JP6229256B2 - Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method - Google Patents

Description

The present invention is sensitive light element, a method of manufacturing a forming method and a printed wiring board of the resist pattern.

  In the field of manufacturing printed wiring boards, a photosensitive resin composition is widely used as a resist material used for etching treatment or plating treatment. A photosensitive resin composition includes a support film and a layer (hereinafter, referred to as “photosensitive resin composition layer”) formed using the photosensitive resin composition on the support film. Often used as a laminate.

  A printed wiring board is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the substrate (lamination step). Next, after peeling off and removing the support film, the exposed portion is cured by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays (exposure step). Thereafter, by removing (developing) the unexposed portion from the substrate, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate (developing step). An etching process or a plating process is performed on the obtained resist pattern to form a circuit on the substrate (circuit forming process), and finally the resist is peeled and removed to produce a printed wiring board (peeling process).

  As an exposure method in the exposure step, conventionally, a method of exposing through a photomask using a mercury lamp as a light source has been used. In recent years, a direct drawing exposure method called DLP (Digital Light Processing) or LDI (Laser Direct Imaging) for directly writing digital data of a resist pattern on a photosensitive resin composition layer has been proposed. This direct drawing exposure method is being introduced for the production of a high-density package substrate because it has better alignment accuracy than the exposure method through a photomask and a high-definition pattern can be obtained.

  In the exposure process, it is necessary to shorten the exposure time in order to improve production efficiency. However, in the above-described direct drawing exposure method, in addition to using monochromatic light such as a laser as a light source and irradiating a light beam while scanning the substrate, a long exposure time is required as compared with an exposure method using a conventional photomask. Tend. Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition than before.

  In the stripping step, it is necessary to shorten the resist pattern stripping time in order to improve production efficiency. In addition, it is necessary to reduce the size of the peeling piece in order to prevent the peeling piece of the resist from reattaching to the circuit board and to improve the production yield. Thus, the photosensitive resin composition excellent in the peeling characteristic (peeling time, peeling piece size) of the resist pattern after hardening is requested | required.

  Further, with the recent increase in the density of printed wiring boards, there is an increasing demand for a photosensitive resin composition having excellent resolution (resolution) and adhesion of a resist pattern to be formed. In particular, a photosensitive resin composition capable of forming a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less in package substrate production is required.

  Furthermore, in a high-density package substrate, since the width between circuits is narrow, it is important that the resist pattern shape (hereinafter also simply referred to as “resist shape”) is excellent. When the cross-sectional shape of the resist pattern is trapezoidal or inverted trapezoidal, or when there is resist pattern skirting, there is a possibility that a short circuit or disconnection may occur in a circuit formed by the subsequent etching process or plating process. Therefore, the resist shape is required to be rectangular and not skirted.

  In addition, it is desirable that the resist pattern to be formed has excellent tenting properties and flexibility. If these characteristics are poor, the resist pattern is likely to be chipped, which causes a short circuit of the copper wiring pattern in the subsequent process.

  Furthermore, it is desirable that the resist pattern to be formed has excellent chemical resistance. If this characteristic is poor, plating will be easily stripped during the plating process, causing a short circuit of the copper wiring pattern.

  Conventionally, various photosensitive resin compositions have been studied in response to these requirements (see, for example, Patent Documents 1 to 8).

JP 2007-279381 A International Publication No. 2007/004619 Pamphlet JP 2009-003177 A JP 11-327137 A JP 2004-004294 A JP 2004-317874 A JP 2008-276194 A JP 2010-085605 A

  However, conventional photosensitive resin compositions may not be sufficient in terms of resolution, adhesion, or resist shape. In particular, since it is difficult to form a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less, photosensitivity capable of improving resolution and adhesion in units of 1 μm. There is a strong demand for a functional resin composition.

  Further, when a resist pattern is formed on a thin plate substrate of 0.5 mm or less, if the resist pattern is peeled off from the substrate due to the deflection of the substrate or the like, it causes a short circuit of the copper wiring pattern in the subsequent process. Therefore, good flexibility is required for the formed resist pattern.

The present invention is particularly resolution, adhesion, and to provide a method for producing a flexible and resist shape, a resist pattern excellent in can forming sensitive optical element, resist pattern forming method and printed wiring board.

  As a result of intensive studies to solve the above problems, the present inventors have formed a resist pattern that is particularly excellent in resolution, adhesion, flexibility, and resist shape by using a binder polymer having a specific copolymer composition. The inventors have found that a possible photosensitive resin composition can be obtained, and have completed the present invention. That is, the present invention is as follows.

<1> A support film and a photosensitive resin composition layer formed on the support film and being a coating film of the photosensitive resin composition, wherein the photosensitive resin composition is (A) (meta). A binder polymer having a structural unit derived from acrylic acid and a structural unit derived from (EO) -modified dicyclopentenyl (meth) acrylate (provided that the photopolymerizable compound having a (meth) acryloyl group and the following formula: (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a photosensitive element containing a sensitizing dye having an absorption maximum at 340 nm to 430 nm. It is.


(R4, R5, and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R7 represents an alkyl group having 8 to 18 carbon atoms.)

By taking the above embodiment, the photosensitive element can efficiently form a resist pattern excellent in resolution, adhesion, resist shape and flexibility. According to the photosensitive element , a resist pattern having L / S (line width / space width) of 10/10 (unit: μm) or less can be formed.

<2> The photosensitive element according to <1>, wherein the (A) binder polymer further includes a structural unit derived from at least one polymerizable monomer selected from the group consisting of styrene and a styrene derivative. Thereby, the resolution and adhesiveness of the resist pattern to be formed can be further improved.

<3> The photosensitive element according to <1> or <2>, wherein the (B) photopolymerizable compound includes a bisphenol A di (meth) acrylate compound. Thereby, the alkali developability at the time of resist pattern formation, the resolution of the resist pattern formed, and a peeling characteristic can be improved more.

<4> The photosensitive element according to any one of <1> to <3>, wherein the (C) photopolymerization initiator includes a 2,4,5-triarylimidazole dimer. Thereby, it is excellent in the sensitivity at the time of resist pattern formation, and the resolution and adhesiveness of the resist pattern formed can be improved more.

< 5 > A step of laminating the photosensitive resin composition layer of the photosensitive element according to any one of <1> to <4> on the substrate, and at least a part of the photosensitive resin composition layer. An exposure step of irradiating the region with actinic rays to cure the region to form a photocured portion, and removing the region other than the photocured portion of the photosensitive resin composition layer from the substrate, And a development step of forming a resist pattern made of a photocured product of the photosensitive resin composition on a substrate. According to this formation method, it is possible to efficiently and efficiently form a resist pattern having good resolution, adhesion, resist shape, and flexibility.

< 6 > A method for producing a printed wiring board including a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the formation method according to < 5 >. According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density package substrate can be efficiently manufactured with high accuracy.

According to the present invention, in particular resolution, adhesion, to provide a method for manufacturing a flexible and resist shape, a resist pattern excellent in can forming sensitive optical element, resist pattern forming method and printed wiring board.

It is a schematic cross section which shows one Embodiment of the photosensitive element concerning this invention. It is an example of the SEM photograph which the meandering or the fall has arisen in the resist pattern. It is an example of the SEM photograph which the meandering or the fall has arisen in the resist pattern. It is an example of the SEM photograph which the chip | tip or the rack has arisen in the resist pattern. It is a perspective view which shows typically an example of the manufacturing process of the wiring board by a semi-additive construction method.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or the corresponding methacrylate, and (meth) acryloyl group means acryloyl. Means a group or a methacryloyl group. The (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene group, and the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene group. Furthermore, “(EO) modified” means a compound having a (poly) oxyethylene chain, and “(PO) modified” means a compound having a (poly) oxypropylene chain. “(EO) · (PO) modified” means a compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain. In addition, in this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. It is. Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

[Photosensitive resin composition]
The photosensitive resin composition of this embodiment is a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, and the above (A) binder The polymer is a structural unit derived from (meth) acrylic acid, (EO) modified dicyclopentenyl (meth) acrylate, (EO) modified dicyclopentanyl (meth) acrylate, (EO) modified isobornyl (meth) acrylate, And a structural unit derived from at least one (meth) acrylate selected from the group consisting of (EO) -modified adamantyl (meth) acrylate and (EO) -modified cyclohexyl (meth) acrylate. As a result, the resist has excellent sensitivity at the time of resist pattern formation, and in addition to various properties such as tent reliability (tenting property), peelability and plating resistance, it is particularly excellent in resolution, adhesion, flexibility and resist shape. A pattern can be formed. Furthermore, it is possible to form a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less.

