WO2009154194A1 - Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board - Google Patents
Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board Download PDFInfo
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- WO2009154194A1 WO2009154194A1 PCT/JP2009/060929 JP2009060929W WO2009154194A1 WO 2009154194 A1 WO2009154194 A1 WO 2009154194A1 JP 2009060929 W JP2009060929 W JP 2009060929W WO 2009154194 A1 WO2009154194 A1 WO 2009154194A1
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- resin composition
- photosensitive resin
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- acrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board.
- the photosensitive element When a printed wiring board is manufactured using a photosensitive element, first, the photosensitive element is laminated on a circuit forming substrate such as a copper substrate, and after pattern exposure through a mask film, the unexposed portion of the photosensitive element. Is removed with a developer to form a resist pattern. Next, using this resist pattern as a mask, the circuit forming substrate on which the resist pattern is formed is etched or plated to form a circuit pattern, and finally the cured portion of the photosensitive element is peeled and removed from the substrate.
- a circuit forming substrate such as a copper substrate
- a mask film After pattern exposure through a mask film, the unexposed portion of the photosensitive element. Is removed with a developer to form a resist pattern.
- the circuit forming substrate on which the resist pattern is formed is etched or plated to form a circuit pattern, and finally the cured portion of the photosensitive element is peeled and removed from the substrate.
- a laser direct drawing method in which actinic rays are directly irradiated in an image form using digital data without passing through a mask film has been put into practical use.
- a light source used in the direct drawing method a YAG laser and a semiconductor laser are used from the viewpoint of safety and handleability, and recently, a technology using a gallium nitride blue laser having a long life and a high output is used. Proposed.
- DLP Digital Light Processing
- active light having a wavelength of 390 to 430 nm using a blue-violet semiconductor laser as a light source
- an exposure method using a polygon multi-beam having a wavelength of 355 nm using a YAG laser as a light source which can deal with a small variety of products in general-purpose printed wiring boards, is also used. Therefore, various sensitizers have been studied in the photosensitive resin composition to cope with each wavelength (for example, see Patent Documents 1 and 2).
- the direct drawing method in which exposure is performed by moving the laser at a high speed is a conventional exposure method that uses a light source that effectively emits ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp.
- a light source that effectively emits ultraviolet rays such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp.
- the amount of exposure energy per spot is small and the production efficiency is low. Therefore, in the direct drawing method, a photosensitive resin composition with higher sensitivity is required.
- the photoinitiator or sensitizer contained in the photosensitive resin composition is increased in order to improve the photosensitivity, the photoreaction proceeds locally at the top of the photosensitive resin composition layer, and the bottom is cured. Therefore, the resolution obtained after photocuring is deteriorated and the resist shape is deteriorated (inverted trapezoid). As the resist pattern becomes higher in resolution and higher in density, the problem of the resist shape becomes serious. If the resist shape is an inverted trapezoid, defects such as disconnection or short circuit may occur after etching or plating. Thus, with the conventional photosensitive resin composition, it is difficult to sufficiently achieve the required photosensitivity, resolution, and resist shape.
- the present invention has been made in view of the above problems, and is a photosensitive resin composition that is excellent in light sensitivity and resolution, and can form a resist pattern having a good resist shape even when a direct drawing method is used. It is an object to provide a product, a photosensitive element using the same, a resist pattern forming method, and a printed wiring board manufacturing method.
- the present invention is a photosensitive resin composition
- a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator.
- the (C) photopolymerization initiator includes a compound represented by the following general formula (I) and a compound represented by the following general formula (II).
- R 1 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms.
- R 2 represents an aryl group which may have a substituent.
- the photosensitive resin composition of the present invention is excellent in photosensitivity and resolution by having the above configuration. Further, according to the photosensitive resin composition of the present invention, a resist pattern having a good resist shape can be formed even when the direct drawing method is used. A resist pattern having a good resist shape is effective for forming a printed wiring board having a fine pattern with high definition and high density without causing defects such as disconnection and short circuit after etching or plating.
- the (C) photopolymerization initiator preferably further contains a compound represented by the following formula (III).
- the photosensitive resin composition of this invention becomes the thing which was further excellent in photosensitivity and resolution, and can be used suitably for formation of the resist pattern by a direct drawing method.
- the present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer made of the photosensitive resin composition formed on the support.
- the photosensitive resin composition layer can be easily laminated on a substrate or the like.
- the photosensitive element of the present invention is excellent in light sensitivity and resolution, and the resist pattern formed using the photosensitive element has a good resist shape.
- the present invention also includes an irradiation step of irradiating a predetermined portion of the photosensitive resin composition layer formed of the photosensitive resin composition formed on the circuit forming substrate with an actinic ray and photocuring an exposed portion; And a removing step of removing a portion other than the predetermined portion of the conductive resin composition layer from the substrate. Since the resist pattern formed by the forming method of the present invention uses the photosensitive resin composition of the present invention, the resist pattern has a good resist shape.
- the present invention irradiates a predetermined portion of the photosensitive resin composition layer formed of the photosensitive resin composition formed on the circuit forming substrate with an actinic ray in an image shape by a direct drawing method, and illuminates an exposed portion.
- a resist pattern forming method including an irradiation step of curing and a removing step of removing a portion other than a predetermined portion of the photosensitive resin composition layer from the substrate.
- a high-definition and high-density resist pattern can be easily formed by adopting a direct drawing method as the irradiation method in the irradiation step.
- the photosensitive resin composition of the present invention since the photosensitive resin composition of the present invention is used, a resist pattern with a good resist shape can be obtained even when actinic rays are irradiated by a direct drawing method.
- the present invention provides a method for manufacturing a printed wiring board, in which a circuit forming substrate on which a resist pattern has been formed by the above resist pattern forming method is etched or plated. According to such a manufacturing method, a high-definition and high-density printed wiring board can be obtained with high production efficiency.
- the photosensitive resin composition which can form the resist pattern which has a favorable resist shape even when a direct drawing method is used, and the photosensitive property using this An element, a resist pattern forming method, and a printed wiring board manufacturing method can be provided.
- (meth) acrylic acid indicates acrylic acid or methacrylic acid
- (meth) acrylate means acrylate or a corresponding methacrylate
- (meth) acryloyl group corresponds to an acryloyl group or corresponding to it.
- the photosensitive resin composition according to this embodiment includes (A) a binder polymer (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable polymer having at least one ethylenically unsaturated bond.
- component (B) a binder polymer
- component (C) a photopolymerizable polymer having at least one ethylenically unsaturated bond.
- the component (A) examples include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like alone or in combination of two or more. Can be used.
