as substrate Epithelium insulation board, corrosion-resisting pattern is formed by above-mentioned corrosion-resisting pattern forming method, then by conductive pattern formation process, so that Carry out.In conductive pattern formation process, by the substrate surface (for example, copper face) that exposes of developing using known etching method or Plating method forms conductive pattern.
And then this 3rd embodiment is suitable for for example following purposes.
The manufacture method ＞ of ＜ circuit boards
After manufacturing conductive pattern by the manufacture method of conductive pattern, further carrying out utilizing has the alkali stronger than developer solution Stripping process of the aqueous solution of property by corrosion-resisting pattern from strippable substrate, so as to obtain that there is the circuit of desired wiring pattern Plate (for example, printed circuit board (PCB)).
On the aqueous alkali (hereinafter also referred to " stripper ") of stripping, it is not particularly limited, usually using 2 mass % The aqueous solution of the NaOH or KOH of the concentration of~5 mass % or organic amine system stripper.It can be added in stripper on a small quantity Water-soluble solvent.As water-soluble solvent, such as alcohol etc. can be included.The temperature of stripper in stripping process is preferably 40 DEG C In the range of~70 DEG C.
The manufacture ＞ of ＜ lead frames
The metallic plate of copper, copper alloy or iron-based alloy etc. is used as substrate, is formed by corrosion-resisting pattern forming method anti- Corrosion figure case, then by following process, so as to manufacture lead frame.First, carry out to by develop the substrate that exposes into The process that row etches and forms conductive pattern.Then, by the method same with the manufacture method of circuit board peel off against corrosion The stripping process of pattern, can obtain desired lead frame.
＜ has the manufacture ＞ of the base material of relief pattern
The corrosion-resisting pattern formed by corrosion-resisting pattern forming method may be used as that substrate is implemented to process by sandblasting engineering method When protection mask member.At this time, as substrate, such as glass, silicon wafer, non-crystalline silicon, polysilicon, ceramics, indigo plant can be included Jewel, metal material etc..Corrosion-resisting pattern is formed by the method same with corrosion-resisting pattern forming method on these substrates.So Afterwards, carry out blowing material spray above the corrosion-resisting pattern formed and being cut to the blasting treatment process of target depth and shelled with alkali Chaotropic etc. removes the stripping process for remaining in the corrosion-resisting pattern part on substrate from substrate, can manufacture on substrate with fine Relief pattern base material.
In blasting treatment process, known material spray can be used, such as usually using including SiC, SiO2、Al2O3、 CaCO3, ZrO, glass, stainless steel etc. 2 μm~100 μm of particle diameter particulate.
The manufacture ＞ of ＜ semiconductor package bodies
The chip for completing large scale integrated circuit (LSI) formation is used as substrate, passes through corrosion-resisting pattern forming method After forming corrosion-resisting pattern on chip, by following process, so as to manufacture semiconductor package body.First, carry out logical Cross the process that the opening portion that development is exposed applies the column plating of copper, solder etc. and forms conductive pattern.Then, carry out by with The same method of the manufacture method of circuit board peels off the stripping process of corrosion-resisting pattern, and then, remove column by etching and plate Coated with the process of the thin metal layer of outer part, so as to obtain desired semiconductor package body.
In this 3rd embodiment, photosensitive polymer combination can be used for the manufacture of printed circuit board (PCB)；IC chip is carried Manufactured with lead frame；The metal foil Precision Machinings such as metal mask manufacture；Ball grid array (BGA), chip size packages (CSP) etc. are sealed Fill the manufacture of body；Chip on film (COF), belt engage the manufacture of the belt substrate such as (TAB) automatically；The manufacture of semiconductor convex block； And the manufacture of the partition wall of the flat-panel monitor such as ITO electrode, addressing electrode, electromagnetic wave shielding.
It should be noted that the value on above-mentioned each parameter, in case of no particular description, according to aftermentioned embodiment In assay method measure.
The 4th embodiment ＞ of ＜
Hereinafter, mode (hereinafter referred to as " this 4th implementation of the 4th embodiment for implementing the present invention is illustrated Mode ").
＜ photosensitive polymer combinations ＞
In this 4th embodiment, photosensitive polymer combination contains (A) alkali solubility macromolecule, (B) containing olefinic unsaturation Key compound and (C) Photoepolymerizationinitiater initiater.According to expectation, photosensitive polymer combination further includes (D) stabilizer etc Other components.
It should be noted that " (methyl) acrylic acid " refers to acrylic or methacrylic acid in this specification, " (methyl) third Enoyl- " refers to acryloyl group or methylacryloyl, and " (methyl) acrylate " refers to " acrylate " or " methyl-prop Olefin(e) acid ester ".
[(A) alkali solubility macromolecule]
From the viewpoint of the extension of resolution ratio and minimum developing time, foregoing (A) alkali solubility macromolecule includes acid monomers The content ratio of unit is less than the first copolymerization that the content ratio of 25 mass % and aromatic monomer unit is more than 30 mass % Thing.First copolymer can also include other monomer lists according to expectation on the basis of acid monomer units and aromatic monomer unit Member.The dispersion degree of the copolymer represented with the weight average molecular weight (aftermentioned) of copolymer with the ratio of number-average molecular weight is preferably more than 1 And less than 6.
As acid monomers, such as (methyl) acrylic acid, penetenoic acid, unsaturated dicarboxylic acid anhydride, hydroxy styrenes can be included Deng.As above-mentioned unsaturated dicarboxylic acid anhydride, such as maleic anhydride, itaconic anhydride, fumaric acid, citraconic anhydride etc. can be included.Its In, preferred (methyl) acrylic acid.
It is excellent relative to the gross mass of whole monomeric units as the copolymerization ratios of the acid monomer units in foregoing (A) component Select less than the mass % of 25 mass %, the more preferably mass % of 10 mass %~24, more preferably 15 mass %~23.It is sour single It is excellent from the viewpoint of the raising of resolution ratio and the extension of minimum developing time when the content ratio of body unit is in the scope Choosing.
Aromatic monomer is also referred to as unsaturated aromatic compound.As aromatic monomer, for example, can include styrene, α-methylstyrene, vinyl naphthalene etc.；(methyl) acrylic acid aralkyl ester etc..As (methyl) acrylic acid aralkyl ester, such as (methyl) benzyl acrylate etc. can be included.
As the copolymerization ratios of the aromatic monomer unit (be preferably styrene units) in foregoing (A) component, relative to The gross mass of whole monomeric units, is preferably more than 30 mass %, the more preferably mass % of 32 mass %~60, further preferably For the mass % of 35 mass %~55.By hydrophobicity height, it is difficult to being total to for the aromatic monomer compatible with developer solution and development ejected wash water It is preferable from the viewpoint of the raising of resolution ratio and the extension of minimum developing time when poly- ratio is set as above range.
As other monomers, for example, can include (methyl) alkyl acrylate, conjugated diene compound, polar monomer, Cross-linkable monomer etc..
(methyl) alkyl acrylate is the concept for including both chain-like alkyl ester and cyclic alkyl ester, specifically, example It is different that (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid can such as be included Propyl ester, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (first Base) decyl acrylate, (methyl) lauryl acrylate, (methyl) n-myristyl base ester, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate etc..
As conjugated diene compound, such as 1,3-butadiene, isoprene, 2,3- dimethyl -1,3- fourths can be included Diene, 2- phenyl -1,3- butadiene, 1,3- pentadienes, 2- methyl-1,3-pentylenes, 1,3- hexadienes, 4,5- diethyl -1, 3- octadienes, 3- butyl -1,3- octadienes etc..
As polar monomer, such as can include：
(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, pentenol Deng hydroxyl monomer；The emulsion stabilities such as methacrylic acid 2- amino ethyl esters；
The amide-containing monomers such as (methyl) acrylamide, N- methylols (methyl) acrylamide；
The cyano-containing monomers such as acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, alpha-cyano ethyl propylene acid esters；
(methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- epoxy cyclohexyls etc. contain epoxy based monomers；
Deng.
As cross-linkable monomer, such as trimethylolpropane trimethacrylate, divinylbenzene etc. can be included.
Foregoing first copolymer is particularly preferably the copolymer of (methyl) acrylic acid, styrene and other monomers.
In this 4th embodiment, from the viewpoint of resolution ratio and developability and aggregation, it is also preferred that comprising above stating The content ratio of bright aromatic monomer unit for the mass % of 45 mass %~90 the second copolymer.In second copolymer, virtue The content ratio of fragrant race's monomeric unit is 45 mass %, so as to be present to ensure that the hydrophobicity of the corrosion-resisting pattern comprising the second copolymer Tendency.In addition, relative to the gross weight of whole copolymers, when the weight rate of the second copolymer is more than 25 mass %, from It is preferable from the viewpoint of improvement aggregation.
Second copolymer can also include the acid monomer units of described above and other monomeric units.As for making second The aromatic monomer of copolymer polymerization, from the viewpoint of hydrophobicity, optimization styrene.From the viewpoint of developability, second The upper limit of the content ratio of aromatic monomer unit in copolymer is more preferably 80 mass % or 70 mass %.
Second copolymer can include the acid monomer units of described above and other monomeric units, from resolution ratio and developability From the viewpoint of aggregation, the content ratios of the acid monomer units of described above is preferably the mass % of 25 mass %~50, more The mass % of preferably 25 mass %~40.As the acid monomers for making the second copolymer polymerization, from the viewpoint of developability, It is preferred that (methyl) acrylic acid.
The weight average molecular weight of foregoing (A) component is (when (A) component includes a variety of copolymers, for the weight of mixture entirety Average molecular weight) it is preferably 5000~1000000, more preferably 10000~500000, more preferably 15000~100000. During by the weight average molecular weight adjustment of (A) component within the range, it is suitable for being made from developing time when forming corrosion-resisting pattern It is preferable from the viewpoint of the operating status of assembly line.
In this 4th embodiment, the content of (A) component in photosensitive polymer combination is with photosensitive polymer combination Solid constituent total amount it is excellent as benchmark (following, be same for respectively containing component in case of no particular description) Elect the matter of the mass %, more preferably 40 mass % of the mass % of 10 mass %~90, more preferably 20 mass %~80~60 as Measure %.The content is preferably more than 10 mass % from the viewpoint of alkali-developable is maintained, and on the other hand, is formed from by exposing Corrosion-resisting pattern to give full play to from the viewpoint of the performance as resist be preferably below 90 mass %.
The content ratio of acid monomer units is 30 mass % less than the content ratio of 25 mass % and aromatic monomer unit More than the first copolymer using the solid constituent total amount of photosensitive polymer combination as benchmark be preferably more than 5 mass % and 50 Below quality %.More preferably more than 10 mass % below 40 mass %.
[(B) compound containing ethylenic unsaturated bond]
(B) compound containing ethylenic unsaturated bond is by its structure with ethylenically unsaturated group and with polymerism Compound.From the viewpoint of addition polymerization, ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group.
In this 4th embodiment, when (A) alkali solubility macromolecule and (B) compound containing ethylenic unsaturated bond is applied in combination, From the fine resolution for ensuring corrosion-resisting pattern and from the viewpoint of extending minimum developing time, (B) contains ethylenic unsaturated bond The weight average molecular weight of compound is preferably less than 900.In this specification, the average mark on (B) compound containing ethylenic unsaturated bond Son amount, (B) compound containing ethylenic unsaturated bond for it is individually a kind of when, it is meant that a kind of contain ethylenic unsaturated bond by independent The weight average molecular weight that the structural formula of compound is derived, when (B) compound containing ethylenic unsaturated bond is by a variety of form, it is meant that each The weighted average of the weight average molecular weight of a compound containing ethylenic unsaturated bond and compounding ratio.
