JP2022027767A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can achieve both of: a satisfactory tenting property of a resist pattern; and the prevention of a short circuit failure due to the remaining water.

SOLUTION: A photosensitive resin composition contains: (A) an alkali soluble polymer; (B) an ethylenically unsaturated bond-containing compound; and (C) a photopolymerization initiator. The (A) alkali soluble polymer includes a constitutional unit of (meth)acrylic acid of 10-24 mass% and a constitutional unit of styrene of 35-90 mass% relative to the total mass of monomers constituting the (A) alkali soluble polymer, with the (B) ethylenically unsaturated bond-containing compound having a weight average molecular weight of 1,200 or more.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

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 relating to the 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>
A third embodiment of the present invention relates to a photosensitive resin composition, etc.

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

<Background Technology Related to First Embodiment of the Present Invention>
Printed wiring boards are generally manufactured by photolithography. In 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. It is a method of forming a desired wiring pattern on a substrate by removing a resist pattern on the substrate.
In this photolithography, when forming a photosensitive resin composition layer on a substrate, a method of removing a solvent after applying a composition solution; a photosensitive element formed by laminating a support and a photosensitive resin composition layer. Alternatively, a method of peeling off the support after laminating a dry film resist on a substrate is known.

Photosensitive elements are often used in the manufacture 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 the method.
For example, Patent Document 1 describes 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.

By the way, in recent years, in order to increase the density of printed wiring boards, the number of substrates is often increased. In a multilayer board, the boards are stacked one above the other and a through hole is provided for conduction between the boards. 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 subjected to spray pressure during development, washing with water, etc. It is required to have a property that does not tear (tent film tear resistance or tenting property).
In this regard, Patent Document 3 discloses a photosensitive resin composition containing a binder polymer having a small dispersity (Mw / Mn), a photopolymerizable compound, and an acridin compound. It is explained that a resist film having excellent tenting property can be formed.

<Background Technology Related to the Second Embodiment of the Present Invention>
Printed wiring boards are generally manufactured by photolithography. In photolithography, a coating film containing a layer made of a photosensitive resin composition is formed on a substrate, the coating film is exposed and developed to form a resist pattern, and then a conductor pattern is formed by etching or plating. After that, it is a method of forming a desired wiring pattern on the substrate by removing the resist pattern on the substrate.
In photolithography, a method of removing a solvent after applying a composition solution when forming a photosensitive resin layer on a substrate; a photosensitive element or a dry film resist formed by laminating a support and a photosensitive resin layer. , A method of peeling off the support after laminating on a substrate, and the like are known.

Photosensitive elements are often used in the manufacture 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 the method.
For example, Patent Document 1 describes 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, and Patent Document 4 describes a specific ethylenically double bond. Each of the photosensitive resin compositions containing an addition-polymerizable monomer having a bond is disclosed.

<Background Technology Related to Third Embodiment of the Present Invention>
Traditionally, printed wiring boards have generally been manufactured by photolithography. In the photolithography method, first, a 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 developing solution (in the case of a positive type). Next, the unexposed portion (in the case of the negative type) or the exposed portion (in the case of the positive type) is removed with a developing solution to form a resist pattern on the substrate. Further, after etching or plating to form a conductor pattern, the resist pattern is peeled off and removed from the substrate. By going through these steps, a conductor pattern is formed on the substrate.

In the photolithography method, generally, a method in which a solution of a photosensitive resin composition is applied to a substrate and dried, or a photosensitive resin laminate (a photosensitive resin laminate in which a photosensitive resin composition layer is laminated on a support) is photosensitive. Any method of laminating the sex resin composition layer on the substrate is used. The latter is often used in the manufacture of printed wiring boards.

With the recent miniaturization of wiring intervals in printed wiring boards, various characteristics have been required for dry film resists. As the wiring spacing becomes finer, the thickness of the dry film resist tends to be thinner, but tough tentability is still 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 water remaining between the patterns, which causes a water residual short circuit defect. In order to reduce this water residual short circuit defect, it is necessary to improve the hydrophobicity of the cured resist.
Various photosensitive resin compositions have been proposed in order to improve the properties of the resist (Patent Documents 5 and 6).

<Background Technology Related to the Fourth Embodiment of the Present Invention>
Printed wiring boards are generally manufactured by photolithography. In 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. It is a method of forming a desired wiring pattern on a substrate by removing a resist pattern on the substrate.

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

Photosensitive elements are often used in the manufacture of printed wiring boards. A method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for the 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 therein. Patent Document 2 describes a photosensitive resin composition containing an addition-polymerizable monomer having a specific ethylenically unsaturated bond.

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

Japanese Unexamined Patent Publication No. 2011-233769 International Publication No. 2009/0222724 Japanese Unexamined Patent Publication No. 2013-109321 Japanese Unexamined Patent Publication No. 2015-60120 International Publication No. 2015/098870 Japanese Unexamined Patent Publication No. 2014-048340

<Problems to be Solved by the First Embodiment of the Present Invention>
In recent years, wiring boards are usually manufactured by a line process in which substrates are sequentially transported while being conveyed in a certain direction. Here, for example, when a conductor pattern of a line / space pattern is formed on a substrate, the conductor lines are parallel to the transport direction of the substrate (MD direction line) and perpendicular to the substrate direction (TD direction). Line), and it may be diagonal. 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 differs between the line in the MD direction and the line in the TD direction, and a so-called vertical / horizontal difference in the wiring width occurs. In many cases, the line in the MD direction is more likely to be invaded by the etching solution than the line in the TD direction, and therefore the etching amount tends to be large and the wiring width tends to be narrow. In order to form a fine conductor pattern by the line process, it is preferable that the wiring width difference between the wiring in the MD direction and the wiring in the TD direction is reduced.

However, in the prior art represented by the above-mentioned Patent Documents 1 to 3, no study has been 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. Therefore, an object of the first embodiment of the present invention is to provide a resist material in which the vertical and horizontal differences in wiring width are suppressed when forming a fine conductor pattern by a line process.

<Problems to be Solved by the Second Embodiment of the Present Invention>
In order to form a resist pattern using the photosensitive resin composition, a developing step is performed. In this developing step, a resist pattern is formed by dissolving and removing the composition in the exposed region in the positive type composition and the composition in the exposed region in the negative type composition. In this developing step, not all of the composition in the unnecessary region is "dissolved" in the developing solution, and at least a part thereof is removed from the substrate by being dispersed in the developing solution in an insoluble state. Therefore, as the development steps are repeated, the amount of unnecessary substances in the developing solution increases, and finally, insoluble components having poor dispersibility may form aggregates. Such agglomerates adhere to and remain on the substrate to be developed later, which may cause a short circuit defect or the like.
Therefore, good developer dispersibility of the photosensitive resin composition used is strongly desired from the viewpoint of improving the product yield in the developing process and reducing the manufacturing cost of the printed wiring board.

By the way, in recent years, the demand for miniaturization and miniaturization of printed wiring boards has become more and more intense. 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, the finely divided pattern is exposed and formed by adopting a photosensitive polymerization initiator according to the exposure wavelength to be used. In itself, it's not that difficult logically. On the other hand, for example, a fine pattern exposed and formed with a size of several tens of μm or less may be peeled off from the substrate in a post-process such as a developing process, and as a result, the miniaturization of the printed wiring board is limited. ing.
Therefore, in order to form a fine printed wiring board, a photosensitive resin composition having a high adhesion of a fine pattern is required.

However, the photosensitive resin compositions described in Patent Documents 1 and 4 cannot withstand today's harsh demands 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, an object of the second embodiment of the present invention is to provide a high level of performance generally required for a photosensitive material such as resolution, and to provide novel photosensitivity with excellent development dispersibility and fine pattern adhesion. It is to provide sex materials.

<Problems to be Solved by the Third Embodiment of the Present Invention>
In Patent Document 5, from the viewpoint of the developability of the photosensitive resin composition and the resolution, adhesion and flexibility of the resist pattern, in the photosensitive resin composition, the structural unit of (meth) acrylic acid, styrene or α- A binder polymer having a structural unit of methylstyrene and a structural unit of (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 12 carbon atoms, and an ethyleneoxy group having 1 to 20 structural units and having 1 to 20 structural units. Combinations with bisphenol-type di (meth) acrylate monomers having a propyleneoxy group having 0 to 7 structural units have been studied.

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

Both Patent Documents 5 and 6 focus on a photosensitive resin composition containing a polymer having a structural unit of styrene in a specific ratio and a specific monomer, and are described in Patent Documents 5 and 6. The photosensitive resin composition used has room for improvement from the viewpoint of achieving both the tentability of the resist pattern and the ability to suppress short circuit defects in water.

Therefore, an object to be solved by the third embodiment of the present invention is to provide a photosensitive resin composition capable of achieving both a tent property of a resist pattern and a water residue short-circuit defect suppressing property.

<Problems to be Solved by the Fourth Embodiment of the Present Invention>
In recent years, wiring boards are usually manufactured by a line process in which substrates are sequentially transported while being conveyed in a certain direction. At this time, the treatment of the developer or the etching solution on the substrate is performed by spraying. In the formation of 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, when the development time is short, the developer tends to have in-plane variation on the substrate, which may cause the above-mentioned problems. Therefore, it is required to extend the development time.
Here, the development time is the time during which the substrate stays in the developing tank and is developed, and is determined as, for example, twice the minimum developing time. The minimum development time is the minimum time required for the unexposed portion of the photosensitive resin layer to be completely dissolved and removed, and is the concentration or temperature of the developer, the direction or amount of the spray, the pressure, and the frequency of oscillation. It changes depending on such things.

Here, it is considered that the dissolution reaction of the resist by development generally occurs by the diffusion rate-determining 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 developer is not sufficiently supplied over the entire surface of the substrate, and the variation in the resist line width becomes remarkably large. On the other hand, when the developing time is long, it is considered that the supply of the developing solution on the substrate becomes uniform and therefore the variation in the line width becomes small. Therefore, it is considered effective to use a photosensitive resin composition having a slow minimum development time itself from the viewpoint of suppressing variations in line width.

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

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

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

Therefore, an object to be solved by the fourth embodiment of the present invention is to provide a photosensitive resin composition capable of achieving both good resolution of a resist pattern and extension of a minimum development time.

<Means to solve 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 component of the following (A) to (C),
(A) Ingredient: Alkali-soluble polymer,
A component (B): a compound having an ethylenic double bond, and a component (C): a photosensitive resin composition containing a photopolymerization initiator.
A photosensitive resin layer made of the photosensitive resin composition is laminated with a thickness of 25 μm on a copper-clad laminate on which a copper foil having a thickness of 18 μm is laminated, and line / space = 50 μm / 30 μm pattern-shaped light irradiation and development. A cured resist pattern is formed through the treatment, and after performing a copper etching treatment 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 content of (meth) acrylic acid unit of 10% by mass or more and 24% by mass or less.
[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 or more and 60% by mass or less.
[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 component of the following (A) to (C),
(A) Ingredient: Alkali-soluble polymer,
Component (B): a compound having an ethylenic double bond, and component (C): a photosensitive resin composition containing a photopolymerization initiator.
The component (A) contains a copolymer having a content of (meth) acrylic acid unit of 10% by mass or more and 24% by mass or less and a content of styrene unit of 32% by mass or more.
The component (C) is a photosensitive resin composition containing an acridine compound.
[9]
The component (A) contains a copolymer having a content of (meth) acrylic acid unit of 10% by mass or more and 24% by mass or less and a content of styrene unit of 32% by mass or more and 60% by mass or less. 8] The photosensitive resin composition.
[10]
The photosensitive resin composition according to [8] or [9], wherein the component (B) contains a pentaerythritol compound.
[11]
The photosensitive resin composition according to any one of [8] to [10], wherein the component (B) contains a trimethylolpropane 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 composed 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 conductor substrate.
An exposure step of exposing the laminated photosensitive resin composition layer, and a developing step of removing an unexposed portion after the exposure with a developing solution.
A method for forming a resist pattern, which comprises.
[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 conductor substrate.
The exposure step of exposing the laminated photosensitive resin composition layer,
A developing step of removing an unexposed portion after exposure with a developing solution.
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the development, and a peeling step of peeling off the resist pattern.
A method for manufacturing a wiring board, which comprises.
[17]
The method for manufacturing a wiring board according to [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.

