WO2018100640A1

WO2018100640A1 - Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for producing printed wiring board

Info

Publication number: WO2018100640A1
Application number: PCT/JP2016/085412
Authority: WO
Inventors: 彩桃崎; 翔太岡出
Original assignee: 日立化成株式会社
Priority date: 2016-11-29
Filing date: 2016-11-29
Publication date: 2018-06-07

Abstract

A photosensitive resin composition which contains a binder polymer, a photopolymerizable compound and a photopolymerization initiator, and wherein: the binder polymer contains a binder polymer that has a structural unit derived from a (meth)acrylic acid; and the photopolymerizable compound contains a bisphenol A di(meth)acrylate and a compound that has a caprolactone structure and two or more polymerizable unsaturated bonds.

Description

Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board

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 is performed on a circuit forming substrate. The photosensitive resin composition is often used for obtaining a photosensitive layer in a photosensitive element (laminated body) including a support and a photosensitive layer provided on the support.

The printed wiring board is manufactured as follows, for example. First, a photosensitive layer is formed using a photosensitive element on a circuit forming substrate (hereinafter sometimes simply referred to as “substrate”) (photosensitive layer forming step). Next, the exposed portion is cured by irradiating a predetermined portion of the photosensitive layer with actinic rays (exposure step). Then, after peeling off and removing the support, a resist pattern made of a cured product of the photosensitive resin composition is formed on the circuit-forming substrate by removing (developing) the unexposed portion of the photosensitive layer from the substrate. (Development process). After the conductor pattern (circuit) is formed on the substrate by etching or plating the substrate using the formed resist pattern as a mask (circuit formation process), the resist is finally peeled off and removed. (Peeling step) to produce a printed wiring board.

As an exposure method, 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) (exposure method for directly drawing a pattern on a photosensitive layer) has been proposed. This direct drawing exposure method has been 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.

Generally, in the exposure process, it is desired 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 the conventional exposure method via 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 than before.

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

In response to these demands, various photosensitive resin compositions have been conventionally studied. For example, Patent Document 1 below proposes a photosensitive resin composition using a polyfunctional monomer having a caprolactone structure and two or more polymerizable unsaturated bonds. Patent Documents 2 to 5 below propose photosensitive resin compositions using specific binder polymers, photopolymerizable compounds, photopolymerization initiators, and sensitizing dyes.

International Publication No. 2009/113275 JP 2005-122123 A JP 2007-114452 A International Publication No. 10/098183 International Publication No. 12/067107

By the way, it is required for the resist pattern formed by the photosensitive resin composition to further improve the resolution and adhesion (independent fine line adhesion, isolated fine line adhesion). If the photosensitive resin composition can provide a resist pattern with excellent resolution and adhesion, it is possible to sufficiently reduce short circuits and disconnections between circuits. However, although the photosensitive resin compositions described in Patent Documents 1 to 5 have relatively high sensitivity, there is still room for improvement in the resolution and adhesion of the formed resist pattern.

The present disclosure aims to provide a photosensitive resin composition capable of obtaining a resist pattern having excellent resolution and adhesion. Moreover, this indication aims at providing the manufacturing method of the photosensitive element using the said photosensitive resin composition, the board | substrate with a resist pattern, and the printed wiring board.

The photosensitive resin composition according to the present disclosure includes a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, wherein the binder polymer has a structural unit derived from (meth) acrylic acid. The photopolymerizable compound includes a bisphenol A type di (meth) acrylate and a compound having a caprolactone structure and two or more polymerizable unsaturated bonds.

According to the photosensitive resin composition according to the present disclosure, it is possible to obtain a resist pattern that is excellent in resolution and adhesion (independent fine line adhesion). Moreover, according to the photosensitive resin composition which concerns on this indication, the resist pattern which is excellent in the resolution, adhesiveness (independent fine line adhesiveness), and a mechanical characteristic can be formed.

The compound having a caprolactone structure and two or more polymerizable unsaturated bonds preferably includes a compound represented by the following general formula [I].

Wherein the six ^{R 1} is aspect all ^{R 1} is a group represented by the following general formula [II], or one to five ^{R 1} is represented by the following general formula [II] And the remaining R ¹ is a group represented by the following general formula [III]. ]

[Wherein R ² represents a hydrogen atom or a methyl group, m represents 1 or 2, and “*” represents a bond. ]

[Wherein R ³ represents a hydrogen atom or a methyl group, and “*” represents a bond. ]

The content of the compound having a caprolactone structure and two or more polymerizable unsaturated bonds may be less than 100 parts by mass with respect to 100 parts by mass of the binder polymer.

The photopolymerization initiator may contain a compound represented by the following general formula [X].

[Wherein, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group which may be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy 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 represents an integer of 1 to 5. When p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different. ]

The photosensitive element according to the present disclosure includes a support and a photosensitive layer provided on the support, and the photosensitive layer includes the above-described photosensitive resin composition.

A method of manufacturing a substrate with a resist pattern according to the present disclosure includes a step of forming a photosensitive layer on a substrate using the above-described photosensitive resin composition or the above-described photosensitive element, and at least a partial region of the photosensitive layer. And irradiating actinic light to form a cured product region by photocuring the region, and 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. And a process. The wavelength of the actinic ray may be 340 nm to 430 nm.

The method for producing a printed wiring board according to the present disclosure includes a step of applying at least one selected from the group consisting of etching treatment and plating treatment to a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern described above. Have

According to the present disclosure, it is possible to provide a photosensitive resin composition capable of obtaining a resist pattern having excellent resolution and adhesion. Moreover, according to this indication, the manufacturing method of the photosensitive element using the said photosensitive resin composition, the board | substrate with a resist pattern, and the printed wiring board can be provided.

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

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

In this specification, “(meth) acrylic acid” means at least one of acrylic acid and methacrylic acid corresponding thereto. The same applies to other similar expressions such as “(meth) acrylate”. The “(poly) ethyleneoxy group” means at least one of an ethyleneoxy group (hereinafter also referred to as “EO group”) and a polyethyleneoxy group in which two or more ethylene groups are connected by an ether bond. The “(poly) propyleneoxy group” means at least one of a propyleneoxy group (hereinafter also referred to as “PO group”) and a polypropyleneoxy group in which two or more propylene groups are connected 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” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. The term “stacked” indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.

In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

In this specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this 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 numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

In the present specification, the content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the plurality of substances in the composition. It means the total amount. The materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified.

<Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment contains (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator. The component (A) includes a binder polymer having a structural unit derived from (meth) acrylic acid. The component (B) contains bisphenol A type di (meth) acrylate and a compound having a caprolactone structure and two or more polymerizable unsaturated bonds. The photosensitive resin composition according to the present embodiment may contain other components as necessary.

