JP6724445B2 - Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for producing printed wiring board - Google Patents

Description

The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for manufacturing a substrate with a resist pattern, and a method for manufacturing a printed wiring board.

In the field of manufacturing printed wiring boards, a photosensitive resin composition is widely used as a resist material used when etching or plating a circuit forming substrate. The photosensitive resin composition includes a support and a photosensitive element (laminate, which is provided on the support and a layer (hereinafter, also referred to as “photosensitive layer”) formed using the photosensitive resin composition). Often used as.

The printed wiring board is manufactured, for example, as follows. First, a photosensitive layer is formed on a circuit-forming substrate using a photosensitive element (photosensitive layer forming step). Next, an actinic ray is irradiated to a predetermined portion of the photosensitive layer to cure the exposed portion (exposure step). After that, the support is peeled off and removed, and then the unexposed portion of the photosensitive layer is removed (developed) from the substrate to form a resist pattern made of a cured product of the photosensitive resin composition on the circuit-forming substrate. Do (development step). After the conductor pattern (circuit) is formed on the substrate by performing etching treatment or plating treatment on the substrate using the formed resist pattern as a resist (circuit forming step), the resist pattern is finally peeled and removed. (Peeling step) to manufacture a printed wiring board.

As an exposure method, a method of exposing a mercury lamp as a light source through a photomask has been conventionally used. Further, in recent years, a direct drawing exposure method called DLP (Digital Light Processing) or LDI (Laser Direct Imaging) for directly drawing a pattern on a photosensitive layer has been proposed. The direct writing exposure method has better alignment accuracy than the exposure method using a photomask and can obtain a high-definition pattern, and thus has been introduced for manufacturing a high-density package substrate.

Generally, in the exposure process, it is desired to shorten the exposure time in order to improve production efficiency. However, in the above-mentioned direct drawing exposure method, a monochromatic light such as a laser is used as a light source, and since a light beam is emitted while scanning the substrate, a longer exposure time is required as compared with the conventional exposure method using a photomask. There is a tendency. 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 more than ever before.

On the other hand, with the recent increase in density of printed wiring boards, there is an increasing demand for a photosensitive resin composition capable of forming a resist pattern having excellent resolution (resolution) and adhesion.

To meet these demands, various photosensitive resin compositions have been studied so far. For example, Patent Document 1 proposes a photosensitive resin composition in which the above-mentioned required characteristics are improved by using a styrylpyridine compound as a sensitizing dye. Further, in Patent Documents 2 to 5, a photosensitive resin composition in which the required properties are improved by using a specific binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a sensitizing dye is disclosed. Proposed.

Chinese Patent Application Publication No. 101738861 JP, 2005-122123, A JP, 2007-114452, A International Publication No. 10/098183 International Publication No. 12/067107

By the way, it is preferable that the resist pattern formed of the photosensitive resin composition has excellent chemical resistance. When a substrate is plated with a resist pattern having poor chemical resistance as a resist, a plating gap may occur. Here, the "plating dive" means a phenomenon in which the plating solution penetrates between the resist pattern and the substrate. In recent years, printed wiring boards have been highly densified, and therefore, when a plating subside occurs, the conductor patterns may be connected to each other to cause a short circuit. In particular, it has been found that when a resist pattern having a line width and a space width of 8 μm or less is formed, product defects caused by plating subsides may increase.

However, although the photosensitive resin compositions described in Patent Documents 1 to 5 have relatively high sensitivity, there is still room for improvement in chemical resistance of the resist pattern to be formed.

The present disclosure provides a photosensitive resin composition having a line width and a space width of 8 μm or less and capable of forming a resist pattern having excellent chemical resistance with excellent sensitivity, and a photosensitive resin composition using the photosensitive resin composition. An object of the present invention is to provide an element, a method for manufacturing a substrate with a resist pattern, and a method for manufacturing a printed wiring board.

Specific means for solving the above problems include the following embodiments.
<1> A resin pattern containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a styrylpyridine compound represented by the following formula (1), and having a line width and a space width of 8 μm or less, respectively. A photosensitive resin composition used for forming.

[In the formula (1), R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, An amino group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth)acryloyl group, wherein a, b, and c are each independently 0 to 5; Indicates an integer. ]

<2> The photosensitive resin composition according to <1>, wherein the photopolymerization initiator contains a 2,4,5-triarylimidazole dimer represented by the following formula (2).

[In the formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Optionally represents an aryl group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5. Show. ]

<3> The photosensitive resin composition according to <1> or <2>, wherein the photopolymerizable compound contains a bisphenol A type di(meth)acrylate having less than 6 structural units of ethyleneoxy groups.

<4> A photosensitive element comprising a support and a photosensitive layer provided on the support, the photosensitive layer comprising the photosensitive resin composition according to <1> to <3>.

<5> A step of forming a photosensitive layer on the substrate using the photosensitive resin composition according to <1> to <3>,
Irradiating actinic rays to at least a part of the region of the photosensitive layer, and photo-curing the region to form a cured product region,
And a step of removing at least a part of the photosensitive layer other than the cured product region from the substrate to form a resist pattern on the substrate.

<6> The method for producing a substrate with a resist pattern according to <5>, wherein the wavelength of the actinic ray is in the range of 340 to 430 nm.

<7> A printed wiring board having a step of performing at least one of an etching treatment and a plating treatment on a substrate having a resist pattern formed by the method for producing a substrate with a resist pattern according to <5> or <6>. Production method.

According to the present disclosure, a photosensitive resin composition having a line width and a space width of 8 μm or less and capable of forming a resist pattern having excellent chemical resistance with excellent sensitivity, and the photosensitive resin composition are used. A method for manufacturing a photosensitive element, a substrate with a resist pattern, and a method for manufacturing a printed wiring board can be provided.

It is a schematic cross section which shows an example of a photosensitive element. It is a perspective view which shows typically an example of the manufacturing process of the printed wiring board by the semi-additive construction method.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.

In the present specification, “(meth)acrylic acid” means acrylic acid or methacrylic acid, “(meth)acrylate” means acrylate or methacrylate, and “(meth)acryloyl” means acryloyl. It also means methacryloyl. The “(poly)ethyleneoxy group” means at least one of an ethyleneoxy group (hereinafter, also referred to as “EO group”) or a polyethyleneoxy group in which two or more ethylene groups are linked by an ether bond. The “(poly)propyleneoxy group” means at least one of a propyleneoxy group (hereinafter, also referred to as “PO group”) or a polypropyleneoxy group in which two or more propylene groups are linked by an ether bond. "EO-modified" means a compound having a (poly)ethyleneoxy group, "PO-modified" means a compound having a (poly)propyleneoxy group, and "EO-PO". "Modified" means a compound having both a (poly)ethyleneoxy group and a (poly)propyleneoxy group.

In the present specification, the term “layer” is formed only in a part of the region when the region in which the layer is present is observed, in addition to when it is formed in the entire region. The case is also included. The term "laminate" refers to stacking layers, two or more layers may be joined together and two or more layers may be removable.
In addition, in the present specification, the term “process” is not limited to an independent process, and even if the process is not clearly distinguishable from other processes, the term is used as long as the intended purpose of the process is achieved. include.
Further, in the present specification, the numerical range indicated by using "to" indicates a range including the numerical values before and after "to" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. Good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In addition, in the present specification, the content of each component in the composition is such that, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content of the plurality of types present in the composition is Means the total amount of a substance.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment has a component (A): a binder polymer, a component (B): a photopolymerizable compound, a component (C): a photopolymerization initiator, and a component (D): formula (1). ) And a styrylpyridine compound represented by the formula (1). The photosensitive resin composition is used for forming a resin pattern having a line width and a space width of 8 μm or less. The photosensitive resin composition may contain other components as needed.