- the component (A) is preferably an acrylic resin because the alkali developability of the photosensitive resin composition is improved.
- the component (A) can be produced, for example, by radical polymerization of a polymerizable monomer.
- the polymerizable monomer include styrene; a polymerizable styrene derivative having a substituent at the ⁇ -position or aromatic ring such as vinyl toluene and ⁇ -methylstyrene; acrylamide such as diacetone acrylamide; acrylonitrile; vinyl-n-.
- Esters of vinyl alcohol such as butyl ether; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid dicyclopentanyl ester, (meth) acrylic acid adamantyl ester, (meth) acrylic acid Benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid furfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl Ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, ⁇ -bromo (meth) acrylic acid, ⁇ -chloro Maleic acid monoesters such as (meth) acrylic acid, ⁇ -fury
- Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (IV).
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents an alkyl group having 1 to 12 carbon atoms which may have a substituent.
- substituent include a hydroxyl group, an epoxy group, and a halogen group.
- the alkyl group having 1 to 12 carbon atoms represented by R 4 may be linear or branched.
- Examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof.
- Examples of the polymerizable monomer represented by the general formula (IV) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid isopropyl ester, (Meth) acrylic acid butyl ester, (meth) acrylic acid t-butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, Examples include (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These can be used alone or in combination of two or more.
- the component (A) is preferably a binder polymer having a carboxyl group (hereinafter sometimes referred to as “carboxyl group-containing polymer”) in order to improve the alkali developability of the photosensitive resin composition.
- the carboxyl group-containing polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.
- the polymerizable monomer having a carboxyl group (meth) acrylic acid is preferable, and methacrylic acid is more preferable.
- the carboxyl group-containing polymer has a content of repeating units derived from a polymerizable monomer having a carboxyl group (hereinafter referred to as “carboxyl group content”) of 12 to 50 mass based on the total amount of the carboxyl group-containing polymer. %, More preferably 12 to 40% by mass, still more preferably 15 to 30% by mass, and particularly preferably 15 to 25% by mass.
- the photosensitive resin composition containing such a carboxyl group-containing polymer is further excellent in alkali developability and has good alkali resistance after curing. When the carboxyl group content is less than 12% by mass, the alkali developability tends to be inferior, and when it exceeds 50% by mass, the alkali resistance tends to be inferior.
- the component (A) is a binder containing styrene or a styrene derivative as a polymerizable monomer unit in order to improve the adhesion and release characteristics of the photosensitive resin composition layer comprising the photosensitive resin composition to the substrate and the like.
- a polymer is preferred.
- the content of repeating units derived from styrene or a styrene derivative is preferably 0.1 to 30% by mass, more preferably 1 to 28% by mass, and more preferably 1.5 to 27%, based on the total amount of the binder polymer. More preferably, it is mass%. If the content is less than 0.1% by mass, the adhesion tends to be inferior, and if it exceeds 30% by mass, the peel piece tends to be large and the peel time tends to be long.
- the weight average molecular weight of the component (A) is preferably 20000 to 300000, more preferably 30000 to 150,000, still more preferably 40000 to 120,000, and particularly preferably 50000 to 110000.
- the weight average molecular weight of the component (A) is in the above range, the alkali developability of the photosensitive resin composition and the mechanical strength of the photocured product become better.
- the weight average molecular weight of the component (A) is less than 20000, the developing solution resistance of the cured product of the photosensitive resin composition tends to decrease, and when it exceeds 300,000, the time required for development tends to increase.
- the weight average molecular weight in this invention is the value measured by the gel permeation chromatography method, and converted with the analytical curve created using standard polystyrene.
- the above-mentioned binder polymers can be used alone or in combination of two or more.
- the combination of two or more types includes a combination of two or more types of binder polymers composed of different copolymerization components, a combination of two or more types of binder polymers having different weight average molecular weights, a combination of two or more types of binder polymers having different degrees of dispersion, etc. Is mentioned.
- the component (B) is a photopolymerizable compound having at least one ethylenically unsaturated bond.
- a compound obtained by reaction of a polyhydric alcohol and an ⁇ , ⁇ -unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound, a glycidyl group-containing compound and an ⁇ , ⁇ -unsaturated carboxylic acid Compounds obtained by the reaction, urethane monomers (for example, (meth) acrylate compounds having a urethane bond), nonylphenoxypolyalkyleneoxy (meth) acrylate, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxy Ethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloy
- Examples of the compound obtained by the reaction of the polyhydric alcohol and the ⁇ , ⁇ -unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups.
- the component (B) preferably contains a bisphenol A (meth) acrylate compound because the photosensitivity and resolution of the photosensitive resin composition are further improved.
- bisphenol A-based (meth) acrylate compounds examples include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, and the like.
- Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane and 2,2-bis. (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Loxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynononaethoxy) Phenyl) propane, 2,2-bis (4-((meth)
- 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.) or FA-321M (product name, manufactured by Hitachi Chemical Co., Ltd.).
- BPE-1300 manufactured by Shin-Nakamura Chemical Co., Ltd., product name. Is possible. These may be used alone or in combination of two or more.
- Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane and 2,2-bis. (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Loxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylo) Sinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy
- 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane, and the like.
- These may be used alone or in combination of two or more.
- Component (B) preferably contains 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane in order to further improve the photosensitivity and resolution of the photosensitive resin composition. More preferably, it contains 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (for example, product name “FA-321M” manufactured by Hitachi Chemical Co., Ltd.).
- the content is preferably 10 to 50 parts by mass with respect to 100 parts by mass as the total of the components (A) and (B). 15 to 40 parts by mass is more preferable.
- the content of the bisphenol A (meth) acrylate compound is within the above range, the photosensitivity and resolution of the photosensitive resin composition are improved in a well-balanced manner.
- the component (B) preferably contains a urethane monomer because the flexibility and tentability of the cured film of the photosensitive resin composition are improved.
- the urethane monomer indicates a photopolymerizable compound having at least one ethylenically unsaturated bond and one urethane bond.
- urethane monomer an addition reaction between a (meth) acrylic monomer having a hydroxyl group at the ⁇ -position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate
- a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate
- PO represents propylene oxide
- the PO-modified compound has a block structure of propylene oxide groups.
- Examples of the EO-modified urethane di (meth) acrylate include product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd.
- Examples of the EO, PO-modified urethane di (meth) acrylate include product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.
- the component (B) preferably contains a compound represented by the following general formula (V) as a urethane monomer.
- R 5 represents a divalent organic group
- R 6 represents a group represented by the following general formula (VI)
- a plurality of R 5 may be the same or different from each other.
- a plurality of R 6 may be the same as or different from each other.