(B) raising and the extension of minimum developing time of the weight average molecular weight of the compound containing ethylenic unsaturated bond from resolution ratio From the viewpoint of more preferably less than 850, more preferably less than 800, also, from suppress photoresist layered product side It is preferably more than 50, more preferably more than 100 from the viewpoint of edge amalgamation.Herein, Fusion Edges refer to, photoresist The phenomenon that photosensitive polymer combination layer is oozed out from the end face of volume when layered product coils into web-like.
(B) compound containing ethylenic unsaturated bond can be included and is selected from by following (b1)~(b6) composition group at least 1 Kind：
(b1) ethylene glycol two (methyl) acrylate compounds shown in the following general formula (I)：
In formula, R1And R2Hydrogen atom or methyl, and m are represented independently of one another1To meet 2~40 number.}；
(b2) alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in the following general formula (II)：
In formula, R3And R4Hydrogen atom or methyl, A C are represented independently of one another2H4, B C3H6, n1、n2、n3And n4It is full Sufficient n1+n2+n3+n4The integer of=2~50 relation, the arrangement of the repetitive unit of-(A-O)-and-(B-O)-can be random Can be block, optionally any one of-(A-O)-and-(B-O)-is in double phenyl sides in the case of block.}；
(b3) three (methyl) acrylate compounds shown in the following general formula (III)：
In formula, R5~R7Hydrogen atom or methyl are represented independently of one another, and X represents the alkylidene of carbon number 2~6, m2、m3And m4 Independently of one another be 0~40 integer, m2+m3+m4For 0~40, and m2+m3+m4In the case of more than 2, multiple X optionally that This is identical or different }；
(b4) carbamate two (methyl) acrylate compounds shown in the following general formula (IV)：
In formula, R8And R9Hydrogen atom or methyl are represented independently of one another, and Y represents the alkylidene of carbon number 2~6, and Z represents divalence Organic group, also, s and t independently of one another be 0~40 integer, and s+t >=1；
(b5) four (methyl) acrylate compounds shown in the following general formula (XI)：
In formula, R5~R8Hydrogen atom or methyl are represented independently of one another, and X represents the alkylidene of carbon number 2~6, m2、m3、m4With m5Independently of one another be 0~40 integer, m2+m3+m4+m5For 0~50, and m2+m3+m4+m5It is multiple in the case of more than 2 X is optionally same to each other or different to each other }；And
(b6) remove above-mentioned (b1)~(b5) outside addition-polymerizable monomer.
From the viewpoint of the splitting time and the size of stripping film for adjusting corrosion-resisting pattern, (B) contains ethylenic unsaturated bond Compound preferably comprises (b1) ethylene glycol two (methyl) acrylate compounds shown in logical formula (I).
In logical formula (I), m1It is preferably more than 2 from the viewpoint of splitting time and stripping chip size, from resolution ratio, resistance to plating It is preferably less than 40 from the viewpoint of the property covered and elching resistant.m1More preferably 4~20, it is more preferably 6~12.
As the concrete example of ethylene glycol two (methyl) acrylate compounds shown in logical formula (I), preferably m1=4 tetrem Glycol two (methyl) acrylate, m1=9 nine ethylene glycol, two (methyl) acrylate or m1=14 two (first of polyethylene glycol Base) acrylate.
Go out from the viewpoint for suppressing aggregation generation in the photo-sensitive resin development formed by photosensitive polymer combination Hair, (B) compound containing ethylenic unsaturated bond preferably comprise (b2) alkylene oxide modified bisphenol A type two (methyl) shown in logical formula (II) Acrylate compounds.B in logical formula (II) can be-CH2CH2CH2- or-CH (CH3)CH2-。
The hydrogen atom on aromatic rings in logical formula (II) can be substituted by hetero atom and/or substituent.
As hetero atom, such as halogen atom etc. can be included, also, be used as substituent, carbon number 1~20 can be included Alkyl, the cycloalkyl of carbon number 3~10, the aryl of carbon number 6~18, phenacyl, amino, the alkyl amino of carbon number 1~10, carbon The dialkyl amido of number 2~20, nitro, cyano group, carbonyl, sulfydryl, the alkyl thiol of carbon number 1~10, aryl, hydroxyl, carbon number 1~ Acyl group that 20 hydroxy alkyl, carboxyl, the carboxyalkyl that the carbon number of alkyl is 1~10, the carbon number of alkyl are 1~10, carbon number 1~ 20 alkoxy, the alkoxy carbonyl of carbon number 1~20, the alkyl-carbonyl of carbon number 2~10, the alkenyl of carbon number 2~10, carbon number 2~ 10 N- alkyl-carbamoyls or the aryl etc. substituted containing heterocyclic group or with these substituents.These substituents can be with shape Into fused rings, or hydrogen atom in these substituents can be substituted by hetero atoms such as halogen atoms.Fragrance in logical formula (II) When ring has multiple substituents, multiple substituents can be identical or different.
R in logical formula (II)3And R4It is independently of one another hydrogen atom or methyl, is formed from by photosensitive polymer combination Photo-sensitive resin just expose after ensure contrast from the viewpoint of, preferably R3And R4One of or both be hydrogen atom, more It is preferred that R3And R4Both are hydrogen atom.
From the viewpoint of the raising of resolution ratio and the extension of minimum developing time, it is preferred that (b2) lead to formula (II) institute Addition has the alkylene oxide compared with short chain on alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown.More specifically, In logical formula (II), n1、n2、n3And n4Preferably satisfy n1+n2+n3+n4=0~30 relation, more preferably meet n1+n2+n3+n4=0 ~25 relation, further preferably meet n1+n2+n3+n4=0~20 relation, particularly preferably meet n1+n2+n3+n4=0~10 Relation.
From the viewpoint of the raising of resolution ratio and the extension of minimum developing time, (B) compound containing ethylenic unsaturated bond In more than 40 mass % be preferably (b2) alkylene oxide modified bisphenol A type two (methyl) acrylate chemical combination shown in logical formula (II) N in thing, more preferably logical formula (II)1、n2、n3And n4Meet n1+n2+n3+n4The alkylene oxide modified bisphenol A of=0~20 relation Type two (methyl) acrylate compounds.50 mass % more preferably in (B) compound containing ethylenic unsaturated bond, further preferably More than 55 mass %, most preferably 60 mass % are (b2) alkylene oxide modified bisphenol A type two (methyl) propylene shown in logical formula (II) Ester compound.
As (b2) alkylene oxide modified bisphenol A type two (methyl) acrylate compounds shown in logical formula (II) preferred tool Body example, can include and addition is distinguished at the both ends of bisphenol-A be averaged two (methyl) of polyethylene glycol that the ethylene oxide of 1 unit forms Acrylate, distinguish at the both ends of bisphenol-A addition and be averaged two (methyl) propylene of polyethylene glycol that the ethylene oxide of 2 units forms Acid esters, distinguish at the both ends of bisphenol-A addition and be averaged two (methyl) acrylic acid of polyethylene glycol that the ethylene oxide of 5 units forms Ester, distinguish at the both ends of bisphenol-A addition be averaged 7 units the polyethylene glycol that forms of ethylene oxide two (methyl) acrylate, Distinguish addition at the both ends of bisphenol-A to be averaged the polyalkylene two that the ethylene oxide of 6 units and the propylene oxide of average 2 units form Two (methyl) acrylate of alcohol, distinguish at the both ends of bisphenol-A addition and be averaged the polyalkylene that the ethylene oxide of 15 units forms Two (methyl) acrylate of glycol, the difference addition of the both ends of bisphenol-A be averaged 15 units ethylene oxide and 2 units that are averaged Two (methyl) acrylate for the polyalkylene glycol that propylene oxide forms etc..
In logical formula (II), from the viewpoint of resolution ratio is improved, n1、n2、n3And n4It is also preferred that meet n1+n2+n3+n4=2~ 20 relation, also particularly preferably meets n1+n2+n3+n4=2~10 relation.
From the viewpoint of the raising of resolution ratio and the extension of minimum developing time, it is therefore particularly preferred that (B) containing olefinic not Saturation key compound contains at the same time：Meet n in logical formula (II)1+n2+n3+n4R in=2~20 compound, logical formula (II)3And R4 One of or both for methyl compound and logical formula (II) in meet n1+n2+n3+n4=2~16 compound.
Go out from the viewpoint for suppressing aggregation generation in the photo-sensitive resin development formed by photosensitive polymer combination Hair, (B) compound containing ethylenic unsaturated bond preferably comprise (b3) three (methyl) acrylate compounds shown in logical formula (III). X in logical formula (III) is the alkylidene of carbon number 2~6, such as can be-CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2- etc..
From the viewpoint of resolution ratio, (b3) three (methyl) acrylate compounds shown in logical formula (III) preferably have Compared with the alkylene oxide moiety of short chain.More specifically, lead in formula (III), m2+m3+m4Preferably 8~40,9~25 are more preferably.
As (b3) three (methyl) acrylate compounds shown in logical formula (III) preferred concrete example, ring can be included Oxidative ethane (EO) is modified trimethylolpropane tris (methyl) acrylate, and (EO is averaged addition molal quantity：1~40), propylene oxide (PO) (PO is averaged addition molal quantity for modified trimethylolpropane tris (methyl) acrylate：1~40) etc..
From the viewpoint of resolution ratio, (B) compound containing ethylenic unsaturated bond preferably comprises (b4) lead to shown in formula (IV) Carbamate two (methyl) acrylate compounds.
In logical formula (IV), Z represents divalent organic group, such as can be the alkylidene of carbon number 1~10, carbon number 2~10 Epoxy alkyl, optionally divalence ester ring type group of carbon number 3~10 with substituent etc..
In logical formula (IV), Y represents the alkylidene of carbon number 2~6, such as can be-CH2CH2-、-CH2CH2CH2-、-CH (CH3)CH2- etc..
From the viewpoint of resolution ratio is further improved, it is also preferred that in logical formula (IV)-(Y-O)s- partly and- (Y-O)t- part is independently of one another by-(C2H5O)-(C3H6O)9- replace.
As (b4) carbamate two (methyl) acrylate compounds shown in logical formula (IV) preferred concrete example, can Include in β (methyl) acrylic monomers with hydroxyl and isophorone diisocyanate, 2,6- toluene diisocynates The addition reactions of diisocyanate cpd such as ester, 2,4 toluene diisocyanate and 1,6- hexamethylene diisocyanates, Three ((methyl) acryloxy tetraethylene glycol isocyanates) hexa-methylene isocyanuric acid esters, two (first of EO modified urethanes Base) acrylate and EO, PO modified urethane two (methyl) acrylate.It should be noted that EO represents epoxy second Alkane, the compound that EO is modified have the block structure of Oxyranyle.In addition, PO represents propylene oxide, the compound that PO is modified Block structure with propylene oxide base.As EO modified urethanes two (methyl) acrylate, such as can include new Trade name " UA-11 " of middle village's chemical industry Co., Ltd. manufacture etc..In addition, as two (first of EO, PO modified urethane Base) acrylate, such as the trade name " UA-13 " of chemical industry Co., Ltd. of Xin Zhong villages manufacture can be included etc..They can be with It is used alone or in combination of two or more.
Go out from the viewpoint for suppressing aggregation generation in the photo-sensitive resin development formed by photosensitive polymer combination Hair, (B) compound containing ethylenic unsaturated bond preferably comprise (b5) four (methyl) acrylate compounds shown in general formula (XI).
X in general formula (XI) is the alkylidene of carbon number 2~6, such as can be-CH2CH2-、-CH2CH2CH2-、-CH(CH3) CH2- etc..
As (b5) four (methyl) acrylate compounds shown in general formula (XI) preferred concrete example, season penta can be included Tetrol four (methyl) acrylate, four (methyl) acrylate of pentaerythrite (more) alkoxy etc..