According to the photosensitive resin composition described above, it is possible to form a resist pattern having a line width and a space width of 8 μm or less and excellent chemical resistance (particularly resistance to a plating solution) with excellent sensitivity. .. Although the detailed reason for achieving the above effect is not always clear, the present inventors presume as follows. By using a photosensitive resin composition containing a styryl pyridine compound having excellent photosensitivity, it is possible to increase the reaction rate particularly on the substrate-side surface (bottom part) of the resist pattern while having high adhesion to the substrate. A resist pattern having a line width and a space width of 8 μm or less can be formed. It is presumed that, as a result, the crosslinked network in the resist pattern is more densified, and the curing rate at the bottom of the resist pattern is improved, whereby chemical resistance is improved and the occurrence of product defects can be reduced.

Component (A): Binder Polymer The photosensitive resin composition contains at least one binder polymer as the component (A). The binder polymer is obtained, for example, by radically polymerizing a polymerizable monomer by a conventional method.

As the polymerizable monomer, (meth)acrylic acid; (meth)acrylic acid alkyl ester, (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid hydroxyalkyl ester, (meth)acrylic acid benzyl, (meth) Furfuryl acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth)acrylic Acid diethylaminoethyl, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate, 2,2,3,3-tetrafluoropropyl(meth)acrylate, dicyclopentenyloxy(meth)acrylate Ethyl, dicyclopentanyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, adamantyloxyethyl (meth)acrylate, dicyclo(meth)acrylate (Meth)acrylic acid such as pentenyloxypropyloxyethyl, (meth)acrylic acid dicyclopentanyloxypropyloxyethyl, (meth)acrylic acid dicyclopentenyloxypropyloxyethyl, (meth)adamantyloxypropyloxyethyl Ester; (meth)acrylic acid derivative such as α-bromoacrylic acid, α-chloroacrylic acid, β-furyl(meth)acrylic acid, β-styryl(meth)acrylic acid; styrene; α-methylstyrene; aromatic ring Polymerizable styrene derivative substituted in acrylamide; acrylamide such as diacetone acrylamide; acrylonitrile; ether compound of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; monomethyl maleate, monoethyl maleate, malein Maleic acid monoesters such as acid monoisopropyl; unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These polymerizable monomers may be used alone or in combination of two or more.

The binder polymer may have a structural unit derived from (meth)acrylic acid from the viewpoint of improving the developability. When the binder polymer has a structural unit derived from (meth)acrylic acid, the content of the structural unit derived from (meth)acrylic acid is excellent in a well-balanced development property and adhesiveness of the resist pattern. Based on the total mass of the polymerizable monomers constituting the composition (100 mass %, the same applies below), it may be 15 to 40 mass %, 18 to 38 mass %, or 20 to 35 mass %. It may be. From the viewpoint of further improving the developability, the content may be 15% by mass or more, 18% by mass or more, and 20% by mass or more. Further, from the viewpoint of further improving the adhesiveness of the resist pattern, this content may be 40% by mass or less, 38% by mass or less, or 35% by mass or less.

Further, the binder polymer may have a structural unit derived from styrene or α-methylstyrene. When the binder polymer has a structural unit derived from styrene or α-methylstyrene, the content of the structural unit derived from styrene or α-methylstyrene, from the viewpoint of further improving the adhesiveness and releasability of the resist pattern, the binder It may be 10 to 70% by mass, 15 to 60% by mass, or 20 to 55% by mass, based on the total mass of the polymerizable monomers constituting the polymer. From the viewpoint of further improving the adhesiveness of the resist pattern, the content may be 10% by mass or more, 15% by mass or more, and 20% by mass or more. From the viewpoint of further improving the releasability of the resist pattern, the content may be 70% by mass or less, 60% by mass or less, or 55% by mass or less.

In addition, the binder polymer may have a structural unit derived from a polymerizable monomer other than (meth)acrylic acid, styrene, and α-methylstyrene. When the binder polymer has a structural unit derived from another polymerizable monomer, the content of the structural unit derived from another polymerizable monomer, from the viewpoint of further improving the resolution and releasability of the resist pattern, Based on the total weight of the polymerizable monomers constituting the binder polymer, it may be 3 to 85% by mass, 5 to 75% by mass, or 10 to 70% by mass, It may be 10 to 50% by mass.

The acid value of the binder polymer may be 90 to 250 mgKOH/g, 100 to 240 mgKOH/g, or 120 to 235 mgKOH/g, from the viewpoint of excellent balance in developability and adhesiveness of the resist pattern. It may be present or may be 130 to 230 mg KOH/g. From the viewpoint of further shortening the development time, the acid value may be 90 mgKOH/g or more, 100 mgKOH/g or more, 120 mgKOH/g or more, and 130 mgKOH/g or more. May be. Further, from the viewpoint of further improving the adhesion of the resist pattern, the acid value may be 250 mgKOH/g or less, 240 mgKOH/g or less, 235 mgKOH/g or less, 230 mgKOH or 230 mgKOH/g. It may be less than /g.

The weight average molecular weight (Mw) of the binder polymer, when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), has excellent balance in developability and adhesiveness of resist pattern, It may be 10,000 to 200,000, 15,000 to 100,000, 20,000 to 80,000, or 23,000 to 60,000. From the viewpoint of further shortening the development time, the weight average molecular weight may be 200,000 or less, 100,000 or less, 80,000 or less, or 60,000 or less. From the viewpoint of further improving the adhesiveness of the resist pattern, the weight average molecular weight may be 10,000 or more, 15,000 or more, 20,000 or more, 23,000 or more, 25,000. It may be more than.

The dispersity (weight average molecular weight/number average molecular weight) of the binder polymer may be 3.0 or less, or 2.8 or less, from the viewpoint of further improving the resolution and adhesion of the resist pattern. It may be 2.5 or less.

The binder polymer may have, in the molecule thereof, a characteristic group having photosensitivity to light having a wavelength in the range of 340 to 430 nm, if necessary. Examples of the characteristic group include groups formed by removing at least one hydrogen atom from the sensitizing dye such as the component (D) described below.

The content of the component (A) in the photosensitive resin composition is 100 parts by mass as the total amount of the components (A) and (B) from the viewpoint of further improving the formability of the photosensitive layer, the sensitivity, and the resolution of the resist pattern. On the other hand, it may be 30 to 70 parts by mass, 35 to 65 parts by mass, or 40 to 60 parts by mass. From the viewpoint of further improving the formability of the photosensitive layer, the content may be 30 parts by mass or more, 35 parts by mass or more, and 40 parts by mass or more. Further, from the viewpoint of further improving the sensitivity and the resolution of the resist pattern, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

Component (B): Photopolymerizable Compound The photosensitive resin composition contains at least one photopolymerizable compound as the component (B). The component (B) may contain at least one kind of bisphenol A type di(meth)acrylate (hereinafter, referred to as “specific photopolymerizable compound”) having less than 6 structural units of EO group. If necessary, it may further contain a photopolymerizable compound other than the specific photopolymerizable compound.

In the specific photopolymerizable compound, the number of structural units of the EO group is less than 6. Here, it can be said that the number of structural units of the EO group (structural unit) indicates how much the EO group is added to the molecule. Therefore, an integer value is shown for a single molecule. Hereinafter, the same applies to the number of structural units of the structural unit. In the specific photopolymerizable compound, the number of structural units of the EO group may be less than 4 or less than 3 from the viewpoint of improving the chemical resistance of the resist pattern. The lower limit of the number of structural units of the EO group is 0 or more, and may be 2 or more.

The specific photopolymerizable compound may be a compound represented by the following formula (3).

In formula (3), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group. XO's each independently represent an EO group. (XO) _m1 and (XO) _m2 each represent a (poly)ethyleneoxy group. m1 and m2 can each independently take a numerical value of 0 or more and less than 6. m1+m2 is 0 or more and less than 6. m1 and m2 show the number of structural units of a structural unit.