- R 7 represents a hydrogen atom or a methyl group
- X represents an ethylene group or a propylene group
- m represents an integer of 1 to 14
- m present Xs may be the same or different from each other. It may be.
- the propylene group includes a 1-methylethylene group and a 2-methylethylene group.
- UA-41 in general formula (V)
- R 7 is a methyl group
- X is a propylene group
- m is 5 (average value)
- R 5 Is a hexamethylene group, Shin-Nakamura Chemical Co., Ltd.
- trade name UA-42 (in general formula (V)
- R 7 is a methyl group
- X is a propylene group
- m is 9 (average value)
- UA-44 in general formula (V)
- R 7 is a hydrogen atom
- X is a propylene group
- m is 6 (average value)
- R 5 Are compounds having a hexamethylene group, trade name of Shin-Nakamura Chemical Co., Ltd.). These may be used alone or in combination of two or more.
- R 5 is preferably an alkylene group having 1 to 12 carbon atoms.
- X is preferably an ethylene group.
- the cured product of the photosensitive resin composition containing such a component (B) is further excellent in flexibility and tent property.
- the content thereof is 5 to 25 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is preferably 7 to 15 parts by mass.
- the content of the compound represented by the general formula (V) is within the above range, the flexibility and tent property of the cured product of the photosensitive resin composition are further improved.
- the component (B) preferably contains nonylphenoxypolyalkyleneoxy (meth) acrylate.
- nonylphenoxypolyalkyleneoxy (meth) acrylate examples include nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, and nonylphenoxypolybutyleneoxy (meth) acrylate. These may be used alone or in combination of two or more.
- Nonylphenoxypolyethyleneoxy (meth) acrylate includes nonylphenoxyethyleneoxy (meth) acrylate, nonylphenoxydiethyleneoxy (meth) acrylate, nonylphenoxytriethyleneoxy (meth) acrylate, nonylphenoxytetraethyleneoxy (meth) acrylate, nonyl Phenoxypentaethyleneoxy (meth) acrylate, Nonylphenoxyhexaethyleneoxy (meth) acrylate, Nonylphenoxyheptaethyleneoxy (meth) acrylate, Nonylphenoxyoctaethyleneoxy (meth) acrylate, Nonylphenoxynonaethyleneoxy (meth) acrylate, Nonyl Phenoxydecaethyleneoxy (meth) acrylate etc. are mentioned. These may be used alone or in combination of two or more.
- Nonylphenoxypolypropyleneoxy (meth) acrylate includes nonylphenoxypropyleneoxy (meth) acrylate, nonylphenoxydipropyleneoxy (meth) acrylate, nonylphenoxytripropyleneoxy (meth) acrylate, nonylphenoxytetrapropyleneoxy (meth) acrylate, Nonylphenoxypentapropyleneoxy (meth) acrylate, nonylphenoxyhexapropyleneoxy (meth) acrylate, nonylphenoxyheptapropyleneoxy (meth) acrylate, nonylphenoxyoctapropyleneoxy (meth) acrylate, nonylphenoxynonapropyleneoxy (meth) acrylate, Nonylphenoxydecapropyleneoxy (meth) acrylate etc. are mentioned. These may be used alone or in combination of two or more.
- the component (B) preferably contains nonylphenoxypolyethyleneoxy (meth) acrylate, and nonylphenoxytetraethyleneoxy (meth) acrylate (for example, product name “M-113” manufactured by Toagosei Co., Ltd.) or nonylphenoxyocta More preferably, it contains ethyleneoxy (meth) acrylate (for example, product name “NP-8EA” manufactured by Kyoeisha Chemical Co., Ltd.).
- the component (B) contains these compounds, the peeling property of the resist made of a cured product of the photosensitive resin composition is further improved.
- the content thereof is 3 to 40 parts by mass with respect to 100 parts by mass as the total of the components (A) and (B).
- the amount is preferably 5 to 30 parts by mass, more preferably 5 to 20 parts by mass.
- the component (B) contains a compound represented by the following general formula (VII) in order to improve the resolution of the photosensitive resin composition and the peeling characteristics of the resist made of a cured product of the photosensitive resin composition. Is preferred.
- R 8 represents a hydrogen atom or a methyl group
- R 9 represents a hydrogen atom, a methyl group or a halogenated methyl group
- R 10 represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or Represents a hydroxyl group
- n represents an integer of 0 to 4.
- n R 10 s may be the same as or different from each other.
- Examples of the compound represented by the general formula (VII) include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ ′-(meth) acryloyloxy. And ethyl-o-phthalate, ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl-o-phthalate, and the like. Among them, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl -O-phthalate is preferred.
- ⁇ -Chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., product name). These are used individually by 1 type or in combination of 2 or more types.
- the content thereof is 3 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 5 to 15 parts by mass.
- the content of the compound represented by the general formula (VII) is within the above range, the resolution of the photosensitive resin composition is further improved. Moreover, the peeling characteristic of the resist which consists of the hardened
- the photopolymerization initiator which is the component (C) includes a compound represented by the general formula (I) and a compound represented by the general formula (II).
- R 1 is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 4 to 14 carbon atoms, and an alkylene group having 7 carbon atoms. Is more preferable.
- a photosensitive resin composition containing such a compound improves the photosensitivity and resolution in a well-balanced manner. And according to such a photosensitive resin composition, the resist pattern which has a still more favorable resist shape can be formed.
- Examples of the compound in which R 1 is an alkylene group having 7 carbon atoms include “N-1717” manufactured by Asahi Denka Kogyo Co., Ltd.
- the content of the compound represented by the general formula (I) in the photosensitive resin composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass.
- the content of the compound represented by the general formula (I) is less than 0.01 parts by mass, the photosensitivity of the photosensitive resin composition tends to be inferior, and when it exceeds 20 parts by mass, a good resist shape is obtained. It becomes difficult, and there exists a tendency for the adhesiveness and resolution of a resist to fall.
- R 2 is preferably a phenyl group which may have a substituent, and more preferably a phenyl group.
- substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, and an amino group.
- the photosensitive resin composition containing such a compound is further excellent in photosensitivity and resolution.
- the compound in which R 2 is a phenyl group include a product name “9-PA” manufactured by Nippon Steel Chemical Co., Ltd.
- the content of the compound represented by the general formula (II) in the photosensitive resin composition is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 0.05 to 5 parts by mass, more preferably 0.07 to 3 parts by mass. If the content of the compound represented by the general formula (II) is less than 0.01 parts by mass, the photosensitivity of the photosensitive resin composition tends to be inferior, and if it exceeds 10 parts by mass, a good resist shape is obtained. It becomes difficult, and there exists a tendency for the adhesiveness and resolution of a resist to fall.