  This can be considered as follows, for example. A resist pattern formed by a conventional photosensitive resin composition has excellent flexibility (high flexibility), but is easily swelled with respect to the developer, or is not easily swelled with respect to the developer, but has flexibility. Since it is small, it is considered difficult to satisfy all of the resolution, adhesion, flexibility, and resist shape. Even if the formed resist pattern is excellent in flexibility, if the resist pattern easily swells with respect to the developer, the resist pattern tends to meander or fall (see, for example, FIGS. 2 and 3). Further, even if the formed resist pattern is difficult to swell with respect to the developer, if the flexibility is small, the resist pattern tends to be chipped or cracked (see, for example, FIG. 4). Therefore, in particular, when a resist pattern is formed on a thin plate substrate of 0.5 mm or less, a photosensitive resin composition that is difficult to swell with respect to a developing solution and can form a resist pattern excellent in flexibility is considered necessary. . In the present invention, the binder polymer contains a structural unit having an oxyethylene chain and a specific aliphatic ring in addition to the structural unit derived from (meth) acrylic acid, thereby allowing the flexibility and rigidity of the binder polymer. It is considered that a photosensitive resin composition capable of forming a resist pattern that is difficult to swell with respect to the developer and has excellent flexibility is obtained. Moreover, the utilization efficiency of the actinic ray irradiated by the binder polymer being comprised including the structural unit which has an oxyethylene chain and a specific aliphatic ring in addition to the structural unit derived from (meth) acrylic acid is effective. It is considered that the resist shape is improved, the sensitivity is excellent, and a good resist shape can be achieved.

<(A) component: Binder polymer>
First, the binder polymer (hereinafter also referred to as “component (A)” or “(A) binder polymer”) will be described.

  The photosensitive resin composition includes a structural unit derived from (meth) acrylic acid, (EO) -modified dicyclopentenyl (meth) acrylate, (EO) -modified dicyclopentanyl (meth) acrylate, and (EO) -modified isobornyl. At least one (meth) acrylate selected from the group consisting of (meth) acrylate, (EO) modified adamantyl (meth) acrylate and (EO) modified cyclohexyl (meth) acrylate (hereinafter referred to as “(EO) modified alicyclic ( And a structural unit derived from “meth) acrylate”.) At least one binder polymer.

  As the (EO) -modified alicyclic (meth) acrylate, any (meth) acrylate having a (poly) oxyethylene chain and having a specific aliphatic ring group can be used without particular limitation. In particular, a structure in which a specific aliphatic cyclic group is ester-bonded to (meth) acrylic acid via at least a (poly) oxyethylene chain is preferable. In that case, a (poly) oxypropylene chain may be further interposed in addition to the (poly) oxyethylene chain. Specific aliphatic ring groups include dicyclopentenyl, dicyclopentanyl, isobornyl, adamantyl and cyclohexyl groups. Among these, from the viewpoint of resolution, at least one selected from the group consisting of a dicyclopentenyl group, a dicyclopentanyl group, an isobornyl group and an adamantyl group is preferable, and a dicyclopentenyl group or a dicyclopentanyl group is more preferable. And more preferably a dicyclopentenyl group.

  The content of the oxyethylene group is appropriately selected according to the purpose. The content of the oxyethylene group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 1. Furthermore, the number of oxypropylene groups contained as necessary is preferably 0 to 10, more preferably 0 to 5, still more preferably 0 to 3, and particularly preferably 0. .

  The binder polymer is not particularly limited as long as it is a copolymer containing a structural unit derived from (meth) acrylic acid in addition to the structural unit derived from the (EO) -modified alicyclic (meth) acrylate. Specific examples include a binder polymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II).

Here, each R ¹ independently represents a hydrogen atom or a methyl group. X represents any of a dicyclopentenyl group, a dicyclopentanyl group, an isobornyl group, an adamantyl group, and a cyclohexyl group. a shows 0-10, b shows 1-10. In addition, the arrangement order of the oxyethylene group (OC ₂ H ₄ ) and the oxypropylene group (OC ₃ H ₆ ) may be different from the above, and when they are composed of three or more, that is, a + b is 3 or more. In this case, the oxyethylene group and the oxypropylene group may be arranged randomly or in a block form. Here, a and b indicate the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the number of structural units is defined similarly.

  In the structural unit represented by the general formula (I), from the viewpoint of excellent resolution, a is preferably 0 to 10, more preferably 0 to 5, still more preferably 0 to 3, and particularly preferably 0.

  Moreover, 1-10 are preferable, as for b, 1-5 are more preferable, 1-3 are still more preferable, and 1 is especially preferable. If b is 1 or more, the developability tends to be better. If it is 10 or less, sufficient resolution tends to be easily obtained.

  Examples of the polymerizable monomer that can form the structural unit represented by the general formula (I) include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, (meth) Isobornyloxyethyl acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclopentenyl di (oxyethyl) (meth) acrylate, dicyclopentanyl di (meth) acrylate ( Oxyethyl), isobornyl di (oxyethyl) (meth) acrylate, cyclohexyl di (oxyethyl) (meth) acrylate, adamantyl di (oxyethyl) (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, (meth) ) Dicyclopentanyl acrylate Propyl oxyethyl, (meth) acrylic acid dicyclopentenyl oxy propyloxyethyl include (meth) adamantyloxy propyloxyethyl acrylate.

  (A) The content of the structural unit represented by the general formula (I) in the binder polymer is preferably 3% by mass to 85% by mass based on the total mass of the molecule, and is 4% by mass to 83% by mass. More preferably, the content is more preferably 5% by mass to 80% by mass, particularly preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 80% by mass. If the content is 3% by mass or more, the adhesion, flexibility, and flexibility tend to be more excellent. Moreover, there exists a tendency for the resolution to be more excellent in this content rate being 85 mass% or less.

  Examples of the polymerizable monomer capable of forming the structural unit represented by the general formula (II) include acrylic acid and methacrylic acid. (A) The content of the structural unit represented by the general formula (II) in the binder polymer is preferably 10% by mass to 60% by mass, and 15% by mass to 50% by mass based on the total mass of the molecule. More preferably, the content is more preferably 20% by mass to 35% by mass. When this content is 10% by mass or more, the alkali solubility tends to be further improved and the peeling time tends to be shorter. Moreover, there exists a tendency for the resolution to be more excellent in this content rate being 60 mass% or less.

  The (A) binder polymer may further contain other structural units other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). Other polymerizable monomers that can form structural units include (meth) acrylic acid alkyl esters, (meth) acrylic acid cycloalkyl esters, (meth) acrylic acid benzyl, (meth) acrylic acid benzyl derivatives, (meth) ) Furfuryl acrylate, hydroxyalkyl ester (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetra (meth) acrylate (Meth) acrylic acid esters such as fluoropropyl; α-bromine (Meth) acrylic acid derivatives such as acrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid; styrene; α-position such as vinyltoluene, α-methylstyrene or the like Polymerizable styrene derivatives substituted in the aromatic ring; acrylamides such as diacetone acrylamide; acrylonitrile; esters of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; monomethyl maleate; Examples thereof include maleic acid monoesters such as monoethyl and monoisopropyl maleate; unsaturated carboxylic acids such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These can be used alone or in any combination of two or more.