As a commercial item of the compound represented by the formula (3), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (EO group: 4 mol (average value)) (manufactured by Hitachi Chemical Co., Ltd., “FA -324ME"), 2,2-bis(4-(acryloxypolyethoxy)phenyl)propane (EO group: 3 mol (average value)) (Shin-Nakamura Chemical Co., Ltd., "ABE-300"), 2, 2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.6 mol (average value)) (Shin-Nakamura Chemical Co., Ltd., "BPE-100"), 2,2-bis(4- (Methacryloxyethoxy)phenyl)propane (EO group: 2.3 mol (average value)) (manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-80N") and the like. These compounds may be used alone or in combination of two or more.

The content of the specific photopolymerizable compound in the photosensitive resin composition is (A) component and (B) component from the viewpoint of suppressing swelling by suppressing molecular movement in the crosslinked network after curing and improving chemical resistance. 1 to 60 parts by mass, 5 to 55 parts by mass, or 10 to 50 parts by mass with respect to 100 parts by mass in total.

The photosensitive resin composition may contain, as the component (B), a photopolymerizable compound other than the specific photopolymerizable compound. Other photopolymerizable compounds are not particularly limited as long as they are photopolymerizable. The other photopolymerizable compound may be a compound having an ethylenically unsaturated bond group. Examples of the compound having an ethylenically unsaturated bond group include a compound having one ethylenically unsaturated bond group in the molecule, a compound having two ethylenically unsaturated bond groups in the molecule, and an ethylenically unsaturated bond in the molecule. The compound etc. which have three or more groups are mentioned.

When the component (B) contains other photopolymerizable compound, the content of the specific photopolymerizable compound is from the viewpoint of suppressing swelling by suppressing molecular movement in the crosslinked network after curing and improving chemical resistance ( It may be 1 to 60 parts by mass, 6 to 50 parts by mass, or 10 to 40 parts by mass based on 100 parts by mass of the total amount of the component B).

The component (B) may contain at least one compound having two ethylenically unsaturated bond groups in the molecule (excluding the specific photopolymerizable compound) as another photopolymerizable compound. When the component (B) contains, as another photopolymerizable compound, a compound having two ethylenically unsaturated bond groups in the molecule, the content is 100 parts by mass of the total amount of the components (A) and (B). On the other hand, it may be 5 to 60 parts by mass, 5 to 55 parts by mass, or 10 to 50 parts by mass.

Examples of the compound having two ethylenically unsaturated bond groups in the molecule include bisphenol A-type di(meth)acrylate different from the specific photopolymerizable compound, hydrogenated bisphenol A-type di(meth)acrylate, and EO group in the molecule. And polyalkylene glycol di(meth)acrylate having at least one of PO groups, di(meth)acrylate having a urethane bond in the molecule, and trimethylolpropane di(meth)acrylate.

From the viewpoint of improving the resolution and releasability of the resist pattern, the component (B) is another photopolymerizable compound, which is different from the specific photopolymerizable compound, such as bisphenol A-type di(meth)acrylate and hydrogenated bisphenol A-type di(meth)acrylate. At least one of compounds having two ethylenically unsaturated bond groups in the molecule selected from the group consisting of (meth)acrylate and polyalkylene glycol di(meth)acrylate having at least one of an EO group and a PO group in the molecule. It may contain seeds.

Examples of the bisphenol A type di(meth)acrylate different from the specific photopolymerizable compound include compounds represented by the following formula (4).

In formula (4), R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an EO group or a PO group. (XO) _x1 , (XO) _x2 , (YO) _y1 and (YO) _y2 each represent a (poly)ethyleneoxy group or a (poly)propyleneoxy group. x1, x2, y1, and y2 can each independently take a numerical value of 0-40. x1, x2, y1 and y2 represent the number of structural units of the structural unit.

When the compound represented by the formula (4) has a PO group, the number of structural units of the PO group in the molecule may be 2 or more or 3 or more from the viewpoint of improving the resolution of the resist pattern. Good. Further, the number of structural units of the PO group in the molecule may be 5 or less from the viewpoint of improving the developability.

When the compound represented by formula (4) has an EO group, the number of structural units of the EO group in the molecule may be 6 or more, or 8 or more, from the viewpoint of improving the developability. .. The number of structural units of the EO group in the molecule may be 16 or less, or 14 or less, from the viewpoint of improving the resolution of the resist pattern.

As a commercial product of the compound represented by the formula (4), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane (EO group: 12 mol (average value), PO group: 4 mol (average value)) (Manufactured by Hitachi Chemical Co., Ltd., "FA-3200MY"), 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO group: 10 mol (average value)) (manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-500"), 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (EO group: 10 mol (average value)) (manufactured by Hitachi Chemical Co., Ltd., "FA-321M"), 2, 2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO group: 30 mol (average value)) (manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-1300") and the like can be mentioned. These compounds may be used alone or in combination of two or more.

When the component (B) contains a bisphenol A-type di(meth)acrylate different from the specific photopolymerizable compound, the content thereof suppresses swelling by suppressing molecular movement in the crosslinked network after curing and improves chemical resistance. From the viewpoint of making the total amount of the components (A) and (B) 100 parts by mass, it may be 1 to 65 parts by mass, 5 to 60 parts by mass, or 10 to 55 parts by mass. It may be. Further, the content of bisphenol A-type di(meth)acrylate having a total number of structural units of EO groups and PO groups of 10 or less is (B) from the viewpoint of improving the resolution, adhesiveness, and chemical resistance of the resist pattern. It may be 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the components.

Examples of hydrogenated bisphenol A-type di(meth)acrylate include 2,2-bis(4-(methacryloxypentaethoxy)cyclohexyl)propane.
When the component (B) contains hydrogenated bisphenol A-type di(meth)acrylate, its content is (A) from the viewpoint of suppressing swelling by suppressing molecular movement in the crosslinked network after curing and improving chemical resistance. 1) to 50 parts by mass, or 5 to 40 parts by mass, based on 100 parts by mass of the total amount of the component) and the component (B).

The component (B) is a polyalkylene glycol dipolymer having at least one of an EO group and a PO group in the molecule, as another photopolymerizable compound, from the viewpoint of improving the flexibility, resolution, and adhesion of the resist pattern in a well-balanced manner. It may contain at least one kind of (meth)acrylate. When the component (B) contains polyalkylene glycol di(meth)acrylate, its content is 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of resolution and flexibility of the resist pattern. , 1 to 30 parts by mass, 2 to 20 parts by mass, or 2 to 15 parts by mass.

The polyalkylene glycol di(meth)acrylate may be EO/PO modified polyalkylene glycol di(meth)acrylate. In the molecule of the polyalkylene glycol di(meth)acrylate, the (poly)ethyleneoxy group and the (poly)propyleneoxy group may be continuously present in a block form or may be present randomly. The PO group in the (poly)propyleneoxy group may be either an n-propyleneoxy group or an isopropyleneoxy group. In the (poly)isopropyleneoxy group, the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.

The polyalkylene glycol di(meth)acrylate is a (poly)n-butyleneoxy group, a (poly)isobutyleneoxy group, a (poly)n-pentyleneoxy group, a (poly)hexyleneoxy group, a structural isomer of these, or the like. May have a (poly)alkyleneoxy group having about 4 to 6 carbon atoms.

The component (B) may contain at least one photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule as another photopolymerizable compound.

Examples of the compound having three or more ethylenically unsaturated bond groups include trimethylolpropane tri(meth)acrylate and EO-modified trimethylolpropane tri(meth)acrylate (having 1 to 5 structural unit of EO group). , PO-modified trimethylolpropane tri(meth)acrylate, EO/PO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate , And dipentaerythritol hexa(meth)acrylate. These compounds may be used alone or in combination of two or more.