｛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 to solve 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 component of the following (A) to (C),
(A) Ingredient: Alkali-soluble polymer with an acid equivalent of 100 to 600,
A component (B): a compound having an ethylenic double bond, and a component (C): 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 the following general formula (I):

{In the formula, R is an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2 and n3 are independently integers of 0 to 30, except 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 with respect to the solid content of the photosensitive resin composition, and the component (C) is described. However, the photosensitive resin composition is characterized by containing an acridine compound.
[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 of 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 composed 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 conductor substrate.
An exposure step of exposing the laminated photosensitive resin layer, and a developing step of removing an unexposed portion after the exposure with a developing solution.
A method for forming a resist pattern, which comprises.
[7]
A laminating step of laminating the photosensitive resin layer of the photosensitive element according to [5] on a conductor substrate.
The exposure step of exposing the laminated photosensitive resin layer,
A developing step of removing an unexposed portion after exposure with a developing solution.
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the development, and a peeling step of peeling off the resist pattern.
A method for manufacturing a wiring board, which comprises.

｛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 to solve 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) Alkali-soluble polymer;
(B) Ethylene unsaturated bond-containing compound; and (C) Photopolymerization initiator;
A photosensitive resin composition containing
The (A) alkali-soluble polymer is a structural unit of (meth) acrylic acid of 10% by mass to 24% by mass and 35% by mass based on the total mass of the monomers constituting the (A) alkali-soluble polymer. The photosensitive resin composition containing up to 90% by mass of a structural unit of styrene and having the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound of 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]
Of the ethylenically unsaturated bond-containing compound (B), 40% by mass or more is the following general formula (II):

{In the equation, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and 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 sequence of repeating units of-(AO)-and-(BO)-is random. In the case of a block, either-(AO)-or-(BO)-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 the 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 the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10.
[6]
The ethylenically unsaturated bond-containing compound (B) has the following general formula (III):

{In the formula, R ₅ , R ₆ and R ₇ each independently represent 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. Independently, if m 2 + m 3 + m 4 is an integer from 0 to 40, m ₂ + m ₃ + m ₄ is 1 to 40, and m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of X's are identical to each other. May be present or different}
The photosensitive resin composition according to [1] or [2], which comprises a tri (meth) acrylate compound represented by.
[7]
The ethylenically unsaturated bond-containing compound (B) has the following general formula (IV):

{In the formula, R ₈ and R ₉ 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 is an integer of 0 to 40 independently, and s + t ≧ 1}
The photosensitive resin composition according to [1] or [2], which comprises a urethane di (meth) acrylate compound represented by.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein the alkali-soluble polymer (A) further contains a structural unit of butyl (meth) acrylate.
[9]
The photosensitive resin composition according to any one of [1] to [8], which is used for direct imaging exposure.
[10]
Laminating step of laminating a photosensitive resin layer composed of the photosensitive resin composition according to any one of [1] to [9] on a support;
An exposure step for exposing the photosensitive resin layer; and a developing step for developing the exposed photosensitive resin layer;
A method for forming a resist pattern including.
[11]
Laminating step of laminating a photosensitive resin layer composed of the photosensitive resin composition according to any one of [1] to [9] on a substrate;
An exposure step for exposing the photosensitive resin layer;
A developing 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 a substrate on which the resist pattern is formed; and a peeling step of peeling off the resist pattern;
Manufacturing method of 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 to solve 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. A fourth embodiment of the present invention is as follows.
[1]
(A) Alkali-soluble polymer;
(B) Ethylene unsaturated bond-containing compound; and (C) Photopolymerization initiator;
A photosensitive resin composition containing
The alkali-soluble polymer (A) 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 ethylene (B) ethylene. The weight average molecular weight of the sex unsaturated bond-containing compound is 900 or less.
The photosensitive resin composition.
[2]
The photosensitive resin composition according to [1], wherein the (C) photopolymerization initiator contains an acridine compound.
[3]
The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble polymer (A) contains a second copolymer having an aromatic monomer unit content of 45% by mass to 90% by mass. thing.
[4]
The ethylenically unsaturated bond-containing compound (B) has the following general formula (III):

{In the formula, R ₅ , R ₆ and R ₇ each independently represent 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. Independently, if m 2 + m 3 + m 4 is an integer of 0 to 40, m ₂ + m ₃ + m ₄ is 0 to 40, and m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of X's are identical to each other. May be present or different}
The photosensitive resin composition according to any one of [1] to [3], which comprises a tri (meth) acrylate compound represented by.
[5]
The (B) ethylenically unsaturated bond-containing compound has the following general formula (II):

{In the equation, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and 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 sequence of repeating units of-(AO)-and-(BO)-is random. In the case of a block, either-(AO)-or-(BO)-may be on the bisphenyl group side}.
The photosensitive resin composition according to any one of [1] to [4], which comprises an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by.
[6]
As hindered phenol, the following general formula (V):

{In the formula, R ⁵¹ may be substituted via a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, and a divalent linking group. A branched alkyl group represented by 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 independently hydrogenated or substituted, respectively. 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, and a divalent linking group may be used. Represents an aryl group via a cyclohexyl group or a divalent linking group. } The photosensitive resin composition according to any one of [1] to [5], further comprising the compound represented by.
[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 composed of the photosensitive resin composition according to any one of [1] to [7] is laminated on a support.
[9]
Laminating step of laminating the photosensitive resin layer of the photosensitive element according to [8] on a conductor substrate;
An exposure step for exposing the laminated photosensitive resin layer; and a developing step for developing the exposed photosensitive resin layer;
A method for forming a resist pattern, including.
[10]
Laminating step of laminating the photosensitive resin layer of the photosensitive element according to [8] on a conductor substrate;
An exposure step for exposing the laminated photosensitive resin layer;
A developing step of developing the exposed photosensitive resin layer to form a resist pattern on the conductor 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 off the resist pattern;
A method of manufacturing a wiring board, including.

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

<Effect of the second embodiment>
According to the second embodiment of the present invention, it has high levels of performance generally required for photosensitive materials such as sensitivity and resolution, and is excellent in both development dispersibility and fine pattern adhesion. A new photosensitive material is provided.

<Effect of the third embodiment>
According to the third embodiment of the present invention, there is provided a photosensitive resin composition capable of achieving both a tent property of a resist pattern and a water residue short-circuit defect suppressing property.

<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 wiring board using the photosensitive resin composition. A method of forming is provided.

<First embodiment>
Hereinafter, an embodiment 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 comprises the following components (A) to (C).
(A) Ingredient: Alkali-soluble polymer,
Component (B): Compound having an ethylenic double bond, and Component (C): Photopolymerization initiator,
Contains.

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

The copolymerization ratio of the (meth) acrylic acid unit in the component (A) is preferably 10% by mass to 24% by mass, preferably 15% by mass to 23% by mass, based on the total mass of all the monomer units. It is more preferable to have. The content ratio of the (meth) acrylic acid unit in this range means that the etching rate at the time of forming the conductor pattern 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 and horizontal differences.

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, and polar monomers. Examples thereof include crosslinkable monomers.
Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, vinylnaphthalene and the like. Of these, styrene is preferable.

The (meth) acrylic acid alkyl ester is a concept that includes both chain alkyl esters and cyclic alkyl esters, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth). ) 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 mentioned. ..

Examples of the (meth) acrylic acid aralkyl ester 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 thereof include 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadien, 3-butyl-1,3-octadien, and the like.
Examples of the polar monomer include, for example.
Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
Amino group-containing monomers such as 2-aminoethyl methacrylate;
Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
Cyan 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;
And so on.

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 the styrene unit in the component (A) is preferably 32% by mass or more, more preferably 35% by mass or more, based on the total mass of all the monomer units. The copolymerization ratio of the styrene unit 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 the monomer units. It is preferable to set the copolymerization ratio of styrene, which has high hydrophobicity and is difficult to be compatible with the developer and the developing water, from the viewpoint of suppressing the vertical / horizontal difference in the wiring width.

The weight average molecular weight of the component (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is 5,000 to 1,000,000. It 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 developing time at the time of 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 the same for each content component based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified). (There is), 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 40% by mass to 60% by mass is further preferable. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, and 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 having an 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 is based on the total solid content of the photosensitive resin composition. It 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 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 is based on the total solid content of the photosensitive resin composition. It may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 27 / 99.19 × 100% by mass or less, and 20% by mass. It may be less than or equal to%.

[Component (B): compound having an ethylenic double bond]
The component (B) may have one or more ethylenic double bonds. It is preferable to use a compound having two or more ethylenic double bonds.
Examples of the compound (B) having two ethylenic double bonds include bisphenol A compounds, particularly di (meth) of polyalkylene glycols in which an average of 2 mol to 15 mol of alkylene oxide is added to both ends of bisphenol A. ) Acrylate or the like is preferably used.
Examples of the compound (B) having three ethylenic double bonds include a trimethylolpropane compound, particularly a triol (meth) of a polyalkylenetriol obtained by adding an average of 3 to 25 mol of alkylene oxide to trimethylolpropane. ) Acrylate or the like is preferably used.
Further, examples of the compound (B) having four ethylenic double bonds include pentaerythritol compounds, particularly tetra (meth) acrylates of polyols obtained by adding an average of 4 mol to 35 mol of alkylene oxide to pentaerythritol. It is preferably used.
Examples of these commercially available products include "BPE-500", "A-TMPT-3EO", "A-9300-1CL", etc. (all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.):
"Aronix M-327" and the like (manufactured by Toagosei Co., Ltd.) and the like 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 curing defects and delay in development time, and 70% by mass or less from the viewpoint of suppressing cold flow and peeling delay of the cured resist. Is preferable.

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 this 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 viewpoint of suppressing the etching rate when forming the conductor pattern and suppressing the vertical and horizontal difference in the wiring width.
The proportion of such a high molecular weight compound in the component (B) is preferably 20% by mass or more, and more preferably 20 to 50% by mass.

Here, the 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 each monomer has a unique value.
When a monomer having a small DD value is used in the photosensitive resin composition, the film after photocuring tends to be flexible.
(B) When the component is composed of a plurality of types, the DD value of each ethylenically unsaturated bond-containing compound and the weighted average of the blending ratios are considered as the DD value of the composition.
From the viewpoint of suppressing the vertical / horizontal difference in the wiring width and improving the tenting property, the range of the DD value of the preferable composition is 0.10 to 0.13. More preferably, it is 0.10 to 0.125.