- the component (C) preferably further contains a compound represented by the above formula (III).
- the compound represented by the formula (III) is available, for example, as N-phenylglycine (manufactured by Mitsui Chemicals, product name).
- the photosensitive resin composition containing such a compound is further excellent in photosensitivity and resolution.
- the content thereof is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is preferably 0.05 to 5 parts by mass, more preferably 0.07 to 3 parts by mass.
- the content of the compound represented by the formula (III) is within the above range, the photosensitivity and resolution of the photosensitive resin composition are further improved.
- the component may further contain other photopolymerization initiator.
- Other photopolymerization initiators include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4 '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1
- Aromatic ketones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinon
- the 2,4,5-triarylimidazole dimer may be a dimer of two 2,4,5-triarylimidazoles whose aryl group substituents are the same as each other. It may be a dimer of two 2,4,5-triarylimidazoles having different groups.
- the former is a symmetric compound and the latter is an asymmetric compound.
- a thioxanthone compound and a tertiary amine compound may be combined and used as a photopolymerization initiator. These are used alone or in combination of two or more.
- the content of the component (A) in the photosensitive resin composition is preferably 30 to 80 parts by mass, and 40 to 75 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 50 to 70 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.
- the content of the component (B) in the photosensitive resin composition is preferably 20 to 60 parts by weight, and preferably 30 to 55 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). More preferably, it is 35 to 50 parts by mass. When the content of the component (B) is within this range, the photosensitivity and coating properties of the photosensitive resin composition become better.
- the content of the component (C) in the photosensitive resin composition is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferably from 10 to 10 parts by mass, and particularly preferably from 0.2 to 5 parts by mass. When the content of the component (C) is within this range, the photosensitivity of the photosensitive resin composition and the photocurability inside the photosensitive resin composition layer become better.
- the photosensitive resin composition may be a dye such as malachite green, Victoria pure blue, brilliant green, or methyl violet as necessary; tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o -Photochromic agent such as chloroaniline; Thermochromic inhibitor; Plasticizer such as p-toluenesulfonamide; Pigment; Filler; Antifoaming agent; Flame retardant; Adhesion imparting agent; Leveling agent; An agent, a fragrance, an imaging agent, a thermal crosslinking agent, and the like may be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). These are used alone or in combination of two or more.
- the photosensitive resin composition may be used in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, as necessary. It can be dissolved and applied as a solution having a solid content of about 30 to 60% by mass. These are used alone or in combination of two or more.
- a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, as necessary. It can be dissolved and applied as a solution having a solid content of about 30 to 60% by mass. These are used alone or in combination of two or more.
- the photosensitive resin composition is not particularly limited, but is applied as a liquid resist on a metal surface and dried, and then coated with a protective film as necessary, or used in the form of a photosensitive element described later. It is preferred that As the metal surface, for example, a metal surface made of an iron-based alloy such as copper, copper-based alloy, nickel, chromium, iron, or stainless steel is used, and preferably a metal surface made of copper, a copper-based alloy, or an iron-based alloy. Used.
- the photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body.
- FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention.
- the photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive resin composition layer 14 provided on the support 10.
- the photosensitive resin composition layer 14 is a layer made of the photosensitive resin composition of the present embodiment described above.
- the photosensitive element 1 of this embodiment may coat
- the support 10 examples include polymer films having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.
- the photosensitive element 1 is obtained by apply
- the support 10 it is preferable to use a polyethylene terephthalate film because of its excellent transparency.
- the thickness of the polymer film is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and particularly preferably 1 to 30 ⁇ m. If the thickness of the polymer film is less than 1 ⁇ m, the mechanical strength tends to decrease and the polymer film tends to be broken at the time of coating. If the thickness exceeds 100 ⁇ m, the film is photosensitive via the polymer film. When irradiating the resin composition layer 14 with actinic rays, the resolution tends to decrease. Further, a support having a thickness exceeding 100 ⁇ m tends to be inferior in inexpensiveness.
- the polymer film can also be used as a protective film, and the surface of the photosensitive resin composition layer 14 opposite to the support 10 may be covered with a polymer film.
- the protective film has a smaller adhesive force with the photosensitive resin composition layer 14 than an adhesive force between the photosensitive resin composition layer 14 and the support 10.
- the protective film is preferably a low fish eye film. "Fish eye” means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.
- Examples of a method of applying the photosensitive resin composition solution on the support 10 include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, and a spray coater.
- Examples of the conditions for drying the photosensitive resin composition solution coated on the support 10 include a drying temperature of 70 to 150 ° C. and a drying time of about 5 to 30 minutes.
- the amount of the remaining organic solvent in the photosensitive resin composition layer 14 is preferably 2% by mass or less based on the total amount of the photosensitive resin composition layer 14 in order to prevent diffusion of the organic solvent in the subsequent step. .
- the thickness of the photosensitive resin composition layer 14 varies depending on the application, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and particularly preferably 10 to 50 ⁇ m after drying. If the thickness is less than 1 ⁇ m, it tends to be difficult to apply industrially, and if it exceeds 200 ⁇ m, the effect of the present invention is small and the photocurability of the resist bottom tends to deteriorate.
- the photosensitive element 1 may further include intermediate layers such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. Moreover, the obtained photosensitive element 1 can be stored in the form of a sheet or wound around the core in a roll shape. It is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll in order to protect the end face. Further, it is preferable to install a moisture-proof end face separator on the end face of the photosensitive element roll for edge fusion resistance.
- the core include a core made of a plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS (acrylonitrile-butadiene-styrene copolymer).
- the resist pattern forming method according to the present embodiment irradiates a predetermined portion of the photosensitive resin composition layer made of the photosensitive resin composition formed on the circuit forming substrate with actinic rays and photocures the exposed portion. And a removing step of removing portions other than the predetermined portion of the photosensitive resin composition layer from the substrate.
- the circuit forming substrate refers to a substrate including an insulating layer and a conductive layer formed on the insulating layer.
- Lamination of the photosensitive resin composition layer on the circuit forming substrate is performed by, for example, applying the photosensitive resin composition to the circuit by a method such as screen printing, spraying, roll coating, curtain coating, or electrostatic coating.
- the coating can be carried out by coating on a forming substrate and drying the coating film at 60 to 110 ° C.
- the photosensitive element includes a protective film
- the protective film is removed, and then the photosensitive resin composition layer is heated to about 70 ° C. to 130 ° C. while being applied to the substrate at 0.1 MPa to 1 MPa.
- a method of pressure bonding at a pressure of about 1 kgf / cm 2 to about 10 kgf / cm 2 can be used. This method is preferably performed under reduced pressure from the viewpoint of adhesion and followability.