When the photosensitive resin composition according to the present embodiment contains the specific compound, it is possible to form a resist pattern that is excellent in resolution, adhesion (independent fine line adhesion), and mechanical properties. Although the detailed reason which produces such an effect is not necessarily clear, the present inventors guess as follows. In other words, long-chain functional groups (caprolactone structure) and short-chain functional groups ((meth) acryloyl group) are present in the composition, so flexibility is maintained with long-chain functional groups without reducing the number of crosslinking points. At the same time, by maintaining the degree of curing with a short-chain crosslinking agent (bisphenol A-type di (meth) acrylate), the crosslinked network in the resist pattern is densified and the mechanical properties are improved. Therefore, it is presumed that the resolution and adhesion (independent fine line adhesion) are improved by suppressing resist collapse and breakage due to hydraulic pressure (water pressure or the like) during development.

(A) Component: Binder Polymer The (A) component of the photosensitive resin composition according to the present embodiment is also referred to as a binder polymer having a structural unit derived from (meth) acrylic acid (hereinafter referred to as “(a1) component”). )including. The component (A) may further contain a binder polymer other than the component (a1) as necessary.

The content of the structural unit derived from (meth) acrylic acid is based on the total mass of the structural unit constituting the component (a1) from the viewpoint of excellent balance between developability and resist pattern adhesion (100% by mass or less). Similarly, it may be 15% by mass to 40% by mass, 18% by mass to 38% by mass, or 20% by mass to 35% by mass. From the viewpoint of further improving developability, the content of the structural unit derived from (meth) acrylic acid may be 15% by mass or more based on the total mass of the structural unit constituting the component (a1). 18 mass% or more may be sufficient and 20 mass% or more may be sufficient. The content of the structural unit derived from (meth) acrylic acid is 40% by mass or less based on the total mass of the structural unit constituting the component (a1) from the viewpoint of further improving the adhesion of the resist pattern. May be 38 mass% or less, and may be 35 mass% or less.

The component (a1) may further have at least one selected from the group consisting of a structural unit derived from styrene and a structural unit derived from α-methylstyrene. In this case, the contents of the structural unit derived from styrene and the structural unit derived from α-methylstyrene constitute the component (a1) from the viewpoint of further improving the adhesion and peelability of the resist pattern. Based on the total mass of the structural unit, it may be 10% by mass to 70% by mass, 15% by mass to 60% by mass, or 20% by mass to 55% by mass. The content of each of the structural unit derived from styrene and the structural unit derived from α-methylstyrene is the total mass of the structural unit constituting the component (a1) from the viewpoint of further improving the adhesion of the resist pattern. As a reference | standard, 10 mass% or more may be sufficient, 15 mass% or more may be sufficient, and 20 mass% or more may be sufficient. The content of each of the structural unit derived from styrene and the structural unit derived from α-methylstyrene is the total mass of the structural unit constituting the component (a1) from the viewpoint of further improving the releasability of the resist pattern. As a reference | standard, 70 mass% or less may be sufficient, 60 mass% or less may be sufficient, and 55 mass% or less may be sufficient.

(A1) The component may have other structural units other than the above-mentioned structural unit. Examples of the other structural units include structural units derived from the following other polymerizable monomers (monomers).

Other polymerizable monomers can be polymerized with (meth) acrylic acid, styrene or α-methylstyrene, and may be different from (meth) acrylic acid, styrene and α-methylstyrene. There is no particular limitation. Other polymerizable monomers include (meth) acrylic acid alkyl esters (such as methyl (meth) acrylate), (meth) acrylic acid cycloalkyl esters, (meth) acrylic acid hydroxyalkyl esters ((meth) acrylic acid) 2-hydroxyethyl, etc.), benzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethacrylate (meth) acrylate Cyclopentanyl, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Tetrafluoropropyl (meth) acrylate, (meth) acryl Dicyclopentenyloxyethyl acid, dicyclopentanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, (meta ) Dicyclopentenyloxypropyloxyethyl acrylate, dicyclopentanyloxypropyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, adamantyloxypropyloxyethyl (meth) acrylate, etc. (Meth) acrylic acid ester; (meth) acrylic acid derivatives such as α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid; substituted on aromatic ring Polymerization possible Functional styrene derivatives; acrylamides such as diacetone acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic acid monomethyl, maleic acid monoethyl, maleic acid monoisopropyl maleate, etc. Acid monoesters; 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 individually by 1 type, and may be used in combination of 2 or more type.

When the component (a1) has a structural unit derived from a polymerizable monomer different from (meth) acrylic acid, styrene, and α-methylstyrene, the content of the structural unit depends on the resolution of the resist pattern and the releasability. From the viewpoint of further improving the ratio, it may be 3% by mass to 85% by mass, 5% by mass to 75% by mass, or 10% by mass based on the total mass of the structural units constituting the component (a1). It may be from mass% to 70 mass%, or from 10 mass% to 50 mass%.

The component (a1) can be obtained, for example, by radically polymerizing (meth) acrylic acid as a polymerizable monomer by a conventional method, and if necessary, (meth) acrylic acid, styrene, α -It can be radically polymerized with methylstyrene or other polymerizable monomers.

The acid value of the component (a1) may be 90 mgKOH / g to 250 mgKOH / g, or 100 mgKOH / g to 240 mgKOH / g, from the viewpoint of excellent balance between developability and resist pattern adhesion. It may be 120 mgKOH / g to 235 mgKOH / g, or 130 mgKOH / g to 230 mgKOH / g. From the viewpoint of shortening the development time, the acid value of the component (a1) may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g. It may be the above. The acid value of the component (a1) may be 250 mgKOH / g or less, 240 mgKOH / g or less, or 235 mgKOH / g or less from the viewpoint of further improving the adhesion of the resist pattern. 230 mgKOH / g or less.

The weight average molecular weight (Mw) of the component (a1) may be 10,000 to 200,000, 15,000 to 100,000, or 20,000 to 80,000 from the viewpoint of excellent balance between developability and resist pattern adhesion. It may be 23,000 to 60,000. From the viewpoint of shortening the development time, the weight average molecular weight of the component (a1) may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. From the viewpoint of further improving the adhesion of the resist pattern, the weight average molecular weight of the component (a1) may be 10,000 or more, 15000 or more, 20000 or more, or 23000 or more. It may be 25000 or more. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. More specifically, the weight average molecular weight can be measured under the conditions described in the examples.

The dispersity (weight average molecular weight / number average molecular weight) of the component (a1) 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 component (a1) may have a characteristic group in its molecule that is sensitive to light having a wavelength in the range of 340 nm to 430 nm, if necessary. Examples of the characteristic group include a group constituted by removing at least one hydrogen atom from a sensitizing dye described later.

As the component (A), the component (a1) may be used alone, or two or more components (a1) may be used in any combination. Other binder polymers other than the component (a1) may be used together with the component (a1).