(B) compound containing ethylenic unsaturated bond can include and remove (b1)~(b5) addition-polymerizable monomer outside component makees For (b6) component.
As (b6) component, following material can be included：
Except (b3) three (methyl) acrylate outside component, such as trimethylolpropane tris (methyl) acrylate, second Oxygen nitro three (methyl) acrylate, ethoxylation isocyanuric acid three (methyl) acrylate, pentaerythrite three (methyl) Acrylate etc.；
Except (b5) four (methyl) acrylate outside component, such as two trimethylolpropane four (methyl) acrylate, Dipentaerythritol four (methyl) acrylate etc.；Five (methyl) acrylate, such as dipentaerythritol five (methyl) acrylate Deng；
Six (methyl) acrylate, for example, dipentaerythritol six (methyl) acrylate, in 6 ends of dipentaerythritol Addition amounts to six (methyl) acrylate, the 6 terminal additions total in dipentaerythritol that 1~24 moles of ethylene oxide forms Six (methyl) acrylate that 1~10 mole of 6-caprolactone forms etc.；
Acrylate compounds with 1 (methyl) acryloyl group；
Make polyalcohol and compound obtained from alpha, beta-unsaturated carboxylic acid reaction；
Make containing glycidyl compound and compound obtained from alpha, beta-unsaturated carboxylic acid reaction；And
Phthalic acid based compound, such as γ-chloro- 2- hydroxy propyl-Betas '-(methyl) acryloyl-oxyethyl-O-phthalic Acid esters and beta-hydroxy alkyl-β '-(methyl) acryloxyalkyl-phthalic acid ester etc..
In this 4th embodiment, from the viewpoint of the Fusion Edges of photoresist layered product and adaptation, sense The total content of whole (B) compound containing ethylenic unsaturated bond in photosensitive resin composition be preferably the mass % of 1 mass %~70, In the range of the mass % of the mass % of more preferably 2 mass %~60, more preferably 4 mass %~50.
[(C) Photoepolymerizationinitiater initiater]
(C) component is the component that the free radical that foregoing (B) component can be triggered to polymerize is produced by the irradiation of light.
As this (C) component, such as aromatic ketone compound, naphtoquinone compounds, benzoin ether compound, benzene can be used Acyloin com, benzil compound, six aryl united imidazoles, acridine compounds etc..Among them, from the resolution of height From the viewpoint of rate and good hole covering character, preferably using a kind in six aryl united imidazoles and acridine compounds More than.In addition, from the viewpoint of the sensitivity of photosensitive polymer combination, (C) component preferably comprises acridine compounds.
As above-mentioned six aryl united imidazole, such as 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole bases can be included Dimer, 2,2 ', 5- tri--(Chloro-O-Phenyl) -4- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl-imidazole base dimer, 2, 4- is double-(Chloro-O-Phenyl) -5- (3,4- Dimethoxyphenyls)-diphenyl-imidazole base dimer, 2,4,5- tri--(Chloro-O-Phenyl) - Diphenyl-imidazole base dimer, 2- (Chloro-O-Phenyl)-bis- -4,5- (3,4- Dimethoxyphenyls)-imidazole radicals dimer, 2,2 ' - Double-(2- fluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3- difluoromethyls Phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,4 difluorobenzene base) -4,4 ', 5, 5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,5- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxies Base phenyl)-imidazole radicals dimer, 2,2 '-bis--(2,6- difluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazoles Base dimer, 2,2 '-bis--(2,3,4- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2, 2 '-bis--(2,3,5- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-it is bis--(2,3, 6- trifluorophenyls) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,4,5- trifluoro-benzenes Base) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,4,6- trifluorophenyls) -4,4 ', 5, 5 '-four-(3- methoxyphenyls)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,5- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- Methoxyphenyl)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,6- tetrafluoros phenyl) -4,4 ', 5,5 '-four-(3- methoxybenzenes Base)-imidazole radicals dimer, 2,2 '-bis--(2,3,4,5,6- pentafluorophenyl groups) -4,4 ', 5,5 '-four-(3- methoxyphenyls)-miaow Oxazolyl dimer etc..
In addition, as above-mentioned acridine compounds, such as can include：
Double (9- acridinyls) hexanes of acridine, 9- phenylacridines, 1,6-, double (9- acridinyls) heptane of 1,7-, double (the 9- a word used for translations of 1,8- Piperidinyl) octane, double (9- acridinyls) nonanes of 1,9-, double (9- acridinyls) decane of 1,10-, double (9- acridinyls) hendecanes of 1,11-, Double (9- acridinyls) dodecanes of 1,12- etc..
The content of (C) component in the photosensitive polymer combination of this 4th embodiment is preferably the matter of 0.1 mass %~2 Measure the model of %, the more preferably mass % of the scope of the mass % of 0.2 mass %~1.8, more preferably 0.3 mass %~1.7 Enclose, the particularly preferably mass % of 0.4 mass %~1.6.It is good from obtaining when the content of (C) component is set as this scope Sensitivity and peel property from the viewpoint of be preferable.
From the viewpoint of sensitivity and the raising of resolution ratio, (C) component can further include sensitizer.As this Sensitizer, such as N- aryl amino acids, organohalogen compound, other sensitizers can be included.
Respectively, as above-mentioned N- aryl amino acids, such as can include：
N-phenylglycine, N- Methyl-N-phenyls glycine, N- ethyl, N-phenyl glycine etc.；
As organohalogen compound, such as can include：
Amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, diphenylmethyl bromide, benzyl bromide a-bromotoluene, methylene bromide, tribromo Methyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3- dibromopropyls) ester, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1- Three chloro- 2,2- double (rubigan) ethane, chlorination triaizine compounds etc..
As above-mentioned other sensitizers, such as can include：
2- ethyl hydrazine, octaethyl anthraquinone, 1,2 benzae thracene quinone, 2,3- benzos anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl Anthraquinone, 1- chloroanthraquinones, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl-1,4-naphthaquinones, 2,3- dimethyl anthraquinone, 3- chloro-2-methyl anthracenes The naphtoquinone compounds such as quinone；
Benzophenone, michaelis ketone [4,4 '-bis- (dimethylamino) benzophenone], 4,4 '-bis- (diethylamino) hexichol The aromatic ketone compound such as ketone；
The benzoin ether chemical combination such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethyl benzoin Thing；
Benzil dimethyl ketal, benzil diethyl ketal, 1- phenyl -1,2- pentanedione -2-O- benzoyls oxime, 1- The oxime ester compounds such as phenyl -1,2- pentanediones -2- (O- carbethoxyl groups) oxime；
Deng.
It is quick in this 4th embodiment from the viewpoint of from the fissility of the sensitivity of composition and resist cured film The content of agent is preferably the mass % of the mass % of 0.01 mass %~5, more preferably 0.05 mass %~3, more preferably The mass % of 0.1 mass %~2.
It should be noted that in the photosensitive polymer combination of this 4th embodiment, acridine is used as (C) component Compound and N- aryl amino acids, when they are applied in combination in the range of above-mentioned use ratio, from formed conductive pattern when It is preferable from the viewpoint of etching speed suppression and the suppression poor in length and breadth of wiring width.
[(D) stabilizer]
Photosensitive polymer combination can include stabilizer according to expectation.In this 4th embodiment, improved from resolution ratio From the viewpoint of, as stabilizer, preferably using hindered phenol.In general, hindered phenol refers to, the big phenol of steric hindrance.Photonasty tree Oil/fat composition is comprising the compound shown in the following general formula (V) as hindered phenol：
In formula, R51Represent optionally substituted, straight chained alkyl, branched alkyl, aryl, cyclohexyl, clip divalent linker The straight chained alkyl of group, clip the branched alkyl of divalent linker, clip the cyclohexyl of divalent linker or clip divalence company Meet the aryl of group, and R52、R53And R54Represent independently of one another hydrogen or optionally substituted, straight chained alkyl, branched alkyl, Aryl, cyclohexyl, the straight chained alkyl for clipping divalent linker, the branched alkyl for clipping divalent linker, clip divalence company Connect the cyclohexyl of group or clip the aryl of divalent linker.}.
Compound shown in logical formula (V) is improving the viewpoint of the resolution ratio of photosensitive polymer combination and is suppressing photonasty tree It is excellent in the viewpoint of the sensitivity decrease of oil/fat composition.It should be noted that the compound shown in logical formula (V) will not be 1 There are more than 2 phenolic hydroxyl group, and an ortho position only in two ortho positions of phenolic hydroxyl group has substitution on a aromatic rings Base, has feature in the control of the steric hindrance around phenolic hydroxyl group.Think by for this structure it is above-mentioned excellent to show Different performance.
From the viewpoint for the resolution ratio for improving photosensitive polymer combination and the sensitivity drop of suppression photosensitive polymer combination From the viewpoint of low, the compound shown in logical formula (V) is preferably, the R in formula (V)51、R52、R53And R54In at least 1 tool There is aromatic rings.From the same viewpoint, the hydroxyl concentration of hindered phenol is preferably 0.10mol/100g~0.75mol/100g.Separately Outside, from the same viewpoint, it is preferred that in above-mentioned logical formula (V), R51、R52、R53And R54In at least 1 be straight chain or branch Alkyl group or the aryl for clipping divalent linker, also, preferable alkyl is used as, such as methyl, ethyl, just can be included Propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl group etc., also, preferable divalent linker is used as, such as can Thioether group, substituted or unsubstituted alkylidene etc. are included, moreover, aryl can be substituted by hydroxyl or alkyl.
In addition, from the same viewpoint, as the compound shown in above-mentioned logical formula (V), such as preferably the following general formula (VI) compound shown in compound, the following general formula (VIII) shown in, the compound shown in the following general formula (IX), the following general formula (X) compound shown in：
In formula, R55Represent logical formula (VII), and R56、R57And R58Hydrogen or the following general formula (VII) are represented independently of one another：
[in formula, R59And R60Hydrogen or optionally substituted straight chained alkyl, branched alkyl, aryl, ring are represented independently of one another Hexyl.].}、
In formula, R61And R64Straight or branched alkyl, and R are represented independently of one another62、R63、R65And R66Independently of one another Represent hydrogen or straight or branched alkyl, X1Represent divalent linker.}、
In formula, R67、R70And R73Straight or branched alkyl, and R are represented independently of one another68、R69、R71、R72、R74And R75 Hydrogen or straight chain or branched alkyl, Y are represented independently of one another1Represent the linking group of trivalent.}、
In formula, R76、R79、R82And R85Straight or branched alkyl, and R are represented independently of one another77、R78、R80、R81、R83、 R84、R86And R87Hydrogen or straight chain or branched alkyl, Z are represented independently of one another1Represent the linking group of tetravalence.}.Moreover, make For the X in above-mentioned logical formula (VIII)1, thioether group, substituted or unsubstituted alkylidene etc. can be included.
From the viewpoint for the resolution ratio for improving photosensitive polymer combination and the sensitivity drop of suppression photosensitive polymer combination From the viewpoint of low, lead to the compound shown in formula (V) preferably with about 130~about 1000 molecular weight, more preferably from about 200 ~about 800 molecular weight, further preferably with about 300~about 500 molecular weight, most preferably with about 300~about 400 divide Son amount.It is further preferred, that with about 1.02~about 1.12 proportion or more than about 155 DEG C (for example, more than about 208 DEG C) Fusing point；Alternatively, being slightly solubility for water, and it is ease of solubility in the organic solvents such as methanol, acetone, toluene；Or using When be solid (for example, powder, crystal etc.) or liquid.