  (A) The binder polymer preferably further has a structural unit derived from at least one polymerizable monomer selected from the group consisting of styrene and a styrene derivative from the viewpoint of improving resolution and adhesion. That is, (A) the binder polymer is at least one selected from the group consisting of at least one of (meth) acrylic acid, at least one of (EO) -modified alicyclic (meth) acrylate, and styrene and a styrene derivative. It is preferably obtained by radical polymerization with a polymerizable monomer, and preferably has a structural unit derived from these polymerizable monomers.

  (A) When the binder polymer has a structural unit derived from styrene or a derivative thereof, the content is preferably 10% by mass to 70% by mass based on the total mass of the molecule, and 15% by mass to 60% by mass. %, More preferably 20% by mass to 50% by mass. There exists a tendency for sufficient adhesiveness to become easy to be obtained as this content rate is 10 mass% or more. Moreover, when this content rate is 70 mass% or less, it is suppressed that a peeling piece becomes large too much, and there exists a tendency for peeling time to become short.

  In addition, (A) the binder polymer is at least one polymerizable monomer selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid benzyl, from the viewpoint of improving alkali developability and peelability. It is preferable to further have a structural unit derived from.

  The alkyl group in the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, from the viewpoint of improving alkali developability and peeling properties. Even more preferred are 1-12 alkyl groups. Specific examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, 2-ethylhexyl (meth) acrylate, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  When the (A) binder polymer has a structural unit derived from at least one polymerizable monomer selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid benzyl, the content is It is preferably 1% by mass to 50% by mass based on the total mass of the molecule, more preferably 2% by mass to 40% by mass, and still more preferably 3% by mass to 30% by mass. When the content is 1% by mass or more, the peeling piece is prevented from becoming too large, and the peeling time tends to be short. Moreover, there exists a tendency for sufficient resolution and adhesiveness to become easy to be obtained as this content rate is 50 mass% or less.

  (A) The acid value of the binder polymer is preferably 90 mgKOH / g to 250 mgKOH / g, more preferably 100 mgKOH / g to 230 mgKOH / g, and still more preferably 110 mgKOH / g to 210 mgKOH / g. 120 mg KOH / g to 200 mg KOH / g is particularly preferable. When the acid value is 90 mgKOH / g or more, the development time tends to be short, and when it is 250 mgKOH / g or less, sufficient developer resistance (adhesion) of the cured product of the photosensitive resin composition is obtained. There is a tendency to become easily. In addition, when performing solvent image development in the image development process mentioned later, it is preferable to prepare the structural unit derived from the polymerizable monomer which has carboxyl groups, such as (meth) acrylic acid, in a small quantity.

  (A) The weight average molecular weight (Mw) of the binder polymer is preferably 10,000 to 200,000 when measured by gel permeation chromatography (GPC) (converted with a calibration curve using standard polystyrene). 20,000 to 150,000, more preferably 25,000 to 120,000. When the weight average molecular weight (Mw) is 10,000 or more, the developer resistance (adhesion) of the cured product of the photosensitive resin composition tends to be sufficiently obtained, and is 200,000 or less. The development time tends to be short.

  In addition, the (A) binder polymer may have, in the molecule, a characteristic group having photosensitivity to light having a wavelength in the range of 340 nm to 430 nm as necessary. As the component (A), one kind of binder polymer may be used alone, or two or more kinds of binder polymers may be used in any combination.

  The content of the component (A) is preferably 30 parts by mass to 70 parts by mass, and 35 parts by mass to 65 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. More preferably, it is particularly preferably 40 to 60 parts by mass. When this content is 30 parts by mass or more, a film (photosensitive resin composition layer) tends to be easily formed, and when it is 70 parts by mass or less, sensitivity and resolution tend to be sufficiently obtained. is there.

<(B) component: photopolymerizable compound>
Next, (B) the photopolymerizable compound (hereinafter also referred to as “component (B)”) will be described.

  The component (B) is not particularly limited as long as it can be photopolymerized, but a compound having an ethylenically unsaturated bond is preferably used. Examples of the compound having an ethylenically unsaturated bond include a compound having one ethylenically unsaturated bond, a compound having two ethylenically unsaturated bonds, and a compound having three or more ethylenically unsaturated bonds. Among these, it is preferable that (B) component contains the compound which has an ethylenically unsaturated bond and a (poly) oxyethylene chain | strand from a viewpoint of adhesiveness and developability.

  Furthermore, it is preferable that (B) component contains at least 1 sort (s) of the compound which has two ethylenically unsaturated bonds. (B) When a component contains the compound which has two ethylenically unsaturated bonds, the content is 10 mass parts-80 mass parts, when the total amount of (A) component and (B) component is 100 mass parts It is preferable that it is 30 mass parts-70 mass parts.

  Examples of the compound having two ethylenically unsaturated bonds include a bisphenol A-based di (meth) acrylate compound, a hydrogenated bisphenol A-based di (meth) acrylate compound, and a di (meth) acrylate compound having a urethane bond in the molecule (hereinafter referred to as “a”). , "Urethane monomer"), polyalkylene glycol di (meth) acrylate compounds having both (poly) oxyethylene chains and (poly) oxypropylene chains, and trimethylolpropane di (meth) acrylate compounds. Among these, from the viewpoint of plating resistance and adhesion, a compound having two ethylenically unsaturated bonds is a bisphenol A di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, or an intramolecular compound. Are preferably polyalkylene glycol di (meth) acrylate compounds having both (poly) oxyethylene chains and (poly) oxypropylene chains, (EO) modified bisphenol A di (meth) acrylate compounds, (EO) modified hydrogenated A bisphenol A di (meth) acrylate compound or a polyalkylene glycol di (meth) acrylate compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain is more preferred.

  Among the above, the component (B) preferably contains at least one bisphenol A di (meth) acrylate compound from the viewpoint of improving sensitivity and resolution, and (EO) modified bisphenol A di (meth) acrylate. More preferably, it contains at least one compound. By combining at least one of (EO) -modified bisphenol A-based di (meth) acrylate compounds as the component (B) with the binder polymer, a resist pattern that is superior in resolution, adhesion, and resist shape can be formed.

  Examples of the bisphenol A-based di (meth) acrylate compound include compounds represented by the following general formula (2).

In the general formula (2), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.
XO and YO each independently represent an oxyethylene group or an oxypropylene group, which are different from each other. (XO) m ₁ , (XO) m ₂ , (YO) n ₁ and (YO) n ₂ each independently represent a (poly) oxyethylene chain or a (poly) oxypropylene chain. m ₁ , m ₂ , n ₁ and n ₂ each independently represent 0 to 40. When XO is an oxyethylene group and YO is an oxypropylene group, m ₁ + m ₂ is 1 to 40, n ₁ + n ₂ is 0 to 20, and when XO is an oxypropylene group and YO is an oxyethylene group, m ₁ + _{m 2} is _{0~20, n} 1 + n ₂ is 1 to 40.

  Among the compounds represented by the general formula (2), 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) or It is commercially available as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is 2,2-bis (4- (methacryloxy) as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Diethoxy) phenyl) propane is commercially available as BPE-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These may be used alone or in any combination of two or more.

  In the case where the component (B) includes a compound represented by the general formula (2), from the viewpoint of improving sensitivity and resolution, the content is 100 parts by mass of the total amount of the component (A) and the component (B). In this case, it is preferably 3 to 60 parts by mass, more preferably 10 to 50 parts by mass, further preferably 15 to 45 parts by mass, and 15 to 30 parts by mass. Part is particularly preferred.

  In addition, the component (B) preferably contains at least one polyalkylene glycol di (meth) acrylate compound from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition. When the component (B) contains a polyalkylene glycol di (meth) acrylate compound, the content is 3 parts by mass to 50 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. Part, preferably 5 parts by weight to 40 parts by weight.