The content of the component (A) in the photosensitive resin composition is 100 parts by mass of the total amount of the component (A) and the component (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 of the component (A) may be 30 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be greater than or equal to 40 parts by weight. From the viewpoint of further improving the sensitivity and resolution of the resist pattern, the content of the component (A) may be 70 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be 65 parts by mass or less, or 60 parts by mass or less.

(B) Component: Photopolymerizable Compound The photopolymerizable compound in the photosensitive resin composition according to the present embodiment is bisphenol A type di (meth) acrylate (hereinafter also referred to as “(b1) component”) and caprolactone. And a compound having a structure and two or more polymerizable unsaturated bonds (hereinafter also referred to as “component (b2)”). Each of (b1) component and (b2) component may be used individually by 1 type, and may be used in combination of 2 or more type. The component (B) may further contain a photopolymerizable compound other than the components (b1) and (b2) as necessary.

The component (b1) may be a compound represented by the following formula [A] from the viewpoint of further improving resolution and adhesion.

[Wherein, R ^a1 and R ^a2 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 to 40. x1, x2, y1, and y2 represent the number of structural units. ]

In the component (b1), the EO chain structural unit and the PO chain structural unit are not particularly specified. Here, the number of structural units of the EO group (structural unit) can be said to indicate how much the EO group is added in the molecule. The number of structural units of the PO group (structural unit) can be said to indicate how much PO group is added in the molecule. Therefore, an integer value is shown for a single molecule, but a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.

As a commercial product of the compound represented by the formula [A], 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trade names: BPE-100, BPE-80N) ), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-3200MY), 2,2-bis (4- (acryloxypolyethoxy) phenyl) Propane (made by Shin-Nakamura Chemical Co., Ltd., trade name: ABE-300), 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., trade name: BPE- 500, BPE-1300), 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-32 M), 2,2-bis (4- (methacryloxydiethoxyphenyl Siji ethoxy) phenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: BPE-200, FA-324ME), and the like. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the component (b1) in the photosensitive resin composition is such that, after curing, the molecular motion in the crosslinked network is suppressed to suppress swelling, and from the viewpoint of further improving resolution and adhesion, The following range may be sufficient with respect to 100 mass parts of total amounts of (B) component. The content of the component (b1) may be 1 part by mass to 60 parts by mass, 5 parts by mass to 55 parts by mass, 10 parts by mass to 50 parts by mass, or 20 parts by mass. To 45 parts by mass, or 30 to 40 parts by mass. The content of the component (b1) may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 It may be greater than or equal to parts by mass. The content of the component (b1) may be 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, It may be less than or equal to parts by mass.

The content of the component (b1) is to suppress swelling by suppressing molecular motion in the crosslinked network after curing, and from the viewpoint of further improving resolution and adhesion, from the viewpoint of further improving the resolution and adhesion, The following range may be used. The content of the component (b1) may be 50 to 100 parts by mass, 60 to 90 parts by mass, or 70 to 85 parts by mass. The content of the component (b1) may be 50 parts by mass or more, 60 parts by mass or more, or 70 parts by mass or more. 100 mass parts or less may be sufficient as content of (b1) component, 90 mass parts or less may be sufficient, and 85 mass parts or less may be sufficient.

Examples of the component (b2) include polymethyl alcohols such as trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylol melamine. And ε-caprolactone structure-containing polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ε-caprolactone. The component (b2) preferably contains a compound represented by the following general formula [I] from the viewpoint of obtaining higher resolution and adhesion (independent fine line adhesion) by obtaining further excellent mechanical properties. .

Wherein the six ^{R 1} is aspect all ^{R 1} is a group represented by the following general formula [II], or one to five ^{R 1} is represented by the following general formula [II] that a group, and the remainder of R ¹ is a mode which is a group represented by the following general formula [III]. ]

The number of groups represented by the formula [II] in the compound represented by the formula [I] is preferably 2 or more, and more preferably 3 or more from the viewpoint of further improving the resolution and adhesion.

Examples of commercially available compounds represented by the formula [I] include KAYARD DPCA series manufactured by Nippon Kayaku Co., Ltd. The commercially available products include DPCA-20 (number of groups represented by formula [II]: 2, m: all 1, R ² and R ³ : all hydrogen atoms), DPCA-30 (expressed by formula [II] the number of groups: 3, m: all 1, ^{R 2} and ^{R 3:} the number of groups represented by all hydrogen atoms) DPCA-60 (formula [II]: 6, m: all 1, ^{R 2} and R ³ : all hydrogen atoms) DPCA-120 (number of groups represented by formula [II]: 6, m: all 2, R ² and R ³ : all hydrogen atoms) and the like. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The viewpoint that the content of the component (b2) in the photosensitive resin composition is improved by maintaining the flexibility while suppressing the swelling by suppressing the molecular motion in the crosslinked network after curing, and maintaining the flexibility. In addition, the following range may be used with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The content of the component (b2) may be 1 part by mass to 60 parts by mass, 1 part by mass to 50 parts by mass, 1 part by mass to 40 parts by mass, or 3 parts by mass. To 30 parts by mass, or 5 to 10 parts by mass. The content of the component (b2) may be 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more. The content of the component (b2) may be 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 10 It may be less than or equal to parts by mass.

The content of the component (b2) is the component (B), from the viewpoint of improving the adhesion of the independent fine line by maintaining the flexibility while suppressing the swelling by suppressing the molecular motion in the crosslinked network after curing. The following range may be sufficient with respect to 100 mass parts. The content of the component (b2) may be 1 part by mass to 50 parts by mass, 5 parts by mass to 30 parts by mass, or 10 parts by mass to 20 parts by mass. The content of the component (b2) may be 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more. The content of the component (b2) may be 50 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less.

The content of the component (b2) is the component (A), from the viewpoint of improving the adhesion of independent fine lines by maintaining flexibility while suppressing swelling by suppressing molecular motion in the crosslinked network after curing. The following range may be sufficient with respect to 100 mass parts. The content of the component (b2) may be 1 part by weight or more and less than 100 parts by weight, 2 parts by weight to 50 parts by weight, 3 parts by weight to 30 parts by weight, or 5 parts by weight. It may be 10 to 10 parts by mass. The content of the component (b2) may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 5 parts by mass or more. The content of the component (b2) may be less than 100 parts by mass, 50 parts by mass or less, 30 parts by mass or less, or 10 parts by mass or less.

(B) component in the photosensitive resin composition which concerns on this embodiment may contain other photopolymerizable compounds other than (b1) component and (b2) component. Other photopolymerizable compounds are not particularly limited as long as photopolymerization is possible. The other photopolymerizable compound may be a compound having an ethylenically unsaturated bond. The compound having an ethylenically unsaturated bond includes a compound having one ethylenically unsaturated bond in the molecule, a compound having two ethylenically unsaturated bonds in the molecule, and three ethylenically unsaturated bonds in the molecule. Examples thereof include the compounds described above.