- a pre-heat treatment of the circuit forming substrate can be performed before the pressure bonding.
- the surface of the substrate on which the photosensitive resin composition layer is laminated is usually a metal surface, but is not particularly limited.
- a photosensitive resin composition layer and a support are sequentially laminated on a circuit forming substrate.
- the support has transparency
- the photosensitive resin composition may be exposed by irradiating active light from the support.
- the support may be removed from the possibility resin composition layer, and the photosensitive resin composition may be directly irradiated with actinic rays.
- an actinic ray is irradiated in an image form through a negative or positive mask pattern called an artwork.
- the active light source include those that effectively emit ultraviolet rays such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, and xenon lamps, or visible light such as photographic flood bulbs and solar lamps. Can be used that effectively radiate.
- a method of irradiating actinic rays a method of irradiating actinic rays in an image form by a laser direct drawing method such as a DLP (Digital Light Processing) exposure method may be employed.
- a light source such as a YAG laser, a semiconductor laser, and a gallium nitride blue-violet laser can be used as the active light source.
- the portion other than the portion irradiated with the actinic ray of the photosensitive resin composition layer is removed from the substrate.
- the removal step when a support is present on the photosensitive resin composition layer, the support is removed, and then a non-exposed portion is removed by a method such as wet development or dry development to produce a resist pattern. be able to.
- wet development development can be performed by a method such as spraying, rocking immersion, brushing, and scraping using a developer such as an alkaline aqueous solution, an aqueous developer, and an organic solvent.
- a developer used in the wet development a developer such as an alkaline aqueous solution having high safety and stability and good operability is used.
- the alkaline aqueous solution is an aqueous solution containing a base.
- the base include alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate.
- Alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate can be used.
- Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass sodium hydroxide, A dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred.
- the pH of the alkaline aqueous solution used for development is preferably 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer.
- a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
- aqueous developer a solution composed of water or an alkaline aqueous solution and one or more organic solvents is used.
- the base contained in the alkaline aqueous solution include the above base, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol. 1,3-diaminopropanol-2, morpholine and the like.
- the pH of the aqueous developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, and more preferably pH 9-10.
- organic solvent examples include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. Etc. These are used alone or in combination of two or more.
- the concentration of the organic solvent is usually preferably 2 to 90% by weight, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent and the like can be mixed in the aqueous developer.
- organic solvent developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone. These organic solvents are preferably added in an amount of 1 to 20% by weight in order to prevent ignition.
- the resist pattern may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm 2 as necessary.
- the printed wiring board manufacturing method according to this embodiment is characterized in that a circuit forming substrate on which a resist pattern is formed by the above-described resist pattern forming method is etched or plated.
- the surface of the circuit forming substrate is etched or plated using the developed resist pattern as a mask. As a result, a conductor pattern based on the resist pattern is formed on the circuit forming substrate.
- a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used.
- a ferric chloride solution from the viewpoint of a good etch factor.
- Copper plating such as copper sulfate plating and copper pyrophosphate plating; solder plating such as high-throw solder plating; nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating; hard gold plating And gold plating such as soft gold plating.
- a known method can be appropriately used for these.
- the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example.
- a stronger alkaline aqueous solution a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used.
- the peeling method include a dipping method and a spray method, and these may be used alone or in combination.
- the manufacturing method of the said printed wiring board is applicable also to manufacture of not only a single layer printed wiring board but a multilayer printed wiring board, and a printed wiring board etc. which have a small diameter through hole.
- binder polymers shown in Table 1 were synthesized according to Synthesis Example 1.
- Synthesis Example 1 To a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, 400 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6/4 (methyl cellosolve / toluene) was added, and nitrogen gas was added. Stirring while blowing and heating to 80 ° C.
- solution a a solution in which 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate, 50 g of styrene and 0.8 g of azobisisobutyronitrile were mixed as a comonomer.
- the solution a was added dropwise to the above mixture of methyl cellosolve and toluene having a mass ratio of 6/4 heated to 80 ° C. over 4 hours, and then kept at 80 ° C. with stirring for 2 hours.
- a solution prepared by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6/4 was dropped into the flask over 10 minutes.
- the solution after dropping was kept at 80 ° C. for 3 hours with stirring, and then heated to 90 ° C. over 30 minutes.
- the mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer solution as component (A).
- Acetone was added to the binder polymer solution to adjust the nonvolatile component (solid content) to 50% by mass.
- the weight average molecular weight of the binder polymer was 80000.
- the weight average molecular weight was measured by a gel permeation chromatography (GPC) method and was derived by conversion using a standard polystyrene calibration curve.
- GPC conditions are shown below.
- Flow rate 2.05 mL / min
- Detector Hitachi L-3300 type RI [manufactured by Hitachi, Ltd., product name]
- the blending amount of each component (B) indicates the solid content (g).
- the obtained photosensitive resin composition solution was uniformly applied onto a 16 ⁇ m-thick polyethylene terephthalate film (product name “G2-16” manufactured by Teijin Limited), and then heated with a hot air convection dryer at 100 ° C. After drying for 10 minutes, the film was protected with a protective film made of polyethylene (manufactured by Tamapoly Co., Ltd., product name “NF-13”) to obtain a photosensitive resin composition laminate (photosensitive element).
- the film thickness after drying of the photosensitive resin composition layer was 30 ⁇ m.
- a brush equivalent to # 600 was applied to the copper surface of a copper-clad laminate (product name “MCL-E-67”, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material laminated with copper foil (thickness 35 ⁇ m) on both sides. Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, and dried with an air flow. The obtained copper-clad laminate was heated to 80 ° C., and the photosensitive resin composition layer was peeled off from the photosensitive resin composition laminate on the copper surface using a 110 ° C. heat roll. The test substrate was obtained by laminating at a speed of 1.5 m / min.
- the above copper-clad laminate is a glass-clad laminate (made by Hitachi Chemical Co., Ltd., product name “MCL-E-67”) made of glass epoxy with copper foil (thickness 35 ⁇ m) laminated on both sides. 24 holes with a diameter of 6 mm were made, and burrs generated when the holes were made were removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was a substrate for evaluating tenting properties It was.
- the photosensitive element was laminated on both surfaces of the tenting property evaluation substrate, and the entire surface was exposed at 17 mJ / cm 2 using the LDI exposure machine.
- the polyethylene terephthalate film was peeled off, and spray development for 60 seconds was performed twice with a 1.0 mass% aqueous sodium carbonate solution at 30 ° C.