As the compound shown in logical formula (V), such as 4 can be included, 4 '-thiobis (the 6- tert-butyl groups-metacresol), 4, 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), styrenated phenol (manufacture of chemical industry Co., Ltd. of Kawaguchi, ANTAGE SP), tribenzyl phenol (manufacture of chemical industry Co., Ltd. of Kawaguchi, TBP, the phenol with 1~3 benzyl) etc..Among these, Due to lead to formula (I) shown in compound content it is more, thus from carry high-resolution viewpoint and suppress photosensitive polymer combination Sensitivity decrease from the viewpoint of preferably 4,4 '-thiobis (the 6- tert-butyl groups-metacresol), 4,4 '-butylidenebis (3- methyl- 6- tert-butyl phenols).
Compound phase shown in above-mentioned logical formula (V) is 0.001 matter for the ratio of the gross mass of photosensitive polymer combination Measure the mass % of %~10.The ratio is more than 0.001 mass % from the viewpoint of resolution ratio is improved, is preferably 0.01 mass % More than, more preferably more than 0.05 mass %, more preferably more than 0.1 mass %, particularly preferably 0.5 mass % with Upper, most preferably more than 0.7 mass %.On the other hand, the ratio is from the improve of the few viewpoint of sensitivity decrease and resolution ratio Viewpoint sets out as below 10 mass %, is preferably below 5 mass %, more preferably below 3 mass %, more preferably 2 matter Measure below %, particularly preferably below 1.5 mass %.
In this 4th embodiment, as hindered phenol, can also further it contain in addition to the compound shown in logical formula (V) Compound.As the compound in addition to the compound shown in logical formula (V), such as 2,6- di-t-butyl -4- first can be included Base phenol, bis--amyl hydroquinones of 2,5-, DBH 2,5 di tert butylhydroquinone, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), Double (the 2- hydroxyl -3- tert-butyl group -5- ethylphenyls) methane, triethylene glycol-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) Propionic ester], 1,6- hexane diols-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], [3- (3,5- of pentaerythrite four Di-tert-butyl-hydroxy phenyl) propionic ester], 2,2- it is thio-di ethylene bis [3- (3,5- di-tert-butyl-hydroxy phenyls) third Acid esters], 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid stearyl, N, N '-hexamethylene bis (3,5- di-t-butyls- 4- hydroxy-hydrocineamides), 3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester, 1,3,5- trimethyls -2,4,6- Three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, three-(3,5- di-tert-butyl-4-hydroxyl benzyls)-isocyanuric acid esters etc..
In this 4th embodiment, relative to the gross mass of photosensitive polymer combination, in photosensitive polymer combination The total content of whole hindered phenols is preferably the mass % of 0.001 mass %~10.
In this 4th embodiment, photosensitive polymer combination can also include the stabilizer in addition to hindered phenol.As Stabilizer in addition to hindered phenol, preferably comprises at least one kind of in the group by following material composition：Radical polymerization suppresses Agent, such as p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, stannous chloride, 2,6- di-t-butyls-right Cresols, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), two Phenyl nitrosamine, triethylene glycol-bis- (the 3-3- tert-butyl group -5- methyl -4- hydroxy-phenylpropionic acids esters) and nitroso phenylhydroxylamine Aluminium salt etc.；Benzotriazole, such as 1,2,3- benzotriazole, 1- chloro- 1,2,3- benzotriazole, double (N-2- ethylhexyls) amino Methylene-l, 2,3 triazole, double (N-2- ethylhexyls) aminomethylene -1,2,3- tolyl-triazoles, (2- bis- is just pungent by 1- Base amino methyl)-benzotriazole and double (N-2- hydroxyethyls) aminomethylene-l, 2,3 triazoles etc.；Carboxyl benzo three Azole, such as 4- carboxyls -1,2,3- benzotriazole, 5- carboxyls -1,2,3- benzotriazole, 6- carboxyls -1,2,3- benzotriazole, 1- (2- di-n-butyls amino methyl) -5- carboxyl benzotriazoles and 1- (2- di-n-butyls amino methyl) -6- carboxyl benzotriazoles 1：1 mixture, N- (bis- -2- ethylhexyls of N, N-) aminomethylene carboxyl benzotriazole, N- (bis- -2- hydroxyethyls of N, N-) ammonia Methylene carboxyl benzotriazole and N- (bis- -2- ethylhexyls of N, N-) aminoethylene carboxyl benzotriazole etc.；And with contracting The glyceryl oxirane compounds of water, such as neopentylglycol diglycidyl ether (for example, Kyoeisha Chemical Co., Ltd.'s manufacture Epolight1500NP), nine ethylene glycol diglycidylethers (such as Kyoeisha Chemical Co., Ltd. manufacture Epolight400E), 2 moles of addition product diglycidyl ethers of bisphenol-A-propylene oxide are (for example, Kyoeisha Chemical Co., Ltd.'s system The Epolight3002 made), hydrogenated bisphenol A diglycidyl ether (for example, Kyoeisha Chemical Co., Ltd. manufacture Epolight4000), 1,6- hexane diols diglycidyl ether is (for example, what Kyoeisha Chemical Co., Ltd. manufactured Epolight1600) etc..
In this 4th embodiment, the total content of whole stabilizers in photosensitive polymer combination is preferably 0.001 matter Measure the mass %'s of the mass %, more preferably 0.05 mass % of the mass % of %~3, more preferably 0.01 mass %~1~0.7 In the range of.The total content of stabilizer is preferably from the viewpoint of good storage stability is assigned to photosensitive polymer combination More than 0.001 mass %, is preferably below 3 mass % from the viewpoint of the sensitivity for maintaining photo-sensitive resin.
[other components]
The photosensitive polymer combination of this 4th embodiment can be with addition to (A)~(D) components of described above Contain other components.As this other components, for example, can include leuco dye, basic-dyeable fibre, plasticizer, antioxidant, Radical polymerization inhibitor, solvent etc..
[leuco dye]
Above-mentioned leuco dye can in order to assign suitable colour rendering and excellent peel property to resist cured film and It is compounded in the photosensitive polymer combination of this 4th embodiment.
As the concrete example of leuco dye, such as leuco crystal violet (three [4- (dimethylamino) phenyl] first can be included Alkane), double (to the dimethylaminophenyl) -6- dimethylaminos phthalides of 3,3-, 3- (4- diethylaminos phenyl) -3- (1- ethyls - 2 methyl indole -3- bases) phthalide, 3- (4- diethylamino -2- ethoxyl phenenyls) -3- (1- Ethyl-2-Methyl indoles -3- Base) -4- azepines phthalide, 1,3- dimethyl -6- diethylaminos fluorane, the chloro- 3- methyl -6- dimethylaminos fluoranes of 2-, 3- bis- Butylamino -6- methyl -7- anilino fluoranes, 3- diethylamino -6- methyl -7- anilino fluoranes, 3- diethylaminos -6- Methyl -7- diformazans are for phenylamino fluorane, 2- (2- chloroanilinos) -6- dibutylamino fluorans, 3,6- dimethoxys fluorane, 3,6- bis- N-butoxy fluorane, 1,2- benzo -6- diethylaminos fluorane, 1,2- benzo -6- dibutylamino fluorans, 1,2- benzos -6- Ethyl isoamylamino fluorane, 2- methyl -6- (N- is to toluene-N- ethylaminos) fluorane, 2- (N- benzyl-N-methyls) - 6- (N- is to toluene-N- ethylaminos) fluorane, 2- (3 '-trifluoromethylbenzene amido) -6- diethylaminos fluorane, the chloro- 6- rings of 3- Hexylamino fluorane, 2- methyl -6- Cyclohexylaminos fluorane, 3- methoxyl group -4- dodecyloxy styryl quinoline etc..They Among, preferred leuco crystal violet.
The content of leuco dye in the photosensitive polymer combination of this 4th embodiment be preferably 0.6 mass %~ 1.6 mass %, more preferably the mass % of 0.7 mass %~1.2.By the way that the use ratio of leuco dye is set as the scope, It can realize good colour rendering and good fissility.
[basic-dyeable fibre]
As above-mentioned basic-dyeable fibre, for example, can include Viride Nitens 1 [CAS number (similarly hereinafter)：633-03-4] (for example, Aizen Diamond Green GH, trade name, Baotugu Chemical Industrial Co., Ltd manufacture), malachite green oxalates [2437-29-8] (such as Aizen Malachite Green, trade name, Baotugu Chemical Industrial Co., Ltd's manufacture), brilliant green [633-03-4], pinkish red [632-99-5], crystal violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62- 9], methyl green [82-94-0], victoria blue B [2580-56-5], Blue 7 [2390-60-5] are (for example, Aizen Victoria Pure Blue BOH, trade name, Baotugu Chemical Industrial Co., Ltd manufacture), rhodamine B [81-88-9], sieve Red bright 6G [989-38-8], basic yellow 2 [2465-27-2], diamond green etc..Among them, Viride Nitens 1, malachite are preferably selected from More than a kind in greenweed hydrochlorate, Blue 7 and diamond green, from the viewpoint of form and aspect stability and exposure contrast, especially It is preferred that Viride Nitens 1.
The content of basic-dyeable fibre in the photosensitive polymer combination of this 4th embodiment be preferably 0.001 mass %~ The mass %'s of 3 mass %, the more preferably scope of the mass % of 0.01 mass %~2, more preferably 0.01 mass %~1.2 Scope.By using the use ratio of the scope, good colour rendering and high sensitivity can be taken into account.
[solvent]
The photosensitive polymer combination of this 4th embodiment can be above-mentioned (A)~(C) component and optionally employ The mixture of other components, or can also be to add appropriate solvent in these components and be formed photosensitive resin composition The form of thing seasoning liquid uses.
As solvent used herein, such as the ketone compounds such as methyl ethyl ketone (MEK) can be included；Ethanol, ethanol and isopropyl The alcohol such as alcohol；Deng.
Use ratio as solvent, it is preferred to use can make viscosity of the photosensitive polymer combination seasoning liquid at 25 DEG C be The ratio of 500~4000mPa seconds.
＜ photosensitive elements ＞
In this 4th embodiment, photosensitive element is the photoresist that will be formed by above-mentioned photosensitive polymer combination The layered product (photoresist layered product) that layer stackup forms on supporter.As needed, can also be in photosensitive tree Lipid layer has protective layer with the surface of supporter opposite side.
[supporter]
As supporter, the preferably transparent base through the light from exposure light source radiation.As this supporter, such as can Include pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, poly- It is vinylidene chloride film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, polystyrene film, poly- Acrylonitrile film, styrol copolymer film, polyamide film, cellulose derivative film etc..As these films, according to need Will, the film of drawn can also be used.
The mist degree of supporter is preferably less than 5.
It is favourable in terms of image formative and economy during the thinner thickness of supporter, but need to maintain intensity.Consider Both, can be preferably used 10 μm~30 μm of supporter.
[photo-sensitive resin]
In the case that the photosensitive polymer combination used in the formation of photo-sensitive resin contains solvent, solvent can be residual Stay in photo-sensitive resin, but preferred solvent has been removed.
The thickness of photo-sensitive resin is preferably 5 μm~100 μm, more preferably 7 μm~60 μm.The thickness is thinner, differentiates Rate more improves, and the thickness is thicker, and film-strength more improves.Therefore, the thickness of said composition layer can be according to purposes in above range Interior appropriate adjustment.
[protective layer]
The key property of protective layer is to be sufficiently smaller than supporter and photo-sensitive resin with the closing force of photo-sensitive resin Closing force, can be easily peeled off.As protective layer, such as polyethylene film, polypropylene film etc. can be preferably used, In addition it is possible to use the film that fissility for example disclosed in Japanese Unexamined Patent Application 59-202457 publications is excellent.
The thickness of protective layer is preferably 10 μm~100 μm, more preferably 10 μm~50 μm.
[manufacture method of photosensitive element]
Photosensitive element can by stack gradually supporter and photo-sensitive resin and protective layer as needed and Manufacture.As the laminating method of supporter, photo-sensitive resin and protective layer, known method can be used.
