JPWO2017043544A1 - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition comprising an alkali-soluble polymer, a compound having an ethylenic double bond, and a photopolymerization initiator, wherein the photosensitive property is formed on a copper-clad laminate on which a copper foil having a thickness of 18 μm is laminated. A photosensitive resin layer made of a resin composition is laminated with a thickness of 25 μm, a cured resist pattern is formed through light irradiation and development processing in a pattern shape of line / space = 50 μm / 30 μm, and a copper etching process at 50 ° C. for 55 seconds. The said photosensitive resin composition characterized by the bottom width | variety of the copper line pattern obtained by removing the said hardening resist pattern after giving this to 38 micrometers or more.

Description

<Technical field relating to the first embodiment of the present invention>
The first embodiment of the present invention relates to a photosensitive resin composition.

<Technical Field Related to Second Embodiment of the Present Invention>
The second embodiment of the present invention relates to a photosensitive resin composition and the like.

<Technical field relating to the third embodiment of the present invention>
The third embodiment of the present invention relates to a photosensitive resin composition and the like.

<Technical field relating to the fourth embodiment of the present invention>
The fourth embodiment of the present invention relates to a photosensitive resin composition.

<Background Technology Related to First Embodiment of the Present Invention>
A printed wiring board is generally manufactured by photolithography. With photolithography, a layer made of a photosensitive resin composition is formed on a substrate, a resist pattern is formed by pattern exposure and development on the coating film, and then a conductor pattern is formed by etching or plating, In this method, a desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.
In this photolithography, when a photosensitive resin composition layer is formed on a substrate, a method of removing the solvent after applying the composition solution; a photosensitive element formed by laminating a support and a photosensitive resin composition layer A method of peeling the support after laminating a dry film resist on a substrate is known.

Photosensitive elements are often used in the production of printed wiring boards. There are many known examples of a method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for this method.
For example, Patent Document 1 discloses a method capable of easily forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used in the method;
Patent Document 2 discloses a photosensitive resin composition containing an addition polymerizable monomer having a specific ethylenic double bond.

In recent years, in order to increase the density of printed wiring boards, substrates are often multilayered. In the multilayer substrate, the through-holes are provided so as to be stacked one above the other for conduction between the substrates. When a wiring pattern is formed by photolithography on a substrate having a through hole used for a multilayer substrate, the resist film (tent film) formed on the through hole is caused by a spray pressure at the time of development, washing, etc. It is required to have a property that does not break (tent film resistance or tenting resistance).
In this regard, Patent Document 3 discloses a photosensitive resin composition containing a binder polymer having a low degree of dispersion (Mw / Mn), a photopolymerizable compound, and an acridine compound. It is described that a resist film having excellent tenting properties can be formed.

<Background Technology Related to Second Embodiment of the Present Invention>
A printed wiring board is generally manufactured by photolithography. With photolithography, a coating film including a layer made of a photosensitive resin composition is formed on a substrate, the coating film is subjected to pattern exposure and development to form a resist pattern, and then a conductor pattern is formed by etching or plating treatment. Thereafter, a desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.
In photolithography, when a photosensitive resin layer is formed on a substrate, a method of removing the solvent after applying the composition solution; a photosensitive element or dry film resist formed by laminating a support and a photosensitive resin layer; A method of peeling the support after laminating on a substrate is known.

Photosensitive elements are often used in the production of printed wiring boards. There are many known examples of a method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for this method.
For example, Patent Document 1 discloses a method capable of easily forming a copper wiring pattern having a good cross-sectional shape and a photosensitive resin composition used in the method. Patent Document 4 discloses a specific ethylenic double layer. A photosensitive resin composition containing an addition polymerizable monomer having a bond is disclosed.

<Background Technology Related to Third Embodiment of the Present Invention>
Conventionally, a printed wiring board is generally manufactured by a photolithography method. In the photolithography method, first, pattern exposure is performed on the photosensitive resin composition layer laminated on the substrate. The exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (in the case of a positive type). Next, the unexposed portion (in the case of negative type) or the exposed portion (in the case of positive type) is removed with a developer to form a resist pattern on the substrate. Furthermore, after a conductor pattern is formed by etching or plating, the resist pattern is peeled off from the substrate. Through these steps, a conductor pattern is formed on the substrate.

  In general, the photolithography method is a method in which a solution of a photosensitive resin composition is applied to a substrate and dried, or a dry film resist (photosensitive resin laminate in which a photosensitive resin composition layer is laminated on a support). Any method of laminating the conductive resin composition layer on the substrate is used. The latter is frequently used in the production of printed wiring boards.

With the recent miniaturization of wiring intervals in printed wiring boards, various characteristics have been required for dry film resists. With the miniaturization of the wiring interval, the thickness of the dry film resist tends to be reduced, but still strong tent properties are required to protect the through holes on the substrate.
Further, when the resist pattern is developed, the resist component is eluted between the patterns due to the moisture remaining between the patterns, causing a short circuit failure due to the remaining water. In order to reduce this water residue short circuit defect, it is necessary to improve the hydrophobicity of the cured resist.
In order to improve the characteristics of the resist, various photosensitive resin compositions have been proposed (Patent Documents 5 and 6).

<Background Technology Regarding the Fourth Embodiment of the Present Invention>
A printed wiring board is generally manufactured by photolithography. With photolithography, a layer made of a photosensitive resin composition is formed on a substrate, a resist pattern is formed by pattern exposure and development on the coating film, and then a conductor pattern is formed by etching or plating, In this method, a desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.

  In photolithography, when a photosensitive resin layer is formed on a substrate, a method of removing the solvent after applying the composition solution; a photosensitive element or dry film resist formed by laminating a support and a photosensitive resin layer; A method of peeling the support after laminating on a substrate is known.

  Photosensitive elements are often used in the production of printed wiring boards. A method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for this method are known (Patent Documents 1 and 2). Patent Document 1 describes a general method for forming a copper wiring pattern having a good cross-sectional shape and a photosensitive resin composition used therefor. Patent Document 2 describes a photosensitive resin composition containing an addition polymerizable monomer having a specific ethylenically unsaturated bond.

  By the way, with recent miniaturization of wiring intervals in a printed wiring board, dry film resists are required to have characteristics such as resolution. For example, various photosensitive resin compositions have been proposed in order to improve the characteristics of resist patterns (Patent Documents 5 and 6).

JP2011-233769A International Publication No. 2009/022724 JP2013-109321A Japanese Patent Laid-Open No. 2015-60120 International Publication No. 2015/098870 JP 2014-048340 A

<Problem to be solved by the first embodiment of the present invention>
In recent years, the manufacture of a wiring board is usually performed by a line process in which processing is sequentially performed while a substrate is conveyed in a certain direction. Here, for example, when a conductor pattern of a line / space pattern is formed on a substrate, when the conductor line is parallel (MD direction line) or perpendicular to the substrate transport direction (TD direction) Line) and an oblique case. When a conductor pattern of a line / space pattern is formed by a line process using a resist material of the prior art, the wiring width is different between the MD direction line and the TD direction line, and a so-called vertical / horizontal difference in wiring width occurs. In many cases, the MD direction line is more easily affected by the etchant than the TD direction line, and thus the etching amount increases and the wiring width tends to be narrow. In order to form a fine conductor pattern by a line process, it is preferable that the wiring width difference between the MD wiring and the TD wiring is reduced.

However, in the conventional techniques represented by the above Patent Documents 1 to 3, no examination is made from such a viewpoint, and a resist material for reducing the vertical / horizontal difference of the wiring width is not known.
The first embodiment of the present invention has been made in view of the above situation. Accordingly, an object of the first embodiment of the present invention is to provide a resist material in which a vertical and horizontal difference in wiring width is suppressed when a fine conductor pattern is formed by a line process.

<Problem to be solved by the second embodiment of the present invention>
In order to form a resist pattern using the photosensitive resin composition, a development process is performed. In this development step, a resist pattern is formed by dissolving and removing the composition in the exposed region in the positive composition and the composition in the exposed region in the negative composition. In this development step, not all of the composition in the unnecessary region is “dissolved” in the developer, but at least a part of the composition is removed from the substrate by being dispersed in the developer while remaining insoluble. Therefore, each time the development process is repeated, the amount of unnecessary substances in the developer increases, and finally insoluble components with poor dispersibility may form aggregates. Such agglomerates may remain attached to a substrate to be developed later, which may cause a short circuit failure.
Accordingly, it is strongly desired that the photosensitive resin composition to be used has good developer dispersibility from the viewpoint of improving the product yield in the development process and reducing the production cost of the printed wiring board.

By the way, in recent years, demands for miniaturization and refinement of printed wiring boards have been increasing. Therefore, it is required that a fine pattern can be formed even for the photosensitive resin composition used for forming the printed wiring board. Here, since the minimum size of the pattern formed on the substrate depends on the exposure wavelength, by adopting a photosensitive polymerization initiator corresponding to the exposure wavelength to be used, a finer pattern can be formed by exposure. It is not that difficult logically. On the other hand, for example, a fine pattern formed by exposure with a size of several tens of μm or less may be peeled off from the substrate in a later process such as a development process. As a result, miniaturization of the printed wiring board is limited. ing.
Therefore, in order to form a fine printed wiring board, a photosensitive resin composition having high adhesion of a fine pattern is required.

  However, the photosensitive resin compositions described in Patent Documents 1 and 4 cannot withstand today's strict requirements for both development dispersibility and fine pattern adhesion, and there is still room for improvement in this field. It exists.

The second embodiment of the present invention has been made in view of such a current situation.
Therefore, the object of the second embodiment of the present invention is to provide a novel photosensitivity that has a high level of performance such as resolution, which is generally required for photosensitive materials, and is excellent in development dispersibility and fine pattern adhesion. Is to provide a sex material.

<Problem to be solved by the third embodiment of the present invention>
In Patent Document 5, from the viewpoint of developability of the photosensitive resin composition and resolution, adhesion, and flexibility of the resist pattern, in the photosensitive resin composition, a structural unit of (meth) acrylic acid, styrene or α- A binder polymer having a structural unit of methylstyrene and a structural unit of a hydroxyalkyl ester of (meth) acrylic acid having a hydroxyalkyl group having 1 to 12 carbon atoms, an ethyleneoxy group having 1 to 20 structural units, and A combination with a bisphenol-type di (meth) acrylate monomer having 0 to 7 structural units of a propyleneoxy group has been studied.

  Patent Document 6 proposes a content of a structural unit of styrene or a styrene derivative in the alkali-soluble polymer of 30% by mass or more from the viewpoint of the space width and tent property of the positive resist pattern, and addition polymerization is proposed. A weight average molecular weight of 1,100 or more has been proposed.

  Both Patent Documents 5 and 6 focus on a photosensitive resin composition containing a polymer having a specific proportion of styrene structural units and a specific monomer, but are described in Patent Documents 5 and 6. The photosensitive resin composition that has been used still has room for improvement from the viewpoint of achieving both a tent property of the resist pattern and a water residue short-circuit defect suppressing property.

  Therefore, the problem to be solved by the third embodiment of the present invention is to provide a photosensitive resin composition capable of satisfying both the tent property of a resist pattern and the water short-circuit defect suppression property.

<Problem to be solved by the fourth embodiment of the present invention>
In recent years, the manufacture of a wiring board is usually performed by a line process in which processing is sequentially performed while a substrate is conveyed in a certain direction. At this time, the processing of the developing solution or the etching solution on the substrate is performed by spraying. In forming a resist pattern by photolithography, it is important that the resist line width after development does not vary. However, in the formation of a resist pattern by spray development, if the development time is short, variations in the substrate surface of the developer are likely to occur, and the above problem may occur, so that the development time must be extended.
Here, the developing time is a time during which the substrate stays in the developing tank and is developed, and is determined as, for example, a time twice as long as the minimum developing time. The minimum development time is the minimum time required for the unexposed part of the photosensitive resin layer to be completely dissolved and removed. The developer concentration or temperature, spray direction or spray amount, pressure, and oscillation frequency It changes depending on etc.

  Here, the dissolution reaction of the resist by development is considered to occur almost at the diffusion-limited rate of the developer. Therefore, from the viewpoint of promoting development, it is necessary to positively supply the developer onto the substrate by spraying or the like. Since this supply takes some time, it is considered that when the development time is short, the supply of the developer does not sufficiently spread over the entire surface of the substrate, and the variation of the resist line width becomes remarkably large. On the other hand, when the development time is long, it is considered that the supply of the developer on the substrate becomes uniform, and therefore the variation in line width is also reduced. Therefore, it is considered effective to use a photosensitive resin composition having a slow minimum development time itself from the viewpoint of suppressing variation in line width.

  In Patent Document 5, from the viewpoint of developability of the photosensitive resin composition and resolution, adhesion, and flexibility of the resist pattern, in the photosensitive resin composition, a structural unit of (meth) acrylic acid, styrene or α- A binder polymer having a structural unit of methylstyrene and a structural unit of a hydroxyalkyl ester of (meth) acrylic acid having a hydroxyalkyl group having 1 to 12 carbon atoms, an ethyleneoxy group having 1 to 20 structural units, and A combination with a bisphenol-type di (meth) acrylate monomer having 0 to 7 structural units of a propyleneoxy group has been studied.

  Patent Document 6 proposes a content of a structural unit of styrene or a styrene derivative in the alkali-soluble polymer of 30% by mass or more from the viewpoint of the space width and tent property of the positive resist pattern, and addition polymerization is proposed. A weight average molecular weight of 1,100 or more has been proposed.

  Both Patent Documents 5 and 6 focus on a photosensitive resin composition containing a polymer having a specific proportion of styrene structural units and a specific monomer, but are described in Patent Documents 5 and 6. The photosensitive resin composition described above still has room for improvement from the viewpoint of achieving both good resolution of the resist pattern and extending the minimum development time.

  Therefore, the problem to be solved by the fourth embodiment of the present invention is to provide a photosensitive resin composition that can achieve both good resolution of a resist pattern and extension of the minimum development time.

<Means for solving the first problem>
The present inventors have found that the above object can be achieved by the following technical means, and have reached the first embodiment of the present invention. The first embodiment of the present invention is as follows.
[1]
Each of the following components (A) to (C),
(A) component: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and (C) component: a photosensitive resin composition containing a photopolymerization initiator,
A photosensitive resin layer made of the photosensitive resin composition is laminated to a thickness of 25 μm on a copper clad laminate on which a copper foil having a thickness of 18 μm is laminated, and light irradiation and development in a pattern shape of line / space = 50 μm / 30 μm. A cured resist pattern is formed through the treatment, and after performing a copper etching process at 50 ° C. for 55 seconds, the bottom width of the copper line pattern obtained by removing the cured resist pattern is 38 μm or more. The photosensitive resin composition.
[2]
The photosensitive resin composition according to [1], wherein the component (A) is a copolymer having a (meth) acrylic acid unit content of 10% by mass to 24% by mass.
[3]
The photosensitive resin composition according to [1] or [2], wherein the component (A) is a copolymer having a styrene unit content of 32% by mass to 60% by mass.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the component (C) contains an acridine compound.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the component (B) contains a pentaerythritol compound.
[6]
The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) contains a trimethylolpropane compound.
[7]
The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) contains a bisphenol A compound.
[8]
Each of the following components (A) to (C),
(A) component: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and (C) component: a photosensitive resin composition containing a photopolymerization initiator,
The component (A) includes a copolymer having a (meth) acrylic acid unit content of 10% by mass to 24% by mass and a styrene unit content of 32% by mass or more.
The component (C) is a photosensitive resin composition containing an acridine compound.
[9]
The component (A) includes a copolymer having a (meth) acrylic acid unit content of 10% by mass to 24% by mass and a styrene unit content of 32% by mass to 60% by mass. [8] The photosensitive resin composition according to [8].
[10]
The photosensitive resin composition according to [8] or [9], wherein the component (B) contains a pentaerythritol compound.
[11]
The photosensitive resin composition as described in any one of [8]-[10] in which the said (B) component contains a trimethylol propane compound.
[12]
The photosensitive resin composition according to any one of [8] to [11], wherein the component (B) contains a bisphenol A compound.
[13]
A photosensitive element in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [12] is laminated on a support.
[14]
A laminating step of laminating the photosensitive resin layer of the photosensitive element according to [13] on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin composition layer, and a development step of removing an unexposed portion after the exposure with a developer,
A method of forming a resist pattern, comprising:
[15]
The method for forming a resist pattern according to [14], wherein the laminating step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent.
[16]
A laminating step of laminating the photosensitive resin composition layer of the photosensitive element according to [13] on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin composition layer;
A developing step of removing the unexposed portion after the exposure with a developer;
A conductor pattern forming step of etching or plating a conductive substrate on which a resist pattern is formed by the development; and a peeling step of peeling the resist pattern;
A method for producing a wiring board, comprising:
[17]
The method for manufacturing a wiring board according to [16], wherein the laminating step is a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate via a wetting agent.

｛式中、Ｒは、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基であり、ｎ１、ｎ２及びｎ３は、それぞれ独立に、０〜３０の整数であり、ただし、ｎ１＋ｎ２＋ｎ３≧６の条件を満たす。｝で表される化合物を含有し、該一般式（Ｉ）で表される化合物の含有量が前記感光性樹脂組成物の固形分に対して５質量％以上であり、そして 前記（Ｃ）成分が、アクリジン化合物を含有することを特徴とする、前記感光性樹脂組成物。
［２］
前記一般式（Ｉ）中のｎ１、ｎ２及びｎ３は、２０≧ｎ１＋ｎ２＋ｎ３＞９を満たす、［１］に記載の感光性樹脂組成物。
［３］
前記一般式（Ｉ）中のＲの全ては、水素原子である、［１］又は［２］に記載の感光性樹脂組成物。
［４］
前記（Ｂ）成分が、ペンタエリスリトール変性モノマーを更に含有する、［１］〜［３］のいずれか１項に記載の感光性樹脂組成物。
［５］
［１］〜［４］のいずれか１項に記載の感光性樹脂組成物から成る感光性樹脂層が支持体上に積層された、感光性エレメント。
［６］
［５］に記載の感光性エレメントの感光性樹脂層を導体基板上に積層するラミネート工程、
前記積層された感光性樹脂層を露光する露光工程、及び
前記露光後の未露光部を現像液で除去する現像工程、
を含むことを特徴とする、レジストパターンの形成方法。
［７］
［５］に記載の感光性エレメントの感光性樹脂層を導体基板上に積層するラミネート工程、
前記積層された感光性樹脂層を露光する露光工程、
前記露光後の未露光部を現像液で除去する現像工程、
前記現像によりレジストパターンが形成された導体基板をエッチング又はめっきする導体パターン形成工程、及び
前記レジストパターンを剥離する剥離工程、
を含むことを特徴とする、配線板の製造方法。<Means for solving the second problem>
The present inventors have found that the above object can be achieved by the following technical means, and have reached the second embodiment of the present invention. The second embodiment of the present invention is as follows.
[1]
Each of the following components (A) to (C),
(A) component: alkali-soluble polymer having an acid equivalent of 100 to 600,
(B) component: a compound having an ethylenic double bond, and (C) component: a photosensitive resin composition containing a photopolymerization initiator,
The component (A) contains a copolymer containing 50% by mass or more of styrene units,
The component (B) is represented by the following general formula (I):

{In the formula, each R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2, and n3 are each independently an integer of 0 to 30, provided that n1 + n2 + n3 ≧ 6 Meet the conditions. The content of the compound represented by the general formula (I) is 5% by mass or more based on the solid content of the photosensitive resin composition, and the component (C) Contains the acridine compound. The photosensitive resin composition described above.
[2]
The photosensitive resin composition according to [1], wherein n1, n2, and n3 in the general formula (I) satisfy 20 ≧ n1 + n2 + n3> 9.
[3]
The photosensitive resin composition according to [1] or [2], wherein all R in the general formula (I) are hydrogen atoms.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the component (B) further contains a pentaerythritol-modified monomer.
[5]
A photosensitive element in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [4] is laminated on a support.
[6]
A laminating step of laminating the photosensitive resin layer of the photosensitive element according to [5] on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin layer; and a development step of removing the unexposed portion after the exposure with a developer;
A method of forming a resist pattern, comprising:
[7]
A laminating step of laminating the photosensitive resin layer of the photosensitive element according to [5] on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin layer;
A developing step of removing the unexposed portion after the exposure with a developer;
A conductor pattern forming step of etching or plating a conductive substrate on which a resist pattern is formed by the development; and a peeling step of peeling the resist pattern;
A method for producing a wiring board, comprising:

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜５０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい｝
で表されるアルキレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート化合物である、［１］又は［２］に記載の感光性樹脂組成物。
［４］
前記一般式（ＩＩ）中のｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝３０〜５０の関係を満たす、［３］に記載の感光性樹脂組成物。
［５］
前記一般式（ＩＩ）中のｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜１０の関係を満たす、［３］に記載の感光性樹脂組成物。
［６］
前記（Ｂ）エチレン性不飽和結合含有化合物は、下記一般式（ＩＩＩ）：

｛式中、Ｒ_５、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４は、１〜４０であり、そしてｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるトリ（メタ）アクリレート化合物を含む、［１］又は［２］に記載の感光性樹脂組成物。
［７］
前記（Ｂ）エチレン性不飽和結合含有化合物は、下記一般式（ＩＶ）：

｛式中、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、炭素数２〜６のアルキレン基を表し、Ｚは、２価の有機基を表し、ｓ及びｔは、それぞれ独立に、０〜４０の整数であり、かつｓ＋ｔ≧１である｝
で表されるウレタンジ（メタ）アクリレート化合物を含む、［１］又は［２］に記載の感光性樹脂組成物。
［８］
前記（Ａ）アルカリ可溶性高分子は、（メタ）アクリル酸ブチルの構造単位をさらに含む、［１］〜［７］のいずれか１項に記載の感光性樹脂組成物。
［９］
ダイレクトイメージング露光用である、［１］〜［８］のいずれか１項に記載の感光性樹脂組成物。
［１０］
［１］〜［９］のいずれか１項に記載の感光性樹脂組成物から成る感光性樹脂層を支持体に積層するラミネート工程；
該感光性樹脂層を露光する露光工程；及び
該露光された感光性樹脂層を現像する現像工程；
を含むレジストパターンの形成方法。
［１１］
［１］〜［９］のいずれか１項に記載の感光性樹脂組成物から成る感光性樹脂層を基板に積層するラミネート工程；
該感光性樹脂層を露光する露光工程；
該露光された感光性樹脂層を現像して、レジストパターンが形成された基板を得る現像工程；
該レジストパターンが形成された基板をエッチング又はめっきする導体パターン形成工程；及び
該レジストパターンを剥離する剥離工程；
を含む配線板の製造方法。<Means for solving the third problem>
The present inventor has found that the above problems can be solved by the following technical means. The third embodiment of the present invention is as follows.
[1]
(A) an alkali-soluble polymer;
(B) an ethylenically unsaturated bond-containing compound; and (C) a photopolymerization initiator;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer is 10% by mass to 24% by mass of (meth) acrylic structural unit and 35% by mass based on the total mass of the monomers constituting the (A) alkali-soluble polymer. The photosensitive resin composition comprising a structural unit of styrene of ˜90% by mass, and wherein the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is 1,200 or more.
[2]
The photosensitive resin composition according to [1], wherein the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is 1,300 or more.
[3]
40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is represented by the following general formula (II):

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of — (A—O) — and — (B—O) — is random, May be a block, and in the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenyl group side}
The photosensitive resin composition according to [1] or [2], which is an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by:
[4]
The photosensitive resin composition according to [3], wherein n ₁ , n ₂ , n _3, and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50.
[5]
The photosensitive resin composition according to [3], wherein n ₁ , n ₂ , n _3, and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10.
[6]
The (B) ethylenically unsaturated bond-containing compound has the following general formula (III):

{Wherein R ₅ , R ₆ and R ₇ each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ represent Each independently represents an integer of 0 to 40, m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs are the same as each other May or may be different}
The photosensitive resin composition as described in [1] or [2] containing the tri (meth) acrylate compound represented by these.
[7]
The (B) ethylenically unsaturated bond-containing compound has the following general formula (IV):

{Wherein R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, s and t is each independently an integer of 0 to 40, and s + t ≧ 1}
The photosensitive resin composition as described in [1] or [2] containing the urethane di (meth) acrylate compound represented by these.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein the (A) alkali-soluble polymer further includes a structural unit of butyl (meth) acrylate.
[9]
The photosensitive resin composition according to any one of [1] to [8], which is for direct imaging exposure.
[10]
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [9] on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A resist pattern forming method including:
[11]
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [9] on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed; and a peeling step of peeling off the resist pattern;
A method of manufacturing a wiring board including:

｛式中、Ｒ_５、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４は、０〜４０であり、そしてｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるトリ（メタ）アクリレート化合物を含む、［１］〜［３］のいずれか１項に記載の感光性樹脂組成物。
［５］
前記（Ｂ）エチレン性不飽和結合含有化合物は、下記一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜５０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい｝
で表されるアルキレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート化合物を含む、［１］〜［４］のいずれか１項に記載の感光性樹脂組成物。
［６］
ヒンダードフェノールとして、下記一般式（Ｖ）：

｛式中、Ｒ^５１は、置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表し、そしてＲ^５２、Ｒ^５３及びＲ^５４は、各々独立に、水素、又は置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表す。｝で表される化合物をさらに含む、［１］〜［５］のいずれか１項に記載の感光性樹脂組成物。
［７］
ダイレクトイメージング露光用である、［１］〜［６］のいずれか１項に記載の感光性樹脂組成物。
［８］
［１］〜［７］のいずれか１項に記載の感光性樹脂組成物から成る感光性樹脂層が支持体上に積層された、感光性エレメント。
［９］
［８］に記載の感光性エレメントの前記感光性樹脂層を導体基板上に積層するラミネート工程；
積層された前記感光性樹脂層を露光する露光工程；及び
露光された前記感光性樹脂層を現像する現像工程；
を含む、レジストパターンの形成方法。
［１０］
［８］に記載の感光性エレメントの前記感光性樹脂層を導体基板上に積層するラミネート工程；
積層された前記感光性樹脂層を露光する露光工程；
露光された前記感光性樹脂層を現像して、前記導体基板上にレジストパターンを形成する現像工程；
前記レジストパターンが形成された前記導体基板をエッチング又はめっきする導体パターン形成工程；及び
前記レジストパターンを剥離する剥離工程；
を含む、配線板の製造方法。<Means for solving the fourth problem>
The present inventors have found that the above object can be achieved by the following technical means, and have reached the fourth embodiment of the present invention. The fourth embodiment of the present invention is as follows.
[1]
(A) an alkali-soluble polymer;
(B) an ethylenically unsaturated bond-containing compound; and (C) a photopolymerization initiator;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer contains a first copolymer having an acid monomer unit content of less than 25% by mass and an aromatic monomer unit content of 30% by mass or more, and the (B) ethylene The weight average molecular weight of the unsaturated unsaturated bond-containing compound is 900 or less,
The photosensitive resin composition.
[2]
(C) The photoinitiator is the photosensitive resin composition as described in [1] containing an acridine compound.
[3]
The photosensitive resin composition according to [1] or [2], wherein the (A) alkali-soluble polymer includes a second copolymer having an aromatic monomer unit content of 45% by mass to 90% by mass. object.
[4]
The (B) ethylenically unsaturated bond-containing compound has the following general formula (III):

{Wherein R ₅ , R ₆ and R ₇ each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ represent Each independently represents an integer of 0 to 40, m ₂ + m ₃ + m ₄ is 0 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs are the same as each other May or may be different}
The photosensitive resin composition of any one of [1]-[3] containing the tri (meth) acrylate compound represented by these.
[5]
The (B) ethylenically unsaturated bond-containing compound has the following general formula (II):

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of — (A—O) — and — (B—O) — is random, May be a block, and in the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenyl group side}
The photosensitive resin composition of any one of [1]-[4] containing the alkylene oxide modified bisphenol A type di (meth) acrylate compound represented by these.
[6]
As a hindered phenol, the following general formula (V):

{Wherein R ⁵¹ is an optionally substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group via a divalent linking group, via a divalent linking group. A branched alkyl group, a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group, and R ⁵² , R ⁵³ and R ⁵⁴ are each independently hydrogen or substituted. A linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, a branched alkyl group via a divalent linking group, or a divalent linking group. Represents an aryl group via a cyclohexyl group or a divalent linking group. } The photosensitive resin composition of any one of [1]-[5] which further contains the compound represented by these.
[7]
The photosensitive resin composition according to any one of [1] to [6], which is used for direct imaging exposure.
[8]
A photosensitive element in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [7] is laminated on a support.
[9]
A laminating step of laminating the photosensitive resin layer of the photosensitive element according to [8] on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A method for forming a resist pattern, comprising:
[10]
A laminating step of laminating the photosensitive resin layer of the photosensitive element according to [8] on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to form a resist pattern on the conductive substrate;
A conductor pattern forming step of etching or plating the conductor substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern;
A method for manufacturing a wiring board, comprising:

<Effect of the first embodiment>
According to the first embodiment of the present invention, there is provided a resist material in which a vertical and horizontal difference in wiring width is suppressed when a fine conductor pattern is formed by a line process.

<Effect of the second embodiment>
According to the second embodiment of the present invention, performances generally required for photosensitive materials such as sensitivity and resolution are provided at a high level, and both development dispersibility and fine pattern adhesion are excellent. Novel photosensitive materials are provided.

<Effect of the third embodiment>
According to 3rd embodiment of this invention, the photosensitive resin composition which can make compatible the tent property of a resist pattern, and water residue short defect suppression property is provided.

<Effect of the fourth embodiment>
According to the fourth embodiment of the present invention, a photosensitive resin composition capable of ensuring good resolution of a resist pattern and extending a minimum development time, and a resist pattern or a wiring board using the same A forming method is provided.

<First embodiment>
Hereinafter, a mode for carrying out the first embodiment of the present invention (hereinafter abbreviated as “the first embodiment”) will be specifically described.

<Photosensitive resin composition>
In the first embodiment, the photosensitive resin composition includes the following components (A) to (C):
(A) component: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and (C) component: a photopolymerization initiator,
Containing.

[(A) component: alkali-soluble polymer]
The component (A) is not particularly limited as long as it is soluble in the developer described later. Preferably, it is a copolymer of (meth) acrylic acid and other monomers. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight (described later) and the number average molecular weight of the copolymer is preferably 1 or more and 6 or less.
Examples of (meth) acrylic acid include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic acid anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic acid anhydride include maleic acid anhydride, itaconic acid anhydride, fumaric acid, citraconic acid anhydride, and the like. Of these, (meth) acrylic acid is preferred.

  The copolymerization ratio of the (meth) acrylic acid unit in the component (A) is preferably 10% by mass to 24% by mass, and 15% by mass to 23% by mass with respect to the total mass of all monomer units. More preferably. The content ratio of the (meth) acrylic acid unit within this range means that the etching rate when the conductor pattern is formed is suppressed (the bottom width of the conductor line pattern described above is maintained above a certain level), and the wiring width. It is preferable from the viewpoint of suppressing the vertical / horizontal difference.

Examples of other monomers include unsaturated aromatic compounds (sometimes referred to as “aromatic monomers”), (meth) acrylic acid alkyl esters, (meth) acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, A crosslinkable monomer etc. can be mentioned.
Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, vinyl naphthalene, and the like. Of these, styrene is preferred.

  The (meth) acrylic acid alkyl ester is a concept including both a chain alkyl ester and a cyclic alkyl ester. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meta) ) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate And the like can be given.

Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate and the like;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and the like.
Examples of polar monomers include:
Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentenol;
Amino group-containing monomers such as 2-aminoethyl methacrylate;
Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
Cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-cyanoethyl acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and (meth) acrylic acid 3,4-epoxycyclohexyl;
Etc.

  Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

  The component (A) is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.

  The copolymerization ratio of styrene units in the component (A) is preferably 32% by mass or more, and more preferably 35% by mass or more with respect to the total mass of all monomer units. The copolymerization ratio of styrene units in the component (A) is preferably 60% by mass or less, more preferably 55% by mass or less, based on the total mass of all monomer units. Setting the copolymerization ratio of styrene, which is highly hydrophobic and hardly compatible with the developer and the washing water for developing water, in the above range is preferable from the viewpoint of suppressing the vertical and horizontal differences in the wiring width.

  The weight average molecular weight of the component (A) (when the component (A) includes a plurality of types of copolymers, the weight average molecular weight of the whole mixture) is 5,000 to 1,000,000. Is preferably 10,000 to 500,000, more preferably 15,000 to 100,000. It is preferable to adjust the weight average molecular weight of the component (A) within this range from the viewpoint of adapting the development time in forming the resist pattern to the operating state of the line process to be used.

  In the first embodiment, the content of the component (A) in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same for each component). 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 60% by mass. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, while 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

The copolymer in which the content ratio of (meth) acrylic acid units is 10% by mass to 24% by mass and the content ratio of styrene units is 32% by mass to 60% by mass is based on the total solid content of the photosensitive resin composition. Is preferably 8% or more, more preferably 10% by mass or more, and particularly preferably 13.5 / 99.19 × 100% by mass or more. The copolymer in which the content ratio of (meth) acrylic acid units is 10% by mass to 24% by mass and the content ratio of styrene units is 32% by mass to 60% by mass is based on the total solid content of the photosensitive resin composition. 50 mass% or less, 40 mass% or less, 30 mass% or less, 27 / 99.19 × 100 mass% or less, and 20 mass % Or less.

[Component (B): Compound having an ethylenic double bond]
The component (B) only needs to have one or more ethylenic double bonds. It is preferable to use a compound having two or more ethylenic double bonds.
Examples of the (B) compound having two ethylenic double bonds include, for example, a bisphenol A compound, particularly a polyalkylene glycol di (meta) having an average of 2 to 15 moles of alkylene oxide added to both ends of bisphenol A. ) Acrylate or the like is preferably used.
The (B) compound having three ethylenic double bonds is, for example, a trimethylolpropane compound, particularly a polyalkylenetriol trimethylolpropane obtained by adding an average of 3 to 25 mol of alkylene oxide to trimethylolpropane. ) Acrylate or the like is preferably used.
Furthermore, as the (B) compound having four ethylenic double bonds, for example, a pentaerythritol compound, in particular, a tetra (meth) acrylate of a polyol obtained by adding an average of 4 mol to 35 mol of alkylene oxide to pentaerythritol, etc. Preferably used.
As these commercially available products, for example, “BPE-500”, “A-TMPT-3EO”, “A-9300-1CL” and the like (all are manufactured by Shin-Nakamura Chemical Co., Ltd.):
"Aronix M-327" etc. (made by Toagosei Co., Ltd.) etc. can be mentioned.

  The content of the component (B) in the photosensitive resin composition of the first embodiment is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and 10% by mass to 50% by mass. Is more preferable. This content is preferably 1% by mass or more from the viewpoint of suppressing poor curing and delay in development time, and on the other hand, it is 70% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist. Is preferred.

As the component (B), it is preferable to use a high molecular weight compound having a molecular weight of 1,000 or more. The molecular weight of the high molecular weight compound is more preferably 1,300 or more and 3,000 or less. It is preferable to contain such a high molecular weight compound from the viewpoints of suppressing the etching rate when forming the conductor pattern and suppressing the vertical / horizontal difference of the wiring width.
In addition, it is preferable that the ratio for which such a high molecular weight compound accounts in (B) component shall be 20 mass% or more, and it is more preferable to set it as 20-50 mass%.

Here, a DD value is defined as an index of the double bond concentration of the component (B). The DD value is the number of double bonds per weight average molecular weight of the monomer, and has a unique value for each monomer.
When a monomer having a small DD value is used in the photosensitive resin composition, the photocured film tends to be flexible.
When the component (B) comprises a plurality of types, the DD value of each ethylenically unsaturated bond-containing compound and the weighted average of the blending ratio are considered as the DD value of the composition.
From the viewpoint of suppressing the vertical / horizontal difference of the wiring width and improving the tenting property, the DD value range of the preferred composition is 0.10 to 0.13. More preferably, it is 0.10-0.125.

[(C) component: photopolymerization initiator]
The component (C) is a component that generates a radical capable of initiating polymerization of the component (B) by light irradiation.
Examples of such component (C) include aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzyl compounds, hexaarylbisimidazole compounds, and acridine compounds.
Among these, it is preferable to use an acridine compound from the viewpoint of high resolution and good tenting properties.
The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass, and 3 mass% is more preferable, and 0.4 mass% is more preferable.
The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and more preferably 1.7% by mass or less. .6% by mass or less is more preferable. Within the above range, it is possible to provide a resist material that suppresses the vertical and horizontal differences in the wiring width, which is preferable.

  Examples of the acridine compound include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. be able to.

It is preferable to use an acridine compound and a hexaarylbisimidazole compound as the component (C).
Examples of the hexaarylbisimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4). -Dimethoxyphenyl) -4 ', 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4, 5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis -(2-Fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoro Methylphenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5 , 5′-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxy Phenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2 , 3,5-trifluorophenyl) -4,4 ', 5,5'-tetraki -(3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -Imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, , 2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- ( 2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4) , 6-Tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxy Ciphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl)- And imidazolyl dimer.

  The content of the component (C) in the photosensitive resin composition of the first embodiment is preferably 0.1% by mass to 2% by mass, and is in the range of 0.2% by mass to 1.8% by mass. Is more preferable, it is still more preferable that it is the range of 0.3 mass%-1.7 mass%, and it is especially preferable that it is 0.4 mass%-1.6 mass%. Setting the content of the component (C) in such a range is preferable from the viewpoint of obtaining good photosensitivity and peeling characteristics.

The component (C) can further contain a sensitizer from the viewpoint of improving sensitivity and resolution. Examples of such sensitizers include N-aryl amino acids, organic halogen compounds, and other sensitizers.
Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like;
Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris ( 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like;
Each can be mentioned.

Examples of the other sensitizers include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone. Quinone compounds such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone;
Aromatic ketone compounds such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone;
Benzoin ether compounds such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin;
Oxime esters such as benzyldimethyl ketal, benzyl diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Compound;
Etc. can be mentioned.

The content of the sensitizer in the first embodiment is preferably 0.01% by mass to 5% by mass, and 0.05% by mass to 3% from the viewpoint of the photosensitivity of the composition and the peelability of the resist cured film. % By mass is more preferable, and 0.1% by mass to 2% by mass is still more preferable.
In the photosensitive resin composition of the first embodiment, an acridine compound and an N-aryl amino acid are used as the component (C), and these can be used in combination within the above range of use. It is preferable from the viewpoints of suppressing the etching rate when forming the film and suppressing the vertical / horizontal difference of the wiring width.

[Other ingredients]
The photosensitive resin composition of the first embodiment may contain other components in addition to the components (A) to (C) described above. Examples of such other components include leuco dyes, base dyes, plasticizers, antioxidants, stabilizers, radical polymerization inhibitors, solvents, and the like.

[Leuco dye]
The leuco dye can be blended in the photosensitive resin composition of the first embodiment in order to impart suitable color developability and excellent peeling properties to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- ( 4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3) -Yl) -4-azaphthalide, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3 -Diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinov Luolan, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 1,2-benz-6-diethylaminofluorane, 1 , 2-Benz-6-dibutylaminofluorane, 1,2-Benz-6-ethylisoamylaminofluorane, 2-methyl-6- (Np-tolyl-N-ethylamino) fluorane, 2- (N -Phenyl-N-methylamino) -6- (Np-tolyl-N-ethylamino) fluorane, 2- (3'-trifluoromethylanilino) -6-diethylaminofluorane, 3-chloro-6 -Cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane, 3-methoxy-4-dodecoxystylinoquinoline, etc. That. Of these, leuco crystal violet is preferred.

  The content of the leuco dye in the photosensitive resin composition of the first embodiment is preferably 0.6% by mass to 1.6% by mass, and 0.7% by mass to 1.2% by mass. It is more preferable. By setting the use ratio of the leuco dye within this range, it is possible to realize good color developability and good peelability.

[Base dye]
Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [ 2437-29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4] , Methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], basic blue 7 [2390-60 -5] (for example, Aizen Victoria Pur e Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], diamond green and the like. It is done. Among these, at least one selected from Basic Green 1, Malachite Green Oxalate, Basic Blue 7, and Diamond Green is preferable, and Basic Green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.

  The content of the base dye in the photosensitive resin composition of the first embodiment is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and further Preferably, it is the range of 0.01 mass%-1.2 mass%. By setting the use ratio within this range, both good color developability and high sensitivity can be achieved.

