JP4645776B2 - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method - Google Patents

Description

  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.

  Conventionally, in the field of production of printed wiring boards, as a resist material used for etching and plating, a photosensitive resin composition and a photosensitive element that is laminated on a support and covered with a protective film are widely used. Yes.

  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.

  In such a printed wiring board manufacturing method, in recent years, 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. As 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.

  Further, in recent years, a direct drawing method called a DLP (Digital Light Processing) exposure method capable of forming a fine pattern has been introduced with higher definition and higher density in a printed wiring board. In general, in the DLP exposure method, active light having a wavelength of 390 to 430 nm using a blue-violet semiconductor laser as a light source is used. In addition, 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).

JP 2004-301996 A JP-A-2005-107191

  By the way, 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. Compared with the exposure method, 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.

  However, when 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.

［一般式（Ｉ）中、Ｒ¹は炭素数２〜２０のアルキレン基、炭素数２〜２０のオキサジアルキレン基又は炭素数２〜２０のチオジアルキレン基を示す。］

［一般式（ＩＩ）中、Ｒ²は置換基を有していてもよいアリール基を示す。］The present invention is 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).

[In General Formula (I), 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. ]

[In General Formula (II), R ² represents an aryl group which may have a substituent. ]

  The photosensitive resin composition of this invention is excellent in photosensitivity and resolution by having the said structure. 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). Thereby, 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.

  Moreover, this invention provides the photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body. According to the photosensitive element of the present invention, the photosensitive resin composition layer can be easily laminated on a substrate or the like. Further, 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.

  Further, 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. There is provided 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. In the formation method of the present invention, 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. Moreover, according to the formation method 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.

  Furthermore, the present invention provides a method for producing a printed wiring board, in which a circuit forming substrate on which a resist pattern is formed by the above-described 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.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in photosensitivity and resolution, and 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.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. In the present invention, (meth) acrylic acid indicates acrylic acid or methacrylic acid, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloyl group corresponds to an acryloyl group or corresponding to it. Means a methacryloyl group;

(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)”).

  Examples of the component (A) 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. Examples of the polymerizable monomer include styrene; a polymerizable styrene derivative having a substituent at the α-position or aromatic ring such as vinyl toluene and α-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, α-bromo (meth) acrylic acid, α-chloro Maleic acid monoesters such as (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate , Fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These can be used alone or in combination of two or more.

  As said (meth) acrylic-acid alkylester, the compound represented by the following general formula (IV) is mentioned, for example.

In said general formula (IV), R < ³ > shows a hydrogen atom or a methyl group, R < ⁴ > shows the C1-C12 alkyl group which may have a substituent. Here, examples of the 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. For example, a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, 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”) because the alkali developability of the photosensitive resin composition is improved. 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. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  In the carboxyl group-containing polymer, the content of the repeating unit derived from the polymerizable monomer having a carboxyl group (hereinafter referred to as “carboxyl group content”) is 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 styrene derivatives 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, further preferably 40000 to 120,000, and particularly preferably 50000 to 110000. When 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. When 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. In addition, 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.

  (A) As a component, the binder polymer mentioned above can be used individually or in combination of 2 or more types. 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. As the component (B), a compound obtained by a reaction between a polyhydric alcohol and an α, β-unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound, a glycidyl group-containing compound and an α, β-unsaturated carboxylic acid Compound obtained by reaction of (1), urethane monomer (for example, (meth) acrylate compound having urethane bond), nonylphenoxy polyalkyleneoxy (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxy Ethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, alkyl (meth) acrylate And esters. These may be used alone or in combination of two or more.

  Examples of the compound obtained by the reaction of the polyhydric alcohol and the α, β-unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, polypropylene having 2 to 14 propylene groups Glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpro Pantripolyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta Examples include erythritol polyethoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

  The component (B) preferably contains a bisphenol A (meth) acrylate compound since the photosensitive sensitivity and resolution of the photosensitive resin composition are further improved.