For example, photosensitive polymer combination is prepared into photosensitive resin combination seasoning liquid, first, applied using rod Machine or roll coater are coated on supporter and make its drying, on supporter formed formed by photosensitive polymer combination it is photosensitive Property resin bed.Then, as needed, protective layer is laminated on the photo-sensitive resin of formation, so as to manufacture photonasty member Part.
The forming method ＞ of ＜ corrosion-resisting patterns
Photosensitive element as described above can be used, corrosion-resisting pattern is formed on substrate.
The forming method of corrosion-resisting pattern preferably includes following process successively：
The lamination process photo-sensitive resin of photosensitive element being layered on conductor substrate；
The exposure process being exposed to the photo-sensitive resin of stacking；And
The developing procedure to develop to the photo-sensitive resin of exposure.
In the forming method of the corrosion-resisting pattern of this 4th embodiment, first, in process is laminated, using laminating machine in base Photo-sensitive resin is formed on plate.Specifically, when photosensitive element has protective layer, after protective layer is peeled off, lamination is used Photo-sensitive resin heating is crimped on substrate surface to be laminated by machine.
As substrate, using metallic plate or the insulative substrate with metal epithelium.As the material of metal, such as can arrange Enumerate copper, stainless steel (SUS), glass, tin indium oxide (ITO) etc..These substrates, which can also have, to be used to tackle multilager base plate Through hole.
Herein, photo-sensitive resin can only be laminated to the single side of substrate surface, can also be laminated to substrate as needed It is two-sided.Heating-up temperature at this time is preferably set to 40 DEG C~160 DEG C.From obtained corrosion-resisting pattern is further improved to the close of substrate From the viewpoint of conjunction property, preferably heating crimping is carried out more than 2 times.When carrying out the crimping of more than 2 times, can use possess bigeminy The sandwich of substrate and photo-sensitive resin, can also be repeated several times by roller to be pressed by the second order segmentation laminating machine of roller Connect.
In addition, in lamination process, the photo-sensitive resin of photosensitive element can be clipped wetting agent and be stacked in conductor base On plate.This is the preferable laminating method from the viewpoint of tracing ability and yield rate is improved.As wetting agent, preferably comprise and be selected from More than a kind in pure water, deionized water and electrolysis water and copper chelator (are selected from by imidazolium compounds, triazole chemical combination More than a kind compound in the group of thing, pyridine compounds and pyrazole compound composition).
Then, in exposure process, photo-sensitive resin is exposed using exposure machine.The exposure can not peel off branch Support body and across the supporter carry out, can also as needed by supporter peel off after carry out.
By carrying out the exposure with pattern-like, after aftermentioned developing procedure, it can obtain that there is the anti-of desired pattern Lose film (corrosion-resisting pattern).The exposure of pattern-like can be by across appointing in the method and maskless exposure that photomask is exposed One method carries out.When photomask is exposed, light exposure is determined by light illumination and time for exposure.Light exposure can make Measured with quantometer.
In maskless exposure, without using photomask, it is exposed on substrate using direct drawing apparatus.As light source, Use the semiconductor laser of wavelength 350nm~410nm, ultrahigh pressure mercury lamp etc..In maskless exposure, depicting pattern passes through computer To control, light exposure is determined by the illumination of exposure light source and the translational speed of substrate.
Then, in developing procedure, develop to exposed photo-sensitive resin.For example, it will be felt using developer solution The unexposed portion of photosensitive resin layer removes.After exposure, in the case of there is supporter on photo-sensitive resin, preferably gone Except afterwards for developing procedure.
In developing procedure, using the developer solution formed by aqueous alkali, unexposed portion is developed and is removed, obtains resist pattern Picture.As aqueous alkali, for example, it is preferable to use Na2CO3、K2CO3Deng aqueous solution.Aqueous alkali is according to photo-sensitive resin Characteristic selects, preferably using the Na of the concentration of the mass % of 0.2 mass %~22CO3Aqueous solution.It can also be mixed in the aqueous alkali Enter surfactant, defoamer, a small amount of organic solvent etc. for promoting development.
The temperature of developer solution in developing procedure is preferably maintained at steady temperature in the range of 20 DEG C~40 DEG C.
Corrosion-resisting pattern is obtained by above-mentioned operation.According to circumstances, 100 DEG C~300 DEG C of heater can further be carried out Sequence.It is suitable from the viewpoint of chemical proofing is further improved to implement the heating process.Heating can use hot wind, The heating furnace of the suitable mode such as infrared ray, far infrared.
The forming method ＞ of ＜ circuit boards
The forming method of the circuit board of this 4th embodiment preferably includes following process successively：
The lamination process photo-sensitive resin of photosensitive element being layered on conductor substrate；
The exposure process being exposed to the photo-sensitive resin of stacking；
The developing procedure to develop to the photo-sensitive resin of exposure；
To being etched by development and the conductor substrate formed with corrosion-resisting pattern or the conductive pattern formation process of plating； And
Peel off the stripping process of corrosion-resisting pattern.
In conductive pattern formation process, it can expose on the substrate formed with corrosion-resisting pattern by developing procedure Substrate surface (such as copper face) form conductive pattern using known etching method or plating method.
In above-mentioned stripping process, the substrate formed with conductive pattern is set to be contacted with appropriate stripper, so that by resist pattern Case, which is peeled off, to be removed.By the process, desired circuit board is obtained.
The stripper used in stripping process is preferably aqueous alkali.As the aqueous alkali, such as preferably using 2 matter Measure the NaOH aqueous solutions or KOH aqueous solutions of the mass % of %~5.In stripper, a small amount of water-soluble solvent, such as alcohol can be added Deng.The temperature of stripper in stripping process is preferably set to 40 DEG C~70 DEG C.
The photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern and circuit of this 4th embodiment The manufacture method of plate can be well suited for such as printed circuit board (PCB), lead frame, the base material with relief pattern, semiconductor packages The manufacture of body etc..
It should be noted that the assay method on above-mentioned various parameters, in case of no particular description, according to rear The assay method in embodiment is stated to measure.
Embodiment
Embodiment and comparative example ＞ involved by ＜ first embodiments
Hereinafter, the photosensitive polymer combination on this first embodiment, is specifically described in the form of embodiment.
(1) measure of raw material physics value
The measure ＞ of ＜ weight average molecular weight
On high molecular weight average molecular weight, the gel permeation chromatography (GPC) manufactured using Japan Spectroscopy Corporation (pump：Gulliver, PU-1580 type, column：Shodex (registration mark) (KF-807, KF- of Showa Denko K. K's manufacture 806M, KF-806M, KF-802.5) 4 pieces series connection, mobile phase solvent：Tetrahydrofuran, using by polystyrene standard sample (Showa The Shodex STANDARD SM-105 of electrician Co., Ltd. manufacture) obtained standard curve), with the shape of polystyrene scaled value Formula is obtained.
＜ acid equivalents ＞
In this specification, acid equivalent refers to, the quality (gram) of the polymer of the carboxyl with 1 equivalent in molecule.Using flat The flat natural pond automatic titration device (COM-555) of natural pond Industry Co., Ltd manufacture is water-soluble by using the sodium hydroxide of 0.1mol/L The potential difference titration of liquid measures acid equivalent.
(2) production method of sample for evaluation and analysis
The making ＞ of ＜ photosensitive elements
Each component shown in table 1 and following each component are mixed, methyl ethyl ketone (MEK) is further added, prepares solid The photosensitive polymer combination of 53 mass % of constituent concentration.
As coloring material, 0.04 mass parts of diamond green；
As leuco dye, 0.6 mass parts of leuco crystal violet；
As halogen compounds, 0.7 mass parts of trisbromomethyl phenyl sulfone；
As plasticizer, 2 mass parts of para toluene sulfonamide；
As benzotriazole, 0.05 mass parts of carboxyl benzotriazole；
As benzotriazole, 0.15 mass parts of 1- (2- di-n-octyls amino methyl)-benzotriazole；
As antioxidant, hydrogenated bisphenol A diglycidyl ether (common prosperity society chemistry, Epolight4000) 0.05 mass Part；And
As radical polymerization inhibitor, three (nitroso phenylhydroxylamine) aluminium, 0.004 mass parts.
Each numeral into subfield in table 1 is the amount (mass parts) of each component prepared for composition.
Obtained photosensitive polymer combination is spread evenly across using bar coater and is used as 16 μm of the thickness of supporter On pet film (R310, the haze value 2.1% of Mitsubishi Plastics Inc's manufacture), then, adjusting Temperature forms the photosensitive resin composition of 25 μm of thickness to carry out 2.5 minutes heat dryings in 95 DEG C of drying machine on supporter Nitride layer.
Then, pasted on the face with supporter opposite side of above-mentioned photosensitive polymer combination layer as protective layer The polyethylene film (GF-18 of Tamapoly Co., Ltd.s manufacture) that 19 μm of thickness, so as to obtain photosensitive element.
The substrate ＞ used in ＜ evaluations
Respectively, the substrate as hole covering character evaluation, uses the thickness 1.6mm's in the copper foil for being laminated with 35 μm of thickness The substrate of through hole formed with 1008 diameter 6mm on copper-clad laminated substrate；
As the evaluation substrate in addition to hole covering character, covered using the thickness 0.4mm for the copper foil for being laminated with 18 μm of thickness Layers of copper laminated substrate.
The substrate of hole covering character evaluation by using the surface treatment of injecting type frosted grinder after surface adjustment is carried out For evaluation.
The substrate of evaluation beyond hole covering character carry out successively using soft etching agent (water chestnut river Chemical Co., Ltd. manufacture, CPE-900 10 mass %H of surface treatment and utilization)2SO4The surface clean of aqueous solution is carried out after the adjustment of surface for evaluation.
＜ is laminated ＞
On substrate after being adjusted on surface, while peeling off the poly- second of the photosensitive element obtained by each embodiment or comparative example Alkene film, while using hot roll laminator (Asahi Kasei Corporation's manufacture, AL-70) with 105 DEG C of roll temperature, air pressure The condition of 0.35MPa and laminate speed 1.5m/min are laminated.
＜ exposes ＞
Use direct rendering style exposure device (Orbotech Ltd. manufactures, Paragon Ultra 200, dominant wavelength 355nm), it is exposed by direct rendering style exposure method.
On exposing patterns, behind illustrate in the item of each assessment item.
＜ developments ＞
From after exposure photosensitive polymer combination layer peel off supporter after, using alkali development machine (FUJI KIKOU CO., LTD. manufacture, dry film developing machine), with 1 mass %Na of 30 DEG C of 2 times of the time spraying of minimum developing time2CO3Aqueous solution, The unexposed portion of photosensitive polymer combination layer is dissolved and is removed.After development, with 1.5 times of time pure water of developing time Cleaned, carried out carrying out warm air drying after removing water process with air knife, so as to obtain the substrate with evaluation cured film.
Above-mentioned minimum developing time refers to, is removed until the unexposed portion of photosensitive polymer combination layer is dissolved completely Untill the required minimum time.
The evaluation ＞ of ＜ sensitivity
In the evaluation of sensitivity, the laminated substrate being laminated in above-mentioned ＜ after ＞ after 15 minutes is used.
For the laminated substrate, after the mask pattern of 10 lines of line/interval=40 μm/40 μm directly is described exposure, Developed by the above-mentioned ＜ methods developed described in ＞.The against corrosion of obtained corrosion-resisting pattern is measured by light microscope Agent top width, according to following benchmark evaluation sensitivity.
The light exposure that resist top width reaches 39.0 μm is below 28mJ：Sensitivity " zero (good) "
Resist top width reaches 39.0 μm of light exposure more than 28mJ：Sensitivity " × (bad) "
Herein, the 5th article of line, the end away from length direction from end being set among 10 bars of lines that locate of resist line The position of portion about 5mm, the average value of 3 measure is used as measured value.In the end of pattern and central portion, because of developer solution and clear The influence of the diffusion of wash water and line width is different, there are the tendency that attenuates of resist line of end side.