[Component (C): Photopolymerization Initiator]
The component (C) is a component that generates a radical capable of initiating the polymerization of the component (B) by irradiation with light.
Examples of such the component (C) include aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzyl compounds, hexaarylbisimidazole compounds, aclysine compounds and the like.
Of these, it is preferable to use an acridine compound from the viewpoint of high resolution and good tenting property.
The content of the acridin 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, still more preferably 0.2% by mass, and 0. 3% by mass is more preferable, and 0.4% by 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. It is more preferably 6.6% by mass or less. Within the above range, it becomes possible to provide a resist material that suppresses the vertical and horizontal difference 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, and 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'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4 , 4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrakis -(3-Methenylphenyl) -imidazolyl dimer, 2,2'-bis- (2,5-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyldi. Quantum, 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'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,5-) Trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4, 4', 5,5'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4', 5,5' -Tetraxyl- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxy) Phenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyldi Quantitative, 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)- 4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and the like can be mentioned.

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, and it is further preferably in the range of 0.3% by mass to 1.7% by mass, and particularly preferably 0.4% by mass to 1.6% by mass. It is preferable to set the content of the component (C) in such a range from the viewpoint of obtaining good light sensitivity and peeling characteristics.

The component (C) can further contain a sensitizer from the viewpoint of improving sensitivity and resolution. Examples of such a sensitizer 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, and tris ( 2,3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound, etc.;
Each can be listed.

Examples of the other sensitizers include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, and 1-chloroanthraquinone. , 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and other quinone compounds;
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 benzyl dimethyl 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, preferably 0.05% by mass to 3% from the viewpoint of the light sensitivity of the composition and the peelability of the resist cured film. The mass% is more preferable, and 0.1% by mass to 2% by mass is further preferable.
In the photosensitive resin composition of the first embodiment, an acridine compound and an N-aryl amino acid may be used as the component (C), and these may be used in combination within the above-mentioned usage ratio. It is preferable from the viewpoint of suppressing the etching rate at the time of forming the wiring and suppressing the vertical and 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 development property and excellent peeling property 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-methylindol-3) -Il) -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-xylidinofluorane, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3,6-dimethoxyflu Olan, 3,6-di-n-butoxyfluolane, 1,2-Benz-6-diethylaminofluorane, 1,2-Benz-6-dibutylaminofluoran, 1,2-Benz-6-ethylisoamylamino Fluoran, 2-Methyl-6- (N-p-Trill-N-Ethylamino) Fluoran, 2- (N-Phenyl-N-Methylamino) -6- (N-p-Trill-N-Ethylamino) Phenyl, 2- (3'-trifuromethylanilino) -6-diethylaminofluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane, 3-methoxy-4- Dodecoxystylinoquinoline and the like can be mentioned. 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, preferably 0.7% by mass to 1.2% by mass. Is more preferable. By setting the usage ratio of the leuco dye in this range, good color development and good peelability can be realized.

[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], Fuxin [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 Crystal Pure 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. Of these, one or more 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. It is preferably in the range of 0.01% by mass to 1.2% by mass. By setting the usage ratio within this range, both good color development and high sensitivity can be achieved at the same time.

[solvent]
The photosensitive resin composition of the first embodiment can be a mixture of the above-mentioned components (A) to (C) and other components arbitrarily used, or a solvent suitable for these components. May be used as a photosensitive resin composition preparation solution prepared by adding the above.
Examples of the solvent used here include, for example.
Ketone compounds such as methyl ethyl ketone (MEK);
Alcohols such as ethanol, ethanol, and isopropyl alcohol;
And so on.
The ratio of the solvent used is preferably such that the viscosity of the photosensitive resin composition preparation solution 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-mentioned photosensitive resin composition is laminated on a support. If necessary, a protective layer may be provided on the surface opposite to the support of the photosensitive resin layer.

[Support]
As the support, a transparent base material that transmits light 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, and a polymethyl methacrylate copolymer film. Examples thereof include a polystyrene film, a polyvinylidene nitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films can also be used if necessary.
The haze of the support is preferably 5 or less.
The thinner the support, the more advantageous in terms of image formation and economy, but it is necessary to maintain the 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, it is preferable that the solvent is 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, and more preferably 7 μm to 60 μm. The thinner the thickness, the better the resolution, and the thicker the thickness, the better 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 property of the protective layer is that the adhesive force with the photosensitive resin composition layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin composition layer, and the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film or 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.

[Manufacturing method of photosensitive element]
The photosensitive element can be manufactured 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 adopted.
For example, the photosensitive resin composition is prepared as the above-mentioned photosensitive resin composition preparation solution, first coated on the support using a bar coater or a roll coater and dried, and then the photosensitive resin composition is applied on the support. A photosensitive resin composition layer composed of is formed. Then, if necessary, the photosensitive element can be manufactured by laminating a protective layer on the formed photosensitive resin composition layer.

<Method of forming resist pattern>
A resist pattern can be formed on the substrate by using the photosensitive element as described above.
The method of forming the resist pattern is
Laminating process of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer, and a developing step of removing an unexposed portion after the exposure with a developing solution.
Are preferably included in the order described above.
Further, it is preferable that the laminating step is 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 electrolytic water, and one selected from the group consisting of a copper chelating agent (for example, an imidazole compound, a triazole compound, a pyridine compound, and a pyrazole compound). It is preferable to include the above compounds).

In the method for forming a resist pattern according to the first embodiment, first, in the laminating step, a photosensitive resin composition 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 composition layer is heat-bonded to the substrate surface using a laminator and laminated.
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, indium tin oxide (ITO) and the like. These boards may have through holes to accommodate multi-layer boards.

Here, the photosensitive resin composition layer may be laminated on only one side of the substrate surface, or may be laminated on both sides of the substrate if necessary. The heating temperature at this time is preferably 40 ° C to 160 ° C. It is preferable to perform heat crimping twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. When 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 to form a 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 the support, or may be performed after the support is peeled off if necessary.

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

In maskless exposure, a photomask is not used, and the exposure is performed directly on the substrate by a drawing device. 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 composition layer is removed with a developing solution. If there is a support on the photosensitive resin composition layer after exposure, it is preferable to remove the support before subjecting it to the developing step.
In the developing step, an unexposed portion is developed and removed using a developing solution composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, it is preferable to use an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ , or the like. The alkaline aqueous solution is selected according to 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. A surfactant, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
The temperature of the developer in the developing step is preferably kept constant in the range of 20 ° C to 40 ° C.

A resist pattern is obtained by the above steps. In some cases, a heating step of 100 ° C. to 300 ° C. may be further performed. It is preferable to carry out this heating step from the viewpoint of further improving chemical resistance. For heating, an appropriate heating furnace such as hot air, infrared rays, far infrared rays or the like can be used.

<How to form a wiring board>
The method for forming the wiring board according to the first embodiment is as follows.
Laminating process of laminating the photosensitive resin composition layer of the photosensitive element on the conductor substrate,
The exposure step of exposing the laminated photosensitive resin composition layer,
A developing step of removing an unexposed portion after exposure with a developing solution.
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the development, and a peeling step of peeling off the resist pattern.
Are preferably included in the order described above.
Further, it is preferable that the laminating step is 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 electrolytic water, and one selected from the group consisting of a copper chelating agent (for example, an imidazole compound, a triazole compound, a pyridine compound, and a pyrazole compound). It is preferable to include the above compounds).

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

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

Generally, in the formation of a conductor pattern by etching, the etching time having a desired wiring width can be adjusted by, for example, adjusting the transport speed of the etching line regardless of the etching speed. However, if the etching speed is too fast, the transport speed becomes too fast, which may cause a problem that the etching time cannot be set practically.
Moreover, in recent years, the production of wiring boards is usually carried out by a line process in which the substrates are sequentially transported while being transported in a certain direction, and the conductor lines are parallel to the transport direction of the substrates. There are cases (lines in the MD direction), cases where it is vertical (lines in the TD direction), and cases where it is diagonal. Especially when the etching speed is high, the vertical-horizontal difference in the wiring width tends to be more remarkable.

As a result of diligent studies, the present inventors have suppressed the vertical and horizontal differences in the wiring width when forming a fine conductor pattern by the line process when the photosensitive resin composition forming the cured resist pattern has specific physical characteristics. We have found that we can provide resist materials.
That is, in the photosensitive resin composition of the first embodiment, a photosensitive resin layer made of the photosensitive resin composition is laminated with a thickness of 25 μm on a copper-clad laminate in which a copper foil having a thickness of 18 μm is laminated. , Line / space = 50 μm / 30 μm pattern light irradiation and development treatment to form a cured resist pattern, copper etching treatment at 50 ° C. for 55 seconds, and then removing the cured resist pattern. The copper line pattern has a feature that the bottom width is 38 μm or more (preferably 38 μm to 50 μm, more preferably 40 μm to 45 μm).

By the way, the resist pattern causes swelling / shrinkage in each of the development, the washing step, and the etching step, and the swelling / shrinking in the washing step is particularly large. It is considered that the swelling / contraction of the resist pattern reduces 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 developing, washing, and etching steps, and etching proceeds at the interface between the resist pattern and the wiring. It is difficult to do so, and it is thought that the vertical and horizontal differences in wiring width can be suppressed.

In the first embodiment, the specific photosensitive resin composition is distinguished by focusing on the characteristics (the bottom width of the conductor line width is above a certain level) when a specific analysis method (specific etching conditions) is used. That is the means for achieving the effect of the invention.
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 method for forming the wiring board of the first embodiment as described above can make the vertical-horizontal difference of the wiring width of the conductor pattern extremely small. The vertical-horizontal difference in the wiring width is 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, and is an amount represented by TD-MD.
The absolute value of the vertical-horizontal difference of the wiring width in the conductor pattern formed by the method for forming the conductor pattern of the first embodiment is preferably 0 μm to 5 μm, and more preferably 0 μm to 3 μm.

The method for forming the photosensitive resin composition, the photosensitive element, and the wiring board in the first embodiment is extremely suitable for manufacturing, for example, a printed wiring board, a lead frame, a base material having an uneven pattern, a semiconductor package, and the like. Can be applied to.
Unless otherwise specified, the measurement methods for the various parameters described above are measured according to the measurement methods in the examples described later.

<Second embodiment>
Hereinafter, an embodiment 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 comprises the following components (A) to (C).
(A) Ingredient: Alkali-soluble polymer with an acid equivalent of 100 to 600,
Component (B): Compound having an ethylenic double bond, and Component (C): Photopolymerization initiator,
Contains.

[(A) component: alkali-soluble polymer]
The component (A) contains a copolymer having an acid equivalent of 100 to 600 (preferably 200 to 500, more preferably 250 to 450) and containing 50% by mass or more of styrene units. Here, in the present specification, the styrene unit means substituted or unsubstituted styrene. The substituent is not particularly limited, and examples thereof include an alkyl group, a halogen group, and a hydroxyl group.

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, pentene acid, unsaturated dicarboxylic acid anhydride, hydroxystyrene and the like. 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 preferable.

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, and polar monomers. Examples thereof include crosslinkable monomers.

Examples of the unsaturated aromatic compound include vinyl naphthalene and the like.
The (meth) acrylic acid alkyl ester is a concept that includes both chain alkyl esters and cyclic alkyl esters, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth). ) 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 mentioned. ..