- the number of hole breaks was visually measured and evaluated as a tent tear rate, which was defined as tenting property. The lower the tent tear rate, the higher the tenting property, and it is desirable that the tent tear rate is zero.
- ⁇ Evaluation of resist shape> On the test substrate after lamination, drawing data having a wiring pattern with a line width / space width of 5/5 to 47/47 (unit: ⁇ m) is used as a resist shape evaluation pattern. The exposure was performed with an energy amount such that the number of remaining steps after development was 20.0. After developing under the same conditions as the evaluation of the photosensitivity, the resist shape was observed using an S-2100A scanning electron microscope manufactured by Hitachi, Ltd. In the resist shape, if the pattern cross section is trapezoidal or inverted trapezoidal, inconveniences such as failure to obtain a wiring pattern having a design width after etching or plating treatment occur. Therefore, the pattern cross section is preferably rectangular.
- Table 2 shows the evaluation results obtained for the photosensitive elements or test substrates of Examples 1 to 5 and Comparative Examples 1 to 3.
- Examples 1 to 5 were excellent in photosensitivity, resolution and resist shape and had sufficient peelability. Further, Examples 1 and 3 to 5 further exhibited excellent tenting properties.
- photosensitive element 10 ... support, 14 ... photosensitive resin composition layer.
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Abstract
Description
まず、本実施形態に係る感光性樹脂組成物について説明する。本実施形態に係る感光性樹脂組成物は、(A)バインダーポリマー(以下、場合により「(A)成分」と称する。)と、(B)エチレン性不飽和結合を少なくとも一つ有する光重合性化合物(以下、場合により「(B)成分」と称する。)と、(C)光重合開始剤(以下、場合により「(C)成分」と称する。)とを含有する。 (Photosensitive resin composition)
First, the photosensitive resin composition according to this embodiment will be described. The photosensitive resin composition according to this embodiment includes (A) a binder polymer (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable polymer having at least one ethylenically unsaturated bond. A compound (hereinafter sometimes referred to as “component (B)”) and (C) a photopolymerization initiator (hereinafter sometimes referred to as “component (C)”).
次に、本実施形態に係る感光性エレメントについて説明する。本実施形態に係る感光性エレメントは、支持体と、該支持体上に形成された上記感光性樹脂組成物からなる感光性樹脂組成物層とを備えるものである。 (Photosensitive element)
Next, the photosensitive element which concerns on this embodiment is demonstrated. The photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body.
次に本実施形態に係るレジストパターンの形成方法について説明する。本実施形態に係るレジストパターンの形成方法は、回路形成用基板上に形成された上記感光性樹脂組成物からなる感光性樹脂組成物層の所定部分に活性光線を照射し、露光部を光硬化させる照射工程と、上記感光性樹脂組成物層の所定部分以外の部分を上記基板上から除去する除去工程とを含むものである。なお、回路形成用基板とは、絶縁層と絶縁層上に形成された導電層とを備えた基板をいう。 (Method for forming resist pattern)
Next, a resist pattern forming method according to this embodiment will be described. The resist pattern forming method according to the present embodiment irradiates a predetermined portion of the photosensitive resin composition layer made of the photosensitive resin composition formed on the circuit forming substrate with actinic rays and photocures the exposed portion. And a removing step of removing portions other than the predetermined portion of the photosensitive resin composition layer from the substrate. Note that the circuit forming substrate refers to a substrate including an insulating layer and a conductive layer formed on the insulating layer.
次に、本実施形態に係るプリント配線板の製造法について説明する。本実施形態に係るプリント配線板の製造法は、上述したレジストパターンの形成方法によりレジストパターンが形成された回路形成用基板を、エッチング又はめっきすることを特徴とする。 (Printed wiring board manufacturing method)
Next, a method for manufacturing a printed wiring board according to the present embodiment will be described. The printed wiring board manufacturing method according to this embodiment is characterized in that a circuit forming substrate on which a resist pattern is formed by the above-described resist pattern forming method is etched or plated.
(合成例1)
撹拌機、還流冷却器、温度計、滴下ロート及び窒素ガス導入管を備えたフラスコに、質量比6/4(メチルセロソルブ/トルエン)であるメチルセロソルブ及びトルエンの配合物400gを加え、窒素ガスを吹き込みながら撹拌して、80℃まで加熱した。一方、共重合単量体としてメタクリル酸100g、メタクリル酸メチル250g、アクリル酸エチル100g及びスチレン50gと、アゾビスイソブチロニトリル0.8gとを混合した溶液(以下、「溶液a」という)を用意し、80℃に加熱された質量比6/4であるメチルセロソルブ及びトルエンの上記配合物に溶液aを4時間かけて滴下した後、80℃で撹拌しながら2時間保温した。さらに、質量比6/4であるメチルセロソルブ及びトルエンの配合物100gにアゾビスイソブチロニトリル1.2gを溶解した溶液を、10分かけて上記フラスコ内に滴下した。滴下後の溶液を撹拌しながら80℃で3時間保温した後、30分間かけて90℃に加温した。90℃で2時間保温した後、冷却して(A)成分であるバインダーポリマー溶液を得た。このバインダーポリマー溶液に、アセトンを加えて不揮発成分(固形分)が50質量%になるように調整した。バインダーポリマーの重量平均分子量は80000であった。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法によって測定し、標準ポリスチレンの検量線を用いて換算することにより導出した。GPCの条件を、以下に示す。
(GPC条件)
ポンプ:日立 L-6000型[株式会社日立製作所製]
カラム:Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440(計3本)[以上、日立化成工業株式会社製、製品名]
溶離液:テトラヒドロフラン
測定温度:25℃
流量:2.05mL/分
検出器:日立 L-3300型RI[株式会社日立製作所製、製品名] First, binder polymers shown in Table 1 were synthesized according to Synthesis Example 1.
(Synthesis Example 1)
To a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, 400 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6/4 (methyl cellosolve / toluene) was added, and nitrogen gas was added. Stirring while blowing and heating to 80 ° C. On the other hand, a solution (hereinafter referred to as “solution a”) in which 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate, 50 g of styrene and 0.8 g of azobisisobutyronitrile were mixed as a comonomer. The solution a was added dropwise to the above mixture of methyl cellosolve and toluene having a mass ratio of 6/4 heated to 80 ° C. over 4 hours, and then kept at 80 ° C. with stirring for 2 hours. Furthermore, a solution prepared by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6/4 was dropped into the flask over 10 minutes. The solution after dropping was kept at 80 ° C. for 3 hours with stirring, and then heated to 90 ° C. over 30 minutes. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer solution as component (A). Acetone was added to the binder polymer solution to adjust the nonvolatile component (solid content) to 50% by mass. The weight average molecular weight of the binder polymer was 80000. The weight average molecular weight was measured by a gel permeation chromatography (GPC) method and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
(GPC conditions)
Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) [above, manufactured by Hitachi Chemical Co., Ltd., product name]
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI [manufactured by Hitachi, Ltd., product name]
表1に示す配合量(g)で材料を配合し、感光性樹脂組成物の溶液を得た。 (Examples 1 to 5, Comparative Examples 1 to 3)
The materials were blended in the blending amounts (g) shown in Table 1 to obtain a photosensitive resin composition solution.