  The polyalkylene glycol di (meth) acrylate compound is preferably a polyalkylene glycol di (meth) acrylate compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain. In the molecule of the polyalkylene glycol di (meth) acrylate compound, the (poly) oxyethylene chain and the (poly) oxypropylene chain may be continuously present in blocks or randomly. The oxypropylene group in the (poly) oxypropylene chain may be either an oxy-n-propylene group or an oxyisopropylene group. In the (poly) oxyisopropylene chain, the secondary carbon of the isopropylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

  The polyalkylene glycol di (meth) acrylate compound further includes (poly) oxy-n-butylene chain, (poly) oxyisobutylene chain, (poly) oxy-n-pentylene chain, (poly) oxyhexylene chain, It may have a (poly) oxyalkylene chain having about 4 to 6 carbon atoms, which is a structural isomer or the like.

  As the polyalkylene glycol di (meth) acrylate compound, at least one compound represented by any one of the following general formulas (3), (4) and (5) is particularly preferable. These can be used alone or in combination of two or more.

In the general formulas (3), (4) and (5), R ^{5 to} R ¹⁰ each independently represent a hydrogen atom or a methyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. r ₁ , r ₂ , r ₃ and r ₄ represent the number of structural units composed of oxyethylene groups, and s ₁ , s ₂ , s ₃ and s ₄ represent the number of structural units composed of oxypropylene groups. The total number of structural units r ₁ + r ₂ , r ₃ and r ₄ (average value) of the oxyethylene group independently represents 1 to 30, and the total number of structural units s ₁ , s ₂ + s ₃ and s _{4 of the} oxypropylene group (Average value) shows 1-30 each independently.

In the compound represented by the above general formula (3), (4) or (5), the total number of structural units r ₁ + r ₂ , r ₃ and r ₄ of the oxyethylene group is 1 to 30, but the resolution and adhesion From the viewpoint of being more excellent in the resist shape, it is more preferably 1 to 10, more preferably 4 to 9, and particularly preferably 5 to 8.

Further, the total number of structural units s ₁ , s ₂ + s ₃ and s ₄ of the oxypropylene group is 1 to 30, but it is 5 to 20 from the viewpoint of further improving the resolution and further suppressing the generation of sludge. Preferably, it is 8-16, and it is still more preferable that it is 10-14.

As the compound represented by the general formula (3), R ⁵ and R ⁶ = methyl group, r ₁ + r ₂ = 6 (average value), s ₁ = 12 (average value) vinyl compound (Hitachi Chemical Industries) (Trade name: FA-023M). As the compound represented by the general formula (4), R ⁷ and R ⁸ = methyl group, r ₃ = 6 (average value), s ₂ + s ₃ = 12 (average value) vinyl compound (Hitachi Chemical Industries) (Trade name: FA-024M) and the like. As the compound represented by the general formula (5), R ⁹ and R ¹⁰ = hydrogen atom, r ₄ = 1 (average value), s ₄ = 9 (average value) vinyl compound (Shin Nakamura Chemical Co., Ltd. ( Co., Ltd., sample name: NK ester HEMA-9P) and the like. These can be used alone or in combination of two or more.

  Moreover, it is preferable that (B) component contains at least 1 sort (s) of hydrogenated bisphenol A type | system | group di (meth) acrylate compound from a viewpoint of peeling characteristics and resolution. When (B) component contains hydrogenated bisphenol A type | system | group di (meth) acrylate compound, the content is 3 mass parts-50, when the total amount of (A) component and (B) component is 100 mass parts. It is preferable that it is a mass part, and it is more preferable that it is 5 mass parts-45 mass parts.

  Specific examples of the hydrogenated bisphenol A di (meth) acrylate compound include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane.

  The component (B) preferably contains at least one compound having one ethylenically unsaturated bond. In the case where the component (B) contains a compound having one ethylenically unsaturated bond, the content is from the viewpoint of improving the resolution, adhesion, resist shape, and peeling properties in a well-balanced manner (A) component and (B) When the total amount of components is 100 parts by mass, it is preferably 1 part by mass to 30 parts by mass, more preferably 3 parts by mass to 25 parts by mass, and 5 parts by mass to 20 parts by mass. More preferably, it is 5 mass parts-10 mass parts.

  Examples of the compound having one ethylenically unsaturated bond include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters.

  Among the above, it is preferable that nonylphenoxypolyethyleneoxyacrylate or a phthalic acid-based compound is included from the viewpoint of improving the resolution, adhesion, resist shape, and peeling properties in a balanced manner.

  Nonylphenoxypolyethyleneoxyacrylate includes nonylphenoxytriethyleneoxyacrylate, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate Nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, nonylphenoxyundecaethyleneoxyacrylate, and the like. These can be used alone or in any combination of two or more. “Nonylphenoxypolyethyleneoxyacrylate” is also referred to as “nonylphenoxypolyethyleneglycol acrylate”.

  Of these, nonylphenoxyoctaethyleneoxyacrylate is commercially available, for example, as M-114 (trade name, 4-normalnonylphenoxyoctaethyleneoxyacrylate, manufactured by Toagosei Co., Ltd.). Note that “4-normalnonylphenoxyoctaethyleneoxyacrylate” is also referred to as “4-normalnonylphenoxyoctaethylene glycol acrylate”.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate and the like can be mentioned. Among them, γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate is preferable. γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (trade name, manufactured by Hitachi Chemical Co., Ltd.). These can be used alone or in combination of two or more.

  The component (B) preferably contains a photopolymerizable compound having three or more ethylenically unsaturated bonds. In the case where the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bonds, the content of the component (A) is from the viewpoint of improving the resolution, adhesion, resist shape and release properties in a balanced manner. And when the total amount of (B) component is 100 mass parts, it is preferable that it is 3-30 mass parts, and it is more preferable that it is 5-20 mass parts.

  Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate and (EO) -modified trimethylolpropane tri (meth) acrylate (one having 1 to 5 structural units of oxyethylene group). , (PO) modified trimethylolpropane tri (meth) acrylate, (EO) · (PO) modified trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, di Examples include pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. These can be used alone or in combination of two or more. Among these, A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, tetramethylolmethane triacrylate), TMPT21E, TMPT30E (manufactured by Hitachi Chemical Co., Ltd., sample name) are available. (EO) -modified trimethylolpropane trimethacrylate) and the like.

  The photosensitive resin composition comprises the binder polymer, at least one (EO) -modified bisphenol A-based di (meth) acrylate compound as the component (B), a (poly) oxyethylene chain and (poly) in the molecule. By combining at least one selected from the group consisting of a polyalkylene glycol di (meth) acrylate compound having both oxypropylene chains and (EO) -modified trimethylolpropane tri (meth) acrylate, resolution, adhesion, bending It is possible to form a resist pattern that is more excellent in properties and resist shape.

  The total content of component (B) is preferably 30 parts by mass to 70 parts by mass, and 35 parts by mass to 60 parts by mass when the total amount of component (A) and component (B) is 100 parts by mass. It is more preferable to set it as 35 mass parts-50 mass parts. When the content is 30 parts by mass or more, sufficient sensitivity and resolution tend to be easily obtained. If it is 70 parts by mass or less, the film formability tends to be improved, and a good resist shape tends to be easily obtained.

<(C) component: photopolymerization initiator>
Next, the photopolymerization initiator (hereinafter also referred to as “component (C)”) will be described.

  There is no restriction | limiting in particular as a photoinitiator which is (C) component. As the photopolymerization initiator, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketone compounds such as propanone-1; quinone compounds such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) 2,4,5-diarylimidazole dimer such as -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1 , 7- (9,9′-acridinyl) heptane Such as derivative, and the like. These can be used alone or in combination of two or more.

  The component (C) preferably contains a 2,4,5-triarylimidazole dimer from the viewpoint of improving the sensitivity at the time of resist pattern formation and the adhesion of the formed resist pattern, and 2- (o- More preferably, it includes a chlorophenyl) -4,5-diphenylimidazole dimer. The 2,4,5-triarylimidazole dimer may be symmetric or asymmetric in structure.

  The content of component (C) is preferably 0.1 to 10 parts by mass, preferably 1 to 7 parts by mass when the total amount of component (A) and component (B) is 100 parts by mass. Is more preferably 2 parts by mass to 6 parts by mass, and particularly preferably 3 parts by mass to 5 parts by mass. When the content is 0.1 parts by mass or more, good sensitivity, resolution, or adhesion tends to be obtained. Moreover, there exists a tendency for a favorable resist shape to become easy to be obtained as it is 10 mass parts or less.