When (B) component contains other photopolymerizable compounds other than (b1) component and (b2) component, the content is suppressing swelling by suppressing the molecular motion in the crosslinked network after hardening. From the viewpoint of further improving the resolution and adhesion (independent fine line adhesion) by maintaining flexibility, it may be 1 to 60 parts by mass with respect to 100 parts by mass of component (B). It may be from 50 parts by weight to 10 parts by weight, or from 10 parts by weight to 40 parts by weight.

The component (B) may contain at least one compound having two ethylenically unsaturated bonds in the molecule (excluding the component (b1)) as another photopolymerizable compound. When the component (B) includes a compound having two ethylenically unsaturated bonds in the molecule, the content thereof is 2 parts by mass to 100 parts by mass of the total amount of the component (A) and the component (B). It may be 60 parts by mass, 3 to 55 parts by mass, or 5 to 50 parts by mass.

The compound having two ethylenically unsaturated bonds in the molecule includes at least one of bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate, EO group and PO group different from component (b1). Examples include polyalkylene glycol di (meth) acrylate having one in the molecule, di (meth) acrylate having a urethane bond in the molecule, and trimethylolpropane di (meth) acrylate.

Component (B) is a bisphenol A di (meth) acrylate or hydrogenated bisphenol A diester different from component (b1) as another photopolymerizable compound from the viewpoint of further improving the resolution and releasability of the resist pattern. (Meth) acrylate and at least one compound selected from the group consisting of polyalkylene glycol di (meth) acrylates having at least one of EO group and PO group in the molecule (2 ethylenically unsaturated bonds in the molecule Compound).

When the component (B) contains a bisphenol A type di (meth) acrylate different from the component (b1), the content suppresses the swelling by suppressing the molecular motion in the crosslinked network after curing, and the resolution From the viewpoint of further improving the adhesion, the amount may be 1 part by mass to 65 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and may be 5 parts by mass to 60 parts by mass. It may be 10 to 55 parts by mass.

Examples of the hydrogenated bisphenol A type di (meth) acrylate include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane. (B) When a component contains hydrogenated bisphenol A type | mold di (meth) acrylate, the content suppresses swelling by suppressing the molecular motion in the crosslinked network after hardening, and from a viewpoint of improving chemical | medical solution tolerance. The total amount of the components (A) and (B) may be 1 to 50 parts by mass or 5 to 40 parts by mass with respect to 100 parts by mass.

Component (B) is at least one polyalkylene glycol di (meth) acrylate 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 of the resist pattern. May be included. When the component (B) contains such a polyalkylene glycol di (meth) acrylate, the content is the total amount of the component (A) and the component (B) from the viewpoint of further improving the resolution and flexibility of the resist pattern. The amount may be 1 to 30 parts by mass or 5 to 25 parts by mass with respect to 100 parts by mass.

The polyalkylene glycol di (meth) acrylate compound may be EO / PO-modified polyalkylene glycol di (meth) acrylate. In the polyalkylene glycol di (meth) acrylate molecule, the (poly) ethyleneoxy group and the (poly) propyleneoxy group may be present continuously in blocks 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 an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

Polyalkylene glycol di (meth) acrylate includes (poly) n-butyleneoxy group, (poly) isobutyleneoxy group, (poly) n-pentyleneoxy group, (poly) hexyleneoxy group, structural isomers thereof, etc. And 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 bonds in the molecule as the other photopolymerizable compound.

Examples of the photopolymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (EO group having 1 to 5 structural units). 1), PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (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 individually by 1 type, and may be used in combination of 2 or more type.

Commercially available photopolymerizable compounds having three or more ethylenically unsaturated bonds in the molecule include tetramethylol methane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMM-3), EO-modified tri Methylolpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., trade names: TMPT21E and TMPT30E), pentaerythritol triacrylate (manufactured by Sartomer Japan, trade name: SR444), dipentaerythritol hexaacrylate (Shin Nakamura Chemical Co., Ltd.) Company-made, trade name: A-DPH; Nippon Kayaku Co., Ltd., trade name: DPHA), EO-modified pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: ATM-35E), and the like.

When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bonds in the molecule, the content balances the resist pattern shape, and the resolution, adhesion and peelability of the resist pattern. From the viewpoint of well improving, it may be 3 to 30 parts by mass, or 5 to 25 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). It may be 5 to 20 parts by mass.

From the viewpoint of improving the resist pattern shape and the resolution, adhesion and peelability of the resist pattern in a balanced manner, or from the viewpoint of suppressing the occurrence of scum, the component (B) is contained in the molecule as another photopolymerizable compound. A photopolymerizable compound having one ethylenically unsaturated bond may be included.

Examples of the photopolymerizable compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxy (meth) acrylate, phthalic acid compound, and (meth) acrylic acid alkyl ester. Among these, at least one selected from the group consisting of nonylphenoxypolyethyleneoxy (meth) acrylate and phthalic acid compound from the viewpoint of improving the resist pattern shape and the resolution, adhesion and peelability of the resist pattern in a balanced manner. It may be used.

When (B) component contains the photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator, the content is 1 with respect to 100 mass parts of total amounts of (A) component and (B) component. It may be from 20 to 20 parts by weight, from 3 to 15 parts by weight, or from 5 to 12 parts by weight.

The content of the component (B) in the photosensitive resin composition may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). From the viewpoint of further improving the sensitivity and the resolution of the resist pattern, the content of the component (B) may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. There may be. The content of the component (B) may be 70 parts by mass or less from the viewpoint of tending to form a photosensitive layer and the tendency to obtain a good resist pattern shape, and may be 65 parts by mass. Or less, 60 parts by mass or less, or 50 parts by mass or less. From these viewpoints, the content of component (B) may be 30 to 70 parts by mass, 35 to 65 parts by mass, or 35 to 60 parts by mass. It may be 40 to 50 parts by mass.

Component (C): Photopolymerization initiator The photosensitive resin composition according to the present embodiment contains at least one photopolymerization initiator as the component (C). The component (C) may contain a 2,4,5-triarylimidazole dimer from the viewpoint of further improving the sensitivity, resolution and adhesion of the photosensitive resin composition, and the following general formula [X] The compound represented by these may be included.

Wherein, Ar 1, ^Ar ^2, Ar ³ and Ar ⁴ each independently represent an alkyl group, an alkenyl group and at least one substituted aryl group which may be substituted with a group selected from the group consisting of an alkoxy 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 represents an integer of 1 to 5. When p is 2 or more, a plurality of X ¹ 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 1 to 6 carbon atoms, or 1 to 6 carbon atoms It may be an alkoxy group. It is preferable that at least one of X ¹ and X ² is 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. Examples of the substituent that Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. And at least one substituent selected from the group consisting of groups. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the above substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and more preferably 1. More preferably. In addition, when Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the substituent, the substitution position is not particularly limited, and 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 compound represented by the formula [X] include 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer (2,2′-bis (2-chlorophenyl) -4,4 ′, 5 , 5'-tetraphenylbiimidazole, etc.), 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 two 2,4,5-triarylimidazoles may give the same target compound or differently give asymmetric compounds. As the compound represented by the formula [X], one type may be used alone, or two or more types may be used in combination.