*1:メタクリル酸/メタクリル酸メチル/アクリル酸エチル/スチレン=20/50/20/10(質量比)、重量平均分子量=80000、50質量%メチルセロソルブ/トルエン=6/4(質量比)溶液
*2:2,2-ビス(4-((メタ)アクリロキシポリエトキシ)フェニル)プロパン[日立化成工業株式会社製、製品名]
*3:トリス(メタクリロイルオキシテトラエチレングリコールイソシアネートヘキサメチレン)イソシアヌレート[新中村化学株式会社製、製品名]
*4:γ-クロロ-β-ヒドロキシプロピル-β’-メタクリロイルオキシエチル-o-フタレート[日立化成工業株式会社製、製品名]
*5:ノニルフェノキシテトラエチレンオキシアクリレート[東亞合成株式会社製、製品名]
*6:ノニルフェノキシオクタエチレンオキシアクリレート[共栄社化学株式会社製、製品名]
*7:1,7-ビス(9,9-アクリジニル)ヘプタン[旭電化工業株式会社製、製品名]
*8:9-フェニルアクリジン[新日鐵化学株式会社製、製品名]
*9:N-フェニルグリシン[三井化学株式会社製、製品名] In the table, the blending amount of each component (B) indicates the solid content (g).
* 1: Methacrylic acid / methyl methacrylate / ethyl acrylate / styrene = 20/50/20/10 (mass ratio), weight average molecular weight = 80000, 50 mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution * 2: 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 3: Tris (methacryloyloxytetraethylene glycol isocyanate hexamethylene) isocyanurate [product name, manufactured by Shin-Nakamura Chemical Co., Ltd.]
* 4: γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 5: Nonylphenoxytetraethyleneoxyacrylate [Toagosei Co., Ltd., product name]
* 6: Nonylphenoxyoctaethyleneoxyacrylate [manufactured by Kyoeisha Chemical Co., Ltd., product name]
* 7: 1,7-bis (9,9-acridinyl) heptane [product name, manufactured by Asahi Denka Kogyo Co., Ltd.]
* 8: 9-phenylacridine [manufactured by Nippon Steel Chemical Co., Ltd., product name]
* 9: N-phenylglycine [Mitsui Chemicals, product name]
上記試験基板の上に日立41段ステップタブレットを置いて、半導体レーザを光源とした波長355nmのLDI露光機(日本オルボテック株式会社製、製品名「Paragon-9000m」)を用いて、17mJ/cm2で露光した。次いでポリエチレンテレフタレートフィルムを剥離し、30℃で1.0質量%炭酸ナトリウム水溶液を60秒間スプレーし、未露光部分を除去した後、銅張積層板上に形成された光硬化膜のステップタブレットの段数を測定することにより、感光性樹脂組成物の光感度を評価した。光感度は、ステップタブレットの段数で示され、このステップタブレットの段数が高いほど、光感度が高いことを示す。 <Evaluation of photosensitivity>
A Hitachi 41-step tablet was placed on the test substrate, and an LDI exposure machine with a wavelength of 355 nm using a semiconductor laser as a light source (manufactured by Nippon Orbotech Co., Ltd., product name “Paragon-9000m”) was used to provide 17 mJ / cm 2. And exposed. Next, the polyethylene terephthalate film was peeled off, sprayed with a 1.0% by weight aqueous sodium carbonate solution at 30 ° C. for 60 seconds to remove the unexposed portions, and then the number of steps of the step tablet of the photocured film formed on the copper clad laminate Was measured to evaluate the photosensitivity of the photosensitive resin composition. The photosensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the photosensitivity.
上記ラミネート後の試験基板上に、解像度評価用パターンとしてライン幅/スペース幅が5/5~47/47(単位:μm)の配線パターンを有する描画データを使用し、日立41段ステップタブレットの現像後の残存ステップ段数が20.0となるエネルギー量で露光を行った。上記光感度の評価と同様の条件で現像処理を行った後、光学顕微鏡を用いてレジストパターンを観察し、未露光部が完全に除去することができ、なおかつラインが蛇行、カケを生じることなく生成されたライン幅間のスペース幅の最小値を解像度として評価した。この数値が小さいほど解像度が良好であることを示す。 <Evaluation of resolution>
Development of Hitachi 41-step tablet using drawing data having a wiring pattern with a line width / space width of 5/5 to 47/47 (unit: μm) as a resolution evaluation pattern on the test substrate after lamination. The exposure was performed with an energy amount so that the number of subsequent remaining steps was 20.0. After performing development processing under the same conditions as the evaluation of the above photosensitivity, the resist pattern is observed using an optical microscope, the unexposed portion can be completely removed, and the lines are not meandering and causing no chipping. The minimum value of the space width between the generated line widths was evaluated as the resolution. The smaller this value, the better the resolution.
テンティング性の評価には、直径6mmの穴が24個空いている1.6mm厚の銅張積層板を使用した。上記銅張積層板は、銅箔(厚さ35μm)を両面に積層したガラスエポキシ材である銅張積層板(日立化成工業株式会社製、製品名「MCL-E-67」)に型抜き機で直径6mmの穴を24個作製し、穴を作製した際に生じたバリを#600相当のブラシを持つ研磨機(三啓株式会社製)を用いて取り除き、これをテンティング性評価用基板とした。上記テンティング性評価用基板の両面に上記感光性エレメントをラミネートし、上記LDI露光機を用いて、17mJ/cm2で全面露光した。次いでポリエチレンテレフタレートフィルムを剥離し、30℃で1.0質量%炭酸ナトリウム水溶液にて60秒間のスプレー現像を2回行った。現像後、穴破れ個数を目視で測定し、テント破れ率として評価し、これをテンティング性とした。テント破れ率は、低いほどテンティング性が高いことを示し、ゼロであることが望ましい。 <Evaluation of tenting properties>
For evaluation of the tenting property, a 1.6 mm thick copper clad laminate having 24 holes with a diameter of 6 mm was used. The above copper-clad laminate is a glass-clad laminate (made by Hitachi Chemical Co., Ltd., product name “MCL-E-67”) made of glass epoxy with copper foil (thickness 35 μm) laminated on both sides. 24 holes with a diameter of 6 mm were made, and burrs generated when the holes were made were removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was a substrate for evaluating tenting properties It was. The photosensitive element was laminated on both surfaces of the tenting property evaluation substrate, and the entire surface was exposed at 17 mJ / cm 2 using the LDI exposure machine. Next, the polyethylene terephthalate film was peeled off, and spray development for 60 seconds was performed twice with a 1.0 mass% aqueous sodium carbonate solution at 30 ° C. After development, the number of hole breaks was visually measured and evaluated as a tent tear rate, which was defined as tenting property. The lower the tent tear rate, the higher the tenting property, and it is desirable that the tent tear rate is zero.