Examples of the (meth) acrylic acid aralkyl ester 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-Pentidiene, 1,3-Hexadiene, 4,5-diethyl-1,3-octadien, 3-butyl-1,3-octadien, etc.;
Each can be listed.

Examples of the polar monomer include, for example.
Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol;
Amino group-containing monomers such as 2-aminoethyl methacrylate;
Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
Cyan 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;
And so on.

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 component (A) contains a copolymer 1 containing 50% by mass or more of styrene units. The amount of the styrene unit in the copolymer 1 is preferably 50% by mass to 80% by mass, more preferably 51% by mass to 70% by mass.

The component (A) in the second embodiment may be composed of only 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, 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, which does not correspond to the copolymer 1 (copolymer 2), is suitable.

The weight average molecular weight of the component (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) may be 5,000 to 1,000,000. It 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 developing time at the time of forming the resist pattern to the operating state of the line process to be used. The dispersity 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 the same for each content component based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified). (There is), 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 40% by mass to 60% by mass is further preferable. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, and 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 the compound (B1) that is essentially contained, and has the following general formula (I):

{In the formula, R is an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1, n2 and n3 are independently integers of 0 to 30, except that n1 + n2 + n3 ≧ 6. Meet the conditions. } Includes compounds represented by.

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

In the formula (I), the value of n1 + n2 + n3 is preferably more than 9 and preferably 20 or less, and more preferably 15 or more and 20 or less, from the viewpoint of improving the development dispersibility.

In the formula (I), from the viewpoint of improving the develop dispersibility, it is preferable that at least one R is a hydrogen atom, and it is more preferable that all Rs are hydrogen atoms.

Further, in the formula (I), from the viewpoint of achieving both development dispersibility and adhesion, 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.

The compound represented by the formula (I) is synthesized by a known method, and for example, 3 mol (meth) acrylic is added to an adduct obtained by adding 6 equivalents or more of ethylene oxide to trimethylolpropane. It can be obtained by adding an acid or exchanging an ester.

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

The component (B) in the second embodiment may be composed of only 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 10% by mass or more, based on the total mass of the mixture. It is 10% by mass to 50% by mass, more preferably 15% by mass to 35% by 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 by mass% to 30% by mass, more preferably 6% by mass to 20% by mass.
Here, by containing the alkali-soluble polymer having a specific acid equivalent and a specific amount of styrene unit, the component (B1), and aclysine, both the development dispersibility and the adhesion of the fine pattern are both. Although the mechanism to realize the excellent photosensitive resin composition is not clear, the interaction between the styrene unit and the aclysine component (by π electron stacking) and the interaction between the acid monomer and the (B1) component (hydrogen bond). However, it is presumed that good expression and improvement of compatibility as a whole contribute to the above-mentioned 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, still 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. It is ~ 15% by mass.

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

The component (B) is the following component:
A bisphenol A compound, for example, a di (meth) acrylate of a polyalkylene glycol having an average of 2 mol to 15 mol of alkylene oxide added to both ends of bisphenol A;
Compounds with three ethylenic double bonds (excluding B1), such as tri (meth) acrylates of polyalkylene triol with an average of 3 to 25 mol of alkylene oxide added to trimethylolpropane;
May include.

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 curing defects and delay in development time, and 70% by mass or less from the viewpoint of suppressing the generation of agglomerates in the developing solution. Is preferable.

[Component (C): Photopolymerization Initiator]
The component (C) is a component that generates a radical capable of initiating the polymerization of the component (B) by irradiation with light.
In the second embodiment, an acridine compound can be used as the (B) photopolymerization initiator. Further, the acridine compound and other photopolymerization initiator may be used in combination. The acridine compound is preferably used to improve 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) acridine, 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, Examples thereof include 9- (3-pyridyl) acridine and 9- (4-pyridyl) acridine.

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'- Diphenyl imidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenyl imidazolyl 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'-Tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-Tetrakiss- (3-Methenylphenyl) -imidazolyl dimer, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -imidazolyl dimer Body, 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'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5 , 5'-Tetrakiss- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4', 5,5'-tetrakis- ( 3-Methenyl Phenyl) -imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl Dimeric, 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'-Tetrakiss- (3-methoxyfe) Nyl) -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 , 5-Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2, 4,5-Triarylimidazole dimer (excluding 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-monohornophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1;
2-Ethyl anthraquinone, phenanthrenquinone, 2-tert-butyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenylanthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, Kinone 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, benzoin phenyl ether;
Benzyl derivatives such as benzylmethyl ketal;
Examples thereof include N-phenylglycine derivatives, coumarin compounds, and 4,4'-bis (diethylamino) benzophenones.

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, 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 content of the entire component (C) including the aclysine compound) may be 0.1% by mass to 2% by mass. It is preferably 0.2% by mass to 1.8% by mass, more preferably 0.3% by mass to 1.7% by mass, and more preferably 0.4% by mass to 1.6% by mass. It is particularly preferable to have.

The component (C) can further contain a sensitizer from the viewpoint of improving sensitivity and resolution. Examples of such a sensitizer 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, and tris ( 2,3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound, etc.;
Each can be listed.

Examples of the above other sensitizers include, for example.
2-Ethlanthraquinone, Octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10- Kinone 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 benzyl dimethyl ketal, benzyl diethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Compound;
And so on.

The content of the sensitizer in the photosensitive resin composition of the second embodiment is preferably 0.01% by mass to 5% by mass, preferably 0, from the viewpoint of the photosensitivity of the composition and the peelability of the resist cured film. It is more preferably 0.05% by mass to 3% by mass, and even more preferably 0.1% by mass to 2% by mass.

[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 the stabilizer include a radical polymerization inhibitor, a benzotriazole compound, a carboxybenzotriazole compound and the like;
Each can be listed.

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

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

<Other coloring substances>
Examples of other coloring substances include fuchsin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green (MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), and the like. Examples include Basic Blue 20, Diamond Green (Aisen (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 this content to 0.001% by mass or more is preferable from the viewpoint of improving handleability, while adjusting this content to 1% by mass or less maintains storage stability. Preferred from the viewpoint.

<Halogen compound>
It is a preferable embodiment to use the leuco dye and the following halogen compound in combination in the photosensitive resin composition 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, and tris (2). , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound and the like. Particularly, tribromomethylphenyl sulfone is 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, and 2,2'-methylenebis. (4-Methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosoamine and the like can be mentioned.

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, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

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, and more preferably 0.05% by mass to 1%. It is 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 is preferable. It is preferable from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.

<Plasticizer>
The photosensitive resin composition may contain a plasticizer, if necessary. Examples of the plasticizer include phthalic acid esters such as diethylphthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, and tri-n-propyl acetyl citrate. , Tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polyproprenene 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 is preferable. It is preferable 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); methanol, ethanol, alcohols typified by isopropanol, and the like. 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 becomes 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-mentioned photosensitive resin composition is laminated on a support. If necessary, the photosensitive element may have a protective layer on the surface opposite to the support of the photosensitive resin layer.

[Support]
As the support, a transparent base material that transmits light emitted from an exposure light source is preferable. Examples of the support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, and polystyrene film. Examples thereof include polyvinylidene nitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. As these films, stretched films can also be used if necessary.
The haze of the support is preferably 5 or less.
The thinner the support, the more advantageous in terms of image formation and economy, but it is necessary to maintain the 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, and more preferably 7 μm to 60 μm. The thinner the thickness, the better the resolution, and the thicker the thickness, the better 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 property 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 the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film or the like can be preferably used, and for example, a film having excellent peelability disclosed in 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.

[Manufacturing method of photosensitive element]
The photosensitive element can be manufactured 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 adopted.
For example, a solvent is added to the photosensitive resin composition and mixed to prepare a mixed solution, which is further applied onto the support using a bar coater or a roll coater and dried, and the photosensitive resin composition is applied onto the support. A photosensitive resin layer composed of is formed. Then, if necessary, the photosensitive element can be manufactured by laminating a protective layer on the formed photosensitive resin layer.

<Method of forming resist pattern>
A resist pattern can be formed on the substrate by using the photosensitive element as described above.
The method of forming the resist pattern is
Laminating process 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 developing step of removing an unexposed portion after the exposure with a developing solution.
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 electrolytic water, and one selected from the group consisting of a copper chelating agent (for example, an imidazole compound, a triazole compound, a pyridine compound, and a pyrazole compound). It is preferable to include the above compounds).

In the resist pattern forming method of the second embodiment, first, in the laminating step, a photosensitive resin layer is formed on the substrate by 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-bonded to the substrate surface using a laminator and laminated.

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, indium tin oxide (ITO) and the like. These boards may have through holes to accommodate multi-layer boards.

The photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides of the substrate if necessary. The heating temperature at the time of laminating is preferably 40 ° C to 160 ° C. It is preferable to perform heat crimping twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. When 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 layer is repeatedly passed through the rolls several times. It may be crimped.

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 the support, or may be performed after the support is peeled off if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after passing through the development step described later. The patterned exposure may be performed by either a method of exposing through a photomask or a maskless exposure method. When exposing through a photomask, the amount of exposure is determined by the illuminance of the light source and the exposure time. The exposure amount may be measured using a photometer.

In maskless exposure, a photomask is not used, and the exposure is performed directly on the substrate with a drawing device. 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 developing solution. If there is a support on the photosensitive resin layer after exposure, it is preferable to remove the support before subjecting it to the developing step.
In the developing step, an unexposed portion is developed and removed using a developing solution composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, it is preferable to use an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ , or the like. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin 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. A surfactant, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
The temperature of the developer in the developing step is preferably kept constant in the range of 20 ° C to 40 ° C.

A resist pattern is obtained by the above steps. In some cases, a heating step of 100 ° C. to 300 ° C. may be further performed. Implementation of this heating step is suitable from the viewpoint of further improving chemical resistance. For heating, an appropriate heating furnace such as hot air, infrared rays, far infrared rays or the like can be used.

<How to form a wiring board>
The method for forming the wiring board according to the second embodiment is as follows.
Laminating process of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate,
The exposure step of exposing the laminated photosensitive resin layer,
A developing step of removing an unexposed portion after exposure with a developing solution.
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the development, and a peeling step of peeling off 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 electrolytic water, and one selected from the group consisting of a copper chelating agent (for example, an imidazole compound, a triazole compound, a pyridine compound, and a pyrazole compound). It is preferable to include the above compounds).

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

In the peeling step, the resist pattern is peeled off by bringing the substrate on which the conductor pattern is formed into contact with an appropriate peeling liquid. By this step, a desired wiring board is obtained.

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

The method for forming the photosensitive resin composition, the photosensitive element, and the wiring board in the second embodiment is extremely suitable for manufacturing, for example, a printed wiring board, a lead frame, a base material having an uneven pattern, a semiconductor package, and the like. Can be applied to.
Unless otherwise specified, the measurement methods for the various parameters described above are measured according to the measurement methods in the examples described later.

<Third embodiment>
Hereinafter, an embodiment 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 of the present invention, 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) additive.

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

(A) Alkali-soluble polymer (A) The alkali-soluble polymer is a polymer that can be dissolved in an alkaline substance. In the third embodiment, the (A) alkali-soluble polymer is the whole of the monomers constituting the (A) alkali-soluble polymer from the viewpoint of achieving both the tentability of the resist pattern and the ability to suppress short-term defects in water. It is preferable to contain 10% by mass to 24% by mass of the structural unit of (meth) acrylic acid and 35% by mass to 90% by mass of the structural unit of styrene based on the mass.