Light exposure in following assessment item as described in the evaluation ＞ of above-mentioned ＜ sensitivity using for line/ Resist top width reaches 39.0 μm of light exposure for=40 μm/40 μm of mask pattern.
The evaluation ＞ of ＜ resolution ratio
The laminated substrate after 15 minutes after above-mentioned ＜ is laminated ＞ is used in the evaluation of resolution ratio.
For the laminated substrate, after the pattern of line/interval=1/1 of various sizes directly is described exposure, by above-mentioned Method described in ＜ developments ＞ is developed.
For obtained pattern, the minimum pattern width formed with light microscope observation, according to following base Quasi- evaluation resolution ratio.
Minimum pattern width is less than 20 μm of situation：Resolution ratio " zero (good) "
Minimum pattern width is more than 20 μm and is less than 24 μm of situation：Resolution ratio " △ (can with) "
Situation of the minimum pattern width more than 24 μm：Resolution ratio " × (bad) "
＜ adaptations ＞
The laminated substrate after 15 minutes after above-mentioned ＜ is laminated ＞ is used in the evaluation of adaptation.
For the laminated substrate, after the pattern of the independent lines of various sizes directly is described exposure, developed by above-mentioned ＜ Method described in ＞ is developed.
Obtained pattern is observed with light microscope, according to following benchmark evaluation adaptation.
The minimum pattern width normally formed is less than 18 μm of situation：Adaptation " zero (good) "
The minimum pattern width normally formed is more than 18 μm and is less than 22 μm of situation：Adaptation " △ (can with) "
The minimum pattern width normally formed is more than 22 μm：Adaptation " × (bad) "
Herein, the situation that line pattern does not normally form refers to, situation which collapses, the line pattern are cranky The situation of the line pattern is not present in situation or substrate.
＜ hole covering characters ＞
The evaluation of hole covering character passes through the laminated substrate after observing the above-mentioned ＜ laminations ＞ obtained using the substrate with through hole Come carry out.
Measurement is formed in the hole count of photosensitive polymer combination layer (cap bore film) rupture on through hole, calculates relative to whole The ratio (cap bore film rupture rate) in hole, according to following benchmark evaluation.
Situation of the cap bore film rupture rate less than 0.1%：Hole covering character " ◎ (extremely good) "
Cap bore film rupture rate is more than 0.1% and the situation less than 2%：Hole covering character " zero (good) "
Cap bore film rupture rate is more than 2% situation：Hole covering character " × (bad) "
＜ etching speeds (wiring bottom width) ＞
The evaluation of etching speed (wiring bottom width) uses the lamination base after above-mentioned ＜ laminations ＞ laggard mistakes 15 minutes Plate.
For laminated substrate, exposure is directly described into line/interval=50 μm/30 μm and the pattern with 10 lines.Expose oneself Light rise after 15 minutes, from photosensitive polymer combination layer peel off supporter, using alkali development machine (FUJI KIKOU CO., LTD. manufacture, dry film developing machine), with 1 mass %Na of 30 DEG C of 2 times of the time spraying of minimum developing time2CO3Aqueous solution, The unexposed portion of photosensitive polymer combination layer is dissolved and is removed.After development, with 1.5 times of time pure water of developing time Cleaned.
Then, by the substrate after the washing with the line/intermittent pattern without dry ground with by line/interval of the substrate Towards the mode for being set to (MD) orthogonal with conveying direction be directed into copper chloride Etaching device (Tokyo Chemical Machinery Co., Ltd.'s manufacture, NLE-2000), with 3.2 moles/L of concentration of hydrochloric acid, 2.0 moles/L of copper chloride concentration, etching atomisation pressure 0.2MPa and etching solution The condition of temperature 50 C, with linear velocity 2.0m/ minutes etch within 55 seconds.
After above-mentioned etching, as the NaOH aqueous solutions of 3.0 mass % of stripper concentration, by substrate under temperature 50 C On cured film peel off and remove, the bottom with the wiring pattern in the MD directions of the thus obtained copper wire of optics measurement microscope is wide Degree.
Herein, locating for the line of wiring pattern is set to the 5th article of line, the end away from length direction from the end of 10 bars of lines The position of portion about 5mm, the average value of 3 measure is used as measured value.In the end of pattern and central portion, by developer solution and clear Difference is influenced caused by the diffusion couple resist of wash water, therefore the line width of final routing is different, there are the wiring width of end side The tendency to attenuate.
The ＞ poor in length and breadth of ＜ wiring widths
The evaluation poor in length and breadth of wiring width uses the laminated substrate being laminated in above-mentioned ＜ after ＞ after 15 minutes.
For laminated substrate, by the pattern of 10 lines of line/interval=50 μm/30 μm along MD directions and TD directions with tile The exposing patterns of shape configuration directly describe exposure.
From exposure after 15 minutes, supporter is peeled off from photosensitive polymer combination layer, uses alkali development machine (FUJI KIKOU CO., LTD. manufacture, dry film developing machine), with 1 mass % of 30 DEG C of 2 times of the time spraying of minimum developing time Na2CO3Aqueous solution, the unexposed portion of photosensitive polymer combination layer is dissolved and is removed.After development, with 1.5 times of developing time Time cleaned with pure water.
Then, by the substrate after the washing with the line/intermittent pattern without dry ground with by line/interval of the substrate Copper chloride vacuum etch device (FUJI KIKOU CO., LTD. are directed into towards the mode for being set to (MD) orthogonal with conveying direction Manufacture, input port width 750mm, slot length 2.6m), with 14 row (pipe arrangement interval about 18cm), every 1 on etching solution pipe arrangement MD directions 14 on spray nozzle number TD directions on root pipe arrangement (gap nozzle, injection direction parallel to TD directions, nozzle pitch about 14cm, with the distance about 5cm of substrate), without friction, 2.85 moles/L of concentration of hydrochloric acid, 2.0 moles/L of copper chloride concentration, etching spray The condition of mist pressure 0.3MPa, vacuum pressure 0.15MPa and 48 DEG C of etching solution temperature, carried out 71 seconds with linear velocity 2.2m/ minutes Etching.
After above-mentioned etching, as the NaOH aqueous solutions of 3.0 mass % of stripper concentration, by substrate under temperature 50 C On cured film peel off remove and obtain MD directions, TD directions 2 groups of copper line pattern, optics measurement microscope bottom is used to it Portion's width.
Herein, locating for the line of wiring pattern is set to the 5th article of line, the end away from length direction from the end of 10 bars of lines The position of portion about 5mm, the average value of 3 measured values is used as measured value.In the end of pattern and central portion, by developer solution, Difference is influenced caused by the diffusion couple resist of ejected wash water, therefore the line width of final routing is different, there are the cloth line width of end side Spend the tendency to attenuate.
In addition, the poor in length and breadth of wiring width is calculated with following numerical expressions, according to following benchmark evaluation.
Poor in length and breadth (μm)=TD-MD of wiring width
Wiring width it is poor in length and breadth be less than 1 μm situation：It is poor in length and breadth " ◎ (extremely good) " to connect up bottom width
Wiring width it is poor in length and breadth more than 1 μm and be less than 2 μm of situation：It is poor in length and breadth " zero (good) " to connect up bottom width
Wiring width it is poor in length and breadth more than 2 μm and be less than 4 μm of situation：It is poor in length and breadth " △ (can with) " to connect up bottom width
The situation more than 4 μm poor in length and breadth of wiring width：It is poor in length and breadth " × (bad) " to connect up bottom width
Embodiment 1~23 and comparative example 1~8
Respectively, the composition of the photosensitive polymer combination used in embodiment and comparative example is shown in table 1,
The details of each component name described in by table 1 are shown in table 2.The compounding amount of each component in table 1 is solid constituent The mass parts of conversion.
The evaluation result carried out using each composition is shown in table 1 in the lump.
2. component details of table (totally 2 in the 1st)
(table 2 is not complete)
2. component details of table the 2nd in totally 2
Embodiment and comparative example ＞ involved by ＜ second embodiments
Hereinafter, the photosensitive polymer combination on this second embodiment, is specifically described in the form of embodiment.
(1) measure of raw material physics value
＜ acid equivalents ＞
Acid equivalent refers to, the high molecular quality of alkali solubility of the carboxyl wherein with 1 equivalent.The measure of acid equivalent uses Automatic titration device (such as the flat natural pond automatic titration device (COM-555) of Ping Zhao Industry Co., Ltd manufacture uses 0.1mol/L Sodium hydrate aqueous solution carried out by potential difference titration.
The measure ＞ of ＜ weight average molecular weight
On high molecular weight average molecular weight, the gel permeation chromatography (GPC) manufactured using Japan Spectroscopy Corporation (pump：Gulliver, PU-1580 type, column：Shodex (registration mark) (KF-807, KF- of Showa Denko K. K's manufacture 806M, KF-806M, KF-802.5) 4 pieces series connection, mobile phase solvent：Tetrahydrofuran, using by polystyrene standard sample (Showa The Shodex STANDARD SM-105 of electrician Co., Ltd. manufacture) obtained standard curve), with the shape of polystyrene scaled value Formula is obtained.
(2) production method of sample for evaluation
The making ＞ of ＜ photosensitive elements
Each component shown in table 3 is mixed, methyl ethyl ketone (MEK) is further added, prepares 55 matter of solid component concentration Measure the photosensitive polymer combination of %.
Obtained photosensitive polymer combination is spread evenly across using bar coater and is used as 16 μm of the thickness of supporter It is dry to 95 DEG C in temperature adjustment after on pet film (Di Ren DuPont Films Co., Ltd. manufacture, GR-16) 4 minutes heat dryings are carried out in dry machine, the photo-sensitive resin of 33 μm of thickness is formed on supporter.
Then, the thickness 19 as protective layer is pasted on the face with supporter opposite side of above-mentioned photo-sensitive resin μm the polyethylene film GF-18 of manufacture (Tamapoly Co., Ltd.s), so as to obtain photosensitive element.
The substrate ＞ used in ＜ evaluations
As evaluation substrate, lead to using by the surface for being laminated with the copper-clad laminated board of the 1.6mm thickness of 35 μm of rolled copper foils Cross the grinding of wet type polishing roll and carry out substrate obtained from the adjustment of surface.The think of that grinding is manufactured using 3M companies is high (registration mark) HD#600 is carried out by 2 times.
＜ is laminated ＞
Adjust and be preheated on 60 DEG C of substrate carrying out surface, while peeling off what is obtained by each embodiment or comparative example The polyethylene film of photosensitive element, while using hot roll laminator (Asahi Kasei Corporation's manufacture, AL-70) with roll temperature It is laminated under conditions of 105 DEG C, air pressure 0.35MPa and laminate speed 1.5m/min.
＜ exposes ＞
Utilize directly description exposure machine (Hitachi Via Mechanics Co., Ltd. manufacture, DE-1DH, light source：GaN Royal purple diode, 405 ± 5nm of dominant wavelength), use Stouffer41 grades of stage exposure meters or the mask of defined DI exposures Pattern, in illumination 80mW/cm2Under conditions of, with equivalent to obtaining 14 grades of exposure in Stouffer41 grades of stage exposure meters Light quantity is exposed.
＜ developments ＞
After the photo-sensitive resin after exposure peels off supporter, alkali development machine (FUJI KIKOU CO., LTD. systems are used Make, dry film developing machine), with 1 mass %Na of 30 DEG C of 2 times of the time spraying of minimum developing time2CO3Aqueous solution, will be photosensitive Property resin bed unexposed portion dissolving remove.After development, 1.5 times of the time of developed time is cleaned with pure water, profit Carried out with air knife after removing water process, warm air drying is carried out, so as to obtain the substrate with evaluation cured film.