(C) When a component contains the compound represented by Formula [X], the content is 100 mass parts of (C) component from a viewpoint which further improves the sensitivity of the photosensitive resin composition, the resolution, and adhesiveness. On the other hand, it may be 25 parts by mass or more, 50 parts by mass or more, 75 parts by mass or more, or 90 parts by mass or more.

(C) In addition to the compound represented by the formula [X], the component (C) may contain other commonly used photopolymerization initiators. Other photopolymerization initiators include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as 1-propanone; 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; 9-phenylacridine, 1,7 And acridine derivatives such as-(9,9'-acridinyl) heptane.

The content of the component (C) in the photosensitive resin composition may be 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). To 7 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, the resolution of the resist pattern, and the adhesion tend to be further improved. When the content of the component (C) is 10 parts by mass or less, a good resist pattern shape tends to be obtained.

Component (D): Sensitizing dye The photosensitive resin composition according to the present embodiment may contain at least one sensitizing dye as the component (D). The sensitizing dye is one that can effectively utilize the absorption wavelength of actinic rays used for exposure, and is preferably a compound having a maximum absorption wavelength of 340 nm to 420 nm.

Examples of the component (D) include distyrylpyridine compounds (such as 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [b, e])-4- (2,4-dimethoxyphenyl) pyridine), pyrazoline Compound (1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline etc.), anthracene compound (9,10-dibutoxyanthracene etc.), benzophenone compound (benzophenone, 4,4′- Diethylaminobenzophenone, etc.), coumarin compounds, xanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, and the like. (D) It is preferable that a component contains at least 1 sort (s) chosen from the group which consists of a pyrazoline compound and an anthracene compound from a viewpoint which can further improve resolution, adhesiveness, and a sensitivity. (D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

When the photosensitive resin composition contains the component (D), the content of the component (D) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Parts, preferably 0.05 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 3 parts by weight, and more preferably 0.1 parts by weight to 1 part by weight. Particularly preferred is 0.1 to 0.8 parts by mass. When the content of component (D) is 0.01 parts by mass or more, excellent sensitivity and resolution tend to be easily obtained. When the content of component (D) is 10 parts by mass or less, a sufficiently good resist shape tends to be easily obtained.

(E) component: amine compound The photosensitive resin composition which concerns on this embodiment may contain at least 1 sort (s) of an amine compound as (E) component. Examples of the amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leuco crystal violet. (E) A component may be used individually by 1 type and may be used in combination of 2 or more type.

When the photosensitive resin composition which concerns on this embodiment contains (E) component, content of (E) component is 0.01 with respect to 100 mass parts of total amounts of (A) component and (B) component. It may be from 10 parts by weight to 10 parts by weight, from 0.05 to 5 parts by weight, or from 0.1 to 2 parts by weight. When the content of component (E) is 0.01 parts by mass or more, sufficient sensitivity tends to be obtained. When the content of the component (E) is 10 parts by mass or less, it tends to be suppressed that the excessive component (E) is deposited as a foreign substance after the formation of the photosensitive layer.

(Other ingredients)
The photosensitive resin composition according to 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, and a dye (malachite) as necessary. Green, Victoria pure blue, brilliant green, methyl violet, etc.), photochromic agent (tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, 2-chloroaniline, etc.), thermal color-preventing agent, plasticizer ( 4-toluenesulfonamide, etc.), pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. The component may be contained. These other components may be used individually by 1 type, and may be used in combination of 2 or more type.

When the photosensitive resin composition which concerns on this embodiment contains these other components, these content is 0.01 mass respectively with respect to 100 mass parts of total amounts of (A) component and (B) component. Part to about 20 parts by mass.

[Solution of photosensitive resin composition]
The photosensitive resin composition according to this embodiment may further contain at least one organic solvent. 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; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Content of the organic solvent contained in the photosensitive resin composition which concerns on this embodiment can be suitably selected according to the objective etc. For example, an organic solvent can be contained in the photosensitive resin composition and used as a solution having a solid content of about 30% by mass to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”.

The photosensitive layer, which is a coating film of the photosensitive resin composition, can be formed by applying the coating solution onto the surface of a support (polymer film, metal plate, etc.) described later and then drying.

The thickness of the photosensitive layer is not particularly limited and can be appropriately selected depending on the application. For example, the thickness of the photosensitive layer may be about 1 μm to 100 μm after drying. When the photosensitive layer is formed on the support, 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 according to this embodiment can be applied to the formation of a photosensitive layer of a photosensitive element described later. That is, another embodiment of the present disclosure is application of a photosensitive resin composition to a photosensitive element.

Moreover, the photosensitive resin composition according to this embodiment 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 an application of a photosensitive resin composition to a method for manufacturing a substrate with a resist pattern.

<Photosensitive element>
The photosensitive element which concerns on this embodiment is provided with the support body and the photosensitive layer provided on the support body, and the photosensitive layer contains the photosensitive resin composition which concerns on this embodiment. The photosensitive layer is a photosensitive layer formed using the photosensitive resin composition according to this embodiment. In addition, a photosensitive layer is a coating film formed using the photosensitive resin composition which concerns on this embodiment, Comprising: The photosensitive resin composition is a thing of an unhardened state. The photosensitive element may be provided with other layers, such as a protective layer, as needed.

FIG. 1 shows an example of a photosensitive element. In the photosensitive element 1 shown in FIG. 1, the support body 2, the photosensitive layer 3, and the protective layer 4 are laminated | stacked in this order. The photosensitive element 1 can be obtained as follows, for example. First, a photosensitive resin composition (for example, a coating solution that is a photosensitive resin composition containing an organic solvent) is coated on the support 2 to form a coating layer, and this is dried to form the photosensitive layer 3. Form. Next, the surface of the photosensitive layer 3 opposite to the support 2 is covered with a protective layer 4, so that the support 2, the photosensitive layer 3 laminated on the support 2, and the photosensitive layer 3 are laminated. The photosensitive element 1 provided with the protective layer 4 obtained is obtained. The photosensitive element 1 does not necessarily have to include the protective layer 4.

As the support, a polymer film, a metal plate or the like can be used. As the polymer film, a polymer film having heat resistance and solvent resistance (for example, a polyester film such as a polyethylene terephthalate film; a polypropylene film; a polyethylene film) can be used. It does not restrict | limit especially as a metal plate, According to the objective etc., it can select suitably. Examples of the metal plate include metal plates such as copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel. As a metal plate, Preferably, metal plates, such as copper, a copper alloy, and an iron alloy, are mentioned.