  Examples of the bisphenol A-based (meth) acrylate compound 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) Enyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadeca) And ethoxy) phenyl) propane. In addition, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi Chemical Co., Ltd., product name). ) And 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as 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) acryloxy) Nonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxide decapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4 -((Meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryl) Roxyhexadecapropoxy) phenyl) propane and the like. These may be used alone or in combination of two or more.

  As the 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, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (for example, product name “FA-321M” manufactured by Hitachi Chemical Co., Ltd.) is included.

  When the component (B) contains a bisphenol A-based (meth) acrylate compound, the content is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). More preferably, it is 15-40 mass parts. When 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 tent property of the cured film of the photosensitive resin composition are improved. Here, the urethane monomer indicates a photopolymerizable compound having at least one ethylenically unsaturated bond and one urethane bond.

  As a urethane monomer, an addition reaction between a (meth) acrylic monomer having a hydroxyl group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Compounds; compounds represented by the following general formula (V); EO-modified urethane di (meth) acrylate; EO, PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and 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 and 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.

In the general formula (V), R ⁵ represents a divalent organic group, R ⁶ represents a group represented by the following general formula (VI), and 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.

In the general formula (VI), 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, and 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.

As a compound represented by the general formula (V), as a commercial product, UA-21 (in the general formula (V), R ⁷ is a methyl group, X is an ethylene group, m is 4 (average value), R ⁵ Is a hexamethylene group, Shin-Nakamura Chemical Co., Ltd. trade name), 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), R ⁵ Is a hexamethylene group, Shin-Nakamura Chemical Co., Ltd. trade name), 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.

In the general formula (V), R ⁵ is preferably an alkylene group having 1 to 12 carbon atoms. In the general formula (VI), 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.

  (B) When a component contains the compound represented by the said general formula (V), the content is 5-25 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. It is preferably 7 to 15 parts by mass. When 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 nonylphenoxy polyalkyleneoxy (meth) acrylate. Thereby, the peeling characteristic of the resist which consists of a hardened | cured material of the photosensitive resin composition improves.

  Nonylphenoxypolyalkyleneoxy (meth) acrylates include nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, nonylphenoxypolybutyleneoxy (meth) acrylate, and the like. 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.). When 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.

  When the component (B) contains nonylphenoxypolyalkyleneoxy (meth) acrylate, 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). Preferably, it is 5-30 mass parts, More preferably, it is 5-20 mass parts. When the content of nonylphenoxypolyalkyleneoxy (meth) acrylate is within the above range, the peeling property of a resist made of a cured product of the photosensitive resin composition is further improved.

  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.

In the above general formula (VII), R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a hydrogen atom, a methyl group or a halogenated methyl group, and R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or Represents a hydroxyl group, and 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 γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxy. And ethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, and the like. Among them, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl -O-phthalate is preferred. γ-Chloro-β-hydroxypropyl-β'-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.

  When (B) component contains the compound represented by the said general formula (VII), the content is 3-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. It is preferably 5 to 15 parts by mass. When 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 hardened | cured material of the photosensitive resin composition becomes more favorable.

  (C) The photoinitiator which is a component contains the compound represented by the said general formula (I), and the compound represented by the said general formula (II).

In the general formula (I), 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. In addition, as a compound whose R < ¹ > is a C7 alkylene group, Asahi Denka Kogyo Co., Ltd. product name "N-1717" is mentioned, for example.

  Content of the compound represented by the said general formula (I) in the photosensitive resin composition is 0.01-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. It is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass. When 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.

In the general formula (II), R ² is preferably a phenyl group which may have a substituent, and more preferably a phenyl group. Here, examples of the 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. Examples of the compound in which R ² is a phenyl group include a product name “9-PA” manufactured by Nippon Steel Chemical Co., Ltd.

  Content of the compound represented by the said general formula (II) in the photosensitive resin composition is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is 0.05-5 mass parts, and it is especially preferable that it is 0.07-3 mass parts. 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 as, for example, N-phenylglycine (product name) manufactured by Mitsui Chemicals. The photosensitive resin composition containing such a compound is further excellent in photosensitivity and resolution.