[solvent]
The photosensitive resin composition of the first embodiment can be a mixture of the above components (A) to (C) and other components optionally used, or a suitable solvent for these components. You may use as a photosensitive resin composition formulation liquid comprised by adding.
As a solvent used here, for example,
Ketone compounds such as methyl ethyl ketone (MEK);
Alcohols such as ethanol, ethanol, and isopropyl alcohol;
Etc.
The proportion of the solvent used is preferably such that the viscosity of the photosensitive resin composition preparation at 25 ° C. is 500 to 4,000 mPa · sec.

<Photosensitive element>
In the first embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer made of the above-described photosensitive resin composition is laminated on a support. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer opposite to the support.

[Support]
As the support, a transparent substrate that transmits light emitted from the exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used.
The haze of the support is preferably 5 or less.
A thinner support is advantageous in terms of image formation and economy, but it is necessary to maintain strength. Considering both of these, a support of 10 μm to 30 μm can be preferably used.

[Photosensitive resin composition layer]
When the photosensitive resin composition used for forming the photosensitive resin composition layer contains a solvent, the solvent is preferably removed in the photosensitive resin composition layer, but the solvent remains. It doesn't matter.
The thickness of the photosensitive resin composition layer is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.

[Protective layer]
An important characteristic of the protective layer is that the adhesive strength with the photosensitive resin composition layer is sufficiently smaller than the adhesive strength between the support and the photosensitive resin composition layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film and the like can be preferably used, and for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[Method for producing photosensitive element]
The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer, and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be employed.
For example, a photosensitive resin composition is prepared as the above-mentioned photosensitive resin composition preparation liquid, first, coated on a support using a bar coater or a roll coater and dried, and then the photosensitive resin composition is formed on the support. A photosensitive resin composition layer is formed. Next, if necessary, a photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin composition layer.

<Method for forming resist pattern>
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The resist pattern formation method is:
A laminating step of laminating a photosensitive resin layer of a photosensitive element on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin composition layer, and a development step of removing an unexposed portion after the exposure with a developer,
Are preferably included in the order described above.
Moreover, it is preferable that a lamination process is a process of laminating | stacking the photosensitive resin layer of a photosensitive element on a conductor substrate through a wetting agent. As the wetting agent, one or more selected from pure water, deionized water, and electrolyzed water, and a copper chelating agent (for example, one selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). The above compound) is preferably included.

In the resist pattern forming method of the first embodiment, first, in the laminating process, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, after the protective layer is peeled off, the photosensitive resin composition layer is heat-pressed and laminated on the substrate surface using a laminator.
As the substrate, an insulating substrate having a metal plate or a metal film is used. Examples of the metal material include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). These substrates may have through holes for accommodating multilayer substrates.

Here, the photosensitive resin composition layer may be laminated only on one side of the substrate surface, or may be laminated on both sides of the substrate as necessary. The heating temperature at this time is preferably 40 ° C to 160 ° C. It is preferable to perform the thermocompression bonding twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. When performing crimping twice or more, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin composition layer is repeated several times on the roll. It may be crimped through.
Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. This exposure may be performed through the support without peeling off the support, or may be performed after peeling off the support, if necessary.

  By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a development process described later. The pattern exposure may be performed by either a method of exposing through a photomask or a maskless exposure method. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter.

  In maskless exposure, a photomask is not used and exposure is performed directly on the substrate by a drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, the unexposed part of the photosensitive resin composition layer is removed with a developer. After exposure, when there is a support on the photosensitive resin composition layer, it is preferably subjected to a development step after removing the support.
In the development step, the unexposed area is developed and removed using a developer comprising an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferably used. The alkaline aqueous solution is selected in accordance with the characteristics of the photosensitive resin composition layer, but it is preferable to use a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
The temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 20 ° C to 40 ° C.

  A resist pattern is obtained by the above-described steps. Depending on the case, you may perform the heating process of 100 to 300 degreeC further. It is preferable to perform this heating step from the viewpoint of further improving chemical resistance. For heating, a heating furnace of an appropriate system such as hot air, infrared rays, far infrared rays or the like can be used.

<Method for forming wiring board>
The method of forming the wiring board of the first embodiment is as follows:
A laminating step of laminating the photosensitive resin composition layer of the photosensitive element on the conductor substrate;
An exposure step of exposing the laminated photosensitive resin composition layer;
A developing step of removing the unexposed portion after the exposure with a developer;
A conductor pattern forming step of etching or plating a conductive substrate on which a resist pattern is formed by the development; and a peeling step of peeling the resist pattern;
Are preferably included in the order described above.
Moreover, it is preferable that a lamination process is a process of laminating | stacking the photosensitive resin layer of a photosensitive element on a conductor substrate through a wetting agent. As the wetting agent, one or more selected from pure water, deionized water, and electrolyzed water, and a copper chelating agent (for example, one selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). The above compound) is preferably included.

  In the conductor pattern forming step, a conductor pattern can be formed on the substrate surface (for example, a copper surface) exposed by the developing step on the substrate on which the resist pattern is formed, using a known etching method or plating method.

In the stripping step, the resist pattern is stripped and removed by bringing the substrate on which the conductor pattern is formed into contact with an appropriate stripping solution. By this step, a desired wiring board is obtained.
The stripping solution used in the stripping step is preferably an alkaline aqueous solution. As this alkaline aqueous solution, it is preferable to use 2 mass%-5 mass% NaOH aqueous solution or KOH aqueous solution, for example. A small amount of a water-soluble solvent such as alcohol may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably 40 ° C to 70 ° C.

In general, in the formation of a conductor pattern by etching, the etching time for a desired wiring width can be adjusted regardless of the etching rate, for example, by adjusting the conveyance speed of the etching line. However, when the etching rate is too high, the transfer rate becomes too high, which may cause a problem that the etching time cannot be set practically.
Moreover, in recent years, the production of wiring boards is usually performed by a line process in which processing is performed sequentially while a substrate is conveyed in a certain direction, and conductor lines are parallel to the substrate conveyance direction. Case (MD direction line), vertical (TD direction line), and diagonal. In particular, when the etching rate is high, the vertical and horizontal differences in the wiring width tend to become more prominent.

As a result of intensive studies, the present inventors have suppressed the vertical and horizontal differences in the wiring width when forming a fine conductor pattern by a line process when the photosensitive resin composition forming the cured resist pattern has specific physical properties. It was found that a resist material can be provided.
That is, the photosensitive resin composition of the first embodiment is obtained by laminating a photosensitive resin layer made of the photosensitive resin composition with a thickness of 25 μm on a copper clad laminate on which a copper foil with a thickness of 18 μm is laminated. , Line / space = 50 μm / 30 μm patterned light irradiation and development treatment to form a cured resist pattern, and after performing a copper etching treatment at 50 ° C. for 55 seconds, the cured resist pattern is removed. The bottom width of the copper line pattern is 38 μm or more (preferably 38 μm to 50 μm, more preferably 40 μm to 45 μm).

By the way, the resist pattern swells / shrinks in each of the development process, the water washing process, and the etching process. This swelling / shrinkage of the resist pattern is considered to reduce the adhesion between the wiring and the resist pattern. The resist pattern formed from the photosensitive resin composition of the first embodiment has small swelling / shrinkage in any of the development, washing step, and etching step, and etching proceeds at the interface between the resist pattern and the wiring. It is difficult to suppress vertical and horizontal differences in wiring width.

In the first embodiment, the specific photosensitive resin composition is discriminated by paying attention to the characteristics (the bottom width of the conductor line width is not less than a certain value) when a specific analysis method (specific etching condition) is used. This is a means for producing the effects of the invention.
Such adjustment of the bottom width of the conductor line width can be adjusted by appropriately setting the composition of the photosensitive resin composition.

The conductor pattern (wiring) formed by the wiring board forming method of the first embodiment as described above can have a very small vertical / horizontal difference in the wiring width of the conductor pattern. The vertical / horizontal difference in the wiring width is an amount represented by the difference between the wiring width (TD) of the conductor line in the TD direction and the wiring width (MD) of the conductor line in the MD direction, TD-MD.
The absolute value of the vertical / horizontal difference of the wiring width in the conductor pattern formed by the conductor pattern forming method of the first embodiment is preferably 0 μm to 5 μm, more preferably 0 μm to 3 μm.

The photosensitive resin composition, the photosensitive element, and the method for forming the wiring board in the first embodiment are extremely suitable for the production of, for example, a printed wiring board, a lead frame, a substrate having a concavo-convex pattern, and a semiconductor package. Can be applied to.
The measurement methods for the various parameters described above are measured according to the measurement methods in the examples described later unless otherwise specified.

<Second Embodiment>
Hereinafter, a mode for carrying out the second embodiment of the present invention (hereinafter abbreviated as “the second embodiment”) will be specifically described.

<Photosensitive resin composition>
In the second embodiment, the photosensitive resin composition includes the following components (A) to (C):
(A) component: alkali-soluble polymer having an acid equivalent of 100 to 600,
(B) component: a compound having an ethylenic double bond, and (C) component: a photopolymerization initiator,
Containing.

[(A) component: alkali-soluble polymer]
The component (A) has an acid equivalent of 100 to 600 (preferably 200 to 500, more preferably 250 to 450), and contains a copolymer containing 50% by mass or more of styrene units. Here, in this specification, the styrene unit means substituted or unsubstituted styrene. In addition, as a substituent, although it does not specifically limit, an alkyl group, a halogen group, a hydroxyl group etc. are mentioned, for example.

The component (A) is a copolymer of a styrene derivative and preferably another monomer such as an acid monomer.
Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic acid anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic acid anhydride include maleic acid anhydride, itaconic acid anhydride, fumaric acid, citraconic acid anhydride, and the like. Of these, (meth) acrylic acid is preferred.

  Examples of other monomers include unsaturated aromatic compounds (sometimes referred to as “aromatic monomers”), (meth) acrylic acid alkyl esters, (meth) acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, A crosslinkable monomer etc. can be mentioned.

As an unsaturated aromatic compound, vinyl naphthalene etc. can be mentioned, for example.
The (meth) acrylic acid alkyl ester is a concept including both a chain alkyl ester and a cyclic alkyl ester. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meta) ) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate And the like can be given.

Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate and the like;
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like;
Each can be mentioned.

Examples of polar monomers include:
Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentenol;
Amino group-containing monomers such as 2-aminoethyl methacrylate;
Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
Cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-cyanoethyl acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and (meth) acrylic acid 3,4-epoxycyclohexyl;
Etc.

  Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

The component (A) is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.
(A) A component contains the copolymer 1 which contains 50 mass% or more of styrene units. The amount of styrene units in the copolymer 1 is preferably 50% by mass to 80% by mass, and more preferably 51% by mass to 70% by mass.

  The component (A) in the second embodiment may be composed only of the copolymer 1 or may be a mixture of the copolymer 1 and other polymers. (The content of the copolymer 1 in the component (A) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and still more preferably 20% by mass to 70% by mass.

  As the other polymer, a copolymer of the acid monomer and the other monomer described above and not corresponding to the copolymer 1 (copolymer 2) is preferable.

  The weight average molecular weight of the component (A) (when the component (A) includes a plurality of types of copolymers, the weight average molecular weight of the whole mixture) is 5,000 to 1,000,000. Preferably, it is 10,000 to 500,000, more preferably 15,000 to 100,000. It is preferable to adjust the weight average molecular weight of the component (A) within this range from the viewpoint of adapting the development time in forming the resist pattern to the operating state of the line process to be used. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight and the number average molecular weight of the component (A) is preferably 1 or more and 6 or less.

  In the second embodiment, the content of the component (A) in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same for each component). 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 60% by mass. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, while 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

｛式中、Ｒは、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基であり、ｎ１、ｎ２及びｎ３は、それぞれ独立に、０〜３０の整数であり、ただし、ｎ１＋ｎ２＋ｎ３≧６の条件を満たす。｝で表される化合物を含む。[Component (B): Compound having an ethylenic double bond]
The component (B) is not particularly limited as long as it has one or more ethylenic double bonds. However, the component (B) in the second embodiment is represented by the following general formula (I) as the essential compound (B1):

{In the formula, each R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2, and n3 are each independently an integer of 0 to 30, provided that n1 + n2 + n3 ≧ 6 Meet the conditions. } Is included.

  In formula (I), each R is independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. n1, n2 and n3 are each independently preferably an integer of 1 to 30, more preferably an integer of 3 to 21.

  In the formula (I), the value of n1 + n2 + n3 is preferably more than 9 and not more than 20 and more preferably not less than 15 and not more than 20 from the viewpoint of improving development dispersibility.

  In the formula (I), from the viewpoint of improving development dispersibility, at least one R is preferably a hydrogen atom, and more preferably all R are hydrogen atoms.

  Furthermore, in the formula (I), it is particularly preferable that all R are hydrogen atoms and the value of n1 + n2 + n3 is 15 or more and 20 or less from the viewpoint of achieving both development dispersibility and adhesion.

  The compound represented by the formula (I) is synthesized by using a known method. For example, an adduct obtained by adding 6 equivalents or more of ethylene oxide to trimethylolpropane is further added with 3 mol of (meth) acrylic. It can be obtained by addition or transesterification of the acid.

  Preferable specific examples of the compound represented by the formula (I) include ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (the total number of added EO is 6 to 20) and the like.

The component (B) in the second embodiment may be composed only of the compound (B1), or may be a mixture of the compound (B1) and another component (B).
When the component (B) of the second embodiment is a mixture, the content of the compound (B1) in the mixture is preferably 10% by mass or more, more preferably based on the total mass of the mixture. It is 10 mass%-50 mass%, More preferably, it is 15 mass%-35 mass%.

The content of the compound (B1) in the photosensitive resin composition of the second embodiment is preferably 5% by mass or more, more preferably 5.5%, based on the total solid content of the photosensitive resin composition. It is from mass% to 30 mass%, and more preferably from 6 mass% to 20 mass%.
Here, by including an alkali-soluble polymer having a specific acid equivalent and a specific amount of styrene units, the component (B1), and acridine, both development dispersibility and fine pattern adhesion are achieved. Although the mechanism realized by the photosensitive resin composition having excellent resistance is not clear, the interaction between the styrene unit and the acridine component (by π electron stacking) and the interaction between the acid monomer and the component (B1) (hydrogen bonding) However, it is presumed that it is expressed well and the compatibility is improved as a whole, which contributes to the above characteristics.

  In the second embodiment, from the viewpoint of development dispersibility, the component (B) preferably contains a pentaerythritol-modified monomer (hereinafter referred to as “compound (B2)”) together with the compound (B1). . As the compound (B2), a tetra (meth) acrylate of a polyol obtained by adding an average of 4 mol to 35 mol, more preferably 8 mol to 28 mol, more preferably 12 mol to 20 mol of alkylene oxide to pentaerythritol. Is used.

  The content of the compound (B2) in the component (B) is preferably 10% by mass to 40% by mass, more preferably 15% by mass to 30% by mass, based on the total mass of the component (B).

  The content of the compound (B2) in the photosensitive resin composition of the second embodiment is preferably 1% by mass or more, more preferably 1% by mass to 20% by mass, and further preferably 5% by mass. ˜15 mass%.

  The component (B) may include a compound having an ethylenic double bond other than the compounds (B1) and (B2).

(B) component is the following components:
Bisphenol A compound, for example, di (meth) acrylate of polyalkylene glycol in which 2 to 15 moles of average of alkylene oxide are added to both ends of bisphenol A, respectively;
Compounds having three ethylenic double bonds (excluding B1), for example, tri (meth) acrylate of polyalkylenetriol obtained by adding an average of 3 to 25 moles of alkylene oxide to trimethylolpropane;
May be included.

  The content of the component (B) in the photosensitive resin composition of the second embodiment is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and 10% by mass to 50% by mass. Is more preferable. This content is preferably 1% by mass or more from the viewpoint of suppressing poor curing and delay in development time, and on the other hand, it is 70% by mass or less from the viewpoint of suppressing generation of aggregates in the developer. Is preferred.

[(C) component: photopolymerization initiator]
The component (C) is a component that generates a radical capable of initiating polymerization of the component (B) by light irradiation.
In the second embodiment, an acridine compound can be used as the (B) photopolymerization initiator. Furthermore, you may use together an acridine compound and another photoinitiator. The acridine compound is preferably used for improving the sensitivity and resolution of the photosensitive resin composition of the second embodiment.

  Examples of the acridine compound include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- ( 4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) Kridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3- Diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine Etc.

Other photopolymerization initiators include, for example,
2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′- Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenyl Imidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- (3-Met Ciphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,6- Difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'- Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′- Su- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4, 5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,6-trifluorophenyl)- 4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′- Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3 4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetrakis - (3-methoxyphenyl) - hexaarylbisimidazole compounds such as imidazolyl dimer;

2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 2,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. 4,5-triarylimidazole dimer (except for those corresponding to the above hexaarylbisimidazole compound);
Benzophenone, N, N′-tetramethyl-4,4′-dimethylaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2- Aromatic ketones such as benzyl-2-dimethylamino-1- (4-monoformophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1;
2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, Quinone compounds such as 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone;
Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether;
Benzyl derivatives such as benzyl methyl ketal;
N-phenylglycine derivatives, coumarin compounds, 4,4′-bis (diethylamino) benzophenone and the like can be mentioned.

  The content of the acridine compound in the photosensitive resin composition of the second embodiment is preferably 0.001% by mass to 2% by mass, more preferably 0.01% by mass to 1.5% by mass, and still more preferably. It is in the range of 0.1% by mass to 1% by mass.

  The content of the component (C) in the photosensitive resin composition of the second embodiment (the total content of the component (C) including the acridine compound) is 0.1% by mass to 2% by mass. Preferably, the content is 0.2% by mass to 1.8% by mass, more preferably 0.3% by mass to 1.7% by mass, and 0.4% by mass to 1.6% by mass. It is particularly preferred.

  The component (C) can further contain a sensitizer from the viewpoint of improving sensitivity and resolution. Examples of such sensitizers include N-aryl amino acids, organic halogen compounds, and other sensitizers.

Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like;
Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris ( 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like;
Each can be mentioned.

Examples of the other sensitizers include:
2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10- Quinone compounds such as phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone;
Aromatic ketone compounds such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone;
Benzoin ether compounds such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin;
Oxime esters such as benzyldimethyl ketal, benzyl diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Compound;
Etc.

  The content of the sensitizer in the photosensitive resin composition of the second embodiment is preferably 0.01% by mass to 5% by mass from the viewpoint of the photosensitivity of the composition and the peelability of the resist cured film. 0.05 mass% to 3 mass% is more preferable, and 0.1 mass% to 2 mass% is still more preferable.

[Other ingredients]
The photosensitive resin composition of the second embodiment may contain other components in addition to the components (A) to (C) described above. Examples of other components include coloring substances, halogen compounds, stabilizers, solvents, and the like.
Coloring substances include leuco dyes and other coloring substances;
Examples of stabilizers include radical polymerization inhibitors, benzotriazole compounds, carboxybenzotriazole compounds, and the like;
Each can be mentioned.

<Leuco dye>
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like. In particular, it is preferable to use leuco crystal violet from the viewpoint of good contrast.

  The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass. Adjusting the content of the leuco dye to 0.1% by mass or more is preferable from the viewpoint of obtaining the contrast between the exposed part and the unexposed part, while adjusting the content to 10% by mass or less, It is preferable from the viewpoint of maintaining storage stability.

<Other coloring substances>
Examples of other coloring substances include fuchsin, phthalocyanine green, auramin base, paramadienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (Eizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20, Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  The content of other coloring substances in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass. Adjusting the content to 0.001% by mass or more is preferable from the viewpoint of improving the handleability, while adjusting the content to 1% by mass or less maintains storage stability. It is preferable from the viewpoint.

<Halogen compounds>
Using a combination of a leuco dye and the following halogen compound in the photosensitive resin composition is a preferred embodiment from the viewpoint of adhesion and contrast.
Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like. Tribromomethylphenyl sulfone is particularly preferable. The content of the halogen compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.

<Radical polymerization inhibitor, benzotriazole compound, and carboxybenzotriazole compound>
Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

  Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.

  The total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1%. % By mass. Adjusting this content to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while adjusting this content to 3% by mass or less, It is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

<Plasticizer>
The photosensitive resin composition may contain a plasticizer as necessary. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tricitrate tri-n-propyl. Acetyl citrate tri-n-butyl, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like.