The content of the structural unit of (meth) acrylic acid in the (A) alkali-soluble polymer is said to suppress the short-circuit defect of residual water based on the total mass of the monomers constituting the (A) alkali-soluble polymer. From the viewpoint, it is preferably 24% by mass or less, and from the viewpoint of ensuring alkali developability and alkali peeling property, it is preferably 10% by mass or more. 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 water residual short defect has a strong correlation with the hydrophobicity of the cured resist, and it is possible to suppress the water residual short defect by increasing the hydrophobicity of the resist, that is, the water contact angle.

(A) Acid equivalent of (A) alkali-soluble polymer in relation to the content of structural units of (meth) acrylic acid in the alkali-soluble polymer (when the component (A) contains a plurality of copolymers. The acid equivalent of the entire 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 preferably 900 or less from the viewpoint of developability and peelability. The acid equivalent of the alkali-soluble polymer (A) is more preferably 250 to 600, and even more preferably 350 to 500. The acid equivalent refers to the mass of a linear polymer having 1 equivalent of a carboxyl group therein.

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 monomers constituting the (A) alkali-soluble polymer. It is preferable that the content is 35% by mass or more, preferably from the viewpoint of resolution and ability to suppress short-circuit defects in water. 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 peeling time delay, and the lower limit is resolution and water. From the viewpoint of suppressing the remaining short circuit defect, it is more preferably 36% by mass, 38% by mass, 40% by mass, or 42% by mass.

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

The content of the structural unit of butyl (meth) acrylate in the (A) alkali-soluble polymer is a single mass constituting the (A) alkali-soluble polymer from the viewpoint of achieving both tentability and water residual short-circuit defect suppression 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.

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

The (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 later and /. Alternatively, it may contain a copolymer obtained by copolymerizing a copolymerization component composed of one or more of the second monomers described later.

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, maleic acid semi-ester and the like.

The second monomer is a monomer (excluding styrene) that is non-acidic and has 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. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. 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 tentability of the resist pattern, and n-butyl (n-butyl (meth) acrylate is preferable from the viewpoint of tentability. Meta) Acrylate is more preferable, and a polymerizable styrene derivative is preferable from the viewpoint of improving the resolution and the ability to suppress short-term defects in water.
Examples of the polymerizable styrene derivative include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimmer and the like.

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

The weight average molecular weight of the alkali-soluble polymer (A) (when the component (A) contains a plurality 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 a uniform thickness of the dry film resist and obtaining resistance to a developing solution, and the developability of the dry film resist is improved. From the viewpoint of maintenance, it is preferably 500,000 or less. The weight average molecular weight of the alkali-soluble polymer (A) is more preferably 10,000 to 200,000, further preferably 20,000 to 100,000. The dispersity of the alkali-soluble polymer (A) 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, each content component is contained. It is the same in the above), preferably in the range of 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 40% by mass to 60% by mass. The content of the alkali-soluble polymer (A) 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 the performance as a resist material. From the viewpoint of sufficient exertion, it is preferably 90% by mass or less.

(B) Ethylene unsaturated bond-containing compound (B) The ethylenically unsaturated bond-containing compound is a compound having a polymerizable property 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, (B) ethylenically unsaturated from the viewpoint of ensuring the tentability of the resist pattern when (A) an alkali-soluble polymer and (B) an ethylenically unsaturated bond-containing compound are used in combination. 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 (B) the ethylenically unsaturated bond-containing compound means that (B) when the ethylenically unsaturated bond-containing compound is a single species, the single species of the ethylenically unsaturated bond-containing compound is used. It means the weight average molecular weight derived from the structural formula, and (B) when the ethylenically unsaturated bond-containing compound is composed of a plurality of kinds, it means the weight average molecular weight and the weighted average of the compounding ratio of each ethylenically unsaturated bond-containing compound. 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, and the resist pattern has a weight average molecular weight of 1,300 or more, more preferably 1,400 or more, from the viewpoint of further improving the tentability of the resist pattern. From the viewpoint of resolution and peelability, it is more preferably 5,000 or less, still more 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 is the following (b ₁ ) to (b ₅ ) :.
(B ₁ ) The following general formula (I):

{In the formula, 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. }
Ethylene glycol di (meth) acrylate compound represented by;
(B ₂ ) The following general formula (II):

{In the equation, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and 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 sequence of repeating units of-(AO)-and-(BO)-is random. In the case of a block, either − (A—O) − or − (BO) − 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):

{In the formula, R ₅ to R ₇ independently represent 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 independently represent each. , 0-40, where m ₂ + m ₃ + m ₄ is 1-40, and m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of Xs are identical to each other. Or may be different}
Tri (meth) acrylate compound represented by;
(B ₄ ) The following general formula (IV):

{In the formula, R ₈ and R ₉ 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 independently integers from 0 to 40, and s + t ≧ 1}
Urethane di (meth) acrylate compound represented by; and (b ₅ ) an addition-polymerizable monomer other than the above (b ₁ ) to (b ₄ );
It may contain at least one selected from the group consisting of.

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

In the general formula (I), m ₁ is preferably 2 or more from the viewpoint of peeling time and peeling piece size, and preferably 40 or less from the viewpoint of resolution, plating resistance and etching resistance. m ₁ is more preferably 4 to 20, 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 m ₁ = 14 polyethylene glycol di (meth) acrylate is preferred.

(B) The ethylenically unsaturated bond-containing compound contains (b ₂ ) an alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II) from the viewpoint of resolution and tentability. Is preferable. 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 heteroatom and / or a substituent.
Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include 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 phenacil group. , Amino group, alkylamino group with 1 to 10 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 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 the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocycle, or a group thereof. Examples thereof include an aryl group substituted with a substituent. These substituents may form a condensed ring, or the hydrogen atom in these substituents may be substituted with a heteroatom 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 independently hydrogen atoms or methyl groups, respectively, but from the viewpoint of ensuring contrast immediately after exposure of the photosensitive resin layer made of the photosensitive resin composition. It is preferable that one or both of R ₃ and R ₄ are hydrogen atoms, and it is more preferable that both R ₃ and R ₄ are hydrogen atoms.

(B ₂ ) From the viewpoint of tentability, 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). 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, and more preferably n ₁ + n. ₂ + n ₃ + n ₄ = 10 to 50 is satisfied, more preferably n ₁ + n ₂ + n ₃ + n ₄ = 20 to 50, and particularly preferably n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50. Meet the relationship.

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

(B ₂ ) A preferable specific example of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) is polyethylene glycol in which an average of 1 unit of ethylene oxide is added to both ends of bisphenol A. Di (meth) acrylate of polyethylene glycol with an average of 2 units of ethylene oxide added to both ends of di (meth) acrylate and bisphenol A, and di (meth) of polyethylene glycol with an average of 5 units of ethylene oxide added to both ends of bisphenol A. Di (meth) acrylate of polyethylene glycol with an average of 7 units of ethylene oxide added to both ends of meth) acrylate and bisphenol A, and an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of bisphenol A, respectively. Di (meth) acrylate of polyalkylene glycol, di (meth) acrylate of polyalkylene glycol with an average of 15 units of ethylene oxide added to both ends of bisphenol A, and an average of 2 units of ethylene oxide at both ends of bisphenol A, respectively. Examples thereof include di (meth) acrylate of polyalkylene glycol to which a unit of propylene oxide is added.

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 shortage defect suppression. It is particularly preferable to satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 4.

(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 tentability and water residue shortage defect suppression property. In particular, it is particularly necessary to simultaneously contain a compound in which one or both of R ₃ and R ₄ are hydrogen atoms in the formula (II), and a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 in the general formula (II). preferable.

The (B) ethylenically unsaturated bond-containing compound preferably contains a tri (meth) acrylate compound represented by (b ₃ ) the general formula (III) from the viewpoint of resolution and tentability. X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, and is, for example, -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH _2- , etc. 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 tentability. More specifically, in the general formula (III), m ₂ + m ₃ + m ₄ is preferably 10 to 40, more preferably 20 to 40.

(B ₃ ) As a preferable specific example of the tri (meth) acrylate compound represented by the general formula (III), ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (EO average number of moles of substance: 10 to 40) ), Propylene oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average number of added moles: 10 to 40) and the like.

The (B) ethylenically unsaturated bond-containing compound preferably contains (b ₄ ) a urethane di (meth) acrylate compound represented by the general formula (IV) from the viewpoint of tentability.

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, and a number of carbon atoms which may have a substituent. A divalent alicyclic group of 3 to 10 may be used.

In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and is, for example, -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH _2- , etc. good.

From the viewpoint of further improving the tentability, the-(YO) _s -part and the-(YO) _t -part in the general formula (IV) are independently-(C ₂ H ₅ O). -(C ₃ H ₆ O) ₉
It is also preferable that it is replaced 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, and 2, Addition reactants with diisocyanate compounds such as 4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO Examples thereof include modified urethane di (meth) acrylate. EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group. Examples of the EO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-11" and the like. Examples of the EO and PO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-13" and the like. These may be used alone or in combination of two or more.

(B) The 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 components of (b ₅ ) are as follows:
Tri (meth) acrylates other than the component (b ₃ ), 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) acrylates, such as dipentaerythritol penta (meth) acrylates;
Hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate, six ends of dipentaerythritol, hexa (meth) acrylate to which a total of 1 to 24 mol of ethylene oxide is added to the six ends of dipentaerythritol. Hexa (meth) acrylate to which a total of 1 to 10 mol of ε-caprolactone was added;
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, for example, γ-chloro-2-hirodoxypropyl-β'-(meth) acryloyloxyeryl-. o-phthalate and β-hydroxyalkyl-β'-(meth) acryloloxyalkyl-o-phthalate, etc .;
Can be mentioned.

In the third embodiment, from the viewpoint of the tentability and adhesion of the resist pattern, the total content of all the (B) ethylenically unsaturated bond-containing compounds in the photosensitive resin composition is preferably 1% by mass. It is in the range of about 70% by mass, more preferably 2% by mass to 60% by mass, and further preferably 4% by mass to 50% by 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% by mass to 10% by mass, and further 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 light is sufficiently transmitted to the bottom surface of the resist to obtain good high resolution. From the viewpoint of obtaining, it is preferably 20% by mass or less.

(C) Examples of the photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoins or benzoin ethers, dialkyl ketals, thioxanthons, dialkylaminobenzoic acid esters, and oxime esters. , Acridines and the like, and further include hexaarylbiimidazole, pyrazoline compounds, N-aryl amino acids or ester compounds thereof (for example, N-phenylglycine), organic halogen compounds and the like. 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, and the like. Acridines such as 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, and 1,12-bis (9-acridinyl) dodecane. Derivatives can be mentioned. 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, still more preferably. Is in the range of 0.5% by mass to 2% by mass.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Can be done. 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. Further, 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 are 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) ) -Diphenyl biimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4' , 5,5'-tetrax- (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'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5,5'- Tetrax- (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'-Tetrakiss- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrax- (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 alone 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 property and / or the sensitivity of the photosensitive resin layer. It is in the range of about 7% by mass, more preferably 0.1% by mass to 6% by mass, and further 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. Of these, N-phenylglycine is particularly preferable. The content of 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 property and / or the sensitivity. %, More preferably 0.1 to 2% by mass.