  (C) When a component contains the compound represented by the said Formula (III), the content is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is 0.05 to 5 parts by mass, and more preferably 0.07 to 3 parts by mass. When 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 (C) 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-phenylanthraquinone, 2,3-diphenylanthraquinone 1-chloroanthraquinone Quinones such as 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ether compounds such as benzoin, benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9 , 10-dibutoxyanthracene, substituted anthracene such as 9,10-dipentoxyanthracene; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl)- , 5-Di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimers such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; coumarin compounds; oxazole compounds; pyrazoline compounds. 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. Further, like a combination of diethylthioxanthone and dimethylaminobenzoic acid, 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). It is more preferable that it is 50-70 mass parts. 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 mass, and 30 to 55 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 35-50 mass parts. 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 preferable that it is -10 mass parts, and it is especially preferable that it is 0.2-5 mass parts. 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.

  In addition, the photosensitive resin composition may be added to 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 melt | dissolves and it can apply | coat as a solution of about 30-60 mass% solid content. 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.

(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.

  Here, 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. Moreover, the photosensitive element 1 of this embodiment may coat | cover the surface F1 on the opposite side to the support body 10 on the photosensitive resin composition layer 14 with a protective film.

  Examples of the support 10 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 | coating the photosensitive resin composition on these polymer films, and drying. As the support 10, it is preferable to use a polyethylene terephthalate film because of its excellent transparency.

  These polymer films need to be removable from the photosensitive resin composition layer 14 later. A film that has been surface-treated so that it can be easily removed from the photosensitive resin composition layer 14 or a film that is made of a material that can be easily removed can be suitably used as the support 10. The thickness of the polymer film is preferably 1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 1 to 30 μm. If the thickness of the polymer film is less than 1 μm, the mechanical strength tends to decrease and the polymer film tends to be broken at the time of coating. If the thickness exceeds 100 μm, 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 μm tends to be inferior in inexpensiveness.

  The said polymer film can be used also as a protective film, and you may coat | cover the surface on the opposite side to the support body 10 of the photosensitive resin composition layer 14 with a polymer film.

  The protective film preferably has an adhesive force with the photosensitive resin composition layer 14 smaller 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 the method for 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. Moreover, as conditions for drying the solution of the photosensitive resin composition apply | coated on the support body 10, the conditions of drying temperature 70-150 degreeC and drying time about 5 to 30 minutes are mentioned, for example. 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. .

  Although the thickness of the photosensitive resin composition layer 14 changes with uses, it is preferable that it is 1-200 micrometers in thickness after drying, it is more preferable that it is 5-100 micrometers, and it is especially preferable that it is 10-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 200 μm, 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 an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, or 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. Examples of 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).

(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.

  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. It can apply by apply | coating on the board | substrate for formation and drying a coating film at 60-110 degreeC.

Moreover, you may laminate | stack the photosensitive resin composition layer on a board | substrate using the photosensitive element mentioned above. As a lamination method in that case, when the photosensitive element is provided with 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. the degree method in which bonding at a pressure of ^{(1kgf / cm 2 ~10kgf / cm} 2 or so) can be mentioned. This method is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Further, in order to further improve the laminating property, 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.

  In the forming method using a photosensitive element, a photosensitive resin composition layer and a support are sequentially laminated on a circuit forming substrate. When the support has transparency, in the irradiation step, the photosensitive resin composition may be exposed by irradiating active light from the support. Moreover, when the transparency of the support is low, the support may be removed from the possibility resin composition layer, and the photosensitive resin composition may be directly irradiated with actinic rays.

  In the irradiation process, for example, actinic rays are irradiated in an image form through a negative or positive mask pattern called an artwork. Examples of 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.

  As a method of irradiating actinic rays, a method of irradiating actinic rays in an image form by a laser direct drawing method such as DLP (Digital Light Processing) exposure method may be employed. In such a method, 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.

  In the removing step, the portion other than the portion irradiated with the actinic ray of the photosensitive resin composition layer is removed from the substrate. In 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. As the 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. As the 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. Examples of 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.