Minimum developing time refers to, required for untill the unexposed portion of photo-sensitive resin is dissolved removal completely The minimum time.
＜ etches ＞
For by the evaluation substrate formed with corrosion-resisting pattern that develops, using (the Tokyo chemical industry machine strain of copper chloride Etaching device The manufacture of formula commercial firm, copper chloride Etaching device), chlorination copper etchant solution (copper chloride concentration 250g/L, HCl concentration of 50 DEG C of spraying 3mol/L) 60 seconds, so that not dissolved by the copper foil of the part of corrosion-resisting pattern covering on copper-clad laminated board be removed.
＜ peels off ＞
For the evaluation substrate after etching, spraying is heated up to the sodium hydrate aqueous solution of 50 DEG C of 3 mass %, so that will Cured resist is peeled off.
(3) evaluation method
(i) aggregation that develops is tested
By 50 μm of thickness, the area 0.6m in optical polymerism resin layered product2Photosensitive layer (resist layer) be dissolved in 200ml 1 mass %Na2CO3Aqueous solution, using circulating spraying device with atomisation pressure 0.1MPa carry out 3 it is small when spray.Then, will Developer solution is placed 1 day, observes the generation of aggregation.When aggregation largely produces, observed in the bottom of spraying device and side Powder or grease.In addition, aggregation also floats in developer solution sometimes.The good composition of developer solution aggregation completely will not This aggregation is produced, alternatively, even if it is also denier to produce, can simply be washed off by washing.Observation is poly- by visual observation Collect the generation state of thing, as described below divided rank.
◎ (significantly good)：Aggregation is not produced completely.
Zero (good)：Aggregation is not present in the bottom of spraying device or side, observing in developer solution can be visually true The floating of the aggregation for the denier recognized, but be simply washed off during washing.
△ (can with)：The adrift aggregation in a part and developer solution for the bottom of spraying device or side.Even if water Wash, whole aggregations can not also be washed off.
× (bad)：In spraying device whole observation to aggregation and in developer solution adrift aggregation.Even if washing, Whole aggregations can not be washed off, its majority residual.
(ii) sensitivity test
It is laminated and is exposed by the above method using the photosensitive element obtained in each embodiment and comparative example, according to Remaining series after each light exposure and development, is investigated equivalent to obtaining 14 grades of exposure in Stouffer41 grades of stage exposure meters Light quantity (mJ/cm2, 14/41ST light exposures), according to following benchmark evaluation.
Sensitivity " 〇 " (good)：14/41ST light exposures are 25mJ/cm2Following situation
Sensitivity "×" (bad)：14/41ST light exposures are more than 25mJ/cm2Situation
(iii) resolution ratio is tested
Using the photosensitive element obtained in each embodiment and comparative example, after being laminated according to the method described above, by 15 Minute, using thus obtained sample, line/interval is set as 1/1, and then carry out directly describing exposure according to the method described above. Then, develop according to the method described above.
And then the minimum mask linewidths for having normally formed and having cured resist line are investigated, evaluated according to following benchmark.
Resolution ratio " 〇 " (good)：Situation of the minimum feature less than 25 μm
Resolution ratio " △ " (can with)：Minimum feature is more than 25 μm and the situation less than 30 μm
Resolution ratio "×" (bad)：Minimum feature is more than 30 μm of situation
(iv) fitness test
After being laminated according to the method described above using the photosensitive element obtained in each embodiment and comparative example, by 15 points Clock, using thus obtained sample, carries out directly describing exposure according to the method described above.Then, develop according to the method described above.
And then when being set to line/interval=X/200, as X, the minimum mask linewidths normally formed are investigated, according to following Benchmark evaluation.
Adaptation " 〇 " (good)：Situation of the minimum feature less than 25 μm
Adaptation " △ " (can with)：Minimum feature is more than 25 μm and the situation less than 30 μm
Adaptation "×" (bad)：Minimum feature is more than 30 μm of situation
Embodiment 1~6 and comparative example 1~5
The composition of the photosensitive polymer combination used in embodiment and comparative example is shown in table 3, and will be each in table 3 The details of component name are shown in table 4.The compounding amount of each component in table 4 is the mass parts of solid constituent conversion.
The evaluation result carried out using each composition is also depicted in table 4.
The details of 4. component of table
Embodiment and comparative example ＞ involved by the 3rd embodiments of ＜
Hereinafter, for the photosensitive polymer combination of this 3rd embodiment, specifically described in the form of embodiment.
Illustrate measure and the making side of embodiment and the sample for evaluation of comparative example of the physics value of macromolecule and monomer Method, then, shows evaluation method and its evaluation result for obtained sample.
(1) measure of physics value or calculating
The measure ＞ of the high molecular weight average molecular weight of ＜ or number-average molecular weight
On high molecular weight average molecular weight or number-average molecular weight, the gel infiltration manufactured using Japan Spectroscopy Corporation Chromatography (GPC) (pump：Gulliver, PU-1580 type, column：Shodex (registration mark) (KF- of Showa Denko K. K's manufacture 807th, KF-806M, KF-806M, KF-802.5) 4 pieces series connection, mobile phase solvent：Tetrahydrofuran, using by polystyrene standard sample The standard curve that the product Shodex STANDARD SM-105 of manufacture (Showa Denko K. K) obtain), changed with polystyrene The form of calculation value is obtained.
And then high molecular dispersion degree is as the ratio of weight average molecular weight and number-average molecular weight (the equal molecule of weight average molecular weight/number Amount) and calculate.
＜ acid equivalents ＞
In this specification, acid equivalent refers to, the quality (gram) of the polymer of the carboxyl with 1 equivalent in molecule.Using flat The flat natural pond automatic titration device (COM-555) of natural pond Industry Co., Ltd manufacture, is led to using the sodium hydrate aqueous solution of 0.1mol/L Overpotential difference titration measuring acid equivalent.
(2) production method of sample for evaluation
Embodiment 1~12 and the sample for evaluation of comparative example 1~5 are made as described below.
The making ＞ of ＜ photoresist layered products
By component (wherein, compounding amount (matter of the digital representation of each component as solid constituent shown in table 5 below or 6 Amount part)) and solvent be sufficiently stirred and mix, obtain photosensitive polymer combination seasoning liquid.By in table 5 and 6 by writing a Chinese character in simplified form expression The title of component is shown in table 7 below.Pet film (the Mitsubishi tree of 16 μ m-thicks is used as support film The manufacture of fat Co., Ltd., R310-16B), the seasoning liquid is uniformly coated to its surface using bar coater, in 95 DEG C of drying Drying in 3 minutes is carried out in machine, forms photosensitive polymer combination layer.The dry thickness of photosensitive polymer combination layer is 30 μm.
Then, on the surface of the side for not being laminated pet film of photosensitive polymer combination layer On, the polyethylene film (manufacture of Tamapoly Co., Ltd.s, GF-818) for pasting 19 μ m-thicks is used as protective layer, obtains photosensitive Property laminated resin body.
＜ substrate surfaces arrange ＞
Using abrasive material (Japan Carlit Co., Ltd.s manufacture, サ Network ラ Application ダ system R (registration mark #220)), for The copper-clad laminated board for being laminated with the 0.4mm thickness of 35 μm of rolled copper foils carries out injection frosted grinding under atomisation pressure 0.2MPa, from And make evaluation substrate.
＜ is laminated ＞
While the polyethylene film of photoresist layered product is peeled off, while adjusting having carried out surface and being preheated to 60 DEG C copper-clad laminated board on hot roll laminator (Asahi Kasei Corporation manufactures, AL-700) in 105 DEG C of lower floor's pressure sensitivity of roll temperature Photosensitive resin layer stack, obtains test film.Air pressure is set to 0.35MPa, and laminate speed is set to 1.5m/ minutes.
＜ exposes ＞
With direct rendering style exposure device (Via Mechanics Co., Ltd. manufacture, DE-1DH, dominant wavelength 405nm) with 15mJ/cm2Light exposure be exposed.
＜ developments ＞
After photoresist layered product peels off pet film, using FUJI KIKOU CO., LTD. the developing apparatus manufactured, with complete tapered nozzle under the atomisation pressure 0.15MPa that develops by 30 DEG C of 1 mass %Na2CO3 Aqueous solution sprays the stipulated time to develop, and the unexposed portion of photo-sensitive resin is dissolved and is removed.At this time, measure does not expose The photo-sensitive resin of light part is completely dissolved the required minimum time as minimum developing time, with minimum developing time 2 times of time develops, and makes corrosion-resisting pattern.At this time, the nozzle of washing step platypelloid type is in washing atomisation pressure The processing with developing procedure same time is carried out under 0.15MPa.
(3) evaluation method of sample
＜ hole covering characters ＞
For the double-sided copper-clad laminated board of the 0.6mm thickness of the through hole with width 2.0mm × length 15mm, jet douche is used (jet scrubbing) formula grinder is surface-treated.The method illustrated in ＞ is laminated in two-sided carry out layer by above-mentioned ＜ Pressure, will be two-sided with direct rendering style exposure device (Via Mechanics Co., Ltd.s manufacture, DE-1DH, dominant wavelength 405nm) Whole face exposes.By above-mentioned ＜ develop the method that illustrates in ＞ carried out development when, measure the cap bore number of rupture, calculate relative to The rupture rate of whole cap bore, according to following benchmark divided rank.
◎ ◎ (optimal)：Film rupture rate after development is less than 2%.
◎ (extremely good)：Film rupture rate after development more than 2% and is less than 4%.
Zero (good)：Film rupture rate after development more than 4% and is less than 10%.
× (bad)：Film rupture rate after development is more than 10%.
＜ contact angles (water residual short trouble inhibition) ＞
In the evaluation of contact angle (water residual short trouble inhibition), by above-mentioned ＜ be laminated the method illustrated in ＞ into After row lamination, the method illustrated in ＞ is exposed by above-mentioned ＜ and carries out whole face development, then by illustrating in above-mentioned ＜ developments ＞ Method develop.
After development, by measure of the sample for contact angle within 30 minutes.
Sessile drop method of the measure of contact angle according to JIS R3257, the optical microphotograph mirror contact angle manufactured using Nic companies Count " LSE-B100 ", after the pure water of 0.5 μ L is added dropwise in cured film in the environment of 23 DEG C of temperature, humidity 50RH%, start to connect The measure of feeler, using the value after 120 seconds, according to following benchmark divided rank.When the value of contact angle is big, represent to cure against corrosion The hydrophobicity of agent is high, can suppress water residual short trouble.
◎ (extremely good)：Contact angle is more than 35 °.
Zero (good)：Contact angle is for more than 30 ° and less than 35 °.
△ (allows)：Contact angle is for more than 25 ° and less than 30 °.
× (bad)：Contact angle is less than 25 °.
(4) evaluation result
The evaluation result of embodiment 1~12 is shown in table 5 below, and the evaluation result of comparative example 1~5 is shown in following Table 6.
Table 7
Embodiment and comparative example ＞ involved by the 4th embodiments of ＜
Hereinafter, for the photosensitive polymer combination of this 4th embodiment, specifically described in the form of embodiment.
(1) measure of raw material physics value
The measure ＞ of ＜ weight average molecular weight
On high molecular weight average molecular weight, the gel permeation chromatography (GPC) manufactured using Japan Spectroscopy Corporation (pump：Gulliver, PU-1580 type, column：Shodex (registration mark) (KF-807, KF- of Showa Denko K. K's manufacture 806M, KF-806M, KF-802.5) 4 pieces series connection, mobile phase solvent：Tetrahydrofuran, using by polystyrene standard sample (Showa The Shodex STANDARD SM-105 of electrician Co., Ltd. manufacture) obtained standard curve), with the shape of polystyrene scaled value Formula is obtained.