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, and tris ( Examples thereof include 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and chlorinated triazine compounds. In particular, tribromomethylphenyl sulfone 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 property and / or the sensitivity. It is preferably 0.1% by mass to 3% by mass, and more preferably 0.1% by mass to 3% by mass.

Other photosensitizers include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone. , 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and quinones such as 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 1-phenyl. Examples thereof include oxime esters such as -1,2-propanedione-2- (O-ethoxycarbonyl) oxime. 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 property and / or the sensitivity. %, More preferably 0.1% by mass to 3% by mass.

Further, in the third embodiment, it is also preferable that the photosensitive resin composition 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) -pyrazolin and 1- (4- (benzoxazole-2-yl) phenyl). -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

(D) Additives The photosensitive resin composition may contain additives such as a discoloring agent, a dye, a plasticizer, an antioxidant, a stabilizer, and the like, if desired. For example, the additives listed in JP2013-156369A and International Publication No. 2009/093706 may be used.

Examples of the discoloring agent include leuco dyes and fluorane dyes. The use of a color changing agent is preferable in terms of visibility due to the color development of the exposed portion. Further, when the inspection machine or the like reads the alignment marker for exposure, it is advantageous that the contrast between the exposed portion and the unexposed portion is large because the position can be easily recognized.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. In particular, from the viewpoint of improving the 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 contrast between the exposed portion and the unexposed portion, 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 Co., Ltd.), Brilliant Green [633-03-4], Fuxin [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 Crystal Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-272-2] ] And so on. 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 the third embodiment, the content of the base dye in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, still 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 in peeling the resist pattern due to the alkali-soluble polymer in which the content of the structural unit of (meth) acrylic acid is 10% by mass to 24% by mass is suppressed, and the peeling time is shortened. Therefore, it is preferable that the photosensitive resin composition contains a toluene sulfonic acid amide such as o-toluene sulfonic acid amide and p-toluene sulfonic acid amide as a plasticizing agent. The content of the 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. , Polypropylene ester such as polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether; phthalic acid esters such as diethylphthalate; tributyl citrate, triethyl citrate, triethyl acetyl citrate, triethyl acetyl citrate -N-propyl and tri-n-butyl acetylcitrate; propylene glycol having propylene oxide added to both sides of bisphenol A, ethylene glycol having ethylene oxide added to both sides of bisphenol A, and the like can be mentioned.

From the viewpoint of thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition can be used as a stabilizer as a radical polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butyl. Cathocol, ferrous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol), diphenylnitrosoamine, triethyleneglycol-bis (3-3-t-butyl-5-methyl-4-hydroxyphenylpropionate), and nitrosophenylhydroxyamine aluminum salts; benzotriazoles such as, for example. , 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-triltriazole, 1- (2-di-n-octylaminomethyl) -benzotriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzo Triazoles 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-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole 1: 1 mixture, N- (N, N -Di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxyl Benzotriazole 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 (eg, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.). ), Bisphenol A-propylene oxide 2 mol additive diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), hydrogenated bisphenol A diglyci Zyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc.;
It is preferred to include at least one selected from the group consisting of.

In the third embodiment, the total content of all the 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 in the range of 0.05% by mass to 0.7% by 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 preferably 3% by mass or less.

The additives described above can be used alone or in combination of two or more.

<Photosensitive resin composition formulation>
In the third embodiment, the 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 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 becomes 500 mPa · sec to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
In the third embodiment, it is possible to provide a photosensitive resin laminate having a support and a photosensitive resin layer made of the above-mentioned photosensitive resin composition 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.

The support is not particularly limited, but a transparent one that transmits light 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, and a polymethyl methacrylate copolymer film. Examples thereof include a polystyrene film, a polyvinylidene nitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched if necessary. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, still more preferably 0.01% to 1.0%. The thinner the film, the more advantageous in terms of image formation and economy, but the thickness of the film is preferably 10 μm to 30 μm because it is necessary to maintain the strength.

Further, an important property of the protective layer used in the photosensitive resin laminate is that the protective layer has a smaller adhesion to the photosensitive resin layer than the support and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferable. For example, a film having excellent peelability described in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, 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. The smaller the thickness of the photosensitive resin layer, the better the resolution of the resist pattern, while the larger the thickness, the stronger the cured film, so that it can be selected according to the application.

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

For example, the above-mentioned photosensitive resin composition formulation is prepared, then applied onto the support using a bar coater or a roll coater and dried, and the photosensitive resin composed of the photosensitive resin composition formulation is applied onto the support. Laminate the layers. Further, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

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

First, in the laminating step, a photosensitive resin layer is formed on the 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-bonded to the substrate surface with a laminator and laminated. 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 on only one side of the substrate surface, or may be laminated on both sides if necessary. The heating temperature at the time of laminating is generally 40 ° C to 160 ° C. Further, by performing the heat crimping at the time of laminating twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of heat crimping, a two-stage laminator provided with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly crimped several times through the rolls.

Next, in the exposure step, the photosensitive resin composition layer is exposed to active light using an exposure machine. Exposure can be performed after the support has been peeled off, if desired. When exposing through a photomask, the amount of exposure is determined by the illuminance of the light source and the exposure time, and may be measured using a photometer. In the exposure step, direct imaging exposure may be performed. In the direct imaging exposure, the photomask is not used and the exposure is performed directly on the substrate by the drawing device. 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 developing step, the unexposed portion or the exposed portion of the photosensitive resin layer after exposure is removed with a developing solution using a developing device. If there is a support on the photosensitive resin layer after exposure, this is excluded. Subsequently, the unexposed portion or the exposed portion is developed and removed using a developing solution 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 according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass is generally used. A surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution. The temperature of the developer in the developing step is preferably kept constant within the range of 20 ° C to 40 ° C.

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

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

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

<Manufacturing method of conductor pattern>
The method for producing the conductor pattern includes a laminating step of laminating a photosensitive resin layer made of the above-mentioned photosensitive resin composition on a substrate such as a metal plate and a metal film insulating plate, an exposure step of exposing the photosensitive resin layer, and exposure. A developing step of 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 developing solution, and a conductor pattern forming step of etching or plating a substrate on which a resist pattern is formed. , Preferably in this order.

In the third embodiment, the method for manufacturing a conductor pattern is carried out by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then passing through a conductor pattern forming step. Will be. In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development by using a known etching method or plating method.

Further, the third embodiment is suitably applied to, for example, the following applications.

<Manufacturing method of wiring board>
After the conductor pattern is manufactured by the method for manufacturing the conductor pattern, a wiring board having a desired wiring pattern (for example, for example) is further subjected to a peeling step of peeling the resist pattern from the substrate with an aqueous solution having a stronger alkalinity than the developing solution. Printed wiring board) can be obtained.

The alkaline aqueous solution for stripping (hereinafter, also referred to as “peeling 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 water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohol and the like. The temperature of the peeling liquid in the peeling step is preferably in the range of 40 ° C to 70 ° C.

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

<Manufacturing of base material with uneven pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when the substrate is processed by the sandblasting method. In this case, examples of the substrate include glass, silicon wafers, amorphous silicon, polycrystalline silicon, ceramics, sapphire, and metal materials. A resist pattern is formed on these substrates by the same method as the resist pattern forming method. After that, a sandblasting step of spraying a blast material onto the formed resist pattern to cut it to a desired depth, and a stripping step of removing the resist pattern portion remaining on the substrate from the substrate with an alkaline stripping solution or the like are performed. , A base material having a fine uneven pattern on a substrate can be manufactured.

In the sandblasting step, known blasting materials may be used, but for example, fine particles having a particle size 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. To.

<Manufacturing of semiconductor packages>
A semiconductor package can be manufactured by using a wafer for which a large-scale integrated circuit (LSI) has been formed as a substrate, forming a resist pattern on the wafer by a resist pattern forming method, and then performing the following steps. .. First, a step of forming a conductor pattern is performed by subjecting the openings exposed by development to columnar plating such as copper and solder. After that, a peeling step of peeling the resist pattern is performed by the same method as the manufacturing method of the wiring board, and further, a step of removing the thin metal layer of the portion other than the columnar plating by etching is performed to obtain a desired semiconductor package. Obtainable.

In the third embodiment, the photosensitive resin composition is used for manufacturing a printed wiring board; manufacturing a lead frame for mounting an IC chip; precision processing of a metal foil such as manufacturing a metal mask; a ball grid array (BGA), a chip, and the like. Manufacture of packages such as size packages (CSP); manufacture of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); manufacture of semiconductor bumps; and ITO electrodes, address electrodes, electromagnetic shields, etc. Can be used in the manufacture of bulkheads for flat panel displays.
Unless otherwise specified, the values of the above-mentioned parameters are measured according to the measurement method in the examples described later.

<Fourth Embodiment>
Hereinafter, an embodiment 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) stabilizer.

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

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

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 the monomer units. It is more preferably 15% by mass to 23% by mass. It is preferable that the content ratio of the acid monomer unit is in this range from the viewpoint of improving the resolution and extending the minimum development time.

Aromatic monomers are also called unsaturated aromatic compounds. Examples of the aromatic monomer include styrene, α-methylstyrene, vinylnaphthalene and the like; (meth) acrylic acid aralkyl ester and the like. Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate and the like.

The copolymerization ratio of the aromatic monomer unit (preferably styrene unit) in the component (A) is preferably 30% by mass or more, preferably 32% by mass to 60% by mass, based on the total mass of all the monomer units. Is more preferable, and 35% by mass to 55% by mass is further preferable. It is preferable to set the copolymerization ratio of the aromatic monomer, which has high hydrophobicity and is difficult to be compatible with the developing solution and the developing water, 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, crosslinkable monomers and the like.

The (meth) acrylic acid alkyl ester is a concept that includes both chain alkyl esters and cyclic alkyl esters, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth). ) 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 mentioned. ..

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 thereof include 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadien, 3-butyl-1,3-octadien and the like.

Examples of the polar monomer include, for example.
Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentenol; Amino group-containing monomers such as 2-aminoethyl methacrylate;
Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;
Cyan 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;
And so on.

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 viewpoint of resolvability, developability and cohesiveness, the second copolymer having the 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, the content ratio of the aromatic monomer unit is 45% by mass, so that the hydrophobicity of the resist pattern containing the second copolymer tends to be ensured. Further, it is preferable that the weight ratio of the second copolymer to the total weight of all the copolymers is 25% by mass or more from the viewpoint of improving the cohesiveness.

The second copolymer may contain the acid monomer unit described above and other monomer units. As the aromatic monomer for polymerizing the second copolymer, styrene is preferable from the viewpoint of hydrophobicity. From the viewpoint of developability, 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.

The second copolymer may contain the acid monomer unit described above and other monomer units, and the content ratio of the acid monomer unit described above is high from the viewpoint of resolution, developability and cohesiveness. It is preferably 25% by mass to 50% by mass, and more preferably 25% by mass to 40% by mass. As the acid monomer for polymerizing the second copolymer, (meth) acrylic acid is preferable from the viewpoint of developability.

The weight average molecular weight of the component (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is 5,000 to 1,000,000. It 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 developing time at the time of 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 the same for each component based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified). (There is), 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 40% by mass to 60% by mass is further preferable. 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 or more based on the total solid content of the photosensitive resin composition. It is preferably mass% or less. More preferably, it is 10% by mass or more and 40% by mass or less.