<(D) component: sensitizing dye>
The photosensitive resin composition preferably further contains at least one sensitizing dye (hereinafter also referred to as “component (D)”), and at least one sensitizing dye having a maximum absorption at a wavelength of 340 nm to 430 nm. More preferably, it further comprises a seed. The sensitizing dye as component (D) will be described below.

  As the sensitizing dye as component (D), dialkylaminobenzophenone compound, pyrazoline compound, anthracene compound, coumarin compound, xanthone compound, thioxanthone compound, oxazole compound, benzoxazole compound, thiazole compound, benzothiazole compound, triazole compound, stilbene Examples thereof include compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, aminoacridine compounds, and the like. These can be used alone or in combination of two or more.

  In particular, when the photosensitive resin composition layer is exposed using an actinic ray having a wavelength of 340 nm to 430 nm, the component (D) is an increase having a maximum absorption at a wavelength of 340 nm to 430 nm from the viewpoint of sensitivity and adhesiveness. It is preferably a sensitizing dye, and includes at least one sensitizing dye selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, triarylamine compounds, thioxanthone compounds, and aminoacridine compounds. More preferably, it is more preferable that at least one selected from the group consisting of a pyrazoline compound, an anthracene compound and a triarylamine compound is included.

  The content of the component (D) is preferably 0.01 parts by mass to 10 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass, More preferably, it is 5 mass parts, and it is still more preferable that it is 0.1-3 mass parts. When this content is 0.01 parts by mass or more, better sensitivity and resolution tend to be easily obtained. If it is 10 parts by mass or less, a sufficiently good resist shape tends to be easily obtained.

  The pyrazoline compound is preferably at least one selected from the group consisting of a compound represented by the following general formula (6) and a compound represented by the general formula (7).

In the general formula (6), R ^{11 to} R ¹³ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 10 carbon atoms. Or a halogen atom is shown. A, b and c each independently represent an integer of 0 to 5, and the sum of a, b and c is 1 to 6. When the sum of a, b and c is 2 or more, a plurality of R ^{11 to} R ¹³ may be the same as or different from each other.

In the general formula (6), at least one of R ^{11 to} R ¹³ is a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched group having 1 to 10 carbon atoms. Is preferably a linear or branched alkyl group having 1 to 3 carbon atoms or a linear or branched alkoxy group having 1 to 3 carbon atoms, more preferably isopropyl. More preferably, it is a group, a methoxy group or an ethoxy group.

  There is no restriction | limiting in particular as a pyrazoline compound represented by the said General formula (6). Specifically, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4- tert-butyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3 , 5-Dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) ) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) Pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2, And pyrazoline compounds corresponding to a = 0 in the general formula (6) such as 4-dimethoxyphenyl) -pyrazoline.

In the general formula (7), R ^{14 to} R ¹⁶ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 10 carbon atoms. Represents a halogen atom or a phenyl group. D, e, and f each independently represent an integer of 0-5, and the sum of d, e, and f is 1-6. When the sum of d, e, and f is 2 or more, a plurality of R ^{14 to} R ¹⁶ may be the same as or different from each other.

In the general formula (7), at least one of R ^{14 to} R ¹⁶ is a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched group having 1 to 10 carbon atoms. Is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a phenyl group. More preferred is a tert-butyl group, isopropyl group, methoxy group, ethoxy group or phenyl group.

Further, the pyrazoline compound represented by the general formula (7) is not particularly limited, but 1-phenyl-3,5-bis (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3,5 -Bis (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (4-methoxyphenyl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-tert-butylphenyl) ) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (4-isopropylphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert -Butylphenyl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxyphenyl) -5- (4-isopropylphenyl) Nyl) -pyrazoline, 1-phenyl-3- (4-isopropylphenyl) -5- (4-methoxyphenyl) -pyrazoline, 1,5-diphenyl-3- (4-tert-butylphenyl) -pyrazoline, 1, 3-diphenyl-5- (4-tert-butylphenyl) -pyrazoline, 1,5-diphenyl-3- (4-isopropylphenyl) -pyrazoline, 1,3-diphenyl-5- (4-isopropylphenyl) -pyrazoline 1,5-diphenyl-3- (4-methoxy-phenyl) -pyrazoline, 1,3-diphenyl-5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3,5-bis (4-tert- Butylphenyl) -pyrazoline, 1,5-diphenyl-3- (4-tert-butylphenyl) -pyrazoline, etc. ) In 1): 1-phenyl-3- (4-biphenyl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5 Examples of the general formula (7) such as-(4-tert-octylphenyl) -pyrazoline include pyrazoline compounds in which e = 1 and R ¹⁵ = phenyl group.

  The anthracene compound preferably includes at least one compound represented by the following general formula (8).

In the general formula (8), R ¹⁷ and R ¹⁸ each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, or a benzyl group. In addition, the aromatic ring in the said General formula (8) may have a substituent, unless the effect of this invention is inhibited.

In the general formula (8), examples of R ¹⁷ and R ¹⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the combination of R ¹⁷ and R ¹⁸ include a combination of ethyl groups, a combination of propyl groups, and a combination of butyl groups.

R ¹⁷ and R ¹⁸ are preferably each independently an alkyl group having 1 to 4 carbon atoms.

  Specific examples of the compound represented by the general formula (8) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.

  The triarylamine compound preferably includes at least one compound represented by the following general formula (9).

In the general formula (9), R ²⁷ , R ²⁸ and R ²⁹ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and g, h and i are , An integer of 0 to 5 selected so that the value of g + h + i is 1 or more. When g is 2 or more, a plurality of R ²⁷ may be the same or different. When h is 2 or more, a plurality of R ²⁸ may be the same or different. When i is 2 or more A plurality of R ²⁹ may be the same or different.

<Other ingredients>
The photosensitive resin composition preferably contains bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, or leucocrystal violet. These can be used alone or in combination of two or more. When the photosensitive resin composition contains these compounds, the content is 0.01 parts by mass to 10 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. It is more preferable that it is 0.05 mass part-5 mass parts, and it is especially preferable that it is 0.1 mass part-2 mass parts. When this content is 0.01 parts by mass or more, sufficient sensitivity tends to be obtained. Moreover, when it is 10 parts by mass or less, it tends to be more effectively suppressed that the above-mentioned compound is precipitated as a foreign substance after film formation.

  If necessary, the photosensitive resin composition of the present embodiment includes a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, and the like. Dyes, tribromomethylphenylsulfone, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, release accelerators, You may contain antioxidant, a fragrance | flavor, an imaging agent, a thermal crosslinking agent, etc. These are used alone or in combination of two or more. These contents should be about 0.01 to 20 parts by mass when the total amount of the component (A) (binder polymer) and the component (B) (photopolymerizable compound) is 100 parts by mass. Is preferred.

<Organic solvent>
The photosensitive resin composition of this embodiment can contain at least 1 sort (s) of the organic solvent as needed. The content of the organic solvent in the photosensitive resin composition is not particularly limited and can be appropriately selected according to the purpose. The photosensitive resin composition can be used, for example, as a solution having a solid content of about 30% by mass to 60% by mass (hereinafter also referred to as “coating liquid”). Here, the solid content means the remaining components obtained by removing volatile components from the photosensitive resin composition.

  Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; hydrocarbon solvents such as toluene; N, N-dimethyl Examples include aprotic polar solvents such as formamide; mixed solvents thereof.

  The said coating liquid can be used for formation of the photosensitive resin composition layer as follows, for example. The said coating liquid is apply | coated on surfaces, such as a metal plate, and the photosensitive resin composition layer which consists of the photosensitive resin composition of this embodiment can be formed by making it dry. Examples of the metal of the metal plate include copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel, and copper, copper-based alloys, iron-based alloys, and the like are preferable.