  Moreover, as alkaline aqueous solution used for image development, 0.1-5 mass% dilute solution of sodium carbonate, 0.1-5 mass% dilute solution of potassium carbonate, 0.1-5 mass% dilute solution of sodium hydroxide, A dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred. Moreover, it is preferable that pH of the alkaline aqueous solution used for image development is 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  As said aqueous developing solution, what consists of water or alkaline aqueous solution and 1 or more types of organic solvent is used. Here, as the base contained in the alkaline aqueous solution, the above-mentioned 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 to 12, more preferably pH 9 to 10.

  Examples of the organic solvent 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 or the like can be mixed in the aqueous developer. Examples of the organic solvent developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by weight in order to prevent ignition.

Moreover, you may use together the 2 or more types of image development method mentioned above as needed. Development methods include a dip method, a battle method, a spray method, brushing, and slapping, and the high pressure spray method is most suitable for improving the resolution. As the treatment after development, the resist pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary.

(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.

  In the above manufacturing method, 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.

  For the etching, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used. Among these, it is desirable to use a ferric chloride solution from the viewpoint of a good etch factor. The above plating methods include 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.

  After completion of the etching or plating, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly 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. Examples of the peeling method include a dipping method and a spray method, and these may be used alone or in combination.

  The method for manufacturing a printed wiring board can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  Hereinafter, the present invention will be described in more detail with reference to examples.

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 (three 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]

(Examples 1-5, Comparative Examples 1-3)
The materials were blended in the blending amounts (g) shown in Table 1 to obtain a photosensitive resin composition solution.

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 [manufactured by Hitachi Chemical Co., Ltd., product name]
* 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]

  Next, the obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (product name “G2-16” manufactured by Teijin Limited), and then heated with a 100 ° C. hot air convection dryer. After drying for 10 minutes, the film was protected with a polyethylene protective film (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 μm.

  Next, a brush equivalent to # 600 is 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 in which copper foil (thickness 35 μm) is laminated 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.

<Evaluation of photosensitivity>
A Hitachi 41-step tablet was placed on the test substrate, and a 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”), 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.

<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.

<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 copper-clad laminate is a copper-clad laminate (product name “MCL-E-67” manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is 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.

<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.

<Evaluation of resist shape>
On the test substrate after the lamination, using drawing data having a wiring pattern with a line width / space width of 5/5 to 47/47 (unit: μm) as a resist shape evaluation pattern, Hitachi 41-step tablet 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.

  As shown in Table 2, in Examples 1-5, it was confirmed that it was excellent in photosensitivity, resolution, and resist shape, and had sufficient peelability. In Examples 1 and 3 to 5, further excellent tenting properties were exhibited.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive resin composition layer.

Claims (9)

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 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).

[In General Formula (I), 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. ]

[In General Formula (II), R ² represents an aryl group which may have a substituent. ] The said (C) photoinitiator is a photosensitive resin composition of Claim 1 which further contains the compound represented by following formula (III).

3. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (B) having at least one ethylenically unsaturated bond contains a bisphenol A (meth) acrylate compound. The said (B) photopolymerizable compound which has at least one ethylenically unsaturated bond is a photosensitive resin composition as described in any one of Claims 1-3 containing a urethane monomer. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (B) having at least one ethylenically unsaturated bond contains nonylphenoxypolyalkyleneoxy (meth) acrylate. . A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition as described in any one of Claims 1-5 formed on this support body. An actinic ray is irradiated to the predetermined part of the photosensitive resin composition layer which consists of the photosensitive resin composition as described in any one of Claims 1-5 formed on the circuit formation board | substrate, and an exposure part is photocured. An irradiation process,
A removal step of removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. An actinic ray is imaged by a direct drawing method on a predetermined portion of the photosensitive resin composition layer formed of the photosensitive resin composition according to any one of claims 1 to 5 formed on a circuit forming substrate. An irradiation step of irradiating and photocuring the exposed portion;
A removal step of removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 7 or 8 .

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