[(B) Ethylene unsaturated bond-containing compound]
(B) The ethylenically unsaturated bond-containing compound is a compound having a polymerizable property 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 fourth embodiment, when (A) an alkali-soluble polymer and (B) an ethylenically unsaturated bond-containing compound are used in combination, good resolution of the resist pattern is ensured and the minimum development time is extended. From this viewpoint, the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound is preferably 900 or less. In the present specification, the average molecular weight of (B) an ethylenically unsaturated bond-containing compound is the structure of (B) a single type of ethylenically unsaturated bond-containing compound when the ethylenically unsaturated bond-containing compound is a single species. It means the weight average molecular weight derived from the formula, and (B) when the ethylenically unsaturated bond-containing compound is composed of a plurality of kinds, it means the weight average molecular weight and the weighted average of the compounding 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, still more preferably 800 or less, and a photosensitive resin laminate, from the viewpoint of improving resolution and extending the minimum development time. From the viewpoint of suppressing the edge fuse property in the body, it is preferably 50 or more, and 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 wound into a roll shape.

｛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 is the following (b ₁ ) to (b ₆ ) :.
(B ₁ ) The following general formula (I):

{In the formula, 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. }
Ethylene glycol di (meth) acrylate compound represented by;
(B ₂ ) The following general formula (II):

{In the equation, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and 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 sequence of repeating units of-(AO)-and-(BO)-is random. In the case of a block, either − (A—O) − or − (BO) − 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):

{In the formula, R ₅ to R ₇ independently represent 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 independently represent each. , 0-40, m ₂ + m ₃ + m ₄ is 0-40, and if m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of X's are identical to each other. Or may be different}
Tri (meth) acrylate compound represented by;
(B ₄ ) The following general formula (IV):

{In the formula, R ₈ and R ₉ 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 independently integers from 0 to 40, and s + t ≧ 1}
Urethane di (meth) acrylate compound represented by;
(B ₅ ) The following general formula (XI):

{In the formula, R ₅ to R ₈ independently represent 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. Independently, each is an integer from 0 to 40, where m ₂ + m ₃ + m ₄ + m ₅ is 0 to 50, and m ₂ + m ₃ + m ₄ + m ₅ is 2 or more, then multiple Xs. , May be the same as or different from each other}
Tetra (meth) acrylate compound represented by; and (b ₆ ) an addition-polymerizable monomer other than the above (b ₁ ) to (b ₅ );
It may contain at least one selected from the group consisting of.

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

In the general formula (I), m ₁ is preferably 2 or more from the viewpoint of peeling time and peeling piece size, and preferably 40 or less from the viewpoint of resolution, plating resistance and etching resistance. m ₁ is more preferably 4 to 20, 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 m ₁ = 14 polyethylene glycol di (meth) acrylate is preferred.

(B) The ethylenically unsaturated bond-containing compound is represented by (b ₂ ) the general formula (II) from the viewpoint of suppressing the generation of aggregates during development of the photosensitive resin layer made of the photosensitive resin composition. It is preferable to contain an alkylene oxide-modified bisphenol A type di (meth) acrylate compound. 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 heteroatom and / or a substituent.
Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include 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 phenacil group. , Amino group, alkylamino group with 1 to 10 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 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 the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocycle, or a group thereof. Examples thereof include an aryl group substituted with a substituent. These substituents may form a condensed ring, or the hydrogen atom in these substituents may be substituted with a heteroatom 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 independently hydrogen atoms or methyl groups, respectively, but from the viewpoint of ensuring contrast immediately after exposure of the photosensitive resin layer made of the photosensitive resin composition. It is preferable that one or both of R ₃ and R ₄ are hydrogen atoms, and it is more preferable that both R ₃ and R ₄ are hydrogen atoms.

(B ₂ ) The alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II) has 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, and more preferably n ₁ + n. ₂ + n ₃ + n ₄ = 0 to 25 is satisfied, more preferably n ₁ + n ₂ + n ₃ + n ₄ = 0 to 20, and particularly preferably n ₁ + n ₂ + n ₃ + n ₄ = 0 to 10. Meet 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). It is 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, 50% by mass, more preferably 55% by mass or more, and most preferably 60% by mass of the (B) ethylenically unsaturated bond-containing compound is represented by (b ₂ ) the general formula (II). It is an oxide-modified bisphenol A type di (meth) acrylate compound.

(B ₂ ) A preferable specific example of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) is polyethylene glycol in which an average of 1 unit of ethylene oxide is added to both ends of bisphenol A. Di (meth) acrylate of polyethylene glycol with an average of 2 units of ethylene oxide added to both ends of di (meth) acrylate and bisphenol A, and di (meth) of polyethylene glycol with an average of 5 units of ethylene oxide added to both ends of bisphenol A. Di (meth) acrylate of polyethylene glycol with an average of 7 units of ethylene oxide added to both ends of meth) acrylate and bisphenol A, and an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of bisphenol A, respectively. Di (meth) acrylate of polyalkylene glycol, di (meth) acrylate of polyalkylene glycol with an average of 15 units of ethylene oxide added to both ends of bisphenol A, and an average of 2 units of ethylene oxide at both ends of bisphenol A, respectively. Examples thereof include di (meth) acrylate of polyalkylene glycol to which a unit of propylene oxide is added.

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 also particularly preferable to satisfy the relationship of ₂ + n ₃ + n ₄ = 2 to 10.

(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 the resolution and extending the minimum development time. In particular, it is particularly preferable to simultaneously contain a compound in which one or both of R ₃ and R ₄ are methyl groups in the formula (II), and a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 16 in the general formula (II). preferable.

(B) The ethylenically unsaturated bond-containing compound is represented by the general formula (III) (b ₃ ) from the viewpoint of suppressing the generation of aggregates during development of the photosensitive resin layer composed of the photosensitive resin composition. It preferably contains a tri (meth) acrylate compound. X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, and is, for example, -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH _2- , etc. 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 ) A preferable specific example of the tri (meth) acrylate compound represented by the general formula (III) is ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (EO average number of moles of substance: 1 to 40). ), Propylene oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average number of added moles: 1 to 40) and the like.

From the viewpoint of resolution, the (B) ethylenically unsaturated bond-containing compound preferably contains (b ₄ ) a urethane di (meth) acrylate compound represented by the general formula (IV).

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, and a number of carbon atoms which may have a substituent. A divalent alicyclic group of 3 to 10 may be used.

In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and is, for example, -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH _2- , etc. good.

From the viewpoint of further improving the resolution, the-(YO) _s -part and the-(YO) _t -part in the general formula (IV) are independently-(C ₂ H ₅ O). )-(C ₃ H ₆ O) _9-
It is also preferable that it is replaced 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, and 2, Addition reactants with diisocyanate compounds such as 4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO Examples thereof include modified urethane di (meth) acrylate. EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group. Examples of the EO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-11" and the like. Examples of the EO and PO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-13" and the like. These may be used alone or in combination of two or more.

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

X in the general formula (XI) is an alkylene group having 2 to 6 carbon atoms, and is, for example, -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH _2- , etc. 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 ).

(B ₆ ) The components are as follows:
Tri (meth) acrylates other than the component (b ₃ ), 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 other than the component (b ₅ ), such as 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, six ends of dipentaerythritol, hexa (meth) acrylate to which a total of 1 to 24 mol of ethylene oxide is added to the six ends of dipentaerythritol. Hexa (meth) acrylate to which a total of 1 to 10 mol of ε-caprolactone was added;
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, for example, γ-chloro-2-hirodoxypropyl-β'-(meth) acryloyloxyeryl-. o-phthalate and β-hydroxyalkyl-β'-(meth) acryloloxyalkyl-o-phthalate, etc .;
Can be mentioned.

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

[(C) Photopolymerization Initiator]
The component (C) is a component that generates a radical capable of initiating the polymerization of the component (B) by irradiation with light.
As such the component (C), for example, an aromatic ketone compound, a quinone compound, a benzoin ether compound, a benzoin compound, a benzyl compound, a hexaarylbisimidazole compound, an acridin compound and the like can be used. Of these, from the viewpoint of high resolution and good tenting property, it is preferable to use one or more selected from hexaarylbisimidazole compounds and acridine compounds. Further, 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'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4 , 4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrakis -(3-Methenylphenyl) -imidazolyl dimer, 2,2'-bis- (2,5-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyldi Quantum, 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'-tetrax- (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'-tetrax- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4', 5,5' -Tetrakiss- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxy) Phenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyldi Quantitative, 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)- 4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and the like can be mentioned.

Further, as the above-mentioned acridine compound, for example,
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) -Acridine) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane and the like can be mentioned.

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, and it is further preferably in the range of 0.3% by mass to 1.7% by mass, and particularly preferably 0.4% by mass to 1.6% by mass. It is preferable to set the content of the component (C) in such a range from the viewpoint of obtaining good light sensitivity and peeling characteristics.

The component (C) can further contain a sensitizer from the viewpoint of improving sensitivity and resolution. Examples of such a sensitizer include N-aryl amino acids, organic halogen compounds, and other sensitizers.
Examples of the N-aryl amino acid include, for example.
N-Phenylglycine, N-Methyl-N-Phenylglycine, N-Ethyl-N-Phenylglycine, etc.;
Examples of the organic halogen compound include, for example.
Amil bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulphon, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate , Trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound, etc.;
Each can be listed.

Examples of the above other sensitizers include, for example.
2-Ethlanthraquinone, Octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10- Kinone 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 benzyl dimethyl 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, preferably 0.05% by mass to 3% from the viewpoint of the photosensitivity of the composition and the peelability of the resist cured film. The mass% is more preferable, and 0.1% by mass to 2% by mass is further preferable.
In the photosensitive resin composition of the fourth embodiment, an acridine compound and an N-aryl amino acid may be used as the component (C), and these may be used in combination within the above-mentioned usage ratio. It is preferable from the viewpoint of suppressing the etching rate at the time of forming the wiring and suppressing the vertical and horizontal difference 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. Generally, hindered phenol refers to phenol having a large steric hindrance. The photosensitive resin composition is a hindered phenol having the following general formula (V):

{In the formula, R ⁵¹ may be substituted via a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, and a divalent linking group. A branched alkyl group represented by 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 independently hydrogenated or substituted, respectively. 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, and a divalent linking group may be used. Represents an aryl group via a cyclohexyl group or a divalent linking group. } Includes compounds represented by.

The compound represented by the general formula (V) is excellent from the viewpoint of improving the resolution of the photosensitive resin composition and from the viewpoint of suppressing the decrease in sensitivity of the photosensitive resin composition. The compound represented by the general formula (V) does not have two or more phenolic hydroxyl groups in one aromatic ring, and is substituted with only one of the ortho positions of the phenolic hydroxyl groups. It has a group and is characterized by the control of steric damage around phenolic hydroxyl groups. It is considered that the above-mentioned excellent performance is exhibited by such a structure.