  The thickness of the photosensitive resin composition layer varies depending on its use, but is preferably about 1 μm to 100 μm in thickness after drying. You may coat | cover the surface on the opposite side to the metal plate of the photosensitive resin composition layer with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

[Photosensitive element]
As shown in FIG. 1, the photosensitive element 1 of the present invention includes a support film 2 and a photosensitive resin composition layer 3 formed on the support film 2 and being a coating film of the photosensitive resin composition. In addition, other components (for example, the protective film 4) are further provided as necessary. By providing the photosensitive resin composition layer formed from the photosensitive resin composition, it is possible to form a resist pattern that is particularly excellent in resolution, adhesion, flexibility, and resist shape.

  The photosensitive element is obtained by forming the photosensitive resin composition layer that is a coating film of the photosensitive resin composition on the support film by applying the coating liquid on the support film and drying it. Can do.

  It does not restrict | limit especially as a support film, It can select suitably from the polymer film used normally. As the support film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  The thickness of the support film (polymer film) is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and still more preferably 5 μm to 30 μm. It can suppress that a support film is torn when this thickness is 1 micrometer or more, when peeling a support film. If it is 100 μm or less, the resolution tends to be sufficiently obtained.

  As shown in FIG. 1, the photosensitive element 1 may include a protective film 4 that covers the surface of the photosensitive resin composition layer 3 opposite to the support film 2 as necessary.

  As a protective film, the adhesive force with respect to the photosensitive resin composition layer is smaller than the adhesive force with respect to the photosensitive resin composition layer of a support film, and a film with a low fish eye is preferable.

  Specifically, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used as the protective film. The protective film may be the same as the support film.

  The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 30 μm, and particularly preferably 15 μm to 30 μm. When the thickness is 1 μm or more, the protective film tends to be difficult to tear when the photosensitive resin composition layer and the protective film are laminated (laminated) on the substrate. Moreover, there exists a tendency for productivity to improve that it is 100 micrometers or less.

  Application of the coating solution onto the support film can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater.

  The coating layer formed by applying the coating solution is preferably dried at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  Although the thickness of the photosensitive resin composition layer in a photosensitive element changes with uses, it is preferable that it is 1 micrometer-100 micrometers in the thickness after drying, it is more preferable that they are 1 micrometer-50 micrometers, and it is that they are 5 micrometers-40 micrometers. Further preferred. When this thickness is 1 μm or more, coating is industrially easy and productivity tends to be further improved. Moreover, there exists a tendency for adhesiveness and the resolution to become fully easy to be acquired as it is 100 micrometers or less.

  The obtained photosensitive element can be stored in the form of a sheet or a roll wound around a core. When it winds up in roll shape, it is preferable to wind up so that a support film may become an outer side.

[Method of forming resist pattern]
The resist pattern forming method of the present invention includes: (i) a lamination step of laminating a photosensitive resin composition layer that is a coating film of the photosensitive resin composition or a photosensitive resin composition of the photosensitive element on a substrate; (Ii) an exposure step of irradiating at least a part of the photosensitive resin composition layer with actinic rays and photocuring the region to form a photocured portion; and (iii) the photosensitive resin composition. And a developing step of forming a resist pattern made of a photocured product of the photosensitive resin composition on the substrate by removing the region other than the photocured portion of the layer from the substrate, and if necessary It has other processes. In the resist pattern forming method, the laminating step is preferably a step of laminating the photosensitive resin composition layer of the photosensitive element by thermocompression bonding on the substrate.

(I) Lamination process First, the photosensitive resin composition layer formed using the photosensitive resin composition is laminated | stacked on a board | substrate.
As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  Lamination of the photosensitive resin composition layer on the substrate is performed, for example, by removing the protective film of the photosensitive element and then pressing the photosensitive resin composition layer of the photosensitive element on the substrate while heating. Is called. Thereby, the laminated body which consists of a board | substrate, the photosensitive resin composition layer, and the support film, and these were laminated | stacked in order is obtained.

This lamination operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The photosensitive resin composition layer and / or heating of the substrate during the bonding is preferably carried out at a temperature of 70 ° C. to 130 DEG ° C., about ^{0.1MPa~1.0MPa (1kgf / cm 2 ~10kgf /} cm 2 of about It is preferable to press-bond with a pressure of (), but these conditions are not particularly limited. In addition, if the photosensitive resin composition layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the substrate may be pre-heated in order to further improve the lamination property. .

(Ii) Exposure Step Next, at least a part of the photosensitive resin composition layer laminated on the substrate is irradiated with actinic rays to expose the region, and photocured to form a photocured portion. Under the present circumstances, when the support film which exists on the photosensitive resin composition layer is permeable with respect to actinic light, actinic light can be irradiated through a support film. On the other hand, when the support film is light-shielding against actinic rays, the photosensitive resin composition layer may be irradiated with actinic rays after the support film is removed.

  Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

The photosensitive resin composition of this invention can be used conveniently for the direct drawing exposure method. That is, one of the preferred embodiments of the present invention includes (A) a structural unit derived from (meth) acrylic acid,
(EO) modified dicyclopentenyl (meth) acrylate, (EO) modified dicyclopentanyl (meth) acrylate, (EO) modified isobornyl (meth) acrylate, (EO) modified adamantyl (meth) acrylate and (EO) modified cyclohexyl A binder polymer having a structural unit derived from at least one (meth) acrylate selected from the group consisting of (meth) acrylates, (B) a photopolymerizable compound, and (C) a photosensitizer containing a photopolymerization initiator. This is an application to the direct drawing exposure method of the conductive resin composition.

  As a light source of actinic light, a known light source can be used, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, an ultraviolet ray such as a semiconductor laser, What emits visible light etc. effectively is used.

  The wavelength of the actinic ray (exposure wavelength) is preferably in the range of 340 nm to 430 nm, more preferably in the range of 350 nm to 420 nm, from the viewpoint of obtaining the effects of the present invention more reliably.

(Iii) Development step Further, a region other than the photocured portion of the photosensitive resin composition layer is removed from the substrate, whereby a resist pattern made of the photocured product of the photosensitive resin composition is formed on the substrate. Form. When the support film is present on the photosensitive resin composition layer, the support film is removed, and then the portion (unexposed portion) other than the photocured portion (exposed portion) is removed (developed). . Development methods include wet development and dry development, but wet development is widely used.

  In the case of wet development, development is performed by a known development method using a developer corresponding to the configuration of the photosensitive resin composition. Examples of the developing method include a method using a dipping method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. The developing method may be performed by combining two or more methods selected from these.

  The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. Specifically, alkaline aqueous solution, aqueous developer, organic solvent developer and the like can be mentioned.

After removal of the unexposed portions, by performing about 60 ° C. to 250 DEG ° C. heating or 0.2J ^/ cm ² ~10J ^/ cm 2 about the exposure as required, the resist pattern may be further cured.

[Method of manufacturing printed wiring board]
The method for producing a printed wiring board of the present invention includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern has been formed by the above-described resist pattern forming method, and other processes as necessary. Process. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  Examples of the etching solution for performing the etching treatment include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide etching solution. In these, it is preferable to use a ferric chloride solution from a point with a favorable etch factor.

  Plating methods for plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate And gold plating such as hard gold plating and soft gold plating.

  After completion of the etching process or the plating process, 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% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution and the like are used. Especially, it is preferable to use 1 mass%-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1 mass%-5 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

  Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

  The photosensitive resin composition of this embodiment can be used suitably for manufacture of a printed wiring board. That is, one preferred embodiment of the present invention includes (A) a structural unit derived from (meth) acrylic acid, (EO) modified dicyclopentenyl (meth) acrylate, (EO) modified dicyclopentanyl ( Derived from at least one (meth) acrylate selected from the group consisting of (meth) acrylate, (EO) modified isobornyl (meth) acrylate, (EO) modified adamantyl (meth) acrylate and (EO) modified cyclohexyl (meth) acrylate. This is an application of a photosensitive resin composition containing a binder polymer having a structural unit, (B) a photopolymerizable compound, and (C) a photopolymerization initiator to the production of a printed wiring board. A more preferred embodiment is application of the photosensitive resin composition to the production of a high-density package substrate, and application of the photosensitive resin composition to a semi-additive construction method. In addition, an example of the manufacturing process of the wiring board by a semi-additive construction method is shown in FIG.