  The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass. Adjusting this content to 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while adjusting this content to 50% by mass or less. From the viewpoint of suppressing insufficient curing and edge fuse.

<Solvent>
The photosensitive resin composition may contain a solvent. Examples of the solvent include ketones typified by methyl ethyl ketone (MEK); alcohols typified by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support film is 500 mPa · s to 4,000 mPa · s at 25 ° C.

<Photosensitive element>
In the second embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer made of the above-described photosensitive resin composition is laminated on a support. If necessary, the photosensitive element may have a protective layer on the surface of the photosensitive resin layer opposite to the support.

[Support]
As the support, a transparent substrate that transmits light emitted from the exposure light source is preferable. As the support, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, Examples include polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. As these films, those stretched as necessary can be used.
The haze of the support is preferably 5 or less.
A thinner support is advantageous in terms of image formation and economy, but it is necessary to maintain strength. Considering both of these, a support of 10 μm to 30 μm can be preferably used.

[Photosensitive resin layer]
When the photosensitive resin composition used for forming the photosensitive resin layer contains a solvent, the solvent is preferably removed from the photosensitive resin layer, but may remain in the photosensitive resin layer.

  The thickness of the photosensitive resin layer is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the photosensitive resin layer can be appropriately selected within the range of 5 μm to 100 μm depending on the application.

[Protective layer]
An important characteristic of the protective layer is that the adhesive force with the photosensitive resin layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, and the like can be preferably used, and a film having excellent peelability disclosed in, for example, JP-A-59-202457 can also be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[Method for producing photosensitive element]
The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer, and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be employed.
For example, a solvent is added to the photosensitive resin composition and mixed to prepare a preparation solution, which is further coated on a support using a bar coater or roll coater and dried, and then the photosensitive resin composition is formed on the support. A photosensitive resin layer is formed. Next, if necessary, a photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin layer.

<Method for forming resist pattern>
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The resist pattern formation method is:
A laminating step of laminating a photosensitive resin layer of a photosensitive element on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin layer; and a development step of removing the unexposed portion after the exposure with a developer;
Are preferably included in the order described above.

  The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate via a wetting agent. As the wetting agent, one or more selected from pure water, deionized water, and electrolyzed water, and a copper chelating agent (for example, one selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). The above compound) is preferably included.

  In the resist pattern forming method of the second embodiment, first, in a laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated to the substrate surface using a laminator.

  As the substrate, an insulating substrate having a metal plate or a metal film is used. Examples of the metal material include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). These substrates may have through holes for accommodating multilayer substrates.

  The photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides of the substrate as necessary. The heating temperature during lamination is preferably 40 ° C to 160 ° C. It is preferable to perform the thermocompression bonding twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. When two or more times of crimping are performed, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer is repeatedly passed through the roll. You may crimp.

Next, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. The exposure may be performed through the support without peeling off the support, or may be performed after peeling off the support if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a development process described later. The pattern exposure may be performed by any of a method of exposing through a photomask and a maskless exposure method. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter.

  In maskless exposure, a photomask is not used and exposure is performed directly on the substrate with a drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the unexposed portion of the photosensitive resin layer is removed with a developer. After exposure, when there is a support on the photosensitive resin layer, it is preferable to use it for the development step after removing it.
In the development step, the unexposed area is developed and removed using a developer comprising an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferably used. The alkaline aqueous solution is selected in accordance with the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
The temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 20 ° C to 40 ° C.

  A resist pattern is obtained by the above-described steps. Depending on the case, you may perform the heating process of 100 to 300 degreeC further. The implementation of this heating step is suitable from the viewpoint of further improving chemical resistance. For heating, a heating furnace of an appropriate system such as hot air, infrared rays, far infrared rays or the like can be used.

<Method for forming wiring board>
The method of forming the wiring board of the second embodiment is as follows:
A laminating step of laminating a photosensitive resin layer of a photosensitive element on a conductive substrate;
An exposure step of exposing the laminated photosensitive resin layer;
A developing step of removing the unexposed portion after the exposure with a developer;
A conductor pattern forming step of etching or plating a conductive substrate on which a resist pattern is formed by the development; and a peeling step of peeling the resist pattern;
Are preferably included in the order described above.

  The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate via a wetting agent. As the wetting agent, one or more selected from pure water, deionized water, and electrolyzed water, and a copper chelating agent (for example, one selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). The above compound) is preferably included.

  In the conductor pattern forming step, a conductor pattern can be formed on the substrate surface (for example, a copper surface) exposed by the developing step on the substrate on which the resist pattern is formed, using a known etching method or plating method.

  In the stripping step, the resist pattern is stripped and removed by bringing the substrate on which the conductor pattern is formed into contact with an appropriate stripping solution. By this step, a desired wiring board is obtained.

  The stripping solution used in the stripping step is preferably an alkaline aqueous solution. As this alkaline aqueous solution, it is preferable to use 2 mass%-5 mass% NaOH aqueous solution or KOH aqueous solution, for example. A small amount of a water-soluble solvent such as alcohol may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably 40 ° C to 70 ° C.

The photosensitive resin composition, the photosensitive element, and the method for forming the wiring board in the second embodiment are extremely suitable for the production of, for example, a printed wiring board, a lead frame, a substrate having a concavo-convex pattern, and a semiconductor package. Can be applied to.
The measurement methods for the various parameters described above are measured according to the measurement methods in the examples described later unless otherwise specified.

<Third embodiment>
Hereinafter, a mode for carrying out the third embodiment of the present invention (hereinafter abbreviated as “the third embodiment”) will be specifically described.

<Photosensitive resin composition>
In the third embodiment, the photosensitive resin composition includes (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. If desired, the photosensitive resin composition may further include other components such as (D) an additive.

  In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acryloyl group” means acryloyl group or methacryloyl group, and “(meth) acrylate” "Means" acrylate "or" methacrylate ".

(A) Alkali-soluble polymer (A) An alkali-soluble polymer is a polymer that can be dissolved in an alkaline substance. In the third embodiment, from the viewpoint of achieving both a tent property of a resist pattern and a water residue short-circuit defect suppressing property, (A) the alkali-soluble polymer is (A) the whole of the monomers constituting the alkali-soluble polymer. It is preferable that 10 mass%-24 mass% of (meth) acrylic acid structural units and 35 mass%-90 mass% of styrene structural units are included based on mass.

  (A) The content of the structural unit of (meth) acrylic acid in the alkali-soluble polymer is that the shortage of water short-circuit is suppressed based on the total mass of the monomer constituting the (A) alkali-soluble polymer. From a viewpoint, it is preferable that it is 24 mass% or less, and it is preferable that it is 10 mass% or more from a viewpoint of ensuring alkali developability and alkali peelability. The upper limit of this content is more preferably 23% by mass or 22.5% by mass, and the lower limit is more preferably 11% by mass, 15% by mass, 18% by mass or 20% by mass. . The remaining water short circuit has a strong correlation with the hydrophobicity of the cured resist, and it is possible to suppress the remaining water short circuit by increasing the hydrophobicity of the resist, that is, the water contact angle.

  (A) In relation to the content of structural units of (meth) acrylic acid in alkali-soluble polymer, (A) acid equivalent of alkali-soluble polymer (when component (A) contains a plurality of types of copolymers) The acid equivalent of the whole mixture) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the development resistance, resolution, and adhesion of the resist pattern. It is preferable that it is 900 or less from a viewpoint of developability of this and peelability. (A) The acid equivalent of the alkali-soluble polymer is more preferably 250 to 600, and further preferably 350 to 500. An acid equivalent means the mass of the linear polymer which has a 1 equivalent carboxyl group in it.

  The content of the structural unit of styrene in the (A) alkali-soluble polymer is 90% by mass or less from the viewpoint of developability, based on the total mass of the monomer constituting the (A) alkali-soluble polymer. It is preferable that the content is 35% by mass or more from the viewpoint of resolution and water residue short circuit defect suppression. The upper limit of this content is more preferably 85% by mass, 80% by mass, 70% by mass, or 60% by mass from the viewpoint of developability and prevention of delay in peeling time, and the lower limit is resolution and water. From the viewpoint of suppressing the remaining short circuit failure, it is more preferably 36% by mass, 38% by mass, 40% by mass, or 42% by mass.

  (A) The alkali-soluble polymer preferably further contains a structural unit of butyl (meth) acrylate from the viewpoint of improving the tent property of the resist pattern. The structural unit of butyl (meth) acrylate includes a repeating unit derived from at least one selected from the group consisting of n-butyl (meth) acrylate, isobutyl (meth) acrylate and tert-butyl (meth) acrylate. Good.

  (A) The content of the structural unit of butyl (meth) acrylate in the alkali-soluble polymer is a single amount constituting the (A) alkali-soluble polymer from the viewpoint of achieving both a tent property and a water residue short-circuit defect suppressing property. It is preferably in the range of 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 1% by mass, based on the total mass of the body.

  (A) Alkali-soluble polymer is 10% by mass to 24% by mass of (meth) acrylic structural unit and 35% by mass to 90% by mass based on the total mass of monomers constituting (A) alkali-soluble polymer. As long as it contains a structural unit of styrene by mass%, it may be a single kind of copolymer, a mixture of plural kinds of copolymers and / or a mixture of plural kinds of homopolymers.

  (A) Alkali-soluble polymer is poly (meth) acrylic acid, poly (meth) butyl acrylate, polystyrene, (meth) acrylic acid and / or styrene and one or more of the first monomers described below and / or Or the copolymer etc. which are obtained by copolymerizing the copolymerization component which consists of 1 or more types of the 2nd monomer mentioned later may be included.

  The first monomer is a monomer (excluding (meth) acrylic acid) containing a carboxyl group in the molecule. Examples of the first monomer include fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester.

The second monomer is a non-acidic monomer (excluding styrene) having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. And vinyl alcohol esters; (meth) acrylonitrile; polymerizable styrene derivatives; and the like.
Among these, n-butyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl (meth) acrylate is preferable from the viewpoint of improving the tent property of the resist pattern, and n-butyl ( (Meth) acrylate is more preferable, and a polymerizable styrene derivative is preferable from the viewpoint of improving the resolution and suppressing the residual short circuit failure.
Examples of the polymerizable styrene derivative include methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, and the like.

  The alkali-soluble polymer is prepared by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, normal propyl alcohol, or isopropanol, to a radical polymerization initiator such as benzoyl peroxide, The synthesis is preferably carried out by adding an appropriate amount of azoisobutyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  (A) The weight average molecular weight of the alkali-soluble polymer (when the component (A) includes a plurality of types of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. . (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer. It is preferable that it is 500,000 or less from a viewpoint of maintaining. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, and further preferably 20,000 to 100,000. (A) The dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0.

  In the third embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified) In the range of 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 60% by mass. (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and the resist pattern formed by exposure has performance as a resist material. It is preferable that it is 90 mass% or less from a viewpoint of fully exhibiting.

(B) Ethylenically unsaturated bond-containing compound (B) An ethylenically unsaturated bond-containing compound is a compound having polymerizability by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerization.

  In the third embodiment, when (A) an alkali-soluble polymer and (B) an ethylenically unsaturated bond-containing compound are used in combination, from the viewpoint of securing the tent property of a resist pattern, (B) The weight average molecular weight of the saturated bond-containing compound is preferably 1,200 or more. In the present specification, the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is defined as (B) when the ethylenically unsaturated bond-containing compound is a single species, Means the weight average molecular weight derived from the structural formula. (B) When the ethylenically unsaturated bond-containing compound comprises a plurality of types, it means the weighted average of the weight average molecular weight and blending ratio of each ethylenically unsaturated bond-containing compound. To do.

  (B) The weight average molecular weight of the ethylenically unsaturated bond-containing compound is more preferably 1,300 or more, still more preferably 1,400 or more, from the viewpoint of further improving the tent property of the resist pattern. From the viewpoint of resolution and peelability, it is more preferably 5,000 or less, further preferably 4,000 or less, and particularly preferably 3,000 or less.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又はメチル基を表し、かつｍ_１は、２〜４０を満たす数である。｝
で表されるエチレングリコールジ（メタ）アクリレート化合物；
（ｂ_２）下記一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜５０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい。｝
で表されるアルキレンオキシド変性ビスフェノールＡ型ジ（メタ）アクリレート化合物；
（ｂ_３）下記一般式（ＩＩＩ）：

｛式中、Ｒ_５〜Ｒ_７は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４は、１〜４０であり、そしてｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるトリ（メタ）アクリレート化合物；
（ｂ_４）下記一般式（ＩＶ）：

｛式中、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、炭素数２〜６のアルキレン基を表し、Ｚは、２価の有機基を表し、かつｓ及びｔは、それぞれ独立に、０〜４０の整数であり、かつｓ＋ｔ≧１である｝
で表されるウレタンジ（メタ）アクリレート化合物；及び
（ｂ_５）上記（ｂ_１）〜（ｂ_４）以外の付加重合性単量体；
から成る群から選択される少なくとも１つを含んでよい。(B) The ethylenically unsaturated bond-containing compound includes the following (b ₁ ) to (b ₅ ):
(B ₁ ) The following general formula (I):

{Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and m ₁ is a number satisfying 2 to 40. }
An ethylene glycol di (meth) acrylate compound represented by:
(B ₂ ) The following general formula (II):

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of — (A—O) — and — (B—O) — is random, May be a block, and in the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenyl group side. }
An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by:
(B ₃ ) The following general formula (III):

{Wherein R _{5 to} R ₇ each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ each independently represent , M ₂ + m ₃ + m ₄ is 1 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs are the same as each other, Or may be different}
A tri (meth) acrylate compound represented by:
(B ₄ ) The following general formula (IV):

{Wherein R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s And t are each independently an integer of 0 to 40 and s + t ≧ 1}
And (b ₅ ) addition polymerizable monomers other than the above (b ₁ ) to (b ₄ );
At least one selected from the group consisting of:

(B) an ethylenically unsaturated bond-containing compound, from the viewpoint of adjusting the size of the release time and release strip of the resist pattern, (b ₁₎ ethylene glycol di (meth) represented by the general formula (I) acrylate compound It is preferable to contain.

In the general formula (I), m ₁ is preferably 2 or more from the viewpoint of peeling time and peeling piece size, and is preferably 40 or less from the viewpoint of resolution, plating resistance, and etching resistance. m ₁ is more preferably 4 to 20, and still more preferably 6 to 12.

Specific examples of the ethylene glycol di (meth) acrylate compound represented by the general formula (I) include tetraethylene glycol di (meth) acrylate having m ₁ = 4 and nonaethylene glycol di (meth) acrylate having m ₁ = 9. Or polyethylene glycol di (meth) acrylate with m ₁ = 14.

(B) The ethylenically unsaturated bond-containing compound contains an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by (b ₂ ) general formula (II) from the viewpoint of resolution and tentability. Is preferred. B in the general formula (II) may be —CH ₂ CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —.

The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and / or a substituent.
Examples of the hetero atom include a halogen atom, and the substituent includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C2-C10 alkylcarbonyl group, C2-C10 alkenyl group, C2-C10 - alkylcarbamoyl group or a group containing a heterocyclic ring, or an aryl group substituted by these substituents. These substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

R ₃ and R ₄ in the general formula (II) may be each independently a hydrogen atom or a methyl group, but from the viewpoint of ensuring contrast immediately after exposure of the photosensitive resin layer comprising the photosensitive resin composition, One or both of R ₃ and R ₄ are preferably hydrogen atoms, and both R ₃ and R ₄ are more preferably hydrogen atoms.

(B ₂ ) It is preferable that a relatively long chain alkylene oxide is added to the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) from the viewpoint of tent properties. More specifically, in the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = _{4 to} 50, more preferably n ₁ + n ₂ + n ₃ + n ₄ = 10 to 50, more preferably n ₁ + n ₂ + n ₃ + n ₄ = 20 to 50, particularly preferably n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50 Satisfy the relationship.

From the viewpoint of tent properties, 40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is preferably (b ₂ ) an alkylene oxide-modified bisphenol A type di (meta) represented by the general formula (II) ) An acrylate compound, and more preferably an alkylene oxide-modified bisphenol A in which n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50 Type di (meth) acrylate compound. More preferably (B) 50% by mass, more preferably 55% by mass or more, most preferably 60% by mass of the ethylenically unsaturated bond-containing compound is (b ₂ ) an alkylene represented by the general formula (II) It is an oxide-modified bisphenol A di (meth) acrylate compound.

(B ₂ ) As a preferred specific example of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II), polyethylene glycol obtained by adding an average of 1 unit of ethylene oxide to both ends of bisphenol A is used. Di (meth) acrylate, polyethylene glycol di (meth) acrylate having an average of 2 units of ethylene oxide added to both ends of bisphenol A, and polyethylene glycol di (5) having an average of 5 units of ethylene oxide to both ends of bisphenol A An average of 6 units of ethylene ox on both ends of polyethylene glycol di (meth) acrylate and bisphenol A each with an average of 7 units of ethylene oxide added to both ends of meth) acrylate and bisphenol A Poly (alkylene glycol) di- (meth) acrylate added with 2 units of propylene oxide and 2 units of propylene oxide on average, Bisphenol A both ends of poly (alkylene glycol) with an average of 15 units of ethylene oxide added on both ends of bisphenol A And poly (alkylene glycol) di (meth) acrylates each having an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide.

In the general formula (II), n ₁ , n ₂ , n _3, and n ₄ may satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 from the viewpoint of resolution and water residue short-circuit defect suppression. It is particularly preferable that n ₁ + n ₂ + n ₃ + n ₄ = 2 to 4 is satisfied.

(B) The ethylenically unsaturated bond-containing compound is a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50 in the general formula (II), from the viewpoint of achieving both tent properties and water short-circuit short-circuit suppressing properties, It is particularly preferable to simultaneously contain a compound in which one or both of R ₃ and R ₄ in formula (II) are hydrogen atoms, and a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 in general formula (II) preferable.

(B) an ethylenically unsaturated bond-containing compound, from the viewpoint of resolution and tents resistance, preferably contains (b ₃₎ tri represented by the general formula (III) (meth) acrylate compound. X in formula (III), an alkylene group having 2 to 6 carbon atoms, _{e.g., -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 - and the like in Good.

(B ₃ ) The tri (meth) acrylate compound represented by the general formula (III) preferably has a relatively long chain alkylene oxide moiety from the viewpoint of tent properties. More specifically, in the general formula (III), m ₂ + m ₃ + m ₄ is preferably 10-40, more preferably 20-40.

_{(B 3)} Preferred examples of tri (meth) acrylate compound represented by formula (III), ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (EO average addition molar number: 10 to 40 ), Propylene oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average added mole number: 10 to 40), and the like.

(B) an ethylenically unsaturated bond-containing compound, from the viewpoint of tent properties, preferably contains (b ₄₎ urethane di represented by the general formula (IV) (meth) acrylate compound.

  In the general formula (IV), Z represents a divalent organic group, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, or an optionally substituted carbon number. A divalent alicyclic group of 3 to 10 may be used.

In General Formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, such as —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ — and the like. Good.

From the viewpoint of further improving the tent property, the — (Y—O) _s — moiety and the — (Y—O) _t — moiety in the general formula (IV) are each independently — (C ₂ H ₅ O). _{- (C 3 H 6 O)} 9
It is also preferred that it is substituted with-.

(B ₄ ) Preferred specific examples of the urethane di (meth) acrylate compound represented by the general formula (IV) include a (meth) acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2, Addition reaction products with diisocyanate compounds such as 4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO Modified urethane di (meth) acrylate is mentioned. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. As EO modified | denatured urethane di (meth) acrylate, Shin-Nakamura Chemical Co., Ltd. make, brand name "UA-11" etc. are mentioned, for example. Examples of EO and PO-modified urethane di (meth) acrylates include trade name “UA-13” manufactured by Shin-Nakamura Chemical Co., Ltd. These are used individually by 1 type or in combination of 2 or more types.

The (B) ethylenically unsaturated bond-containing compound may contain an addition polymerizable monomer other than the components (b ₁ ) to (b ₄ ) as the component (b ₅ ).

The component (b ₅ ) includes the following
Tri (meth) acrylates other than (b ₃ ) component, for example, trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate etc;
Tetra (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxytetra (meth) acrylate, etc .;
Penta (meth) acrylate, such as dipentaerythritol penta (meth) acrylate;
Hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate, hexapenta (meth) acrylate in which 1 to 24 moles of ethylene oxide are added to six ends of dipentaerythritol, six ends of dipentaerythritol A hexa (meth) acrylate having 1 to 10 moles of ε-caprolactone added thereto;
An acrylate compound having one (meth) acryloyl group;
A compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid;
A compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid; and a phthalic acid-based compound such as γ-chloro-2-hydroxypropyl-β ′-(meth) acryloyloxyeryl- o-phthalate and β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate and the like;
Is mentioned.