上記ラミネート後の試験基板上に、剥離性評価用パターンとして60mm×45mmのパターンを有する描画データを使用し、日立41段ステップタブレットの現像後の残存ステップ段数が20.0となるエネルギー量で露光を行った。上記光感度及び解像度の評価と同様の条件で現像処理を行った後、50℃、3.0質量%水酸化ナトリウム水溶液にてビーカー浸漬し、レジストが基板表面から完全に剥離されるまでの時間(単位:秒)を剥離時間として評価し、これを剥離性とした。剥離時間は、短いほど剥離性が良好であることを示す。 <Evaluation of peelability>
Using drawing data having a pattern of 60 mm × 45 mm as a peelable evaluation pattern on the test substrate after the lamination, the exposure is performed with an energy amount that the remaining step step number after development of the Hitachi 41 step tablet is 20.0. Went. After performing development processing under the same conditions as in the evaluation of the photosensitivity and resolution, the time until the resist is completely peeled from the substrate surface is immersed in a beaker at 50 ° C. and a 3.0 mass% sodium hydroxide aqueous solution. (Unit: second) was evaluated as the peeling time, and this was defined as peelability. The shorter the peeling time, the better the peelability.
上記ラミネート後の試験基板上に、レジスト形状評価用パターンとしてライン幅/スペース幅が5/5~47/47(単位:μm)の配線パターンを有する描画データを使用し、日立41段ステップタブレットの現像後の残存ステップ段数が20.0となるエネルギー量で露光を行った。上記光感度の評価と同様の条件で現像処理を行った後、株式会社日立製作所製のS-2100A型走査型電子顕微鏡を用いてレジスト形状を観察した。
レジスト形状において、パターン断面が台形又は逆台形であると、エッチング又はめっき処理後に設計幅の配線パターンが得られない等の不都合が生じるため、パターン断面は矩形であることが好ましい。 <Evaluation of resist shape>
On the test substrate after lamination, drawing data having a wiring pattern with a line width / space width of 5/5 to 47/47 (unit: μm) is used as a resist shape evaluation pattern. The exposure was performed with an energy amount such that the number of remaining steps after development was 20.0. After developing under the same conditions as the evaluation of the photosensitivity, the resist shape was observed using an S-2100A scanning electron microscope manufactured by Hitachi, Ltd.
In the resist shape, if the pattern cross section is trapezoidal or inverted trapezoidal, inconveniences such as failure to obtain a wiring pattern having a design width after etching or plating treatment occur. Therefore, the pattern cross section is preferably rectangular.
Claims (6)
- (A)バインダーポリマーと、(B)エチレン性不飽和結合を少なくとも一つ有する光重合性化合物と、(C)光重合開始剤と、を含有する感光性樹脂組成物であって、
前記(C)光重合開始剤が、下記一般式(I)で表される化合物及び下記一般式(II)で表される化合物を含む、感光性樹脂組成物。
The photosensitive resin composition in which the (C) photopolymerization initiator includes a compound represented by the following general formula (I) and a compound represented by the following general formula (II).
- 支持体と、該支持体上に形成された請求項1又は2記載の感光性樹脂組成物からなる感光性樹脂組成物層とを備える、感光性エレメント。 A photosensitive element comprising: a support; and a photosensitive resin composition layer made of the photosensitive resin composition according to claim 1 or 2 formed on the support.
- 回路形成用基板上に形成された請求項1又は2記載の感光性樹脂組成物からなる感光性樹脂組成物層の所定部分に活性光線を照射し、露光部を光硬化させる照射工程と、
前記感光性樹脂組成物層の所定部分以外の部分を前記基板上から除去する除去工程とを含む、レジストパターンの形成方法。 An irradiation step of irradiating a predetermined portion of the photosensitive resin composition layer formed of the photosensitive resin composition according to claim 1 or 2 formed on a circuit forming substrate with an actinic ray and photocuring an exposed portion;
A removal step of removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. - 回路形成用基板上に形成された請求項1又は2記載の感光性樹脂組成物からなる感光性樹脂組成物層の所定部分に、直接描画法により活性光線を画像状に照射し、露光部を光硬化させる照射工程と、
前記感光性樹脂組成物層の所定部分以外の部分を前記基板上から除去する除去工程とを含む、レジストパターンの形成方法。 An actinic ray is irradiated to a predetermined portion of the photosensitive resin composition layer made of the photosensitive resin composition according to claim 1 or 2 formed on a circuit forming substrate in an image form by a direct drawing method, and an exposed portion is formed. A photocuring irradiation step;
A removal step of removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. - 請求項4又は5記載のレジストパターンの形成方法によりレジストパターンが形成された回路形成用基板を、エッチング又はめっきする、プリント配線板の製造法。 A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern has been formed by the method for forming a resist pattern according to claim 4 or 5.
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CN102754032A (en) * | 2010-03-19 | 2012-10-24 | 日立化成工业株式会社 | Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method |
JP5344034B2 (en) * | 2009-03-13 | 2013-11-20 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method |
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CN102375335B (en) * | 2010-08-10 | 2015-04-15 | 日立化成工业株式会社 | Manufacturing method of resin composition, photosensitive element, resist pattern and circuit board |
CN103076719B (en) * | 2011-10-26 | 2019-08-09 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern and printing distributing board |
CN103064253B (en) * | 2012-12-05 | 2015-04-08 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing acridine oxide |
KR101708343B1 (en) * | 2013-12-27 | 2017-02-20 | 코오롱인더스트리 주식회사 | Photosensitive Resin Composition for Dry Film Photoresist |
TW201546547A (en) * | 2014-05-13 | 2015-12-16 | Hitachi Chemical Co Ltd | Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed circuit board |
JP6774430B2 (en) * | 2015-05-21 | 2020-10-21 | 常州強力先端電子材料有限公司Changzhou Tronly Advanced Electronic Materials Co.,Ltd. | Pyrazoline sensitizers and their manufacturing methods and uses |
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