  In FIG. 5A, a substrate (circuit forming substrate) in which the conductor layer 10 is formed on the insulating layer 15 is prepared. The conductor layer 10 is, for example, a metal copper layer. In FIG.5 (b), the photosensitive resin composition layer 32 is laminated | stacked on the conductor layer 10 of a board | substrate by the said lamination process. In FIG.5 (c), the mask 20 is laminated | stacked on the photosensitive resin composition layer 32, actinic light 50 is irradiated, and areas other than the area | region where the mask 20 was laminated | stacked are exposed, and a photocuring part is formed. . In FIG. 5D, the resist pattern 30 which is a photocuring part is formed on a board | substrate by removing areas other than the photocuring part formed by the said exposure process from a board | substrate by a image development process. In FIG. 5E, the plating layer 42 is formed on the conductor layer 10 by plating using the resist pattern 30 that is a photocured portion as a mask. In FIG. 5F, after the resist pattern 30 which is a photocured portion is peeled off with a strong alkaline aqueous solution, a part of the plating layer 42 and the conductor layer 10 masked by the resist pattern 30 are removed by flash etching. The circuit pattern 40 is formed by removing.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Preparation of photosensitive resin composition)
By mixing the components shown in Table 2 and Table 3 in the blending amounts (unit: parts by mass) shown in the same table, solutions of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 12 were prepared. . In addition, the compounding quantity of (A) component shown in Table 2 and Table 3 is the mass (solid content) of a non volatile matter, and "-" shows that it is unblending. Details of each component shown in Table 2 and Table 3 are as follows.

<(A) Binder polymer>
Table 1 shows the mass ratio (%), acid value, and weight average molecular weight of the polymerizable monomers (monomers) for the binder polymers (A-1) to (A-10). “-” Means not blended.

[Synthesis of Binder Polymer (A-1)]
78 g of methacrylic acid which is a polymerizable monomer (monomer), 75 g of dicyclopentenyloxyethyl methacrylate, 15 g of methyl methacrylate and 132 g of styrene (mass ratio 26/25/5/44) and azobisisobutyronitrile 2 The solution obtained by mixing 5 g was designated as “Solution a”.

  A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 150 g of a mixed solution (mass ratio 3: 2) of 100 g of methyl cellosolve and 50 g of toluene was designated as “Solution b”.

  A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 300 g of a mixture of 180 g of methyl cellosolve and 120 g of toluene (mass ratio 3: 2), and nitrogen gas was introduced into the flask. The mixture was heated with stirring while being blown, and the temperature was raised to 80 ° C.

  The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer (A-1) solution.

  The binder polymer (A-1) had a non-volatile content (solid content) of 42.8% by mass, a weight average molecular weight of 43,000, and an acid value of 170 mgKOH / g.

The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
GPC condition pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: The following three Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymer (A-2)]
As the polymerizable monomer (monomer), a binder polymer was used except that a solution obtained by mixing 0.25 g of azobisisobutyronitrile with the same mass ratio as that of the binder polymer (A-1) was used. A solution of the binder polymer (A-2) was obtained in the same manner as that for obtaining the solution of (A-1).

[Synthesis of Binder Polymers (A-3) to (A-10)]
As the polymerizable monomer (monomer), the binder polymer (A-3) was obtained in the same manner as in the case of obtaining a solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in the same table. ) To (A-10) were obtained.

<(B) Photopolymerizable compound>
TMPT21E (manufactured by Hitachi Chemical Co., Ltd., sample name): (EO) modified trimethylolpropane trimethacrylate (ethylene oxide average 21 mol adduct)
FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane BPE-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) ): 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane / crosslinking agent 1: 2,2-bis (4- (methacryloxydiethoxydiproxy) phenyl) propane / crosslinking agent 2: 2, 2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane / crosslinking agent 3: (EO) / (PO) modified pentaerythritol tetraacrylate (8 mol of ethylene oxide and 8 mol of propylene oxide on average)
FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.): In the above general formula (4), R ⁷ and R ⁸ = methyl group, r ₃ = 6 (average value), s ₂ + s ₃ = 12 ( Vinyl compound FA-023M (trade name, manufactured by Hitachi Chemical Co., Ltd.): In the above general formula (3), R ⁵ and R ⁶ = methyl group, r ₁ + r ₂ = 6 (average value) ), Vinyl compound M-114 (trade name, manufactured by Toagosei Co., Ltd.): s ₁ = 12 (average value): 4-normalnonylphenoxyoctaethylene glycol acrylate

<(C) Photopolymerization initiator>
B-CIM (trade name, manufactured by Hampford): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole

<(D) Sensitizing dye>
PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline DBA (manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name) ): 9,10-dibutoxyanthracene / J205 (manufactured by Nippon Distillation Co., Ltd., trade name): triphenylamine derivative represented by the following formula (10)

EAB (trade name, manufactured by Hodogaya Chemical Co., Ltd.): 4,4'-bis (diethylamino) benzophenone

<(E) Amine compound>
LCV (trade name, manufactured by Yamada Chemical Co., Ltd.): Leuco Crystal Violet <Dye>
・ MKG (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.): Malachite Green

(Photosensitive element)
The photosensitive resin composition obtained above was uniformly applied onto a polyethylene terephthalate film (trade name “HTF-01”, manufactured by Teijin Limited) having a thickness of 16 μm, and hot air convection at 70 ° C. and 110 ° C. A photosensitive resin composition layer having a dried film thickness of 25 μm was formed by sequentially drying with a type dryer. A protective film (manufactured by Tamapoly Co., Ltd., trade name “NF-15”) is laminated on the photosensitive resin composition layer, and a polyethylene terephthalate film (support film), the photosensitive resin composition layer, and a protective film The photosensitive elements according to Examples 1 to 13 and Comparative Examples 1 to 12 were obtained as photosensitive elements in which are stacked in order.

(Laminated substrate)
The copper foil of the core material (made by Hitachi Chemical Co., Ltd., trade name “E-679-F”) is roughened, and the build-up material (made by Hitachi Chemical Co., Ltd., trade name “AS-Z3”) After laminating, Atotech's desmear and electroless copper plating were performed. The copper substrate (hereinafter simply referred to as “substrate”) had a surface roughness Ra of 0.2 μm and a thickness of 0.5 mm. After heating the said board | substrate and heating up to 80 degreeC, the photosensitive element which concerns on Examples 1-13 and Comparative Examples 1-12 was laminated | stacked on the copper surface of the board | substrate. Lamination was performed at a temperature of 120 ° C. and a lamination pressure of 3.9 × 10 ⁵ Pa (4 kgf / cm) so that the photosensitive resin composition layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective film. ^It was performed under the conditions of ² ).
Thus, the laminated substrate by which the photosensitive resin composition layer and the polyethylene terephthalate film were laminated | stacked on the copper surface of the board | substrate was obtained.

(Evaluation of sensitivity)
The obtained laminated substrate was allowed to cool and when the temperature reached 23 ° C., on the polyethylene terephthalate film of the laminated substrate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet size of 20 mm × 187 mm. A photo tool having a 41-step tablet having a size of 3 mm × 12 mm for each step was brought into close contact. Using a direct exposure tool “DE-1UH” (trade name) manufactured by Hitachi Via Mechanics with a blue-violet laser diode having a wavelength of 405 nm as a light source, a photo tool and polyethylene with an energy amount (exposure amount) of 80 mJ / cm ² Exposure was performed with respect to the photosensitive resin composition layer through the terephthalate film. The illuminance was measured using an ultraviolet illuminometer (trade name “UIT-150” manufactured by USHIO INC.) Using a 405 nm probe.