  In the third embodiment, the total content of all the (B) ethylenically unsaturated bond-containing compounds in the photosensitive resin composition is preferably 1% by mass from the viewpoint of tent properties and adhesion of the resist pattern. -70 mass%, More preferably, it is 2 mass%-60 mass%, More preferably, it exists in the range of 4 mass%-50 mass%.

(C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes a monomer by light. The photosensitive resin composition contains a compound generally known in the art as a photopolymerization initiator.

  The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1% by mass. It is in the range of ˜7% by mass. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and sufficiently transmits light to the bottom surface of the resist to provide good high resolution. It is preferable that it is 20 mass% or less from a viewpoint of obtaining.

  (C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters , Acridines and the like, and further hexaarylbiimidazole, pyrazoline compounds, N-aryl amino acids or ester compounds thereof (for example, N-phenylglycine), and organic halogen compounds. These can be used alone or in combination of two or more. Among these, acridines are particularly suitable for direct imaging exposure.

  Examples of acridines include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, Acridine such as 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane Derivatives. From the viewpoint of suitability for direct imaging exposure, the content of acridines in the photosensitive resin composition is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, and still more preferably. Is in the range of 0.5% to 2% by weight.

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. Can do. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3%. It is in the range of mass%.

  Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl)- Biimidazole, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2 , 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4, 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'-tetrakis -(3-methoxyphenyl) Biimidazole, 2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis -(2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,6-tri Fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrakis- (3-methoxyphenyl) -biimidazole And 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole and the like. These can be used singly or in combination of two or more. From the viewpoint of high sensitivity, resolution, and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.

  In the third embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. -7% by mass, more preferably 0.1% by mass to 6% by mass, and still more preferably 1% by mass to 4% by mass.

  Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable. The content of the N-aryl amino acid in the photosensitive resin composition is 0.05% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling characteristics and / or sensitivity. % Is preferable, and 0.1 to 2% by mass is more preferable.

  Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris ( 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and chlorinated triazine compounds, among others In particular, tribromomethylphenylsulfone is preferably used. The content of the organic halogen compound in the photosensitive resin composition is 0.05% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling characteristics and / or sensitivity. It is preferable that it is 0.1 mass%-3 mass%.

  Examples of other photosensitizers include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone. Quinones such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone, benzoin, benzoin Benzoin ethers such as ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, and 1-phenyl-1,2-propanedione-2-O-benzoin oxime, and - oxime esters such as phenyl-1,2-propane-dione-2-(O-ethoxycarbonyl) oxime and the like. The content of the photosensitizer in the photosensitive resin composition is 0.05% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling characteristics and / or sensitivity. %, Preferably 0.1% by mass to 3% by mass.

  In the third embodiment, the photosensitive resin composition preferably contains a pyrazoline compound as a photosensitizer. Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazolin and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

(D) Additive The photosensitive resin composition may contain additives such as a color changing agent, a dye, a plasticizer, an antioxidant, and a stabilizer, as desired. For example, you may use the additive currently enumerated by Unexamined-Japanese-Patent No. 2013-156369 and international publication 2009/093706.

  Examples of the color changing agent include leuco dyes and fluoran dyes. The use of the color changing agent is preferable from the viewpoint of visibility due to coloration of the exposed portion. Further, when an inspection machine or the like reads an alignment marker for exposure, it is advantageous that the position of the exposed portion and the unexposed portion has a higher contrast because the position can be easily recognized.

  Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like. In particular, from the viewpoint of good contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass. This content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed part and the unexposed part, and preferably 10% by mass or less from the viewpoint of maintaining storage stability.

  Examples of the base dye include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Malachite Green Oxalate [2437 -29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Industry), brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], Methyl violet 2B [8004-87-3], Crystal violet [548-62-9], Methyl green [82-94-0], Victoria blue B [2580-56-5], Basic blue 7 [2390-60- 5] (for example, Aizen Victoria Pu e Blue BOH, trade name, manufactured by Hodogaya Chemical), rhodamine B [81-88-9], rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], and the like. Of these, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 is particularly preferable from the viewpoint of improving hue stability and exposure contrast.

  In this 3rd embodiment, content of the base dye in the photosensitive resin composition becomes like this. Preferably it is 0.001 mass%-3 mass%, More preferably, it is 0.01 mass%-2 mass%, More preferably It is in the range of 0.01% by mass to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

  In the third embodiment, the delay of the resist pattern peeling caused by the alkali-soluble polymer having a content of structural units of (meth) acrylic acid of 10% by mass to 24% by mass is suppressed, and the peeling time is shortened. Therefore, it is preferable that toluene amides such as o-toluenesulfonic acid amide and p-toluenesulfonic acid amide are contained in the photosensitive resin composition as a plasticizer. The content of toluenesulfonic acid amide in the photosensitive resin composition is preferably in the range of 0.1% by mass to 5% by mass, more preferably 1% by mass to 4% by mass.

  Examples of other plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl ether. , Glycol esters such as polyoxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether; phthalic acid esters such as diethyl phthalate; tributyl citrate, triethyl citrate, triethyl citrate, triacetyl citrate -N-propyl and tri-n-butyl acetylcitrate; propylene oxide on each side of bisphenol A Pressurized propylene glycol, ethylene glycol, and the like obtained by adding each of ethylene oxide on either side of the Bisphenol A.

From the viewpoint of thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition is used as a stabilizer, as a radical polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butyl. Catechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol), diphenylnitrosamine, triethylene glycol-bis (3-3-tert-butyl-5-methyl-4-hydroxyphenylpropionate), and nitrosophenylhydroxyamine aluminum salts; benzotriazoles such as 1,2,3-benzotriazole, 1-chloro- , 2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, 1- (2-di-n-octylaminomethyl) -benzotriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like; carboxybenzotriazoles such as 4-carboxy-1 , 2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole, 1- (2-di-n-butylaminomethyl) -5 Carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazol N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- ( N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like; and alkylene oxide compounds having a glycidyl group, such as neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol Diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mole adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), hydrogenated bisphenol A diglycid Ethers (e.g., Kyoeisha Chemical Co., Ltd. Epolight 4000), 1,6-hexanediol diglycidyl ether (e.g., Kyoeisha Chemical Co., Ltd. Epolight 1600) and the like;
It is preferable to include at least one selected from the group consisting of:

  In the third embodiment, the total content of all stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass. More preferably, it exists in the range of 0.05 mass%-0.7 mass%. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferable that it is 3 mass% or less.

  The additive demonstrated above can be used individually by 1 type or in combination of 2 or more types.

<Photosensitive resin composition preparation solution>
In the third embodiment, a photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition. Suitable solvents include ketones such as acetone, methyl ethyl ketone (MEK) and the like; and alcohols such as methanol, ethanol, isopropyl alcohol and the like. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 mPa · second to 4000 mPa · second at 25 ° C.

<Photosensitive resin laminate>
In the third embodiment, there can be provided a photosensitive resin laminate having a support and a photosensitive resin layer made of the photosensitive resin composition and laminated on the support. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer.

  Although it does not specifically limit as a support body, The transparent thing which permeate | transmits the light radiated | emitted from an exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. The thinner the film, the more advantageous in terms of image formation and economy, but it is preferably 10 μm to 30 μm in order to maintain the strength.

  In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. are preferable, for example. For example, a film having excellent peelability described in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

  In the third embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. As the thickness of the photosensitive resin layer is smaller, the resolution of the resist pattern is improved. On the other hand, the larger the thickness is, the more the strength of the cured film is improved.

  A known method may be used as a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and, if desired, a protective layer.

  For example, the photosensitive resin composition preparation liquid is prepared, and then coated on the support using a bar coater or a roll coater and dried, and the photosensitive resin comprising the photosensitive resin composition preparation liquid on the support. Laminate the layers. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The resist pattern is formed by laminating a photosensitive resin layer composed of the above-described photosensitive resin composition on a support, an exposure step of exposing the photosensitive resin layer, and developing the exposed photosensitive resin layer. Development steps are preferably included in this order. An example of a specific method for forming a resist pattern in the third embodiment will be described below.

  First, in a laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.

  In the third embodiment, the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature during lamination is generally 40 ° C to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained can be improved by performing the thermocompression bonding at the time of lamination twice or more. At the time of thermocompression bonding, a two-stage laminator provided with two rolls may be used, or the lamination of the substrate and the photosensitive resin layer may be repeated several times and passed through the roll.

  Next, in the exposure step, the photosensitive resin assembly layer is exposed to active light using an exposure machine. The exposure can be performed after peeling the support, if desired. In the case of exposing through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter. In the exposure step, direct imaging exposure may be performed. In direct imaging exposure, exposure is performed directly on a substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm or an ultrahigh pressure mercury lamp is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

  Next, in the development step, the unexposed or exposed portion of the exposed photosensitive resin layer is removed with a developer using a developing device. If there is a support on the photosensitive resin layer after exposure, this is excluded. Subsequently, an unexposed portion or an exposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image.

As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferable. The alkaline aqueous solution is selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. The temperature of the developer in the development step is preferably kept constant within a range of 20 ° C to 40 ° C.

  Although a resist pattern is obtained by the above steps, a heating step can be further performed at 100 ° C. to 300 ° C. if desired. By performing this heating step, the chemical resistance of the resist pattern can be improved. A heating furnace using hot air, infrared rays, or far infrared rays can be used for the heating step.

  The photosensitive resin composition of the third embodiment can be suitably used for forming a printed circuit board. In general, a subtractive process and a semi-additive process (SAP) are used as a circuit formation method for a printed circuit board.

The subtractive process is a method of forming a circuit by removing only a non-circuit portion from a conductor disposed on the entire surface of a substrate by etching.
SAP is a method in which a resist is formed on a non-circuit portion on a conductor seed layer disposed on the entire surface of a substrate, and then only a circuit portion is formed by plating.

<Conductor pattern manufacturing method>
The method for producing a conductor pattern includes a lamination step of laminating a photosensitive resin layer composed of the above-described photosensitive resin composition on a substrate such as a metal plate or a metal film insulating plate, an exposure step of exposing the photosensitive resin layer, and an exposure step. A developing step for obtaining a substrate on which a resist pattern is formed by removing an unexposed portion or an exposed portion of the photosensitive resin layer with a developer, and a conductor pattern forming step for etching or plating the substrate on which the resist pattern is formed. , Preferably in this order.

  In the third embodiment, the conductor pattern manufacturing method is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing a conductor pattern forming step. Is called. In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development using a known etching method or plating method.

  Furthermore, the third embodiment is suitably applied in the following applications, for example.

<Manufacturing method of wiring board>
After the conductor pattern is produced by the conductor pattern production method, the resist pattern is further separated from the substrate with an aqueous solution having alkalinity stronger than that of the developer, whereby a wiring board having a desired wiring pattern (for example, Printed wiring board).

  The alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass or an organic amine-based stripping solution is used. Generally used. A small amount of a water-soluble solvent may be added to the stripping solution. As a water-soluble solvent, alcohol etc. are mentioned, for example. The temperature of the stripping solution in the stripping step is preferably within a range of 40 ° C to 70 ° C.

<Manufacture of lead frames>
A lead frame can be manufactured by forming a resist pattern by a resist pattern forming method using a metal plate such as copper, copper alloy, or iron-based alloy as a substrate, and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Thereafter, a desired lead frame can be obtained by performing a peeling process for peeling the resist pattern by a method similar to the method for manufacturing a wiring board.

<Manufacture of a substrate having an uneven pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when processing the substrate by the sandblasting method. In this case, examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material. A resist pattern is formed on these substrates by the same method as the resist pattern forming method. Thereafter, a blasting material is sprayed from the formed resist pattern to cut to a desired depth, and a resist pattern remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. The base material which has a fine uneven | corrugated pattern on a board | substrate can be manufactured.

In the sand blasting process, a known blasting material may be used. For example, fine particles having a particle diameter of 2 μm to 100 μm including SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like are generally used. The

<Manufacture of semiconductor packages>
A semiconductor package can be manufactured by forming a resist pattern on a wafer by a resist pattern forming method using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate, and then performing the following steps. . First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern is performed by a method similar to the method for manufacturing the wiring board, and further, a thin metal layer other than the columnar plating is removed by etching, thereby obtaining a desired semiconductor package. Can be obtained.

In the third embodiment, the photosensitive resin composition is used for the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; the precision processing of metal foils such as the manufacture of metal masks; ball grid arrays (BGA), Manufacturing of packages such as size packages (CSP); Manufacturing of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); Manufacturing of semiconductor bumps; and ITO electrodes, address electrodes, electromagnetic wave shields, etc. It can be used for manufacturing a partition wall of a flat panel display.
In addition, unless otherwise indicated, the value of each parameter mentioned above is measured according to the measuring method in the Example mentioned later.

<Fourth embodiment>
Hereinafter, a mode for carrying out the fourth embodiment of the present invention (hereinafter abbreviated as “the fourth embodiment”) will be specifically described.

<Photosensitive resin composition>
In the fourth embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. If desired, the photosensitive resin composition may further contain other components such as (D) a stabilizer.

  In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acryloyl group” means acryloyl group or methacryloyl group, and “(meth) acrylate” "Means" acrylate "or" methacrylate ".

[(A) Alkali-soluble polymer]
The (A) alkali-soluble polymer is a first polymer having an acid monomer unit content of less than 25% by mass and an aromatic monomer unit content of 30% by mass or more from the viewpoint of resolution and extension of the minimum development time. Of the copolymer. The first copolymer may contain other monomer units in addition to acid monomer units and aromatic monomer units, if desired. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight (described later) and the number average molecular weight of the copolymer is preferably 1 or more and 6 or less.
Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic acid anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic acid anhydride include maleic acid anhydride, itaconic acid anhydride, fumaric acid, citraconic acid anhydride, and the like. Of these, (meth) acrylic acid is preferred.

  The copolymerization ratio of the acid monomer unit in the component (A) is preferably less than 25% by mass, more preferably 10% by mass to 24% by mass, based on the total mass of all monomer units. More preferably, it is 15 mass%-23 mass%. The content ratio of the acid monomer unit within this range is preferable from the viewpoint of improving the resolution and extending the minimum development time.

  Aromatic monomers are also referred to as unsaturated aromatic compounds. As an aromatic monomer, styrene, (alpha) -methylstyrene, vinyl naphthalene etc .; (meth) acrylic-acid aralkyl ester etc. can be mentioned, for example. Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate.

  The copolymerization ratio of aromatic monomer units (preferably styrene units) in the component (A) is preferably 30% by mass or more, and 32% by mass to 60% by mass with respect to the total mass of all monomer units. It is more preferable that it is 35 mass%-55 mass%. Setting the copolymerization ratio of the aromatic monomer, which is highly hydrophobic and difficult to be combined with the developing solution and the washing water with the developing water, in the above range is preferable from the viewpoint of improving the resolution and extending the minimum developing time.

  Examples of other monomers include (meth) acrylic acid alkyl esters, conjugated diene compounds, polar monomers, and crosslinkable monomers.

  The (meth) acrylic acid alkyl ester is a concept including both a chain alkyl ester and a cyclic alkyl ester. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meta) ) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate And the like can be given.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.

Examples of polar monomers include:
Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentenol; amino group-containing monomers such as 2-aminoethyl methacrylate;
Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
Cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-cyanoethyl acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate and (meth) acrylic acid 3,4-epoxycyclohexyl;
Etc.

  Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

  The first copolymer is particularly preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.

  In the fourth embodiment, from the viewpoints of resolution, developability, and aggregability, the second copolymer having a content ratio of the aromatic monomer unit described above of 45% by mass to 90% by mass is included. It is also preferable. In the second copolymer, when the content of the aromatic monomer unit is 45% by mass, the hydrophobicity of the resist pattern including the second copolymer tends to be ensured. Further, the weight ratio of the second copolymer to the total weight of all the copolymers is preferably 25% by mass or more from the viewpoint of improving the cohesiveness.

  The second copolymer may include the acid monomer unit described above and other monomer units. As an aromatic monomer for polymerizing the second copolymer, styrene is preferable from the viewpoint of hydrophobicity. The upper limit of the content ratio of the aromatic monomer unit in the second copolymer is more preferably 80% by mass or 70% by mass from the viewpoint of developability.

  The second copolymer may contain the acid monomer unit described above and other monomer units. From the viewpoint of resolution, developability, and aggregation, the content ratio of the acid monomer unit described above is , Preferably, it is 25 mass%-50 mass%, More preferably, it is 25 mass%-40 mass%. The acid monomer for polymerizing the second copolymer is preferably (meth) acrylic acid from the viewpoint of developability.

  The weight average molecular weight of the component (A) (when the component (A) includes a plurality of types of copolymers, the weight average molecular weight of the whole mixture) is 5,000 to 1,000,000. Is preferably 10,000 to 500,000, more preferably 15,000 to 100,000. It is preferable to adjust the weight average molecular weight of the component (A) within this range from the viewpoint of adapting the development time in forming the resist pattern to the operating state of the line process to be used.

  In the fourth embodiment, the content of the component (A) in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same for each component). 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 60% by mass. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, while 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

  The first copolymer having an acid monomer unit content of less than 25% by mass and an aromatic monomer unit content of 30% by mass or more is 5% by mass to 50% based on the total solid content of the photosensitive resin composition. It is preferable that it is below mass%. More preferably, it is 10 mass% or more and 40 mass% or less.

[(B) Compound containing ethylenically unsaturated bond]
(B) An ethylenically unsaturated bond containing compound is a compound which has polymerizability by having an ethylenically unsaturated group in the structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerization.

  In the fourth embodiment, when (A) an alkali-soluble polymer and (B) an ethylenically unsaturated bond-containing compound are used in combination, the resist pattern has good resolution and the minimum development time is extended. In view of this, the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is preferably 900 or less. In this specification, the average molecular weight of the (B) ethylenically unsaturated bond-containing compound is the structure of a single type of ethylenically unsaturated bond-containing compound when the (B) ethylenically unsaturated bond-containing compound is a single type. It means the weight average molecular weight derived from the formula, and when (B) the ethylenically unsaturated bond-containing compound comprises a plurality of types, it means the weighted average of the weight average molecular weight and blending ratio of each ethylenically unsaturated bond-containing compound. .

  (B) The weight average molecular weight of the ethylenically unsaturated bond-containing compound is more preferably 850 or less, and still more preferably 800 or less, from the viewpoint of improving the resolution and extending the minimum development time. From the viewpoint of suppressing edge fuse properties in the body, it is preferably 50 or more, more preferably 100 or more. Here, the edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is rolled up.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又はメチル基を表し、かつｍ_１は、２〜４０を満たす数である。｝
で表されるエチレングリコールジ（メタ）アクリレート化合物；
（ｂ_２）下記一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜５０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい。｝
で表されるアルキレンオキシド変性ビスフェノールＡ型ジ（メタ）アクリレート化合物；
（ｂ_３）下記一般式（ＩＩＩ）：

｛式中、Ｒ_５〜Ｒ_７は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４は、０〜４０であり、そしてｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるトリ（メタ）アクリレート化合物；
（ｂ_４）下記一般式（ＩＶ）：

｛式中、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、炭素数２〜６のアルキレン基を表し、Ｚは、２価の有機基を表し、かつｓ及びｔは、それぞれ独立に、０〜４０の整数であり、かつｓ＋ｔ≧１である｝
で表されるウレタンジ（メタ）アクリレート化合物；
（ｂ_５）下記一般式（ＸＩ）：

｛式中、Ｒ_５〜Ｒ_８は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３、ｍ_４及びｍ_５は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４＋ｍ_５は、０〜５０であり、そしてｍ_２＋ｍ_３＋ｍ_４＋ｍ_５が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるテトラ（メタ）アクリレート化合物；及び
（ｂ_６）上記（ｂ_１）〜（ｂ_５）以外の付加重合性単量体；
から成る群から選択される少なくとも１つを含んでよい。(B) The ethylenically unsaturated bond-containing compound includes the following (b ₁ ) to (b ₆ ):
(B ₁ ) The following general formula (I):

{Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and m ₁ is a number satisfying 2 to 40. }
An ethylene glycol di (meth) acrylate compound represented by:
(B ₂ ) The following general formula (II):

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of — (A—O) — and — (B—O) — is random, May be a block, and in the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenyl group side. }
An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by:
(B ₃ ) The following general formula (III):

{Wherein R _{5 to} R ₇ each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ each independently represent , M ₂ + m ₃ + m ₄ is 0 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plurality of Xs are the same as each other, Or may be different}
A tri (meth) acrylate compound represented by:
(B ₄ ) The following general formula (IV):

{Wherein R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s And t are each independently an integer of 0 to 40 and s + t ≧ 1}
A urethane di (meth) acrylate compound represented by:
(B ₅ ) The following general formula (XI):

{Wherein R _{5 to} R ₈ each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ , m _4, and m ₅ represent Each independently represents an integer of 0 to 40, m ₂ + m ₃ + m ₄ + m ₅ is 0 to 50, and when m ₂ + m ₃ + m ₄ + m ₅ is 2 or more, a plurality of X are , May be the same or different from each other}
(B ₆ ) addition polymerizable monomers other than the above (b ₁ ) to (b ₅ );
At least one selected from the group consisting of:

(B) an ethylenically unsaturated bond-containing compound, from the viewpoint of adjusting the size of the release time and release strip of the resist pattern, (b ₁₎ ethylene glycol di (meth) represented by the general formula (I) acrylate compound It is preferable to contain.