Commercially available photopolymerizable compounds having three or more ethylenically unsaturated bond groups in the molecule include EO-modified trimethylolpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., "TMPT21E" and "TMPT30E"), pentaerythritol trimethacrylate. Acrylate (“SR444” manufactured by Sartomer Co., Ltd. and “A-TMM-3” manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol hexaacrylate (“A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.), EO modified Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "ATM-35E") and the like can be mentioned.

When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule, its content is well balanced in resist pattern shape, resist pattern resolution, adhesion and peelability. From the viewpoint of improving, it may be 3 to 30 parts by mass, 5 to 25 parts by mass, or 5 to 20 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B). May be

The component (B) is ethylene in the molecule as another photopolymerizable compound from the viewpoint of improving the resist pattern shape and the resolution, adhesion, and releasability of the resist pattern in a well-balanced manner, or from the viewpoint of suppressing scum generation. A photopolymerizable compound having one unsaturated bond group may be contained.

Examples of the photopolymerizable compound having one ethylenically unsaturated bond group in the molecule include nonylphenoxypolyethyleneoxy (meth)acrylate, phthalic acid compound, and (meth)acrylic acid alkyl ester. Among the above, nonylphenoxypolyethyleneoxy(meth)acrylate or a phthalic acid compound may be contained from the viewpoint of improving the resist pattern shape and the resolution, adhesiveness, and releasability of the resist pattern in a well-balanced manner.

When the component (B) contains a photopolymerizable compound having one ethylenically unsaturated bond group in the molecule, the content thereof is 1 part with respect to 100 parts by mass of the total amount of the components (A) and (B). ˜20 parts by mass, 3 to 15 parts by mass, or 5 to 12 parts by mass.

The content of the component (B) in the photosensitive resin composition may be 30 to 70 parts by mass, or 35 to 65 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). May be When the content of the component (B) is 30 parts by mass or more, the sensitivity and the resolution of the resist pattern tend to be improved. When the content of the component (B) is 70 parts by mass or less, the photosensitive layer tends to be easily formed, and a good resist pattern shape tends to be easily obtained.

Component (C): Photopolymerization Initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). The component (C) is a 2,4,5-triarylimidazole compound represented by the following formula (2) from the viewpoint of improving sensitivity and resolution and adhesiveness of the resist pattern while maintaining the chemical resistance of the resist pattern. It may include a polymer.

In formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Optionally represents an aryl group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5. .. However, when p is 2 or more, a plurality of X ¹ present may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different.

X ¹ and X ² are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be an alkoxy group. At least one of X ¹ and X ² is preferably a chlorine atom.
The substitution position of X ¹ and X ² is not particularly limited and is preferably the ortho position or the para position.
p and q are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1.

Examples of the aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include a phenyl group, a naphthyl group and an anthracenyl group, and a phenyl group is preferable.
As the substituent that Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms At least one substituent selected from the group consisting of groups can be mentioned. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the above-mentioned substituent, the number of substituents is preferably 1-5, more preferably 1-3. More preferably, When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the above-mentioned substituent, the substitution position is not particularly limited, and it is preferably the ortho position or the para position. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are preferably all unsubstituted.

Examples of the 2,4,5-triarylimidazole dimer represented by the formula (2) include 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2-chlorophenyl)-. 4,5-di(methoxyphenyl)imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenylimidazole dimer And 2-(4-methoxyphenyl)-4,5-diphenylimidazole dimer. In addition, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may give the same and symmetrical compounds, or may give different asymmetric compounds. As the 2,4,5-triarylimidazole dimer represented by the formula (2), one type may be used alone, or two or more types may be used in combination.

When the component (C) contains the 2,4,5-triarylimidazole dimer represented by the formula (2), its content is 25 parts by mass based on 100 parts by mass of the total amount of the component (C). Or more, 50 parts by mass or more, or 75 parts by mass or more.

The photopolymerization initiator that is the component (C) may include other photopolymerization initiators that are commonly used, in addition to the 2,4,5-triarylimidazole dimer represented by the formula (2). Good. Other photopolymerization initiators include benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2- Aromatic ketones such as morpholino-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 benzyldimethylketal; 9-phenylacridine, 1 , 7-(9,9′-acridinyl)heptane and other acridine derivatives.

The content of the component (C) in the photosensitive resin composition may be 0.1 to 10 parts by mass, or 1 to 7 parts by mass, relative to 100 parts by mass of the total amount of the components (A) and (B). It may be parts by mass, 2 to 6 parts by mass, or 3 to 5 parts by mass. When the content of the component (C) is 0.1 parts by mass or more, the sensitivity and the resolution and adhesion of the resist pattern tend to be improved. When the content of the component (C) is 10 parts by mass or less, a good resist pattern shape tends to be easily obtained.

Component (D): Styrylpyridine Compound Represented by Formula (1) The photosensitive resin composition contains at least one styrylpyridine compound represented by the following formula (1) as component (D). As the component (D), one type may be used alone, or two or more types may be used in combination.

In formula (1), R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, and amino. Group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth)acryloyl group, and a, b, and c each independently represent an integer of 0 to 5. Indicates. However, when a is 2 or more, a plurality of R ^{1 s} may be the same or different, and when b is 2 or more, a plurality of R ^{2 s} may be the same or different, and c is 2 or more. In the case of, a plurality of R ^3's may be the same or different.
The carbon number of the alkyl ester group means the carbon number of the alkyl portion.

From the viewpoint of further improving the sensitivity, in the formula (1), R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom. It may be an alkyl ester group having 6 to 6, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
Further, a, b, and c each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

Examples of the styrylpyridine compound represented by the formula (1) include 3,5-dibenzylidenedicyclopentano[b,e]-4-phenylpyridine and 3,5-bis(4-methylbenzylidenedicyclopentano). [B,e])-4-(4-methylphenyl)pyridine, 3,5-bis(4-methoxybenzylidenedicyclopentano[b,e])-4-(4-methoxyphenyl)pyridine, 3, 5-bis(4-aminobenzylidenedicyclopentano[b,e])-4-(4-aminophenyl)pyridine, 3,5-bis(4-dimethylaminobenzylidenedicyclopentano[b,e]) -4-(4-Dimethylaminophenyl)pyridine, 3,5-bis(4-carboxybenzylidenedicyclopentano[b,e])-4-(4-carboxyphenyl)pyridine, 3,5-bis(4 -Acetylbenzylidenedicyclopentano[b,e])-4-(4-acetylphenyl)pyridine, 3,5-bis(4-cyanobenzylidenedicyclopentano[b,e])-4-(4- Cyanophenyl)pyridine, 3,5-bis(4-nitrobenzylidenedicyclopentano[b,e])-4-(4-nitrophenyl)pyridine, 3,5-bis(4-acryloylbenzylidenedicyclopentano) [B,e])-4-(4-Acryloylphenyl)pyridine, 3,5-bis(4-(methoxycarbonyl)benzylidenedicyclopentano[b,e])-4-(4-(methoxycarbonyl)) Phenyl)pyridine, and 3,5-bis(2,4-dimethoxybenzylidenedicyclopentano[b,e])-4-(2,4-dimethoxyphenyl)pyridine.

The styrylpyridine compound represented by the formula (1) can be synthesized by, for example, a condensation reaction of a benzaldehyde derivative, a cyclic alkyl ketone, and ammonium acetate.

The content of the component (D) in the photosensitive resin composition may be 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B), and may be 0.05. ˜5 parts by mass, or 0.08 to 3 parts by mass. When the content of the component (D) is 0.01 parts by mass or more, sensitivity and resolution of the resist pattern are improved, and a resist pattern having excellent chemical resistance tends to be easily obtained. When the content of the component (D) is 10 parts by mass or less, a good resist pattern shape tends to be easily obtained.