After the exposure, the polyethylene terephthalate film was peeled from the laminated substrate, the photosensitive resin composition layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 50 seconds to remove unexposed portions. Thus, the cured film which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps (step number) of the step tablet obtained as a cured film. The sensitivity is indicated by the number of step steps, and the higher the step number, the better the sensitivity.
The results are shown in Tables 5 and 6.

(Evaluation of resolution and adhesion)
The remaining 41-step tablet using a drawing pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 3/3 to 30/30 (unit: μm) Exposure (drawing) was performed on the photosensitive resin composition layer of the laminated substrate with an energy amount of 16 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed with the minimum value of the line width / space width values in the resist pattern formed without meandering and chipping. The resolution and adhesion were evaluated. A smaller value means better resolution and adhesion. The results are shown in Tables 5 and 6.

(Evaluation of resist shape)
In the evaluation of the resolution and adhesion, the obtained resist shape (cross-sectional shape of the resist pattern) was observed using a Hitachi scanning electron microscope S-500A. If the resist shape is trapezoidal or inverted trapezoidal, or if there is resist skirting or cracking, a short circuit or disconnection tends to occur in a circuit formed by subsequent etching or plating. Therefore, it is desirable that the resist shape is rectangular (rectangular) and that there is no resist skirting or cracking. Note that “crack” means that a line portion (exposed portion) of the resist pattern is cracked or cracked, or accompanying this, the line portion is chipped or broken. “A” when the resist shape is rectangular and there is no resist skirt or crack, “B” when the resist skirt is partially seen, and “B” when the resist skirt is seen entirely. Evaluated as “C”. The results are shown in Tables 5 and 6.

(Evaluation of peeling properties)
Each photosensitive element is laminated on the copper-clad laminate (substrate), and exposed and developed under the conditions shown in Table 4, whereby a test piece (40 mm × x) in which a cured film (resist pattern) is formed on the substrate. 50 mm). After leaving this test piece for a day and night at room temperature, peeling was performed under the conditions shown in Table 4. The time from the start of stirring until the cured film was completely peeled and removed from the substrate was defined as the peeling time (seconds). Moreover, the shape and size of the peeling piece after peeling were observed visually, and the following references | standards evaluated. The peel piece size was evaluated as an average value of the lengths of the sides when the peel piece was approximated to a rectangular shape. The shorter the peeling time and the smaller the peeling piece size, the better the peeling characteristics. The results are shown in Tables 5 and 6.
Peeling piece size L: sheet shape M: 30 mm square to 40 mm square S: smaller than 30 mm square

(Evaluation of tent reliability)
A photosensitive element is laminated on both sides of a 1.6 mm thick copper-clad laminate with three holes of 4 mm in diameter, and the number of remaining steps after development is 15.0. The exposure was carried out at an exposure amount such that development for 50 seconds was performed twice. After development, the number of broken holes was measured for a total of 18 triple 4 mm holes, and evaluated as a deformed tent breakage rate (the following formula), which was defined as tent reliability.
Deformed tent tear rate (%) = (Number of hole tears (pieces) / 18 (pieces)) x 100

(Evaluation of flexibility)
An FPC board (trade name: F-30VC1, board thickness: 25 μm, copper thickness: 18 μm, manufactured by Nikkan Kogyo Co., Ltd.) was heated to 80 ° C., and Examples 1 to 13 and Comparative Examples 1 to 1 were formed on the copper surface. The photosensitive resin composition layer and the support film of the photosensitive element according to No. 12 were removed by using a 110 ° C. heat roll while peeling off the protective film so that the photosensitive resin composition layer faced the FPC substrate side. Laminated at a rate of minutes. The FPC substrate on which the photosensitive resin composition layer and the support were laminated was used as a test piece for evaluating flexibility. For the test piece, a direct drawing exposure machine DE-1UH manufactured by Hitachi Via Mechanics Co., Ltd. using a blue-violet laser diode having a wavelength of 405 nm as a light source is used, and the number of remaining step stages after development of the 41-step tablet is 11 stages. Exposure was performed with the amount of energy, and the photosensitive resin composition layer was photocured. Thereafter, the support film was peeled and developed to obtain a flexibility evaluation substrate in which a resist pattern was laminated on an FPC substrate.

  The bendability was evaluated by a mandrel test, and the substrate for bendability evaluation was cut into a strip shape having a width of 2 cm and a length of 10 cm, and was rubbed back and forth 5 times at 180 ° with a cylindrical rod. Thereafter, the minimum cylindrical diameter (mm) without peeling between the FPC substrate and the resist pattern was determined. The smaller the diameter of the cylinder, the better the flexibility.

(Evaluation of plating resistance)
Evaluation of plating resistance was performed as follows.
Using the laminated substrate obtained above, exposure was performed with a predetermined exposure amount under the process conditions shown in Table 4, and then a degreasing solution (product name “PC-455”, 25 mass%, manufactured by Meltex Co., Ltd.) 5 minutes immersion, water washing, soft etching solution (ammonium persulfate 150 g / L) 2 minutes immersion, water washing, 10% by weight sulfuric acid 1 minute pre-treatment in order, copper sulfate plating bath (copper sulfate 75 g / L , 190 g / L of sulfuric acid, 50 ppm of chlorine ions, manufactured by Meltex, product name “Capper Grime PCM” 5 mL / L), copper sulfate plating was performed at room temperature, 2 A / dm ² for 40 minutes, and then washed with water.

  In order to examine the plating resistance after washing with water and drying, cellotape (registered trademark) was immediately applied on the resist pattern and peeled off in the vertical direction (90 ° peel-off test), and the presence or absence of peeling of the resist pattern was observed. Further, after the resist pattern was peeled off, the presence or absence of copper plating was observed with an optical microscope from above. In the case where the copper plating is stripped, metallic copper deposited by copper plating is observed in the region masked with the resist pattern.

  As is clear from Tables 5 and 6, the photosensitive resin compositions of Examples 1 to 13 all have sensitivity, resolution, adhesion, flexibility, tent reliability, plating resistance, resist shape, and release characteristics. It was good. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 12 have any one of resolution, adhesion, flexibility, flexibility, tent reliability, plating resistance, and resist shape as compared with the examples. It was inferior. In addition, about the comparative example 11, since the photosensitive resin composition layer was not closely_contact | adhered to the board | substrate at the time of lamination, evaluation was impossible.

DESCRIPTION OF SYMBOLS 1 Photosensitive element 2 Support film 3 Photosensitive resin composition layer 4 Protective film 10 Conductor layer 20 Mask 30 Resist pattern 40 Circuit pattern

Claims (6)

A support film;
A photosensitive resin composition layer formed on the support film and being a coating film of the photosensitive resin composition;
With
The photosensitive resin composition has a binder polymer (provided that ( A) a structural unit derived from (meth) acrylic acid and a structural unit derived from (EO) -modified dicyclopentenyl (meth) acrylate) Except for a photopolymerizable compound having an acryloyl group and a binder polymer having a structural unit represented by the following formula :), (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) 340 nm to 430 nm. A photosensitive element containing a sensitizing dye having an absorption maximum in the surface.


(R4, R5, and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R7 represents an alkyl group having 8 to 18 carbon atoms.)   The photosensitive element according to claim 1, wherein the (A) binder polymer further has a structural unit derived from at least one polymerizable monomer selected from the group consisting of styrene and a styrene derivative.   The photosensitive element according to claim 1, wherein the (B) photopolymerizable compound contains a bisphenol A-based di (meth) acrylate compound.   The photosensitive element according to any one of claims 1 to 3, wherein the (C) photopolymerization initiator includes a 2,4,5-triarylimidazole dimer. A laminating step of laminating the photosensitive resin composition layer of the photosensitive element according to any one of claims 1 to 4 on a substrate,
An exposure step of irradiating at least a part of the photosensitive resin composition layer with actinic rays to cure the region to form a photocured portion;
A developing step of forming a resist pattern made of a photocured product of the photosensitive resin composition on the substrate by removing regions other than the photocured portion of the photosensitive resin composition layer from the substrate;
A method for forming a resist pattern having   A printed wiring board manufacturing method comprising a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the forming method according to claim 5.