In the general formula (I), m ₁ is preferably 2 or more from the viewpoint of peeling time and peeling piece size, and is preferably 40 or less from the viewpoint of resolution, plating resistance, and etching resistance. m ₁ is more preferably 4 to 20, and still more preferably 6 to 12.

Specific examples of the ethylene glycol di (meth) acrylate compound represented by the general formula (I) include tetraethylene glycol di (meth) acrylate having m ₁ = 4 and nonaethylene glycol di (meth) acrylate having m ₁ = 9. Or polyethylene glycol di (meth) acrylate with m ₁ = 14.

(B) The ethylenically unsaturated bond-containing compound is represented by (b ₂ ) general formula (II) from the viewpoint of suppressing the generation of aggregates during development of the photosensitive resin layer comprising the photosensitive resin composition. It is preferable that an alkylene oxide modified bisphenol A type di (meth) acrylate compound is included. B in the general formula (II) may be —CH ₂ CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —.

The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a hetero atom and / or a substituent.
Examples of the hetero atom include a halogen atom, and the substituent includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C2-C10 alkylcarbonyl group, C2-C10 alkenyl group, C2-C10 - alkylcarbamoyl group or a group containing a heterocyclic ring, or an aryl group substituted by these substituents. These substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

R ₃ and R ₄ in the general formula (II) may be each independently a hydrogen atom or a methyl group, but from the viewpoint of ensuring contrast immediately after exposure of the photosensitive resin layer comprising the photosensitive resin composition, One or both of R ₃ and R ₄ are preferably hydrogen atoms, and both R ₃ and R ₄ are more preferably hydrogen atoms.

(B ₂ ) The alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) includes a relatively short chain alkylene oxide from the viewpoint of improving resolution and extending the minimum development time. Is preferably added. More specifically, in the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 0 to 30, more preferably n ₁ + n ₂ + n ₃ + n ₄ = 0 to 25, more preferably n ₁ + n ₂ + n ₃ + n ₄ = 0 to 20, particularly preferably n ₁ + n ₂ + n ₃ + n ₄ = 0 to 10 Satisfy the relationship.

From the viewpoint of improving the resolution and extending the minimum development time, 40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is preferably represented by (b ₂ ) the general formula (II). An alkylene oxide-modified bisphenol A type di (meth) acrylate compound, and more preferably, n ₁ , n ₂ , n ₃ and n _{4 in} the general formula (II) are n ₁ + n ₂ + n ₃ + n ₄ = 0 to 20 It is an alkylene oxide modified bisphenol A type di (meth) acrylate compound that satisfies the above relationship. More preferably (B) 50% by mass, more preferably 55% by mass or more, most preferably 60% by mass of the ethylenically unsaturated bond-containing compound is (b ₂ ) an alkylene represented by the general formula (II) It is an oxide-modified bisphenol A di (meth) acrylate compound.

(B ₂ ) As a preferred specific example of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II), polyethylene glycol obtained by adding an average of 1 unit of ethylene oxide to both ends of bisphenol A is used. Di (meth) acrylate, polyethylene glycol di (meth) acrylate having an average of 2 units of ethylene oxide added to both ends of bisphenol A, and polyethylene glycol di (5) having an average of 5 units of ethylene oxide to both ends of bisphenol A An average of 6 units of ethylene ox on both ends of polyethylene glycol di (meth) acrylate and bisphenol A each with an average of 7 units of ethylene oxide added to both ends of meth) acrylate and bisphenol A Poly (alkylene glycol) di- (meth) acrylate added with 2 units of propylene oxide and 2 units of propylene oxide on average, Bisphenol A both ends of poly (alkylene glycol) with an average of 15 units of ethylene oxide added on both ends of bisphenol A And poly (alkylene glycol) di (meth) acrylates each having an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide.

In the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 20 from the viewpoint of improving the resolution, and n ₁ + n It is particularly preferable that the relationship of ₂ + n ₃ + n ₄ = 2 to 10 is satisfied.

(B) The ethylenically unsaturated bond-containing compound is a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 20 in the general formula (II) from the viewpoint of improving resolution and extending the minimum development time, It is particularly preferable to simultaneously contain a compound in which one or both of R ₃ and R ₄ in formula (II) is a methyl group and a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 16 in general formula (II) preferable.

(B) The ethylenically unsaturated bond-containing compound is represented by (b ₃ ) general formula (III) from the viewpoint of suppressing the generation of aggregates during development of the photosensitive resin layer comprising the photosensitive resin composition. It is preferable that a tri (meth) acrylate compound is included. X in formula (III), an alkylene group having 2 to 6 carbon atoms, _{e.g., -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 - and the like in Good.

(B ₃ ) The tri (meth) acrylate compound represented by the general formula (III) preferably has a relatively short-chain alkylene oxide moiety from the viewpoint of resolution. More specifically, in the general formula (III), m ₂ + m ₃ + m ₄ is preferably 8 to 40, more preferably 9 to 25.

_{(B 3)} Preferred examples of tri (meth) acrylate compound represented by formula (III), ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (EO average addition mole number: 1 to 40 ), Propylene oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average added mole number: 1 to 40), and the like.

(B) an ethylenically unsaturated bond-containing compound, in terms of resolution, preferably comprising (b ₄₎ urethane di represented by the general formula (IV) (meth) acrylate compound.

  In the general formula (IV), Z represents a divalent organic group, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, or an optionally substituted carbon number. A divalent alicyclic group of 3 to 10 may be used.

In General Formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, such as —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ — and the like. Good.

From the viewpoint of further improving the resolution, the — (Y—O) _s — moiety and the — (Y—O) _t — moiety in the general formula (IV) are each independently — (C ₂ H ₅ O )-(C ₃ H ₆ O) ₉ −
It is also preferable that it is substituted with.

(B ₄ ) Preferred specific examples of the urethane di (meth) acrylate compound represented by the general formula (IV) include a (meth) acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2, Addition reaction products with diisocyanate compounds such as 4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO Modified urethane di (meth) acrylate is mentioned. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. As EO modified | denatured urethane di (meth) acrylate, Shin-Nakamura Chemical Co., Ltd. make, brand name "UA-11" etc. are mentioned, for example. Examples of EO and PO-modified urethane di (meth) acrylates include trade name “UA-13” manufactured by Shin-Nakamura Chemical Co., Ltd. These are used individually by 1 type or in combination of 2 or more types.

(B) The ethylenically unsaturated bond-containing compound is represented by (b ₅ ) general formula (XI) from the viewpoint of suppressing the generation of aggregates during development of the photosensitive resin layer comprising the photosensitive resin composition. It is preferable to contain a tetra (meth) acrylate compound.

X in the general formula (XI), an alkylene group having 2 to 6 carbon atoms, _{e.g., -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 - and the like in Good.

(B ₅ ) Preferred specific examples of the tetra (meth) acrylate compound represented by the general formula (XI) include pentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxytetra (meth) acrylate and the like.

(B) The ethylenically unsaturated bond-containing compound may contain an addition polymerizable monomer other than the components (b ₁ ) to (b ₅ ) as the component (b ₆ ).

As the component (b ₆ ), the following:
Tri (meth) acrylates other than (b ₃ ) component, for example, trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate etc;
(B ₅ ) tetra (meth) acrylates other than the component, for example, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc .; penta (meth) acrylate, for example, dipentaerythritol penta (meth) acrylate etc;
Hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate, hexapenta (meth) acrylate in which 1 to 24 moles of ethylene oxide are added to six ends of dipentaerythritol, six ends of dipentaerythritol A hexa (meth) acrylate having 1 to 10 moles of ε-caprolactone added thereto;
An acrylate compound having one (meth) acryloyl group;
A compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid;
A compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid; and a phthalic acid-based compound such as γ-chloro-2-hydroxypropyl-β ′-(meth) acryloyloxyeryl- o-phthalate and β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate and the like;
Is mentioned.

  In the fourth embodiment, the total content of all (B) ethylenically unsaturated bond-containing compounds in the photosensitive resin composition is preferably from the viewpoint of edge fuse property and adhesion in the photosensitive resin laminate. Is in the range of 1% to 70% by weight, more preferably 2% to 60% by weight, and still more preferably 4% to 50% by weight.

[(C) Photopolymerization initiator]
The component (C) is a component that generates a radical capable of initiating polymerization of the component (B) by light irradiation.
As such component (C), for example, aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzyl compounds, hexaarylbisimidazole compounds, acridine compounds, and the like can be used. Among these, it is preferable to use one or more selected from hexaarylbisimidazole compounds and acridine compounds from the viewpoint of high resolution and good tenting properties. Moreover, from the viewpoint of the sensitivity of the photosensitive resin composition, the component (C) preferably contains an acridine compound.

  Examples of the hexaarylbisimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4). -Dimethoxyphenyl) -4 ', 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4, 5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis -(2-Fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3- Fluoromethylphenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3- Methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, , 2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- ( 2,3,5-trifluorophenyl -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4', 5 , 5′-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- ( 3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl Dimer, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 , 2'-bis- (2,3,4,6-tetrafluorofe Nyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,5,6-pentafluorophenyl)- Examples include 4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer.

Examples of the acridine compound include:
Acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9 -Acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane and the like.

  The content of the component (C) in the photosensitive resin composition of the fourth embodiment is preferably 0.1% by mass to 2% by mass, and is in the range of 0.2% by mass to 1.8% by mass. Is more preferable, it is still more preferable that it is the range of 0.3 mass%-1.7 mass%, and it is especially preferable that it is 0.4 mass%-1.6 mass%. Setting the content of the component (C) in such a range is preferable from the viewpoint of obtaining good photosensitivity and peeling characteristics.

The component (C) can further contain a sensitizer from the viewpoint of improving sensitivity and resolution. Examples of such sensitizers include N-aryl amino acids, organic halogen compounds, and other sensitizers.
Examples of the N-aryl amino acid include:
N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like;
As an organic halogen compound, for example,
Amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate , Trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like;
Each can be mentioned.

Examples of the other sensitizers include:
2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10- Quinone compounds such as phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone;
Aromatic ketone compounds such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone;
Benzoin ether compounds such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin;
Oxime esters such as benzyldimethyl ketal, benzyl diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Compound;
Etc. can be mentioned.

The content of the sensitizer in the fourth embodiment is preferably 0.01% by mass to 5% by mass, and 0.05% by mass to 3% from the viewpoint of the photosensitivity of the composition and the peelability of the resist cured film. % By mass is more preferable, and 0.1% by mass to 2% by mass is still more preferable.
In the photosensitive resin composition of the fourth embodiment, an acridine compound and an N-aryl amino acid are used as the component (C), and these may be used in combination within the above-mentioned use ratio. It is preferable from the viewpoints of suppressing the etching rate when forming the film and suppressing the vertical and horizontal differences of the wiring width.

｛式中、Ｒ^５１は、置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表し、そしてＲ^５２、Ｒ^５３及びＲ^５４は、各々独立に、水素、又は置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表す。｝で表される化合物を含む。[(D) Stabilizer]
The photosensitive resin composition may contain a stabilizer, if desired. In the fourth embodiment, it is preferable to use hindered phenol as the stabilizer from the viewpoint of improving the resolution. In general, hindered phenol refers to phenol with large steric hindrance. The photosensitive resin composition has the following general formula (V) as a hindered phenol:

{Wherein R ⁵¹ is an optionally substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group via a divalent linking group, via a divalent linking group. A branched alkyl group, a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group, and R ⁵² , R ⁵³ and R ⁵⁴ are each independently hydrogen or substituted. A linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, a branched alkyl group via a divalent linking group, or a divalent linking group. Represents an aryl group via a cyclohexyl group or a divalent linking group. } Is included.

  The compound represented by the general formula (V) is excellent from the viewpoint of improving the resolution of the photosensitive resin composition and suppressing the decrease in sensitivity of the photosensitive resin composition. In addition, the compound represented by the general formula (V) does not have two or more phenolic hydroxyl groups in one aromatic ring, and is substituted only in one ortho position of both ortho positions of the phenolic hydroxyl group. And has a feature in controlling steric hindrance around the phenolic hydroxyl group. With such a structure, it is considered that the above-described excellent performance is exhibited.

｛式中、Ｒ^５５は、一般式（ＶＩＩ）：

［式中、Ｒ^５９及びＲ^６０は、各々独立に、水素、又は置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基を表す。］を表し、そしてＲ^５６、Ｒ^５７及びＲ^５８は、各々独立に、水素、又は上記一般式（ＶＩＩ）を表す。｝で表される化合物、下記一般式（ＶＩＩＩ）：

｛式中、Ｒ^６１及びＲ^６４は、各々独立に、直鎖若しくは分岐アルキル基を表し、そしてＲ^６２、Ｒ^６３、Ｒ^６５及びＲ^６６は、各々独立に、水素、又は直鎖若しくは分岐アルキル基を表し、Ｘ^１は２価の連結基を表す。｝で表される化合物、下記一般式（ＩＸ）：

｛式中、Ｒ^６７、Ｒ^７０及びＲ^７３は、各々独立に、直鎖若しくは分岐アルキル基を表し、そしてＲ^６８、Ｒ^６９、Ｒ^７１、Ｒ^７２、Ｒ^７４及びＲ^７５は、各々独立に、水素、又は直鎖若しくは分岐アルキル基を表し、Ｙ^１は３価の連結基を表す。｝で表される化合物、下記一般式（Ｘ）：

｛式中、Ｒ^７６、Ｒ^７９、Ｒ^８２及びＲ^８５は、各々独立に、直鎖若しくは分岐アルキル基を表し、そしてＲ^７７、Ｒ^７８、Ｒ^８０、Ｒ^８１、Ｒ^８３、Ｒ^８４、Ｒ^８６及びＲ^８７は各々独立に、水素、又は直鎖若しくは分岐アルキル基を表し、Ｚ^１は４価の連結基を表す。｝で表される化合物であることが好ましい。そして、上記一般式（ＶＩＩＩ）におけるＸ^１としては、チオエーテル基、置換若しくは無置換のアルキレン基などが挙げられる。The compound represented by the general formula (V) is R ⁵¹ or R in the formula (V) from the viewpoint of improving the resolution of the photosensitive resin composition and suppressing the decrease in sensitivity of the photosensitive resin composition. It is preferable that at least one of ⁵² , R ⁵³ and R ⁵⁴ has an aromatic ring. From the same viewpoint, the hydroxyl group concentration of the hindered phenol is preferably 0.10 mol / 100 g to 0.75 mol / 100 g. From the same viewpoint, in the general formula (V), at least one of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ is a linear or branched alkyl group or an aryl group via a divalent linking group. Preferred alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group and the like. Examples of the preferable divalent linking group include a thioether group, a substituted or unsubstituted alkylene group, and the aryl group may be substituted with a hydroxyl group or an alkyl group.
From the same viewpoint, examples of the compound represented by the general formula (V) include the following general formula (VI):

{In the formula, R ⁵⁵ represents the general formula (VII):

[Wherein, R ⁵⁹ and R ⁶⁰ each independently represent hydrogen or an optionally substituted linear alkyl group, branched alkyl group, aryl group, or cyclohexyl group. And R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent hydrogen or the above general formula (VII). }, The following general formula (VIII):

{Wherein R ⁶¹ and R ⁶⁴ each independently represent a linear or branched alkyl group, and R ⁶² , R ⁶³ , R ⁶⁵ and R ⁶⁶ are each independently hydrogen or a linear or branched alkyl group. Represents a group, and X ¹ represents a divalent linking group. }, The following general formula (IX):

{Wherein R ⁶⁷ , R ⁷⁰ and R ⁷³ each independently represents a linear or branched alkyl group, and R ⁶⁸ , R ⁶⁹ , R ⁷¹ , R ⁷² , R ⁷⁴ and R ⁷⁵ are each independently , Hydrogen, or a linear or branched alkyl group, Y ¹ represents a trivalent linking group. }, The following general formula (X):

{Wherein R ⁷⁶ , R ⁷⁹ , R ⁸² and R ⁸⁵ each independently represents a linear or branched alkyl group, and R ⁷⁷ , R ⁷⁸ , R ⁸⁰ , R ⁸¹ , R ⁸³ , R ⁸⁴ , R ⁸⁶ and R ⁸⁷ each independently represent hydrogen or a linear or branched alkyl group, and Z ¹ represents a tetravalent linking group. } Is preferable. Then, as the X ¹ in formula (VIII), a thioether group, and a substituted or unsubstituted alkylene group.

  The compound represented by the general formula (V) has a molecular weight of about 130 to about 1,000 from the viewpoint of improving the resolution of the photosensitive resin composition and suppressing the sensitivity reduction of the photosensitive resin composition. Having a molecular weight of about 200 to about 800, more preferably having a molecular weight of about 300 to about 500, and most preferably having a molecular weight of about 300 to about 400. Further, it has a specific gravity of about 1.02 to about 1.12 or a melting point of about 155 ° C. or higher (for example, about 208 ° C. or higher), or is hardly soluble in water, and methanol, acetone, toluene, etc. It is preferable that it is easily soluble in an organic solvent, or is solid (eg, powder, crystal, etc.) or liquid when used.

  Examples of the compound represented by the general formula (V) include 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol). And styrenated phenol (manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzylphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), and the like. Among these, from the viewpoint of improving the resolution and suppressing the decrease in sensitivity of the photosensitive resin composition due to the large content of the compound represented by the general formula (I), 4, 4 ′ -Thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) are preferred.

  The ratio with respect to the total mass of the photosensitive resin composition of the compound represented by the said general formula (V) is 0.001 mass%-10 mass%. This ratio is 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving resolution. The content is more preferably at least 0.5% by mass, particularly preferably at least 0.5% by mass, and most preferably at least 0.7% by mass. On the other hand, this ratio is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, in terms of less sensitivity reduction and improved resolution. The content is more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less.

  In the fourth embodiment, the hindered phenol may further contain a compound other than the compound represented by the general formula (V). Examples of the compounds other than the compound represented by the general formula (V) include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di- tert-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], penta Erythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethyl Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, etc. Is mentioned.

  In the fourth embodiment, the total content of all hindered phenols in the photosensitive resin composition is 0.001% by mass to 10% by mass with respect to the total mass of the photosensitive resin composition. Is preferred.

  In the fourth embodiment, the photosensitive resin composition may include a stabilizer other than the hindered phenol. Stabilizers other than hindered phenols include radical polymerization inhibitors such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p. -Cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), diphenylnitrosamine, triethylene glycol-bis (3- 3-tert-butyl-5-methyl-4-hydroxyphenylpropionate), and nitrosophenylhydroxyamine aluminum salts and the like; benzotriazoles such as 1,2,3-benzotriazole, 1-chloro-1,2,2, 3-benzotriazole, bis (N- -Ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, 1- (2-di-n-octylaminomethyl) -benzo Triazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, etc .; carboxybenzotriazoles such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1 , 2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole, 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n- Butylaminomethyl) -6-carboxylbenzotriazole 1: 1 mixture, N- (N, N-di-2- Tilhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like; and Alkylene oxide compounds having a glycidyl group, for example, neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A- Propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Epolite manufactured by Kyoeisha Chemical Co., Ltd.) Wright 4000), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

  In the fourth embodiment, the total content of all stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass. More preferably, it exists in the range of 0.05 mass%-0.7 mass%. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferable that it is 3 mass% or less.