The thickness of the support may be 1 μm to 100 μm, 5 μm to 50 μm, or 5 μm to 30 μm. When the thickness of the support is 1 μm or more, it tends to be suppressed that the support is broken when the support is peeled off. When the thickness of the support is 100 μm or less, a reduction in resolution tends to be suppressed when exposure is performed through the support.

The protective layer is preferably a protective layer in which the adhesive force of the photosensitive layer to the protective layer is smaller than the adhesive force of the photosensitive layer to the support. The protective layer is preferably a low fish eye film. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, the “low fish eye” means that there are few foreign substances in the film.

Specifically, a polymer film having heat resistance and solvent resistance (for example, a polyester film such as a polyethylene terephthalate film; a polypropylene film; a polyethylene film) can be used as the protective layer. Examples of commercially available products include polypropylene films such as those manufactured by Oji Paper Co., Ltd. (for example, Alphan MA-410, E-200K) and Shin-Etsu Film Co., Ltd .; PS series (eg, PS-25) manufactured by Teijin Limited, etc. Polyethylene terephthalate film. The protective layer may be the same type of member as the support or a different type of member.

The thickness of the protective layer may be 1 μm to 100 μm, 5 μm to 50 μm, 5 μm to 30 μm, or 15 μm to 30 μm. When the thickness of the protective layer is 1 μm or more, when the photosensitive layer and the support are laminated on a substrate (for example, a circuit forming substrate) while peeling off the protective layer, the protective layer tends to be easily prevented from being broken. is there. When the thickness of the protective layer is 100 μm or less, it tends to be excellent in handleability and inexpensiveness.

The photosensitive element according to the present embodiment can be manufactured, for example, as follows. A step of preparing a coating solution in which each component is dissolved in an organic solvent; a step of coating the coating solution on a support to form a coating layer; and a step of drying the coating layer to form a photosensitive layer. A photosensitive element can be manufactured with a manufacturing method.

Application of the coating liquid onto the support can be performed 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 remaining organic solvent in the photosensitive layer may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

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

The transmittance of the photosensitive layer 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 nm to 420 nm. May be. When the transmittance is 5% or more, sufficient adhesion of the resist pattern tends to be obtained. If the 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. An example of the ultraviolet spectrometer is a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

The photosensitive element according to the present embodiment may include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, for example, the intermediate layers described in JP-A-2006-098982 can be used.

The form of the photosensitive element is not particularly limited. The photosensitive element may be in the form of a sheet, for example, or may be in the form of a roll wound around a core. When it winds up in roll shape, it is preferable to wind up so that a support body may become an outer side. Examples of the winding core include plastics such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint 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 viewpoint of edge fusion resistance, it is preferable to install a moisture-proof end face separator. . As a method for packing the photosensitive element, it is preferable to wrap and wrap the photosensitive element in a black sheet with low moisture permeability.

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

<Method for manufacturing substrate with resist pattern>
A substrate with a resist pattern can be manufactured using the photosensitive resin composition or photosensitive element according to the present embodiment. The method for manufacturing a substrate with a resist pattern according to this embodiment includes (i) a step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to this embodiment or the photosensitive element according to this embodiment. (Photosensitive layer forming step), (ii) irradiating at least a part of the photosensitive layer with actinic rays, photocuring the region to form a cured product region (exposure step), and (iii) photosensitive Removing at least a part of the layer other than the cured product region from the substrate and forming a resist pattern on the substrate (development step). The manufacturing method of the board | substrate with a resist pattern may further have another process as needed.

(I) Photosensitive layer forming step First, a photosensitive layer is formed on a substrate using the photosensitive resin composition according to this embodiment or the photosensitive element according to this embodiment. As the substrate, for example, a substrate (for example, a circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used. As an insulating layer, a glass epoxy material is mentioned, for example. An example of the conductor layer is copper foil.

As a method for forming a photosensitive layer on a substrate, for example, when the photosensitive element has a protective layer, after removing the protective layer, the photosensitive layer of the photosensitive element is pressure-bonded to the substrate while heating. Can be done. Thereby, a laminate in which the substrate, the photosensitive layer, and the support are laminated in this order is obtained. Moreover, you may form a photosensitive layer by apply | coating and drying the photosensitive resin composition which concerns on this embodiment on a board | substrate.

The photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of excellent adhesion and followability. The heating temperature for at least one of the photosensitive layer and the substrate during the pressure bonding is preferably 70 ° C. to 130 ° C. The pressing pressure is preferably about 0.1 MPa to 1.0 MPa (about 1 kgf / cm ² to 10 kgf / cm ² ). The heating temperature and pressure bonding pressure are not limited to these, and are appropriately selected as necessary. If the photosensitive layer is heated to 70 ° C. to 130 ° C., the substrate need not be preheated. Adhesion and follow-up can be further improved by pre-heating the substrate.

(Ii) Exposure Step In the exposure step, at least a part of the photosensitive layer formed on the substrate is irradiated with actinic rays, whereby the exposed portion irradiated with the actinic rays is photocured to form a latent image. The At this time, when the support existing on the photosensitive layer transmits actinic rays, the actinic rays can be irradiated through the support. On the other hand, when the support is light-shielding against actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.

Examples of the exposure method include a method of irradiating actinic rays in the form of an image through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in the form of an image 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 light source for the active light is not particularly limited, and a known light source can be used. Specific examples of light sources include 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), semiconductor lasers, and gallium nitride blue-violet lasers. And a light source that effectively emits ultraviolet light, visible light, and the like.

The wavelength of the actinic ray (exposure wavelength) may be 340 nm to 430 nm or 350 nm to 420 nm. When the wavelength of the actinic ray is 340 nm to 430 nm, there is a tendency that a resist pattern excellent in resolution and adhesion (independent fine line adhesion) can be more efficiently formed with excellent sensitivity.

(Iii) Development Step In the development step, an uncured portion of the photosensitive layer is removed from the substrate by a development process, whereby a resist pattern, which is a cured product obtained by photocuring the photosensitive layer, is formed on the substrate. When a support is present on the photosensitive layer, the unexposed portion can be removed (developed) after the support is removed. Examples of the development treatment 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 photosensitive resin composition. Examples of the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of further improving the resolution, a high pressure spray method is preferable. You may develop by combining these 2 or more types of methods.

The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.

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

Examples of the alkaline aqueous solution include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and a dilute solution of 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1% to 5% by weight sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably 9-11. The temperature of the alkaline aqueous solution is adjusted in accordance with the alkali developability of the photosensitive layer. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like.