Component (E): Amine Compound The photosensitive resin composition may contain at least one amine compound as the component (E). Examples of the amine compound include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet and the like. These amine compounds may be used alone or in combination of two or more.

When the said photosensitive resin composition contains (E) component, the content is 0.01-10 mass parts with respect to 100 mass parts of total amount of (A) component and (B) component. It may be 0.05 to 5 parts by mass, or 0.1 to 2 parts by mass. When the content of the component (E) is 0.01 parts by mass or more, sufficient sensitivity tends to be easily obtained. When the content of the component (E) is 10 parts by mass or less, precipitation of excess component (E) as a foreign substance tends to be suppressed after the formation of the photosensitive layer.

(Other ingredients)
The above-mentioned photosensitive resin composition is a photopolymerizable compound (oxetane compound or the like) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and other than the component (D), if necessary. Sensitizing dyes, malachite green, Victoria pure blue, brilliant green, methyl violet, etc., tribromophenyl sulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, 2-chloroaniline, etc. Inhibitor, plasticizer such as 4-toluenesulfonamide, pigment, filler, defoaming agent, flame retardant, stabilizer, adhesion promoter, leveling agent, peeling accelerator, antioxidant, perfume, imaging agent, heat It may contain other components such as a crosslinking agent. These other components may be used alone or in combination of two or more for each component.

When the said photosensitive resin composition contains these other components, these content is about 0.01-20 mass parts with respect to 100 mass parts of total amount of (A) component and (B) component, respectively. May be

[Solution of photosensitive resin composition]
The photosensitive resin composition may further contain at least one kind of organic solvent. Examples of the organic solvent 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; aromatic hydrocarbon solvents such as toluene; N,N- Examples include aprotic polar solvents such as dimethylformamide. These organic solvents may be used alone or in combination of two or more. The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected according to the purpose and the like. For example, the photosensitive resin composition may contain an organic solvent and be used as a solution having a solid content of about 30 to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as "coating liquid".

A photosensitive layer, which is a coating film of the above-mentioned photosensitive resin composition, can be formed by applying the coating solution onto the surface of a support, a metal plate or the like described later and drying it. The metal plate is not particularly limited and can be appropriately selected depending on the purpose and the like. Examples of the metal plate include metal plates made of copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel. The metal plate is preferably a metal plate made of copper, a copper alloy, an iron alloy, or the like.

The thickness of the photosensitive layer formed is not particularly limited and can be appropriately selected depending on the application. For example, the thickness after drying may be about 1 to 100 μm. When the photosensitive layer is formed on the metal plate, the surface of the photosensitive layer may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

The photosensitive resin composition can be applied to the formation of the photosensitive layer of the photosensitive element described below. That is, another embodiment of the present disclosure is (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: formula (1). And a styryl pyridine compound represented by the formula (4), which is an application of a photosensitive resin composition used for forming a resin pattern having a line width and a space width of 8 μm or less to a photosensitive element.
Further, the above-mentioned photosensitive resin composition can be used in a method for producing a substrate with a resist pattern which will be described later. That is, another embodiment of the present disclosure is (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: formula (1). And a styryl pyridine compound represented by the formula (4), which is an application of a photosensitive resin composition used for forming a resin pattern having a line width and a space width of 8 μm or less to a method for producing a substrate with a resist pattern.

<Photosensitive element>
The photosensitive element of the present embodiment includes a support and a photosensitive layer provided on the support and using the photosensitive resin composition. The photosensitive layer is a coating film formed by using the photosensitive resin composition, and the photosensitive resin composition is in an uncured state. The photosensitive element may have other layers such as a protective layer if necessary.

FIG. 1 shows an example of the photosensitive element. In the photosensitive element 1 shown in FIG. 1, the support 2, the photosensitive layer 3, and the protective layer 4 are laminated in this order. The photosensitive element 1 can be obtained as follows, for example. The photosensitive layer 3 is formed by applying a coating liquid, which is the above-mentioned photosensitive resin composition containing an organic solvent, onto the support 2 to form a coating layer, and drying the coating layer. Then, by covering the surface of the photosensitive layer 3 opposite to the support 2 with a protective layer 4, the support 2, the photosensitive layer 3 formed on the support 2, and the photosensitive layer 3 are laminated. And a protective layer 4 which provides a photosensitive element 1. The photosensitive element 1 does not necessarily have to include the protective layer 4.

As the support 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, or polyethylene can be used.

The thickness of the support 2 may be 1 to 100 μm, 5 to 50 μm, or 5 to 30 μm. When the thickness of the support 2 is 1 μm or more, the support 2 tends to be prevented from being broken when the support 2 is peeled off. Further, when the thickness of the support 2 is 100 μm or less, deterioration of resolution tends to be suppressed.

The protective layer 4 is preferably such that the adhesive force of the photosensitive layer 3 to the protective layer 4 is smaller than the adhesive force of the photosensitive layer 3 to the support 2. Also, a low fish eye film is preferred. Here, "fish eye" means that when a material is heat-melted, kneaded, extruded, biaxially stretched, or produced by a casting method or the like, foreign matter, undissolved material, oxidative deterioration material, etc. of the material are contained in the film. Means something that has been taken into. That is, the "low fish eye" means that the foreign matter and the like in the film are small.

Specifically, as the protective layer 4, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene can be used. Examples of commercially available products include Alfan MA-410, E-200 manufactured by Oji Paper Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., PS series polyethylene terephthalate film such as PS-25 manufactured by Teijin Limited. To be The protective layer 4 may be the same as the support 2.

The thickness of the protective layer 4 may be 1 to 100 μm, 5 to 50 μm, 5 to 30 μm, or 15 to 30 μm. When the thickness of the protective layer 4 is 1 μm or more, the protective layer 4 tends to be prevented from being broken when the photosensitive layer 3 and the support 2 are laminated on the substrate while the protective layer 4 is peeled off. When the thickness of the protective layer 4 is 100 μm or less, it tends to be excellent in handleability and low cost.

Specifically, the photosensitive element can be manufactured, for example, as follows. The component (A): binder polymer, the component (B): photopolymerizable compound, the component (C): photopolymerization initiator, and the component (D): a styrylpyridine compound represented by the formula (1) above. A step of preparing a coating liquid dissolved in an organic solvent, a step of coating the coating liquid on the support 2 to form a coating layer, and a step of drying the coating layer to form the photosensitive layer 3. The photosensitive element can be manufactured by the manufacturing method including the method.

The coating of the coating liquid on the support 2 can be carried out by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating or bar coating.

The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. The coating layer is preferably dried at 70 to 150°C for about 5 to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive layer 3 may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in a subsequent step.

The thickness of the photosensitive layer 3 in the photosensitive element can be appropriately selected depending on the application. The thickness of the photosensitive layer 3 after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. When the thickness of the photosensitive layer 3 is 1 μm or more, industrial coating tends to be easy. When the thickness of the photosensitive layer 3 is 100 μm or less, sufficient adhesion and resolution of the resist pattern tend to be obtained.

The transmittance of the photosensitive layer 3 with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays in the wavelength range of 350 to 420 nm. Good. When the transmittance is 5% or more, the adhesiveness of the resist pattern tends to be sufficiently obtained. When this transmittance is 75% or less, the resolution of the resist pattern tends to be sufficiently obtained. The transmittance can be measured with an ultraviolet spectrometer. Examples of the ultraviolet spectrometer include a 228A type W-beam spectrophotometer manufactured by Hitachi, Ltd.

The photosensitive element may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer and the like. As these intermediate layers, for example, the intermediate layers described in JP-A-2006-098982 can also be applied in this embodiment.