[Other ingredients]
The photosensitive resin composition of the fourth embodiment may contain other components in addition to the components (A) to (D) described above. Examples of such other components include leuco dyes, base dyes, plasticizers, antioxidants, radical polymerization inhibitors, solvents, and the like.

[Leuco dye]
The leuco dye can be blended in the photosensitive resin composition of the fourth embodiment in order to impart suitable color developability and excellent release properties to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- ( 4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3) -Yl) -4-azaphthalide, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinov Oran, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 1,2-benz-6-diethylaminofluorane, 1 , 2-Benz-6-dibutylaminofluorane, 1,2-Benz-6-ethylisoamylaminofluorane, 2-methyl-6- (Np-tolyl-N-ethylamino) fluorane, 2- (N -Phenyl-N-methylamino) -6- (Np-tolyl-N-ethylamino) fluorane, 2- (3'-trifluoromethylanilino) -6-diethylaminofluorane, 3-chloro-6 -Cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane, 3-methoxy-4-dodecoxystylinoquinoline, etc. The Of these, leuco crystal violet is preferred.

  The content of the leuco dye in the photosensitive resin composition of the fourth embodiment is preferably 0.6% by mass to 1.6% by mass, and 0.7% by mass to 1.2% by mass. It is more preferable. By setting the use ratio of the leuco dye within this range, it is possible to realize good color developability and good peelability.

[Base dye]
Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [ 2437-29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4] , Methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], basic blue 7 [2390-60 -5] (for example, Aizen Victoria Pur e Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], diamond green and the like. It is done. Among these, at least one selected from Basic Green 1, Malachite Green Oxalate, Basic Blue 7, and Diamond Green is preferable, and Basic Green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.

  The content of the base dye in the photosensitive resin composition of the fourth embodiment is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and further Preferably, it is the range of 0.01 mass%-1.2 mass%. By setting the use ratio within this range, both good color developability and high sensitivity can be achieved.

[solvent]
The photosensitive resin composition of the fourth embodiment can be a mixture of the above components (A) to (C) and other components optionally used, or a suitable solvent for these components. You may use as a photosensitive resin composition formulation liquid comprised by adding.
Examples of the solvent used here include ketone compounds such as methyl ethyl ketone (MEK); alcohols such as ethanol, ethanol, and isopropyl alcohol;
The solvent is preferably used in such a ratio that the viscosity of the photosensitive resin composition preparation at 25 ° C. is 500 to 4,000 mPa · sec.

<Photosensitive element>
In the fourth embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer made of the above-described photosensitive resin composition is laminated on a support. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer opposite to the support.

[Support]
As the support, a transparent substrate that transmits light emitted from the exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used.
The haze of the support is preferably 5 or less.
A thinner support is advantageous in terms of image formation and economy, but it is necessary to maintain strength. Considering both of these, a support of 10 μm to 30 μm can be preferably used.

[Photosensitive resin layer]
When the photosensitive resin composition used for forming the photosensitive resin layer contains a solvent, the solvent may remain in the photosensitive resin layer, but it is preferably removed.
The thickness of the photosensitive resin layer is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.

[Protective layer]
An important characteristic of the protective layer is that the adhesive force with the photosensitive resin layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film and the like can be preferably used, and for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.
The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[Method for producing photosensitive element]
The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer, and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be employed.
For example, a photosensitive resin composition is prepared as the above-mentioned photosensitive resin composition preparation liquid, first, coated on a support using a bar coater or a roll coater and dried, and then the photosensitive resin composition is formed on the support. A photosensitive resin layer is formed. Next, if necessary, a photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin layer.

<Method for forming resist pattern>
A resist pattern can be formed on a substrate using the photosensitive element as described above.
The resist pattern formation method includes the following steps:
A laminating step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate;
An exposure step of exposing the laminated photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
Are preferably included in the order described above.

In the resist pattern forming method according to the fourth embodiment, first, a photosensitive resin layer is formed on a substrate using a laminator in a laminating step. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated to the substrate surface using a laminator.
As the substrate, an insulating substrate having a metal plate or a metal film is used. Examples of the metal material include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). These substrates may have through holes for accommodating multilayer substrates.

  Here, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces of the substrate as necessary. The heating temperature at this time is preferably 40 ° C to 160 ° C. It is preferable to perform the thermocompression bonding twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. When two or more times of crimping are performed, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer is repeatedly passed through the roll. You may crimp.

  In the laminating step, the photosensitive resin layer of the photosensitive element can be laminated on the conductor substrate via a wetting agent. This is a preferable laminating method from the viewpoint of improvement in followability and yield. As the wetting agent, one or more selected from pure water, deionized water, and electrolyzed water, and a copper chelating agent (for example, one selected from the group consisting of imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds). The above compound) is preferably included.

  Next, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. This exposure may be performed through the support without peeling off the support, or may be performed after peeling off the support, if necessary.

  By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a development process described later. The pattern exposure may be performed by either a method of exposing through a photomask or a maskless exposure method. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter.

  In maskless exposure, a photomask is not used and exposure is performed directly on the substrate by a drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the exposed photosensitive resin layer is developed. For example, the unexposed portion of the photosensitive resin layer is removed with a developer. After exposure, when there is a support on the photosensitive resin layer, it is preferable to use it for the development step after removing it.
In the development step, the unexposed area is developed and removed using a developer comprising an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferably used. The alkaline aqueous solution is selected in accordance with the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
The temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 20 ° C to 40 ° C.

  A resist pattern is obtained by the above-described steps. Depending on the case, you may perform the heating process of 100 to 300 degreeC further. It is preferable to perform this heating step from the viewpoint of further improving chemical resistance. For heating, a heating furnace of an appropriate system such as hot air, infrared rays, far infrared rays or the like can be used.

<Method for forming wiring board>
The method for forming a wiring board according to the fourth embodiment includes the following steps:
A laminating step of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate;
An exposure step of exposing the laminated photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer;
A conductor pattern forming step of etching or plating a conductive substrate on which a resist pattern is formed by development; and a peeling step of peeling the resist pattern;
Are preferably included in the order described above.

  In the conductor pattern forming step, a conductor pattern can be formed on the substrate surface (for example, a copper surface) exposed by the developing step on the substrate on which the resist pattern is formed, using a known etching method or plating method.

In the stripping step, the resist pattern is stripped and removed by bringing the substrate on which the conductor pattern is formed into contact with an appropriate stripping solution. By this step, a desired wiring board is obtained.
The stripping solution used in the stripping step is preferably an alkaline aqueous solution. As this alkaline aqueous solution, it is preferable to use 2 mass%-5 mass% NaOH aqueous solution or KOH aqueous solution, for example. A small amount of a water-soluble solvent such as alcohol may be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably 40 ° C to 70 ° C.

The photosensitive resin composition, photosensitive element, resist pattern forming method and wiring board manufacturing method according to the fourth embodiment are, for example, a printed wiring board, a lead frame, a substrate having a concavo-convex pattern, a semiconductor package, etc. The present invention can be applied extremely favorably.
In addition, about the measuring method of various parameters mentioned above, unless otherwise indicated, it measures according to the measuring method in the below-mentioned Example.

<Examples and comparative examples relating to the first embodiment>
Hereinafter, the photosensitive resin composition of the first embodiment will be specifically described in the form of examples.
(1) Measurement of raw material physical properties <Measurement of weight average molecular weight>
The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, Using KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK), polystyrene conversion Obtained as a value.

<Acid equivalent>
In this specification, an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule | numerator. Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and the acid equivalent was measured by potentiometric titration using a 0.1 mol / L sodium hydroxide aqueous solution.

(2) Preparation method and analysis of sample for evaluation <Preparation of photosensitive element>
Each component shown in Table 1, as well as the following components:
0.04 parts by weight of diamond green as a coloring substance;
As leuco dye, 0.6 parts by mass of leuco crystal violet;
As a halogen compound, 0.7 parts by mass of trimobromomethylphenylsulfone;
As a plasticizer, 2 parts by mass of p-toluenesulfonamide;
As benzotriazoles, 0.05 parts by mass of carboxyl benzotriazole;
As benzotriazoles, 0.15 parts by mass of 1- (2-di-n-octylaminomethyl) -benzotriazole;
As an antioxidant, 0.05 parts by mass of hydrogenated bisphenol A diglycidyl ether (Kyoeisha Chemical Co., Epolite 4000); and as a radical polymerization inhibitor, 0.004 parts by mass of tris (nitrosophenylhydroxyamine) aluminum are mixed. Methyl ethyl ketone (MEK) was added to prepare a photosensitive resin composition having a solid content concentration of 53% by mass. The numbers in each component column in Table 1 are amounts (parts by mass) of the respective components used for the preparation of the composition.
After uniformly coating the obtained photosensitive resin composition on a polyethylene terephthalate film (Mitsubishi Resin Co., Ltd. R310, haze value 2.1%) having a thickness of 16 μm using a bar coater as a support, The photosensitive resin composition layer having a thickness of 25 μm was formed on the support by heating and drying in a dryer adjusted to 95 ° C. for 2.5 minutes.
Next, a 19 μm thick polyethylene film (GF-18 manufactured by Tamapoly Co., Ltd.), which is a protective layer, is pasted on the surface of the photosensitive resin composition layer opposite to the support to obtain a photosensitive element. It was.

<Substrate used for evaluation>
As a substrate for evaluation of tenting properties, a substrate in which 1,008 through-holes having a diameter of 6 mm are formed on a copper-clad laminated substrate having a thickness of 1.6 mm obtained by laminating a copper foil having a thickness of 35 μm;
As a substrate for evaluation other than the tenting property, a copper clad laminated substrate having a thickness of 0.4 mm in which a copper foil having a thickness of 18 μm is laminated;
Each was used.
The substrate for evaluation of tenting properties was subjected to evaluation after being leveled by surface treatment using a jet scrub polishing machine.
The substrate for evaluation other than the tenting property was prepared by sequentially performing a surface treatment using a soft etching agent (manufactured by Hishoe Chemical Co., Ltd., CPE-900) and a surface cleaning with a 10 mass% H ₂ SO ₄ aqueous solution. After facing, it was used for evaluation.

<Laminate>
While peeling the polyethylene film of the photosensitive element obtained in each Example or Comparative Example on the substrate after the surface preparation, a roll temperature of 105 ° C. and an air pressure were applied by a hot roll laminator (Asahi Kasei Co., Ltd., AL-70). Lamination was performed under the conditions of 0.35 MPa and a laminating speed of 1.5 m / min.

<Exposure>
Using a direct drawing type exposure apparatus (Nippon Orbotech Co., Ltd., Paragon Ultra 200, main wavelength 355 nm), exposure was performed by a direct drawing type exposure method.
The exposure pattern will be described later in each evaluation item.

<Development>
After peeling off the support from the photosensitive resin composition layer after exposure, a minimum development time of a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. using an alkali developer (produced by Fuji Kiko Co., Ltd., dry film developer). The unexposed portion of the photosensitive resin composition layer was dissolved and removed by spraying twice as long as. After development, the substrate was washed with pure water for 1.5 times the development time, drained with an air knife, and then dried with warm air to obtain a substrate having a cured film for evaluation.
The minimum development time refers to the minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.

<Evaluation of sensitivity>
For the evaluation of sensitivity, a laminate substrate after 15 minutes had elapsed after the above <laminate> was used.
The laminate substrate was directly drawn and exposed with a mask pattern of 10 lines of line / space = 40 μm / 40 μm, and then developed by the method described in <Development> above. The resist top width of the obtained resist pattern was measured with an optical microscope, and the sensitivity was evaluated according to the following criteria.
Exposure amount at which resist top width is 39.0 μm is 28 mJ or less: Sensitivity “◯ (good)”
Exposure amount at which resist top width is 39.0 μm exceeds 28 mJ: sensitivity “× (defect)”
Here, the measurement location of the resist line was the fifth line from the end of the 10 lines and the position of about 5 mm from the end in the length direction, and the average value of three measurements was used as the measurement value. The line width differs between the edge and the center of the pattern due to the diffusion of the developer and the rinsing water, and the edge-side resist line tends to be thin.

  As described in the above <Evaluation of Sensitivity>, the exposure amount in the following evaluation items was the exposure amount at which the resist top width was 39.0 μm with respect to the mask pattern of line / space = 40 μm / 40 μm.

<Evaluation of resolution>
For evaluation of the resolution, a laminate substrate after 15 minutes had elapsed after the above <lamination> was used.
The laminate substrate was directly drawn and exposed with patterns of various sizes of line / space = 1/1, and then developed by the method described in <Development> above.
About the obtained pattern, the formed minimum pattern width was observed with the optical microscope, and the resolution was evaluated according to the following criteria.
When the minimum pattern width is 20 μm or less: Resolution “◯ (good)”
When the minimum pattern width exceeds 20 μm and is 24 μm or less: Resolution “Δ (possible)”
When the minimum pattern width exceeds 24 μm: Resolution “× (defect)”

<Adhesion>
For the evaluation of adhesion, a laminate substrate after 15 minutes had elapsed after the above <laminate> was used.
The laminate substrate was directly drawn and exposed to patterns of independent lines of various sizes, and then developed by the method described in <Development> above.
The obtained pattern was observed with an optical microscope, and adhesion was evaluated according to the following criteria.
When the minimum pattern width formed normally is 18 μm or less: Adhesion “◯ (good)”
When the normally formed minimum pattern width exceeds 18 μm and is 22 μm or less: Adhesiveness “△ (possible)”
Normally formed minimum pattern width exceeds 22 μm: Adhesiveness “× (defect)”
Here, the case where the line pattern is not normally formed means that the line pattern is tilted, the line pattern is meandering, or the line pattern is not present on the substrate. Say.

<Tentability>
Evaluation of the tenting property was performed by observing the laminate substrate after <Lamination> obtained using a substrate having a through hole.
The number of holes in which the photosensitive resin composition layer (tent film) formed on the through hole was torn was measured, and the ratio to all the holes (tent film breaking rate) was calculated and evaluated according to the following criteria.
When the tent film tear rate is less than 0.1%: Tenting property “「 (very good) ”
When the tent film tear rate is 0.1% or more and less than 2%: Tenting property “Good (good)”
When the tent film tear rate is 2% or more: Tenting property “× (defect)”

<Etching rate (wiring bottom width)>
For the evaluation of the etching rate (wiring bottom width), a laminate substrate after 15 minutes had elapsed after the above <laminate> was used.
A pattern having 10 lines at a line / space = 50 μm / 30 μm was directly drawn and exposed on the laminate substrate. After 15 minutes from the exposure, the support was peeled from the photosensitive resin composition layer, and a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. using an alkali developing machine (Fuji Kiko Co., Ltd., dry film developing machine). Was sprayed for twice the minimum development time to dissolve and remove unexposed portions of the photosensitive resin composition layer. After development, the film was washed with pure water for 1.5 times the development time.
Then, without drying the substrate after washing with water having this line / space pattern, the direction of the line / space of the substrate is perpendicular to the transport direction (MD) in a copper chloride etching apparatus (NLE-2000, manufactured by Tokyo Chemical Industry Co., Ltd.). At a line speed of 2.0 m / min under the conditions of a hydrochloric acid concentration of 3.2 mol / L, a cupric chloride concentration of 2.0 mol / L, an etching spray pressure of 0.2 MPa, and an etching solution temperature of 50 ° C. Etched for 55 seconds.
After the above etching, a bottom width of the wiring pattern in the MD direction of the copper line obtained by peeling off and removing the cured film on the substrate at a temperature of 50 ° C. using a NaOH aqueous solution having a concentration of 3.0% by mass as a stripping solution was measured with an optical microscope. It was measured by.
Here, the measurement place of the line of the wiring pattern was the fifth line from the end of the ten lines and the position of about 5 mm from the end in the length direction, and the average value of the three measurements was used as the measurement value. Since the influence on the resist due to the diffusion of the developer and the washing water is different between the end and the center of the pattern, the line width of the finished wiring is different and the end side wiring width tends to be narrow.

<Vertical width difference of wiring width>
For the evaluation of the vertical / horizontal difference in the wiring width, a laminate substrate after 15 minutes had elapsed after the above <laminate> was used.
An exposure pattern in which patterns of 10 lines of line / space = 50 μm / 30 μm were arranged in a tile shape in the MD direction and the TD direction was directly drawn and exposed on the laminate substrate.
After 15 minutes from the exposure, the support was peeled from the photosensitive resin composition layer, and a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. using an alkali developing machine (Fuji Kiko Co., Ltd., dry film developing machine). Was sprayed for twice the minimum development time to dissolve and remove unexposed portions of the photosensitive resin composition layer. After development, the film was washed with pure water for 1.5 times the development time.
Next, without drying the substrate after washing with water having this line / space pattern, the direction of the line / space of the substrate is perpendicular to the transport direction (MD), and a copper chloride vacuum etching apparatus (Fuji Kiko Co., Ltd., inlet width 750 mm) , Introduced into the tank length 2.6m), 14 rows in the etching solution piping MD direction (pipe interval about 18cm), 14 spray nozzles per pipe in the TD direction (slit nozzle, injection direction is parallel to the TD direction) Nozzle spacing: about 14 cm, distance to substrate: about 5 cm), no oscillation, hydrochloric acid concentration 2.85 mol / L, cupric chloride concentration 2.0 mol / L, etching spray pressure 0.3 MPa, vacuum pressure 0. Etching was performed for 71 seconds at a line speed of 2.2 m / min under conditions of 15 MPa and an etching solution temperature of 48 ° C.

About two sets of copper line patterns in the MD direction and the TD direction obtained by stripping and removing the cured film on the substrate at a temperature of 50 ° C. using a NaOH aqueous solution having a concentration of 3.0 mass% as the stripping solution after the etching. The bottom width was measured with an optical microscope.
Here, the measurement place of the line of the wiring pattern was the fifth line from the end of the ten lines, and the position of about 5 mm from the end in the length direction, and the average value of the three measurement values was used as the measurement value. Since the influence on the resist due to the diffusion of the developer and washing water differs between the edge and the center of the pattern, the line width of the finished wiring differs, and the wiring width on the end side tends to be narrow.
And the following formula:
Vertical / horizontal difference of wiring width (μm) = TD-MD
The vertical and horizontal differences in wiring width were calculated by the following criteria and evaluated according to the following criteria.
When the vertical / horizontal difference of the wiring width is 1 μm or less: wiring bottom width vertical / horizontal difference “◎ (very good)”
When the vertical / horizontal difference of the wiring width is more than 1 μm and 2 μm or less: Wiring bottom width Vertical / horizontal difference “○ (Good)”
When the vertical / horizontal difference of the wiring width exceeds 2 μm and is 4 μm or less: Wiring bottom width Vertical / horizontal difference “△ (possible)”
When the vertical / horizontal difference of the wiring width exceeds 4 μm: the wiring bottom width

Examples 1 to 23 and Comparative Examples 1 to 8
The composition of the photosensitive resin composition used in Examples and Comparative Examples is shown in Table 1.
Details of each component name described in Table 1 are shown in Table 2, respectively. The amount of each component in Table 1 is in mass parts in terms of solid content.
The results of evaluation performed using each composition are shown in Table 1.

<Examples and comparative examples relating to the second embodiment>
Hereinafter, the photosensitive resin composition of the second embodiment will be specifically described in the form of examples.
(1) Measurement of raw material physical properties <acid equivalent>
The acid equivalent means the mass of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration using an automatic titrator (for example, Hiranuma Auto titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) and using 0.1 mol / L sodium hydroxide aqueous solution. .

<Measurement of weight average molecular weight>
The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, Using KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK), polystyrene conversion Obtained as a value.

(2) Preparation method of sample for evaluation <Preparation of photosensitive element>
Each component shown in Table 3 was mixed, and methyl ethyl ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 55% by mass.
The obtained photosensitive resin composition was uniformly coated on a 16 μm thick polyethylene terephthalate film (GR-16, manufactured by Teijin DuPont Films, Ltd.) as a support using a bar coater, and then heated to 95 ° C. The photosensitive resin layer having a thickness of 33 μm was formed on the support by heating and drying for 4 minutes in a temperature-controlled dryer.
Next, a 19 μm-thick polyethylene film (GF-18 manufactured by Tamapoly Co., Ltd.), which is a protective layer, was stuck on the surface of the photosensitive resin layer opposite to the support to obtain a photosensitive element.