Examples of the organic solvent 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. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. When the alkaline aqueous solution contains an organic solvent, the content of the organic solvent is preferably 2% by mass to 90% by 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. In order to prevent ignition, it is preferable to add water in the range of 1% by mass to 20% by mass to these organic solvents to obtain an organic solvent developer.

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

<Method for manufacturing printed wiring board>
The printed wiring board manufacturing method according to the present embodiment is at least one selected from the group consisting 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 the present embodiment. A step of performing a seed treatment. As the substrate, for example, a substrate (for example, a circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer is preferably used. The manufacturing method of a printed wiring board may have other processes, such as a resist removal process, as needed. 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, using the resist pattern (cured resist) formed on the substrate as a mask, the conductor layer not covered with the cured resist (for example, the conductor layer of the circuit forming substrate) is removed by etching to remove the conductor pattern. Form. 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 alkali etching solution, and a hydrogen peroxide etching solution. Among these, it is preferable to use a ferric chloride aqueous solution from the viewpoint of a good etch factor.

In the plating process, using a resist pattern (cured resist) formed on the substrate as a mask, copper, solder, etc. is plated on a conductor layer (for example, a conductor layer of a circuit forming substrate) that is not covered with the cured resist. To do. After the plating treatment, the cured resist is removed, and the conductor layer covered with the cured resist is etched to form a conductor pattern. The plating process may be an electrolytic plating process or an electroless plating process. Plating treatment includes copper plating such as copper sulfate plating and copper pyrophosphate plating; solder plating such as high-throw solder plating; nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating; hard gold plating, Examples thereof include gold plating such as soft gold plating.

After the etching process or the plating process, the resist pattern on the substrate is removed (peeled). The removal of the resist pattern can be performed, for example, using a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As the 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, or the like is used. Among them, it is preferable to use a 1% by mass to 10% by mass sodium hydroxide aqueous solution or a 1% by mass to 10% by mass potassium hydroxide aqueous solution, and a 1% by mass to 5% by mass sodium hydroxide aqueous solution or 1% by mass. It is more preferable to use a 5% by mass aqueous potassium hydroxide solution. Examples of methods for applying a strong alkaline aqueous solution to the resist pattern include an immersion method and a spray method. These methods may be used alone or in combination of two or more.

When the resist pattern is removed after the plating treatment, a desired printed wiring board can be produced by further removing the conductor layer covered with the cured resist by the etching treatment and forming the conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

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

The photosensitive resin composition according to the present embodiment can be suitably used for the production of a printed wiring board. That is, one of the preferred embodiments of the present disclosure is application of the photosensitive resin composition to the production of a printed wiring board.

Further, a more preferred embodiment of the present disclosure is an application of the photosensitive resin composition to the production of a high-density package substrate, and an application of the photosensitive resin composition to a semi-additive construction method. Hereinafter, an example of the manufacturing process of the wiring board by the semi-additive method will be described with reference to FIG. The size of the members in FIG. 2 is conceptual, and the relative relationship between the sizes of the members is not limited to this.

In FIG. 2A, a substrate (for example, a circuit forming substrate) on 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 disposed on the photosensitive layer 32, and an actinic ray 50 is irradiated to the photosensitive layer 32 in an exposure process to expose a region other than the region where the mask 20 is disposed. A photocured portion is formed in the layer 32. In FIG. 2D, a region of the photosensitive layer 32 other than the photocured portion is removed from the substrate by a development process, thereby forming a resist pattern 30 that is a photocured portion on the substrate. In FIG. 2E, 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. 2F, after the resist pattern 30 as the 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 flash-etched. Is removed to form a conductor pattern 40. The conductor layer 10 and the plating layer 42 may be made of the same material or different materials. In FIG. 2, the method of forming the resist pattern 30 using the mask 20 has been described. However, the resist pattern 30 may be formed by a direct drawing exposure method without using the mask 20.

Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited to these examples.

<Synthesis of binder polymer>
(Binder polymer (A-1))
A polymerizable monomer (monomer) of 81 g of methacrylic acid, 135 g of styrene, 69 g of benzyl methacrylate, and 15 g of methyl methacrylate (mass ratio: 27/45/23/5), azobisisobutyronitrile 5 g was mixed to obtain “Solution a”.

0.5 g of azobisisobutyronitrile was dissolved in 100 g of a mixed solution (mass ratio: 3: 2) of 60 g of methyl cellosolve and 40 g of toluene to obtain “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 mixed solution of 180 g of methyl cellosolve and 120 g of toluene (mass ratio: 3: 2), and then nitrogen was introduced into the flask. The mixture was heated to 80 ° C. with stirring while blowing gas.

The solution a was dropped into the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. Next, after the solution b was dropped into the solution in the flask over 10 minutes, 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 nonvolatile content (solid content) of the binder polymer (A-1) was 41.5% by mass, the weight average molecular weight was 44000, the acid value was 176 mgKOH / g, and the dispersity was 2.2. In addition, the weight average molecular weight and the number average molecular weight were measured by a gel permeation chromatography (GPC) method, and were derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.

[GPC conditions]
Pump: Hitachi L-6000 (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 (Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled 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.)

(Binder polymer (A-2))
2. 81 g of a polymerizable monomer, 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, 69 g of benzyl methacrylate (mass ratio: 27/3/47/23) and azobisisobutyronitrile 4 g was mixed to obtain “Solution c”. A solution of the binder polymer (A-2) was obtained in the same manner as that for obtaining the solution of the binder polymer (A-1) except that the solution c was used instead of the solution a.

The nonvolatile content (solid content) of the binder polymer (A-2) was 41.7% by mass, the weight average molecular weight was 38000, the acid value was 176 mgKOH / g, and the dispersity was 1.8.

For the binder polymers (A-1) and (A-2), Table 1 shows the mass ratio (%) of the polymerizable monomer, the acid value, the weight average molecular weight, and the degree of dispersion. “-” Means not blended.

<Preparation of solution of photosensitive resin composition>
By mixing each component shown in Table 2 and Table 3 with 9 g of acetone, 5 g of toluene and 5 g of methanol in the blending amount (unit: g) shown in the same table, the photosensitive resin compositions of Examples and Comparative Examples were mixed. Each solution was prepared. The blending amount of the component (A) shown in Tables 2 and 3 is the mass (solid content) of the nonvolatile content. “-” Means not blended. Details of each component shown in Tables 2 and 3 are as follows.