The form of the obtained photosensitive element is not particularly limited. The photosensitive element may be, for example, in the form of a sheet or in the form of a roll wound around a winding core. When wound in a roll, it is preferable that the support 2 be wound outside. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer). From the standpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and from the standpoint of edge fusion resistance, it is preferable to install a moisture-proof end face separator. As a packing method, it is preferable to wrap and wrap in a black sheet having low moisture permeability.

The photosensitive element can be suitably used, for example, in a method for manufacturing a substrate with a resist pattern described later.

<Method of manufacturing substrate with resist pattern>
A substrate with a resist pattern can be manufactured using the above photosensitive resin composition. The method for manufacturing a substrate with a resist pattern according to the present embodiment includes (i) a step of forming a photosensitive layer using the photosensitive resin composition on the substrate (photosensitive layer forming step), and (ii) the photosensitive layer. Of at least a part of the photosensitive layer to irradiate actinic rays to form a cured product region by photo-curing the region (exposure step), and (iii) at least a part of the photosensitive layer other than the cured product region. Is removed from the substrate to form a resist pattern on the substrate (development step). The method for producing a substrate with a resist pattern may further include other steps, if necessary.

(I) Photosensitive layer forming step First, the photosensitive layer 3 is formed on a substrate using the above-mentioned photosensitive resin composition. As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used. Examples of the insulating layer include a glass epoxy material. Examples of the conductor layer include copper foil.

The formation of the photosensitive layer 3 on the substrate is performed, for example, when the photosensitive element has the protective layer 4 after removing the protective layer 4 and heating the photosensitive layer 3 of the photosensitive element. It is performed by pressure bonding to the substrate. As a result, a laminate in which the substrate, the photosensitive layer 3, and the support 2 are laminated in this order is obtained.

This photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating to at least one of the photosensitive layer 3 and the substrate at the time of pressure bonding is preferably performed at a temperature of 70 to 130° C., and pressure bonding is performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). It is preferable. These conditions are not particularly limited and may be appropriately selected as needed. The substrate need not be preheated if the photosensitive layer 3 is heated to 70 to 130°C. Pre-heat treatment of the substrate can further improve the adhesiveness and the followability.

(Ii) Exposure Step In the exposure step, by irradiating at least a part of the photosensitive layer 3 formed on the substrate with the actinic ray as described above, the exposed portion irradiated with the actinic ray is photocured. As a result, a latent image is formed. At this time, when the support 2 existing on the photosensitive layer 3 is transparent to the actinic rays, the actinic rays can be irradiated through the support 2. On the other hand, when the support 2 has a property of blocking actinic rays, the photosensitive layer 3 is irradiated with actinic rays after the support 2 is removed.

Examples of the exposure method include a method (mask exposure method) of irradiating an actinic ray imagewise through a negative or positive mask pattern called an artwork. Further, a method of irradiating an actinic ray imagewise 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 adopted.

The light source of the actinic ray is not particularly limited, and a known light source can be used. Specifically, carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, ultraviolet rays such as semiconductor lasers and gallium nitride-based blue-violet lasers, visible light, etc. Those that radiate effectively are used.

The wavelength of the actinic ray (exposure wavelength) may be in the range of 340 to 430 nm, or may be in the range of 350 to 420 nm. By setting the wavelength of the actinic ray within the range of 340 to 430 nm, a resist pattern having excellent chemical resistance tends to be formed more efficiently with excellent sensitivity.

(Iii) Developing Step In the developing step, the uncured portion of the photosensitive layer 3 is removed from the substrate by a developing treatment, so that a resist pattern which is a cured product of the photosensitive layer 3 is formed on the substrate. .. When the support 2 is present on the photosensitive layer 3, the support 2 is removed and then the unexposed portion is removed (developed). The development processing includes 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 developing solution corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking dipping, etc., and the high pressure spray method is most suitable from the viewpoint of resolution improvement. You may develop by combining these 2 or more types of methods.

The developing solution is appropriately selected according to the constitution of the photosensitive resin composition. Examples of the developer include alkaline aqueous solutions and organic solvent developers.

When used as a developing solution, the alkaline aqueous solution is safe and stable, and has good operability. As the base of the alkaline aqueous solution, alkali hydroxide such as lithium, sodium or potassium hydroxide; alkali carbonate such as lithium, sodium, potassium or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate Alkali metal phosphates such as sodium pyrophosphate, potassium pyrophosphate and other alkali metal pyrophosphates, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2 -Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.

As the alkaline aqueous solution used for the development, a dilute solution of 0.1 to 5 mass% sodium carbonate, a dilute solution of 0.1 to 5 mass% potassium carbonate, a dilute solution of 0.1 to 5 mass% sodium hydroxide, and 0.1. A dilute solution of 1 to 5 mass% sodium tetraborate or the like is preferable. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted according to the alkali developability of the photosensitive layer 3. The alkaline aqueous solution may contain a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating the development, and the like.

The alkaline aqueous solution may contain one or more organic solvents. Examples of the organic solvent used include 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 and the like. These are used alone or in combination of two or more. When the alkaline aqueous solution contains an organic solvent, the content of the organic solvent is preferably 2 to 90 mass% based on the total amount of the alkaline aqueous solution.

Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. To prevent ignition, it is preferable to add water in the range of 1 to 20% by mass to these organic solvents to prepare an organic solvent developer.

In the method for producing a substrate with a resist pattern, after removing the unexposed portion, heating at 60 to 250° C. or exposure with an energy amount of 0.2 to 10 J/cm ² is performed, if necessary, to obtain a resist pattern. May further have a step of further curing.

<Method of manufacturing printed wiring board>
The method for manufacturing a printed wiring board according to the present embodiment has a step of performing at least one of an etching process and a plating process on a substrate having a resist pattern formed by the method for manufacturing a substrate with a resist pattern. As the substrate, for example, it is preferable to use a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer. The printed wiring board manufacturing method may include other steps such as a resist removing step, if necessary. The etching process and the plating process of the substrate are performed on the conductor layer of the substrate using the formed resist pattern as a mask.

In the etching process, the resist pattern (cured resist) formed on the substrate is used as a mask to etch away the conductor layer of the circuit-forming substrate that is not covered with the cured resist to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include a cupric chloride aqueous solution, a ferric chloride aqueous solution, an alkaline etching solution, and a hydrogen peroxide etching solution. Among these, it is preferable to use an aqueous solution of ferric chloride because of its good etch factor.

On the other hand, in the plating process, using a resist pattern (cured resist) formed on the substrate as a mask, copper, solder or the like is plated on the conductor layer of the circuit forming substrate which is not covered with the cured resist. After the plating process, the cured resist is removed, and the conductor layer covered with the cured resist is etched to form a conductor pattern. The plating method may be electrolytic plating or electroless plating. As the plating treatment, copper sulfate plating, copper plating such as copper pyrophosphate, solder plating such as high-throw solder plating, Watts bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, soft plating Examples thereof include gold plating such as gold plating.

After the etching process and the plating process, the resist pattern on the substrate is removed (peeled). The removal of the resist pattern can be performed using, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the developing step. As this strongly alkaline aqueous solution, 1 to 10 mass% sodium hydroxide aqueous solution, 1 to 10 mass% potassium hydroxide aqueous solution and the like are used. Above all, it is preferable to use a 1 to 10 mass% sodium hydroxide aqueous solution or a 1 to 10 mass% potassium hydroxide aqueous solution, and it is more preferable to use a 1 to 5 mass% sodium hydroxide aqueous solution or a 1 to 5 mass% potassium hydroxide aqueous solution. preferable. Examples of the method of applying the strongly alkaline aqueous solution to the resist pattern include a dipping method and a spray method. These may be used alone or in combination of two or more.