＜ acid equivalents ＞
In this specification, acid equivalent refers to, the quality (gram) of the polymer of the carboxyl with 1 equivalent in molecule.Using flat The flat natural pond automatic titration device (COM-555) of natural pond Industry Co., Ltd manufacture is water-soluble by using the sodium hydroxide of 0.1mol/L The potential difference titration of liquid measures acid equivalent.
(2) production method of sample for evaluation and analysis
The making ＞ of ＜ photosensitive elements
Each component shown in table 8 is mixed, and then additional methyl ethyl ketone (MEK), prepare 56 mass % of solid component concentration Photosensitive polymer combination.Each numeral into subfield in table 8 is the amount (mass parts) of each component prepared for composition.
Obtained photosensitive polymer combination is uniformly coated to 16 μm of the thickness as supporter using bar coater Pet film (Di Ren DuPont Films Co., Ltd. manufacture GR-16, haze value 2.7%) on after, 20 seconds 3 minutes heat dryings are carried out into 95 DEG C of drying machine in temperature adjustment, the photonasty tree of 33 μm of thickness is formed on supporter Lipid layer.
Then, the thickness 19 as protective layer is pasted on the face with supporter opposite side of above-mentioned photo-sensitive resin μm the polyethylene film GF-18 of manufacture (Tamapoly Co., Ltd.s), so as to obtain photosensitive element.
The substrate ＞ used in ＜ evaluations
As evaluation substrate, lead to using by the surface for being laminated with the copper-clad laminated board of the 1.6mm thickness of 35 μm of rolled copper foils Cross the grinding of wet type polishing roll and carry out substrate obtained from the adjustment of surface.The think of that grinding is manufactured using 3M companies is high (registration mark) HD#600 is carried out by 2 times.
＜ is laminated ＞
On substrate after being adjusted on surface, while peeling off the poly- second of the photosensitive element obtained by each embodiment or comparative example Alkene film, while using hot roll laminator (Asahi Kasei Corporation's manufacture, AL-70) in 105 DEG C of roll temperature, air pressure It is laminated under conditions of 1.5m/ points of 0.35MPa and laminate speed.
＜ exposes ＞
Utilize directly description exposure machine (Hitachi Via Mechanics Co., Ltd. manufacture, DE-1AH, light source：GaN Royal purple diode, 405 ± 5nm of dominant wavelength), using the mask pattern of defined DI exposures, in illumination 15mW/cm2Condition Lower exposure.
On exposing patterns and light exposure, behind illustrate in the item of each assessment item.
＜ developments ＞
After the photo-sensitive resin after exposure peels off supporter, alkali development machine (FUJI KIKOU CO., LTD. systems are used Make, dry film developing machine) with 0.8 mass %Na of 29 DEG C of 2 times of the time spraying of minimum developing time2CO3Aqueous solution, will feel The unexposed portion dissolving of photosensitive resin layer removes.After development, cleaned, washed with pure water with the time identical with developing time Afterwards without warm air drying process, and spontaneously dry substrate, so as to obtain the substrate with evaluation cured film.
Above-mentioned minimum developing time refers to, needed for untill the unexposed portion of photo-sensitive resin is dissolved removes completely The minimum time wanted, concentration or temperature dependent on developer solution, the direction of spraying or spray amount, pressure, the frequency of vibration etc. And change.
Herein, by minimum developing time divided rank as described below：
○：Minimum developing time was more than 30 seconds.
×：Minimum developing time is less than 30 seconds.
The evaluation ＞ of ＜ sensitivity
In the evaluation of sensitivity, the laminated substrate being laminated in above-mentioned ＜ after ＞ after 15 minutes is used.
For the laminated substrate, after the mask pattern of 10 lines of line/interval=40 μm/40 μm directly is described exposure, Developed with the method described in above-mentioned ＜ developments ＞.With the resist top of the obtained corrosion-resisting pattern of optics measurement microscope Portion's width, reaches the evaluation of 39 μm of light exposure as sensitivity using resist top width.
Herein, the 5th article of line, the end away from length direction from end being set among 10 bars of lines that locate of resist line The position of portion about 5mm, the average value of 3 measure is used as measured value.In the end of pattern and central portion, because of developer solution and clear The influence of the diffusion of wash water and line width is different, there are the tendency that attenuates of resist line of end side, therefore limit to locate and be Important.
Light exposure in following assessment item is for line/interval as described in the evaluation ＞ of above-mentioned ＜ sensitivity =40 μm/40 μm of mask pattern makes the light exposure that resist top width reaches 39 μm.Herein, according to light exposure by sensitivity Divided rank as described below：
○：The light exposure for reaching 39 μm of line widths is 28mJ/cm2Below.
×：Reach the light exposure of 39 μm of line widths more than 28mJ/cm2。
The evaluation ＞ of ＜ resolution ratio
The laminated substrate after 15 minutes after above-mentioned ＜ is laminated ＞ is used in the evaluation of resolution ratio.
For the laminated substrate, after the pattern of line/interval=1/1 of various sizes directly is described exposure, by above-mentioned Method described in ＜ developments ＞ is developed.
For obtained pattern, the minimum pattern width formed with light microscope observation, according to following base Quasi- evaluation resolution ratio.
○：The minimum pattern width formed is less than 28 μm.
×：The minimum pattern width formed is more than 28 μm.
The evaluation ＞ of ＜ adaptations
The laminated substrate after 15 minutes after above-mentioned ＜ is laminated ＞ is used in the evaluation of adaptation.
For the laminated substrate, after the pattern of the independent lines of various sizes directly is described exposure, developed by above-mentioned ＜ Method described in ＞ is developed.
Obtained pattern is observed with light microscope, according to following benchmark evaluation adaptation.
Herein, the situation that line pattern does not normally form refers to, situation which collapses, the line pattern are cranky The situation of the line pattern is not present in situation or substrate.
○：The minimum pattern width formed is less than 28 μm.
×：The minimum pattern width formed is more than 28 μm.
The evaluation ＞ of ＜ aggregations
By 50 μm of thickness, the area 0.6m in optical polymerism resin layered product2Photosensitive layer (resist layer) be dissolved in 200ml 1 mass %Na2CO3Aqueous solution, carried out using circulating spraying device under atomisation pressure 0.1MPa 3 it is small when spray.Then, Developer solution is stood 1 day, observes the generation of aggregation.When aggregation largely produces, observed in the bottom of spraying device and side To powder or grease.In the good constituent of developer solution aggregation, aggregation as described above is not produced completely.Based on poly- Collect the generation state of thing, by aggregation divided rank as described below：
○：Aggregation is not produced completely.
△：A part in the bottom of spraying device or side observes aggregation.
×：In spraying device whole observation to aggregation.
The evaluation ＞ of ＜ fissilities
Be laminated the substrate in ＞ after the processing that illustrates by 15 minutes using above-mentioned ＜, for the laminated substrate, by 4cm × After the rectangle pattern of 6cm directly describes exposure, developed by the above-mentioned ＜ methods developed described in ＞.
Curing resist on obtained substrate is impregnated in 50 DEG C, the NaOH of 3 mass %, is measured to resist from base Plate be completely exfoliated untill time, as splitting time.
Herein, by fissility divided rank as described below：
○：Time untill being completely exfoliated is less than 40 seconds.
×：Time untill being completely exfoliated was more than 40 seconds.
Embodiment 1~7 and comparative example 1~4
Respectively, the composition of the photosensitive polymer combination used in embodiment and comparative example is shown in table 8, by table 8 The details for each component name recorded are shown in table 9.The compounding amount of each component in table 8 is the mass parts of solid constituent conversion.
The evaluation result carried out using each composition is also depicted in table 8.
Table 9

Claims (17)

  1. A kind of 1. photosensitive polymer combination, it is characterised in that each component containing following (A)~(C),
    (A) component：Alkali solubility macromolecule,
    (B) component：Compound with olefinic double bond and
    (C) component：Photoepolymerizationinitiater initiater,
    It is laminated on the copper-clad laminated board of copper foil for being laminated with 18 μ m thicks with 25 μ m thicks by the photosensitive polymer combination The photo-sensitive resin of formation, curing is formed by the light irradiation and development treatment of the pattern-like of line/interval=50 μm/30 μm Corrosion-resisting pattern, after implementing the copper etching process of 55 seconds at 50 DEG C, removes copper wire pattern obtained from the curing corrosion-resisting pattern Bottom width be more than 38 μm.
  2. 2. photosensitive polymer combination according to claim 1, wherein, (A) component is (methyl) acrylic acid units Content ratio for more than 10 mass % and below 24 mass % copolymer.
  3. 3. photosensitive polymer combination according to claim 1 or 2, wherein, (A) component is containing for styrene units Proportional is more than 32 mass % and the copolymer of below 60 mass %.
  4. 4. according to photosensitive polymer combination according to any one of claims 1 to 3, wherein, (C) component contains acridine Compound.
  5. 5. photosensitive polymer combination according to any one of claims 1 to 4, wherein, (B) component contains season penta Tetrol compound.
  6. 6. according to photosensitive polymer combination according to any one of claims 1 to 5, wherein, (B) component contains three hydroxyls Methylpropane compound.
  7. 7. according to photosensitive polymer combination according to any one of claims 1 to 6, wherein, (B) component contains bis-phenol A compounds.
  8. 8. a kind of photosensitive polymer combination, it contains each component of following (A)~(C),
    (A) component：Alkali solubility macromolecule,
    (B) component：Compound with olefinic double bond and
    (C) component：Photoepolymerizationinitiater initiater,
    (A) component include the content ratio of (methyl) acrylic acid units for more than 10 mass % and below 24 mass %, simultaneously And the copolymer that the content ratio of styrene units is more than 32 mass %,
    (C) component includes acridine compounds.
  9. 9. photosensitive polymer combination according to claim 8, wherein, (A) component includes (methyl) acrylic acid list The content ratio of member be more than 10 mass % and the content ratio of below 24 mass % and styrene units be 32 mass % with Upper and below 60 mass % copolymers.
  10. 10. photosensitive polymer combination according to claim 8 or claim 9, wherein, (B) component contains pentaerythrite Compound.
  11. 11. photosensitive polymer combination according to any one of claims 8 to 10, wherein, (B) component contains three Hydroxymethyl-propane compound.
  12. 12. the photosensitive polymer combination according to any one of claim 8~11, wherein, (B) component contains double Phenol A compound thing.
  13. 13. a kind of photosensitive element, it is will to be formed as the photosensitive polymer combination any one of claim 1~12 Photo-sensitive resin be layered in obtained from supporter.
  14. A kind of 14. forming method of corrosion-resisting pattern, it is characterised in that including：
    The photo-sensitive resin of photosensitive element described in claim 13 is layered in lamination process on conductor substrate,
    The exposure process that is exposed to the photosensitive polymer combination layer of the stacking and
    The developing procedure in the unexposed portion after the exposure is removed with developer solution.
  15. 15. the forming method of corrosion-resisting pattern according to claim 14, wherein, the lamination process is by photosensitive element Photo-sensitive resin clip the process that wetting agent is stacked on conductor substrate.
  16. A kind of 16. manufacture method of circuit board, it is characterised in that including：
    By lamination work of the photosensitive polymer combination layer stackup of the photosensitive element described in claim 13 on conductor substrate Sequence,
    The exposure process that is exposed to the photosensitive polymer combination layer of the stacking,
    With developer solution remove the unexposed portion after the exposure developing procedure,
    To by it is described development the conductor substrate formed with corrosion-resisting pattern be etched or the conductive pattern formation process of plating, with And
    The stripping process that the corrosion-resisting pattern is peeled off.
  17. 17. the manufacture method of circuit board according to claim 16, wherein, the lamination process is by photosensitive element Photo-sensitive resin clips the process that wetting agent is stacked on conductor substrate.
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