<Substrate used for evaluation>
As the substrate for evaluation, a 1.6 mm thick copper clad laminate on which 35 μm rolled copper foil was laminated was used to adjust the surface by wet buffalo polishing. Polishing was performed twice using Scotch Bright (registered trademark) HD # 600 manufactured by 3M Co., Ltd.

<Laminate>
While peeling the polyethylene film of the photosensitive element obtained in each Example or Comparative Example on the substrate that had been surface-conditioned and preheated to 60 ° C., the roll temperature was changed by a hot roll laminator (Asahi Kasei Co., Ltd., AL-70). Lamination was performed under the conditions of 105 ° C., an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min.

<Exposure>
Illuminance using a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm) using a Stower 41-step tablet or a mask pattern for predetermined DI exposure Under the condition of 80 mW / cm ² , the exposure was performed with an exposure amount equivalent to giving 14 steps in a Stower 41-step tablet.

<Development>
After peeling off the support from the photosensitive resin layer after exposure, an alkaline developer (produced by Fuji Kiko Co., Ltd., dry film developer) was used to remove a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. with a minimum development time of 2 The unexposed portion of the photosensitive resin layer was dissolved and removed by spraying for twice the time. After development, the substrate was washed with pure water for 1.5 times the development time, drained with an air knife, and then dried with warm air to obtain a substrate having a cured film for evaluation.
The minimum development time refers to the minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed.

<Etching>
An evaluation substrate on which a resist pattern is formed by development is subjected to a cupric chloride etching solution (cupric chloride) at 50 ° C. using a salt copper etching apparatus (manufactured by Tokyo Chemical Industry Co., Ltd., salt copper etching apparatus). The portion of the copper foil not covered with the resist pattern on the copper-clad laminate was dissolved and removed by spraying for 60 seconds with a concentration of 250 g / L and HCl concentration of 3 mol / L.

<Peeling>
The cured resist was peeled off by spraying a 3% by mass aqueous sodium hydroxide solution heated to 50 ° C. onto the evaluation substrate after etching.

(3) Evaluation method (i) Development cohesion test The photosensitive layer (resist layer) having a thickness of 50 μm and an area of 0.6 m ^{2 in} the photopolymerizable resin laminate was dissolved in 200 ml of a 1% by mass Na ₂ CO ₃ aqueous solution. Then, spraying was performed for 3 hours at a spray pressure of 0.1 MPa using a circulating spray device. Thereafter, the developer was allowed to stand for 1 day, and the generation of aggregates was observed. When a large amount of agglomerates are generated, powdery or oily substances are observed on the bottom and side surfaces of the spray device. In addition, aggregates may float in the developer. A composition having good developer cohesiveness does not generate such aggregates at all, or even if they are generated, they can be easily washed away with water. The state of occurrence of aggregates was ranked by visual observation as follows.
A (remarkably good): no aggregates are generated.
○ (Good): There is no aggregate on the bottom or side of the spray device, and a very small amount of aggregate that can be visually confirmed is observed in the developer, but it is easily washed away when washed with water.
Δ (possible): Aggregates are floating in the bottom or part of the side surface of the spray device and in the developer. Even if washed with water, not all of the aggregates can be washed away.
X (defect): Aggregates are observed in the entire spray apparatus, and aggregates are floating in the developer. It is impossible to wash away all the aggregates even with water washing, and most of them remain.

(Ii) Sensitivity test The photosensitive element obtained in each of the examples and comparative examples was laminated and exposed according to the above-described method, and each of the 14 stages in the Stofa 41-stage step tablet according to each exposure amount and the number of stages remaining after development. The exposure dose (mj / cm ² , 14 / 41ST exposure dose) corresponding to the above was examined and evaluated according to the following criteria.
Sensitivity “◯” (good): 14 / 41ST exposure amount is 25 mj / cm ² or less Sensitivity “×” (bad): 14/41 ST exposure amount exceeds 25 mj / cm ²

(Iii) Resolution test After laminating according to the above method using the photosensitive element obtained in each example and comparative example, using a sample after 15 minutes, the line / space was set to 1/1, and Direct drawing exposure was performed according to the above method. Next, development was performed according to the above-described method.
Furthermore, the minimum mask line width in which the cured resist line was normally formed was examined and evaluated according to the following criteria.
Resolution “◯” (good): When the minimum line width is less than 25 μm Resolution “△” (possible): When the minimum line width is 25 μm or more and less than 30 μm Resolution “X” (defect): Minimum line width is When it is 30μm or more

(Iv) Adhesiveness test After laminating according to said method using the photosensitive element obtained by each Example and the comparative example, using the sample which passed 15 minutes, direct drawing exposure was performed according to said method. Subsequently, it developed according to said method.
Further, when line / space = X / 200, the minimum mask line width that was normally formed was examined as X and evaluated according to the following criteria.
Adhesion “◯” (good): When the minimum line width is less than 25 μm Adhesion “△” (possible): When the minimum line width is 25 μm or more and less than 30 μm Adhesion “×” (defect): Minimum When the line width is 30 μm or more

Examples 1-6 and Comparative Examples 1-5
The composition of the photosensitive resin composition used in Examples and Comparative Examples is shown in Table 3, and details of each component name in Table 3 are shown in Table 4. The compounding amounts of the components in Table 4 are all parts by mass in terms of solid content.
Table 4 also shows the results of evaluation performed using each composition.

<Examples and comparative examples regarding the third embodiment>
Hereinafter, the photosensitive resin composition of the third embodiment will be specifically described in the form of examples.
The measurement of the physical property values of the polymer and the monomer, and the preparation methods of the samples for evaluation of Examples and Comparative Examples will be described, and then the evaluation method and the evaluation results of the obtained samples will be shown.

(1) Measurement or calculation of physical properties <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK). KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) It calculated | required as polystyrene conversion.
Furthermore, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

<Acid equivalent>
In this specification, an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule | numerator. Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and acid equivalent was measured by potentiometric titration using 0.1 mol / L sodium hydroxide aqueous solution.

(2) Preparation method of evaluation sample The evaluation samples in Examples 1 to 12 and Comparative Examples 1 to 5 were prepared as follows.

<Preparation of photosensitive resin laminate>
The components shown in the following Table 5 or 6 (however, the numbers of each component indicate the blending amount (part by mass) as a solid content) and the solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation. . The names of the components represented by abbreviations in Tables 5 and 6 are shown in Table 7 below. Using a polyethylene terephthalate film (R310-16B, manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 16 μm as a support film, uniformly apply this prepared solution using a bar coater on the surface, and in a dryer at 95 ° C. The photosensitive resin composition layer was formed by drying for 3 minutes. The dry thickness of the photosensitive resin composition layer was 30 μm.

  Next, a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) is bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated. A laminate was obtained.

<Board surface preparation>
Using scrub random R (registered trademark # 220, manufactured by Nippon Carlit Co., Ltd.), a 0.4 mm thick copper clad laminate with 35 μm rolled copper foil is jet scrubbed at a spray pressure of 0.2 MPa. Thus, an evaluation substrate was produced.

<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper-clad laminate that had been leveled and preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained by laminating at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
Exposure was performed with an exposure amount of 15 mJ / cm ^{2 using} a direct drawing type exposure apparatus (DE-1DH, manufactured by Via Mechanics, Inc., main wavelength 405 nm).

<Development>
After peeling the polyethylene terephthalate film from the photosensitive resin laminate, 1% by mass Na ₂ CO at 30 ° C. with a developing cone pressure of 0.15 MPa using a developing device manufactured by Fuji Kiko Co., Ltd. and a full cone type nozzle. _Three aqueous solutions were sprayed for a predetermined time and developed, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was measured as the minimum development time, and development was performed in twice the minimum development time to prepare a resist pattern. At that time, the washing process was performed at the same time as the developing process at a washing spray pressure of 0.15 MPa with a flat type nozzle.

(3) Sample evaluation method <Tent characteristics>
A 0.6 mm thick double-sided copper-clad laminate having through-holes with a width of 2.0 mm and a length of 15 mm was surface-treated with a jet scrub polishing machine. Lamination was performed on both surfaces by the method described in the above <Lamination>, and both surfaces were exposed on the entire surface by a direct drawing type exposure apparatus (DE-1DH, main wavelength 405 nm, manufactured by Via Mechanics Co., Ltd.). When developed by the method described in the above <Development>, the number of torn tent holes was measured, the tear rate for all tent holes was calculated, and ranked according to the following criteria.
A (best): film tear rate after development is 2% or less.
A (very good): The film tear rate after development is more than 2% and 4% or less.
○ (good): The film tear rate after development exceeds 4% and is 10% or less.
X (defect): The film tear rate after development exceeds 10%.

<Contact angle (residual short circuit defect suppression)>
In the evaluation of the contact angle (water remaining short circuit defect suppression property), after laminating by the method described in <Laminate> above, the entire surface development is performed by the method described in <Exposure>, and then in <Development> above. Development was carried out by the method described.
Samples were subjected to contact angle measurements within 30 minutes after development.
The measurement of the contact angle is based on the JIS R3257 sessile drop method, using an optical microscope contact angle meter “LSE-B100” manufactured by Nick Co., Ltd., on the cured film in an environment of a temperature of 23 ° C. and a humidity of 50 RH%. After dropping 5 μL of pure water, measurement of the contact angle was started, and the value after 120 seconds was adopted and ranked according to the following criteria. When the value of the contact angle is large, it indicates that the cured resist has high hydrophobicity, and it is possible to suppress water short-circuit failure.
A (very good): The contact angle is 35 ° or more.
○ (Good): The contact angle is 30 ° or more and less than 35 °.
Δ (allowable): The contact angle is 25 ° or more and less than 30 °.
X (defect): The contact angle is less than 25 °.

(4) Evaluation results The evaluation results of Examples 1 to 12 are shown in Table 5 below, and the evaluation results of Comparative Examples 1 to 5 are shown in Table 6 below.

<Examples and comparative examples regarding the fourth embodiment>

Hereinafter, the photosensitive resin composition of the fourth embodiment will be specifically described in the form of examples.
(1) Measurement of raw material physical properties <Measurement of weight average molecular weight>
The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK), polystyrene conversion Obtained as a value.

<Acid equivalent>
In this specification, an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule | numerator. Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and the acid equivalent was measured by potentiometric titration using a 0.1 mol / L sodium hydroxide aqueous solution.

(2) Preparation method and analysis of sample for evaluation <Preparation of photosensitive element>
Each component shown in Table 8 was mixed, and methyl ethyl ketone (MEK) was further added to prepare a photosensitive resin composition having a solid concentration of 56% by mass. The numbers in each component column in Table 8 are amounts (parts by mass) of the respective components used for preparation of the composition.
The obtained photosensitive resin composition is uniformly coated on a 16 μm-thick polyethylene terephthalate film (GR-16 manufactured by Teijin DuPont Films Ltd., haze value 2.7%) using a bar coater. Then, the photosensitive resin layer having a thickness of 33 μm was formed on the support by heating and drying for 3 minutes and 20 seconds in a drier adjusted to 95 ° C.
Next, a 19 μm-thick polyethylene film (GF-18 manufactured by Tamapoly Co., Ltd.), which is a protective layer, was stuck on the surface of the photosensitive resin layer opposite to the support to obtain a photosensitive element.

<Substrate used for evaluation>
As the substrate for evaluation, a 1.6 mm thick copper clad laminate on which 35 μm rolled copper foil was laminated was used to adjust the surface by wet buffalo polishing. Polishing was performed twice using Scotch Bright (registered trademark) HD # 600 manufactured by 3M Co., Ltd.

<Laminate>
While peeling the polyethylene film of the photosensitive element obtained in each Example or Comparative Example on the substrate after the surface preparation, a roll temperature of 105 ° C. and an air pressure were applied by a hot roll laminator (Asahi Kasei Co., Ltd., AL-70). Lamination was performed under conditions of 0.35 MPa and a lamination speed of 1.5 m / min.

<Exposure>
Using a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1AH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm), using a predetermined mask pattern for DI exposure, conditions of illuminance of 15 mW / cm ² Exposed below.
The exposure pattern and the exposure amount will be described later in each evaluation item.

<Development>
After peeling off the support from the photosensitive resin layer after exposure, a minimum development time of 0.8 mass% Na ₂ CO ₃ aqueous solution at 29 ° C. using an alkali developer (produced by Fuji Kiko Co., Ltd., dry film developer). The unexposed portion of the photosensitive resin layer was dissolved and removed by spraying twice as long as. After development, the substrate was washed with pure water for the same time as the development time, and after washing with water, the substrate was naturally dried without performing hot air drying, thereby obtaining a substrate having a cured film for evaluation.
The minimum development time is the minimum time required for the unexposed portion of the photosensitive resin layer to be completely dissolved and removed. The developer concentration or temperature, spray direction or spray amount, pressure, and oscillation It varies depending on the frequency.
Here, the minimum development time was ranked as follows:
○: Minimum development time exceeds 30 seconds.
X: Minimum development time is 30 seconds or less.

<Evaluation of sensitivity>
For the evaluation of sensitivity, a laminate substrate after 15 minutes had elapsed after the above <laminate> was used.
The laminate substrate was directly drawn and exposed with a mask pattern of 10 lines of line / space = 40 μm / 40 μm, and then developed by the method described in <Development> above. The resist top width of the obtained resist pattern was measured with an optical microscope, and the exposure amount at which the resist top width was 39 μm was evaluated as sensitivity.
Here, the measurement location of the resist line was the fifth line from the end of the 10 lines and the position of about 5 mm from the end in the length direction, and the average value of three measurements was used as the measurement value. It is important to specify the measurement position because the line width differs between the edge and the center of the pattern due to the influence of the diffusion of the developing solution and washing water, and the resist line on the edge side tends to be thin.

As described in the above <Evaluation of Sensitivity>, the exposure amount in the following evaluation items was an exposure amount at which the resist top width was 39 μm with respect to a mask pattern of line / space = 40 μm / 40 μm. Here, the sensitivity was ranked according to the exposure amount as follows:
◯: The exposure amount at which the line width is 39 μm is 28 mJ / cm ² or less.
X: The exposure amount with a 39 μm line width exceeds 28 mJ / cm ² .

<Evaluation of resolution>
For evaluation of the resolution, a laminate substrate after 15 minutes had elapsed after the above <lamination> was used.
The laminate substrate was directly drawn and exposed with patterns of various sizes of line / space = 1/1, and then developed by the method described in <Development> above.
About the obtained pattern, the formed minimum pattern width was observed with the optical microscope, and the resolution was evaluated according to the following criteria.
A: The minimum pattern width formed is 28 μm or less.
X: The minimum pattern width formed exceeds 28 μm.

<Evaluation of adhesion>
For the evaluation of adhesion, a laminate substrate after 15 minutes had elapsed after the above <laminate> was used.
The laminate substrate was directly drawn and exposed to patterns of independent lines of various sizes, and then developed by the method described in <Development> above.
The obtained pattern was observed with an optical microscope, and adhesion was evaluated according to the following criteria.
Here, the case where the line pattern is not normally formed means that the line pattern is tilted, the line pattern is meandering, or the line pattern is not present on the substrate. Say.
A: The minimum pattern width formed is 28 μm or less.
X: The minimum pattern width formed exceeds 28 μm.

<Evaluation of cohesiveness>
A photosensitive layer (resist layer) having a thickness of 50 μm and an area of 0.6 m ^{2 in} the photopolymerizable resin laminate is dissolved in 200 ml of a 1% by mass Na ₂ CO ₃ aqueous solution, and the spray pressure is 0 using a circulating spray device. Spraying was performed at 1 MPa for 3 hours. Thereafter, the developer was allowed to stand for 1 day, and the generation of aggregates was observed. When a large amount of aggregates are generated, powdery or oily substances are observed on the bottom and side surfaces of the spray device. In a composition having good developer cohesiveness, the above aggregates are not generated at all. Aggregability was ranked as follows based on the state of occurrence of aggregates:
○: Aggregates are not generated at all.
Δ: Agglomerates are seen at the bottom or part of the side of the spray device.
X: Aggregates are observed in the entire spray device.

<Evaluation of peelability>
Using a substrate that had passed 15 minutes after the treatment described in <Laminate>, a rectangular pattern of 4 cm × 6 cm was directly drawn and exposed on the laminate substrate, and developed by the method described in <Development>.
The obtained cured resist on the substrate was immersed in NaOH of 3 mass% at 50 ° C., and the time until the resist was completely peeled off from the substrate was measured and taken as the peeling time.
Here, the peelability was ranked as follows:
○: Time until complete peeling is 40 seconds or less.
X: Time until complete peeling exceeds 40 seconds.

Examples 1-7 and Comparative Examples 1-4
The composition of the photosensitive resin composition used in Examples and Comparative Examples is shown in Table 8, and the details of each component name shown in Table 8 are shown in Table 9, respectively. All the compounding amounts of the components in Table 8 are parts by mass in terms of solid content.
Table 8 also shows the results of evaluation performed using each composition.

Claims (17)

Each of the following components (A) to (C),
(A) component: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and (C) component: a photosensitive resin composition containing a photopolymerization initiator,
A photosensitive resin layer made of the photosensitive resin composition is laminated to a thickness of 25 μm on a copper clad laminate on which a copper foil having a thickness of 18 μm is laminated, and light irradiation and development in a pattern shape of line / space = 50 μm / 30 μm. A cured resist pattern is formed through the treatment, and after performing a copper etching process at 50 ° C. for 55 seconds, the bottom width of the copper line pattern obtained by removing the cured resist pattern is 38 μm or more. The photosensitive resin composition.   The photosensitive resin composition of Claim 1 whose said (A) component is a copolymer whose content rate of a (meth) acrylic acid unit is 10 mass% or more and 24 mass% or less.   The photosensitive resin composition of Claim 1 or 2 whose said (A) component is a copolymer whose content rate of a styrene unit is 32 mass% or more and 60 mass% or less.   The photosensitive resin composition as described in any one of Claims 1-3 in which the said (C) component contains an acridine compound.   The photosensitive resin composition as described in any one of Claims 1-4 in which the said (B) component contains a pentaerythritol compound.   The photosensitive resin composition as described in any one of Claims 1-5 in which the said (B) component contains a trimethylol propane compound.   The photosensitive resin composition as described in any one of Claims 1-6 in which the said (B) component contains a bisphenol A compound. Each of the following components (A) to (C),
(A) component: alkali-soluble polymer,
(B) component: a compound having an ethylenic double bond, and (C) component: a photosensitive resin composition containing a photopolymerization initiator,
The component (A) includes a copolymer having a (meth) acrylic acid unit content of 10% by mass to 24% by mass and a styrene unit content of 32% by mass or more.
The component (C) is a photosensitive resin composition containing an acridine compound.    The component (A) includes a copolymer having a (meth) acrylic acid unit content of 10% by mass to 24% by mass and a styrene unit content of 32% by mass to 60% by mass. Item 9. The photosensitive resin composition according to Item 8.   The photosensitive resin composition of Claim 8 or 9 in which the said (B) component contains a pentaerythritol compound.   The photosensitive resin composition as described in any one of Claims 8-10 in which the said (B) component contains a trimethylol propane compound.   The photosensitive resin composition as described in any one of Claims 8-11 in which the said (B) component contains a bisphenol A compound.   The photosensitive element by which the photosensitive resin layer which consists of the photosensitive resin composition as described in any one of Claims 1-12 was laminated | stacked on the support body. A laminating step of laminating the photosensitive resin layer of the photosensitive element according to claim 13 on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer, and a development step of removing an unexposed portion after the exposure with a developer,
A method of forming a resist pattern, comprising:   The method for forming a resist pattern according to claim 14, wherein the laminating step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductive substrate via a wetting agent. A laminating step of laminating the photosensitive resin composition layer of the photosensitive element according to claim 13 on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer;
A developing step of removing the unexposed portion after the exposure with a developer;
A conductor pattern forming step of etching or plating a conductive substrate on which a resist pattern is formed by the development; and a peeling step of peeling the resist pattern;
A method for producing a wiring board, comprising:   The method for manufacturing a wiring board according to claim 16, wherein the laminating step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductor substrate via a wetting agent.