When the resist pattern is removed after performing the plating process, the conductor layer covered with the cured resist is removed by the etching process and the conductor pattern is formed, whereby a desired printed wiring board can be manufactured. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-mentioned etching solution can be applied.

The method for manufacturing a printed wiring board described above is applicable 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 above-mentioned photosensitive resin composition can be suitably used for manufacturing a printed wiring board. That is, one of the preferred embodiments is (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: formula (1) And a styryl pyridine compound represented by the formula (4), which is an application of a photosensitive resin composition used for forming a resin pattern having a line width and a space width of 8 μm or less to the production of a printed wiring board.
A more preferred embodiment is the application of the photosensitive resin composition to the production of a high-density package substrate, and the application of the photosensitive resin composition to the semi-additive construction method. Hereinafter, an example of a manufacturing process of a wiring board by the semi-additive method will be described with reference to FIG. The sizes of the members in FIG. 2 are conceptual, and the relative size relationship between the members is not limited to this.

In FIG. 2A, 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. 2B, the photosensitive layer 32 is formed on the conductor layer 10 of the substrate by the photosensitive layer forming step. In FIG. 2C, the mask 20 is arranged on the photosensitive layer 32, and the photosensitive layer 32 is irradiated with the actinic ray 50 by the above-mentioned exposure process to expose the area other than the area where the mask 20 is arranged, A photo-cured portion is formed on the photosensitive layer 32. In FIG. 2D, in the photosensitive layer 32, a region other than the photo-cured portion is removed from the substrate by a developing process to form a resist pattern 30 which is the photo-cured portion on the substrate. In FIG. 2E, a plating layer 42 is formed on the conductor layer 10 by a plating process using the resist pattern 30 which is a photocured portion as a mask. In FIG. 2F, after the resist pattern 30 which is a photo-cured 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 flash-etched. The conductor pattern 40 is formed by removing. The conductor layer 10 and the plating layer 42 may be made of the same material or different materials.
Although the method of forming the resist pattern 30 using the mask 20 has been described with reference to FIG. 2, the resist pattern 30 may be formed by a direct drawing exposure method without using the mask 20.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Examples 1-5 and Comparative Examples 1-3)
<Preparation of solution of photosensitive resin composition>
Each of the components shown in Tables 2 and 3 was mixed with 9 g of acetone, 5 g of toluene, and 5 g of methanol in the blending amounts (unit: g) shown in the same table to obtain the compounds of Examples 1 to 5 and Comparative Examples 1 to 3. Each solution of the photosensitive resin composition was prepared. The blending amount of the component (A) shown in Tables 2 and 3 is the mass (solid content) of the nonvolatile content. Details of each component shown in Table 2 and Table 3 are as follows. In addition, "-" means unblended.

(A) Binder polymer [Synthesis of binder polymer (A-1)]
81 g of methacrylic acid which is a polymerizable monomer (monomer), 135 g of styrene, 69 g of benzyl methacrylate, and 15 g of methyl methacrylate (mass ratio: 27/45/23/5) and 1.5 g of azobisisobutyronitrile. The solution obtained by mixing and was designated as "solution a".

A solution obtained by dissolving 0.5 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio: 3:2) of 60 g of methyl cellosolve and 40 g of toluene was designated as "solution b".

A flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introducing tube was charged with 300 g of a mixed liquid (mass ratio: 3:2) of 180 g of methyl cellosolve and 120 g of toluene, and nitrogen was charged in the flask. The mixture was heated while stirring while blowing gas, 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 the mixture was kept at 80° C. for 2 hours while stirring. Next, the above solution b was added dropwise to the solution in the flask over 10 minutes, and the solution in the flask was kept at 80° C. for 3 hours while stirring. Furthermore, the solution in the flask was heated to 90° C. over 30 minutes, kept at 90° C. for 2 hours, and then cooled to obtain a solution of the binder polymer (A-1).
The binder polymer (A-1) had a nonvolatile content (solid content) of 41.5 mass%, a weight average molecular weight of 44000, an acid value of 176 mgKOH/g, and a dispersity of 2.2.

The weight average molecular weight was derived by measuring it by gel permeation chromatography (GPC) method and converting it using a calibration curve of standard polystyrene. The conditions of GPC are shown below.

GPC conditions Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (above, Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was collected and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40°C
Injection volume: 200 μL
Pressure: 49 kgf/cm ² (4.8 MPa)
Flow rate: 2.05 mL/min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymer (A-2)]
81 g of methacrylic acid which is a polymerizable monomer (monomer), 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, and 69 g of benzyl methacrylate (mass ratio: 27/3/47/23), and azobisisobutyronitrile. The solution obtained by mixing 2.4 g was defined as “solution c”, and the solution c was used in place of the solution a, except that the solution of the binder polymer (A-1) was obtained. A solution of (A-2) was obtained.
The binder polymer (A-2) had a nonvolatile content (solid content) of 41.7% by mass, a weight average molecular weight of 38,000, an acid value of 176 mgKOH/g, and a dispersity of 1.8.

With respect to the binder polymers (A-1) and (A-2), Table 1 shows the mass ratio (%) of the polymerizable monomer (monomer), the acid value, the weight average molecular weight, and the dispersity. In addition, "-" means unblended.

(B) Photopolymerizable compound BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.6 mol (average value))
BPE-80N (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.3 mol (average value))
FA-324ME (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (EO group: 4 mol (average value))
ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(acryloxypolyethoxy)phenyl)propane (EO group: 3 mol (average value))
FA-321M (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (EO group: 10 mol (average value))
FA-024M (manufactured by Hitachi Chemical Co., Ltd.): (PO)(EO)(PO) modified polypropylene glycol #700 dimethacrylate

(C) Photopolymerization initiator B-CIM (manufactured by Hampford): 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole [2-(2-chlorophenyl) )-4,5-Diphenylimidazole dimer]

(D) Styrylpyridine compound represented by the formula (1): 2,4-DMOP-DSP: 3,5-bis(2,4-dimethoxybenzylidenedicyclopentano[b,e])-4-(2 4-dimethoxyphenyl)pyridine

Other sensitizing dyes other than the component (D) PYR-1 (manufactured by Nippon Kagaku Kogyo Co., Ltd.): 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazolin-EAB( Hodogaya Chemical Co., Ltd.): 4,4′-diethylaminobenzophenone ·H-MOP-DSP: 4,6-bis(4-methoxybenzylidenedicyclohexano[b,e])-5-(4-methoxyphenyl) ) Pyridine

(E) Amine compound LCV (manufactured by Yamada Chemical Co., Ltd.): Leuco Crystal Violet

Dye-MKG (Osaka Organic Chemical Co., Ltd.): Malachite Green

<Production of photosensitive element>
The solution of the photosensitive resin composition obtained above was applied onto a polyethylene terephthalate film (“FB-40” manufactured by Toray Industries, Inc., “FB-40”) having a thickness of 16 μm (support), and hot air at 70° C. and 110° C. The photosensitive layer was dried in order by a convection dryer to form a photosensitive layer having a film thickness after drying of 25 μm. A polyethylene film (“E-200K” manufactured by Oji Paper Co., Ltd.) (protective layer) was attached onto the photosensitive layer to obtain a photosensitive element in which a support, a photosensitive layer, and a protective layer were laminated in this order.

<Production of laminated substrate>
A copper clad laminate (“MCL-E-679F” manufactured by Hitachi Chemical Co., Ltd.) (hereinafter, referred to as “substrate”) made of a glass epoxy material and copper foil (thickness 16 μm) formed on both surfaces thereof. After heating to 80° C., the photosensitive elements according to Examples 1 to 5 and Comparative Examples 1 to 3 were laminated on the copper surface of the substrate. Lamination was performed under the conditions of a temperature of 110° C. and a laminating pressure of 4 kgf/cm ² (0.4 MPa) so that the photosensitive layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. .. Thus, a laminated substrate in which the photosensitive layer and the support were laminated on the copper surface of the substrate was obtained. The obtained laminated substrate was left to cool to 23°C.