(A) Binder polymer The following was used as a binder polymer having a structural unit derived from (meth) acrylic acid.
Binder polymers (A-1) and (A-2)

(B) Photopolymerizable compound [component (b1)]
The following was used as the component (b1) which is bisphenol A type di (meth) acrylate.
BPE-100 (made by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis (4- (methacryloxyethoxy) phenyl) propane BPE-80N (made by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis (4- (Methacryloxyethoxy) phenyl) propane FA-324ME (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2 , 2-bis (4- (acryloxypolyethoxy) phenyl) propane FA-321M (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane FA-3200MY (Hitachi Chemical) Manufactured by): 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane [component (b2)]
The following was used as the component (b2) which is a compound having a caprolactone structure and two or more polymerizable unsaturated bonds.
DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.): compound represented by formula [I] (number of groups represented by formula [II]: 2, m: all 1, R ² and R ³ : all hydrogen atom)
DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.): compound represented by formula [I] (number of groups represented by formula [II]: 3, m: all 1, R ² and R ³ : all hydrogen atom)
[(B3) Other photopolymerizable compounds]
The following were used as photopolymerizable compounds other than the above (b1) and (b2).
FA-024M (manufactured by Hitachi Chemical Co., Ltd.): PO / EO / PO-modified polypropylene glycol # 700 dimethacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.): dipentaerythritol hexaacrylate (manufactured by Polysciences): pentaerythritol tetramethacrylate

(C) Photopolymerization initiator B-CIM (Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer): 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5'-Tetraphenylbiimidazole

(D) Sensitizer EAB (manufactured by Hodogaya Chemical Co., Ltd.): 4,4′-diethylaminobenzophenone 2,4-DMOP-DSP: 3,5-bis (2,4-dimethoxybenzylidene dicyclopentano [b , E])-4- (2,4-dimethoxyphenyl) pyridine PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) Pyrazoline DBA (Kawasaki Chemical Industries): 9,10-dibutoxyanthracene

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

Dye MKG (manufactured by Osaka Organic Chemical Industry Co., Ltd.): Malachite Green

<Production of photosensitive element>
The solution of the photosensitive resin composition was applied onto a polyethylene terephthalate film (trade name: FB-40, hereinafter referred to as “support”) having a thickness of 16 μm, respectively, and then heated at 70 ° C. and 110 ° C. A photosensitive layer having a thickness of 25 μm after drying was formed by sequentially drying with a hot air convection dryer. A photosensitive element in which a polyethylene film (manufactured by Oji Paper Co., Ltd., trade name: E-200K, hereinafter referred to as “protective layer”) is bonded onto the photosensitive layer, and the support, the photosensitive layer, and the protective layer are sequentially laminated. Respectively.

<Production of laminated substrate>
A copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-679F, hereinafter referred to as “substrate”) composed of a glass epoxy material and copper foil (thickness 16 μm) formed on both sides thereof is heated. Then, after raising the temperature to 80 ° C., the photosensitive elements according to Examples and Comparative Examples were laminated (laminated) on the copper surface of the substrate. Laminate, while removing the protective layer, the photosensitive layer of the photosensitive element so as to close contact with the copper surface of the substrate, temperature of 110 ° C., was carried out under the conditions of lamination pressure 4kgf ^/ cm 2 (0.4MPa) . In this way, 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 allowed to cool to 23 ° C.

<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) The photosensitive layer of the laminated substrate was exposed (drawn) through the support with an energy amount of 14 steps. Next, after peeling off the support, an unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds. Thus, the resist pattern which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate.

After development, the space portion (unexposed portion) is removed neatly, and the line portion (exposed portion) of the line width / space width value in the resist pattern formed without causing defects (meandering, chipping, etc.) Resolution and adhesion (independent fine line adhesion) were evaluated by the minimum value of. The smaller this value, the better the resolution and adhesion of the resist pattern. The obtained resist pattern was observed with 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 mechanical properties (elongation)>
The photosensitive layer of the laminated substrate was exposed at 150 mJ / cm ² through a mask having a rectangular opening of 10 mm × 60 mm. Next, after peeling off the support, development was performed in a time twice as long as the minimum development time to obtain a cured resist. Using a tabletop precision universal testing machine Autograph (manufactured by Shimadzu Corporation, trade name: AGS-X), the distance between chucks is fixed to 20 mm, and the produced 10 mm × 60 mm cured resist is made at a speed of 5 mm / min. The elongation of the cured resist at that time was evaluated based on the following criteria. The results are shown in Tables 4 and 5.
A: The elongation of the cured resist is 0.2 mm or more.
B: The elongation of the cured resist is 0.1 mm or more and less than 0.2 mm.
C: The elongation of the cured resist is less than 0.1 mm.

As is clear from Tables 4 and 5, in the examples, the resist resolution, adhesion and mechanical properties were all excellent.

On the other hand, in Comparative Examples 1 and 4 using the photosensitive resin composition not containing bisphenol A type di (meth) acrylate (component (b1)), the resolution, adhesion and mechanical properties of the resist pattern were higher than those of the examples. It was inferior. In Comparative Examples 2 and 3 using a photosensitive resin composition not containing a compound having a caprolactone structure and two or more polymerizable unsaturated bonds (component (b2)), the resist pattern of the photosensitive resin composition The mechanical properties were inferior to those of the examples.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 2 ... Support body, 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, 50 ... active light.

Claims

Containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator,
The binder polymer includes a binder polymer having a structural unit derived from (meth) acrylic acid,
The photosensitive resin composition in which the said photopolymerizable compound contains the compound which has bisphenol A type di (meth) acrylate and a caprolactone structure and two or more polymerizable unsaturated bonds.
The photosensitive resin composition of Claim 1 in which the compound which has the said caprolactone structure and two or more polymerizable unsaturated bonds contains the compound represented by the following general formula [I].

Wherein the six R 1 is aspect all R 1 is a group represented by the following general formula [II], or one to five R 1 is represented by the following general formula [II] And the remaining R 1 is a group represented by the following general formula [III]. ]

[Wherein R 2 represents a hydrogen atom or a methyl group, m represents 1 or 2, and “*” represents a bond. ]

[Wherein R 3 represents a hydrogen atom or a methyl group, and “*” represents a bond. ]
The photosensitive resin composition of Claim 1 or 2 whose content of the compound which has the said caprolactone structure and two or more polymerizable unsaturated bonds is less than 100 mass parts with respect to 100 mass parts of said binder polymers. .
The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator includes a compound represented by the following general formula [X].

[Wherein, Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aryl group which may be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy 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 represents an integer of 1 to 5. When p is 2 or more, a plurality of X 1 may be the same or different, and when q is 2 or more, a plurality of X 2 may be the same or different. ]
A support, and a photosensitive layer provided on the support,
A photosensitive element, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of claims 1 to 4.
Forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 4 or the photosensitive element according to claim 5;
Irradiating at least a part of the photosensitive layer with actinic rays and photocuring the region to form a cured product region;
Removing at least a part of the photosensitive layer other than the cured product region from the substrate, and forming a resist pattern on the substrate.
The method for producing a substrate with a resist pattern according to claim 6, wherein the wavelength of the actinic ray is 340 nm to 430 nm.
A printed wiring board comprising a step of applying at least one selected from the group consisting of etching treatment and plating treatment to a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern according to claim 6 or 7. Manufacturing method.