<Evaluation of sensitivity>
On the support of the laminated substrate, a 41-step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm×187 mm, and a size of each step of 3 mm×12 mm is provided. A photo tool was placed. A direct writing exposure machine (“DE-1UH” manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode with a wavelength of 405 nm as a light source was used, and a predetermined energy amount (exposure amount) was passed through the phototool and the support. The photosensitive layer was exposed. In addition, the illuminance was measured using an ultraviolet illuminometer (“UIT-150” manufactured by Ushio Inc.) to which a probe compatible with 405 nm was applied.

After the exposure, the support was peeled off from the laminated substrate to expose the photosensitive layer, and an unexposed portion was removed by spraying a 1 mass% sodium carbonate aqueous solution at 30° C. for 60 seconds. In this way, a resist pattern made of a cured product of the photosensitive resin composition was formed on the copper surface of the substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the remaining step number (step step number) of the step tablet obtained as a resist pattern (cured film). The sensitivity is indicated by the number of steps when the exposure is performed at 100 mJ/cm ² , and the higher the value, the better the sensitivity. The results are shown in Tables 4 and 5.

<Evaluation of resolution and adhesion>
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) The photosensitive layer of the laminated substrate was exposed (drawn) with an energy amount such that the number of steps was 14. After the exposure, the development processing similar to the evaluation of the above sensitivity was performed.

After development, the space part (unexposed part) is removed cleanly, and the line part (exposed part) is the minimum of the line width/space width value in the resist pattern formed without causing defects such as meandering and chipping. The value evaluated the resolution and the adhesiveness. The smaller this value, the better the resolution and adhesiveness of the resist pattern. The obtained resist pattern was observed under an optical microscope at a magnification of 1000 times to confirm the presence or absence of defects. The results are shown in Tables 4 and 5.

<Evaluation of reaction rate>
A 41-step step tablet was exposed to the photosensitive layer of the above-mentioned photosensitive element with an energy amount such that the remaining step number was 14, and a photocured product was obtained. Before and after exposure, FT-IR measurement of the photosensitive layer or a photocured product thereof was performed using a Fourier transform infrared spectroscopy (FT-IR) device (“VERTEX70” manufactured by Bruker Optics Co., Ltd.). Then, using a peak derived from an aromatic at 1570 cm ⁻¹ as an internal standard, a reaction rate (%) was calculated from the peak derived from a vinyl group observed at 1637 cm ⁻¹ according to the following formula. The results are shown in Tables 4 and 5.
Reaction rate (%)=(1−I/I ₀ )×100
I: Peak intensity after exposure I ₀ : Peak intensity before exposure

<Evaluation of plating solution resistance (chemical solution resistance)>
After heating the copper clad laminate for flexible printed wiring boards ("F30VC1" manufactured by Nikkan Kogyo Co., Ltd.) to 80° C., the photosensitive elements according to Examples 1 to 5 and Comparative Examples 1 to 3 were placed. Laminated on the copper surface of the substrate. Lamination was performed under the conditions of a temperature of 110° C. and a laminating pressure of 4 kgf/cm ² (0.4 MPa) so that the photosensitive layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. .. In this way, an evaluation laminate was obtained in which the photosensitive layer and the support were laminated on the copper surface of the substrate. The obtained laminate for evaluation was left to cool to 23°C.

A glass phototool having a wiring pattern having L/S of 5/5, 8/8, 10/10, and 15/15 (unit: μm) was brought into close contact with the support of the evaluation laminate, and developed. The exposure was performed with an energy amount such that the remaining number of remaining step steps was 14. Then, the support was peeled off, and an unexposed portion was removed by spraying a 1% by mass aqueous solution of sodium carbonate at 30° C. to obtain an evaluation substrate. The developing time was set to a time corresponding to twice the shortest developing time (shortest time for removing the unexposed portion).

For the above-mentioned substrate for evaluation, it was immersed in a degreasing solution (“PC-455” manufactured by Meltex Co., Ltd., 25% by mass) for 5 minutes, washed with water, immersed in a soft etching solution (ammonium persulfate 150 g/L) for 2 minutes, washed with water Pretreatments were sequentially performed in the order of immersion in 10 mass% sulfuric acid for 1 minute. Then, it was put in a copper sulfate plating solution (copper sulfate 75 g/L, sulfuric acid 190 g/L, chlorine ion 50 mass ppm, "Capper Gleam PCM", 5 mL/L manufactured by Meltex Co., Ltd.) under the condition of 1 A/dm ² . Copper plating was performed until the plating thickness became 12 μm.

The evaluation substrate after the copper plating treatment was washed with water and dried, and then the resist pattern was peeled off by immersing it in a peeling solution (“R-100”, 0.2% by volume, manufactured by Mitsubishi Gas Chemical Co., Inc.) at 50° C. The base copper was etched with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide. After that, the plating dip was confirmed using an optical microscope from above, and those without the plating dip were evaluated as “A (excellent)” and those with the plating dip were evaluated as “C (defective)”. Note that when plating subsidence occurs, metallic copper deposited by copper plating is observed in the area masked by the resist pattern. The results are shown in Tables 4 and 5.

As is clear from Tables 4 and 5, a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a styrylpyridine compound represented by the formula (1) was used. In Examples 1 to 5, it is possible to form a resin pattern having a line width and a space width of 8 μm or less, and the sensitivity of the photosensitive resin composition, and the resolution, adhesiveness, and chemical resistance of the resist pattern. Was also excellent.

On the other hand, Comparative Examples 1 to 3 using the photosensitive resin composition containing no styrylpyridine compound represented by the formula (1) could not form a resin pattern having a line width and a space width of 8 μm or less, respectively, and The sensitivity of the photosensitive resin composition, and the resolution, adhesiveness, and chemical resistance of the resist pattern were inferior to those of Examples 1-5.

DESCRIPTION OF SYMBOLS 1... Photosensitive element, 2... Support, 3... Photosensitive layer, 4... Protective layer, 10... Conductive layer, 15... Insulating layer, 20... Mask, 30... Resist pattern, 32... Photosensitive layer, 40... Conductor pattern, 42... Plating layer

Claims (6)

Containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a styrylpyridine compound represented by the following formula (1),
The binder polymer has a structural unit derived from (meth)acrylic acid hydroxyalkyl ester,
The photopolymerizable compound includes a bisphenol A type di(meth)acrylate having 4 or less ethyleneoxy structural units.
A photosensitive resin composition used for forming a resin pattern having a line width and a space width of 8 μm or less.


[In the formula (1), R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, An amino group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth)acryloyl group, wherein a, b, and c are each independently 0 to 5; Indicates an integer. ] The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator contains a 2,4,5-triarylimidazole dimer represented by the following formula (2).


[In the formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Optionally represents an aryl group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5. Show. ] A photosensitive element comprising a support and a photosensitive layer provided on the support, the photosensitive layer comprising the photosensitive resin composition according to claim 1 or 2 . A step of forming a photosensitive layer on the substrate, the photosensitive layer comprising the photosensitive resin composition according to claim 1 or 2 ;
Irradiating actinic rays to at least a part of the region of the photosensitive layer, and photo-curing the region to form a cured product region,
And a step of removing at least a part of the photosensitive layer other than the cured product region from the substrate to form a resist pattern on the substrate. The method for manufacturing a substrate with a resist pattern according to claim 4 , wherein the wavelength of the actinic ray is in the range of 340 to 430 nm. A method for manufacturing a printed wiring board, comprising a step of performing at least one of an etching process and a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern according to claim 4 or 5 .