｛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) has ^R51 and 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 preferred that at least one of ⁵² , R ⁵³ and R ⁵⁴ has an aromatic ring. From the same viewpoint, the hydroxyl group concentration of hindered phenol is preferably 0.10 mol / 100 g to 0.75 mol / 100 g. From the same viewpoint, in the above 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. The preferred alkyl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like. The preferred divalent linking group includes, for example, 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, as the compound represented by the above general formula (V), for example, the following general formula (VI):

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

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

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

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

{In the formula, R ⁷⁶ , R ⁷⁹ , R ⁸² and R ⁸⁵ each independently represent a linear or branched alkyl group, and R ⁷⁷ , R ⁷⁸ , R ⁸⁰ , R ⁸¹ , R ⁸³ , R ⁸⁴ , R, respectively. 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. Examples of X ¹ in the above general formula (VIII) include a thioether group, a substituted or unsubstituted alkylene group, and the like.

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 decrease in sensitivity of the photosensitive resin composition. It is preferable to have a molecular weight of about 200 to about 800, more preferably to have a molecular weight of about 300 to about 500, and most preferably to have 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 sparingly soluble in water, and contains methanol, acetone, toluene, etc. It is preferably readily soluble in organic solvents, or solid (eg, powder, crystals, etc.) or liquid at the time of use.

Examples of the compound represented by the general formula (V) include 4,4'-thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidenebis (3-methyl-6-tert-butylphenol). , Stylized 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, 4, 4'from the viewpoint of improving the resolution and suppressing the decrease in sensitivity of the photosensitive resin composition due to the high content of the compound represented by the general formula (I). -Thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) are preferred.

The ratio of the compound represented by the general formula (V) to the total mass of the photosensitive resin composition is 0.001% by mass to 10% by 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, and more preferably 0.1, in terms of improving the resolution. It is more preferably mass% or more, particularly preferably 0.5 mass% or more, and most preferably 0.7 mass% or more. On the other hand, this ratio is preferably 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less, in terms of less decrease in sensitivity and improvement in resolution. It 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 compound other than the compound represented by the general formula (V) include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, and 2,5-di-. tert-Butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-t-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 Ellisrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [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) -Hydrosinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di- Examples thereof include t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isosianurate and the like.

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 preferable.

In the fourth embodiment, the photosensitive resin composition may contain a stabilizer other than hindered phenol. Stabilizers other than hindered phenol include radical polymerization inhibitors such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, ferrous chloride, 2,6-di-tert-butyl-p. -Cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), diphenylnitrosoamine, triethyleneglycol-bis (3- 3-t-butyl-5-methyl-4-hydroxyphenylpropionate), nitrosophenylhydroxyamine aluminum salt, etc .; benzotriazoles such as 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-triltriazole, 1- (2-) Di-n-octylaminomethyl) -benzotriazole, 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-carboxybenzotriazole 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole, etc .; and alkylene oxide compounds having a glycidyl group, such as neopentylglycol. 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 addition diglycidyl ether (for example, Kyoeisha Co., Ltd.) Epolite 3002 manufactured by Kagaku Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Epo manufactured by Kyoeisha Kagaku Co., Ltd.) Light 4000), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc .; preferably contains at least one selected from the group consisting of.

In the fourth embodiment, the total content of all the 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 in the range of 0.05% by mass to 0.7% by 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 preferably 3% by 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 development property and excellent peeling property 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-methylindol-3) -Il) -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-xylidinofluorane, 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-ethyl Isoamylaminofluorane, 2-methyl-6- (N-p-tolyl-N-ethylamino) fluorane, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) Amino) fluorane, 2- (3'-trifuromethylanilino) -6-diethylaminofluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane, 3-methoxy- 4-Dodecoxystylinoquinoline and the like can be mentioned. 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, preferably 0.7% by mass to 1.2% by mass. Is more preferable. By setting the usage ratio of the leuco dye in this range, good color development and good peelability can be realized.

[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], Fuxin [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 Crystal Pure 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. Of these, one or more 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. It is preferably in the range of 0.01% by mass to 1.2% by mass. By setting the usage ratio within this range, both good color development and high sensitivity can be achieved at the same time.

[solvent]
The photosensitive resin composition of the fourth embodiment can be a mixture of the above-mentioned components (A) to (C) and other components arbitrarily used, or a solvent suitable for these components. May be used as a photosensitive resin composition preparation solution prepared by adding the above.
Examples of the solvent used here include ketone compounds such as methyl ethyl ketone (MEK); alcohols such as ethanol, ethanol, and isopropyl alcohol; and the like.
The ratio of the solvent used is preferably such that the viscosity of the photosensitive resin composition preparation solution 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-mentioned photosensitive resin composition is laminated on a support. If necessary, a protective layer may be provided on the surface opposite to the support of the photosensitive resin layer.

[Support]
As the support, a transparent base material that transmits light 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, and a polymethyl methacrylate copolymer film. Examples thereof include a polystyrene film, a polyvinylidene nitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films can also be used if necessary.
The haze of the support is preferably 5 or less.
The thinner the support, the more advantageous in terms of image formation and economy, but it is necessary to maintain the 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 preferable that the solvent is removed.
The thickness of the photosensitive resin layer is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The thinner the thickness, the better the resolution, and the thicker the thickness, the better 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 property 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 the protective layer can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film or 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.

[Manufacturing method of photosensitive element]
The photosensitive element can be manufactured 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 adopted.
For example, the photosensitive resin composition is prepared as the above-mentioned photosensitive resin composition preparation solution, first applied on a support using a bar coater or a roll coater and dried, and then the photosensitive resin composition is applied on the support. A photosensitive resin layer composed of is formed. Then, if necessary, the photosensitive element can be manufactured by laminating a protective layer on the formed photosensitive resin layer.

<Method of forming resist pattern>
A resist pattern can be formed on the substrate by using the photosensitive element as described above.
The method of forming the resist pattern is as follows:
Laminating process of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate;
An exposure process that exposes the laminated photosensitive resin layer; and a development process that develops the exposed photosensitive resin layer;
Are preferably included in the order described above.

In the method for forming a resist pattern according to the fourth embodiment, first, in the laminating step, a photosensitive resin layer is formed on a substrate by 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-bonded to the substrate surface using a laminator and laminated.
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, indium tin oxide (ITO) and the like. These boards may have through holes to accommodate multi-layer boards.

Here, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides of the substrate if necessary. The heating temperature at this time is preferably 40 ° C to 160 ° C. It is preferable to perform heat crimping twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. When 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 layer is repeatedly passed through the rolls several times. It may be crimped.

Further, 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 improving followability and yield. As the wetting agent, one or more selected from pure water, deionized water, and electrolytic water, and one selected from the group consisting of a copper chelating agent (for example, an imidazole compound, a triazole compound, a pyridine compound, and a pyrazole compound). It is preferable to include the above compounds).

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 the support, or may be performed after the support is peeled off if necessary.

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

In maskless exposure, a photomask is not used, and the exposure is performed directly on the substrate by a drawing device. 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 developing solution. If there is a support on the photosensitive resin layer after exposure, it is preferable to remove the support before subjecting it to the developing step.
In the developing step, an unexposed portion is developed and removed using a developing solution composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, it is preferable to use an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ , or the like. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin 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. A surfactant, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
The temperature of the developer in the developing step is preferably kept constant in the range of 20 ° C to 40 ° C.

A resist pattern is obtained by the above steps. In some cases, a heating step of 100 ° C. to 300 ° C. may be further performed. It is preferable to carry out this heating step from the viewpoint of further improving chemical resistance. For heating, an appropriate heating furnace such as hot air, infrared rays, far infrared rays or the like can be used.

<How to form a wiring board>
The method for forming the wiring board according to the fourth embodiment is as follows:
Laminating process of laminating the photosensitive resin layer of the photosensitive element on the conductor substrate;
An exposure process that exposes the laminated photosensitive resin layers;
Development process for developing the exposed photosensitive resin layer;
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by development; and a peeling step of peeling off 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 on which the resist pattern is formed by using a known etching method or plating method on the substrate surface (for example, copper surface) exposed by the developing step.

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

The photosensitive resin composition, the photosensitive element, the method for forming a resist pattern, and the method for manufacturing a wiring board according to the fourth embodiment include, for example, a printed wiring board, a lead frame, a base material having an uneven pattern, a semiconductor package, and the like. It can be very suitably applied to the production of.
Unless otherwise specified, the measurement methods for the various parameters described above are measured according to the measurement methods in the examples described later.

<Examples and Comparative Examples Regarding the First Embodiment>
Hereinafter, the photosensitive resin composition of the first embodiment will be specifically described in the form of an example.
(1) Measurement of raw material property values <Measurement of weight average molecular weight>
The weight average molecular weight of the polymer is gel permeation chromatography (GPC) manufactured by Nippon Kogaku Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK, KF-807, KF-806M, KF-806M, KF-802.5) 4 series, moving layer solvent: tetrahydrofuran, using a polystyrene standard sample (using a calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK), converted to polystyrene Obtained as a value.

<Acid equivalent>
As used herein, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

(2) Preparation method and analysis of evaluation sample <Preparation of photosensitive element>
Each component shown in Table 1 and each component below:
As a coloring substance, 0.04 parts by mass of diamond green;
As a leuco dye, 0.6 parts by mass of leuco crystal violet;
As a halogen compound, 0.7 parts by mass of trimobromomethylphenyl sulfone;
As a plasticizer, 2 parts by mass of p-toluenesulfonamide;
As benzotriazoles, 0.05 parts by mass of carboxylbenzotriazole;
As benzotriazoles, 1- (2-di-n-octylaminomethyl) -benzotriazole 0.15 parts by mass;
0.05 parts by mass of hydrogenated bisphenol A diglycidyl ether (Kyoeisha Chemical Co., Ltd., Epolite 4000) as an antioxidant; and 0.004 parts by mass of Tris (nitrosophenylhydroxyamine) aluminum as a radical polymerization inhibitor are further 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 the amounts (parts by mass) of each component used to prepare the composition.
The obtained photosensitive resin composition was uniformly applied onto a support, a polyethylene terephthalate film having a thickness of 16 μm (R310 manufactured by Mitsubishi Plastics Co., Ltd., haze value 2.1%) using a bar coater, and then uniformly applied. A photosensitive resin composition layer having a thickness of 25 μm was formed on the support by heating and drying in a dryer whose temperature was adjusted to 95 ° C. for 2.5 minutes.
Next, a polyethylene film (GF-18 manufactured by Tamapoli Co., Ltd.) having a thickness of 19 μm, which is a protective layer, is attached on the surface of the photosensitive resin composition layer opposite to the support to obtain a photosensitive element. rice field.

<Substrate used for evaluation>
As a substrate for evaluation of tenting property, 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 in which a copper foil having a thickness of 35 μm is laminated;
As a substrate for evaluation other than 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, is used.
Each was used.
The substrate for tenting property evaluation was subjected to surface treatment by surface treatment using a jet scrub grinding machine and then subjected to evaluation.
The substrate for evaluation other than tenting property is prepared by sequentially performing surface treatment using a soft etching agent (manufactured by Ryoe Chemical Co., Ltd., CPE-900) and surface cleaning with a 10% by mass H ₂ SO ₄ aqueous solution. After facing it, it was used for evaluation.

<Laminate>
While peeling off the polyethylene film of the photosensitive element obtained in each example or comparative example on the substrate after surface preparation, a hot roll laminator (AL-70 manufactured by Asahi Kasei Corporation) was used to roll temperature 105 ° C. and air pressure. Laminating 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 (manufactured by 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 the section of each evaluation item.

<Development>
After peeling the support from the photosensitive resin composition layer after exposure, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. is used in an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film) for a minimum developing time. The unexposed portion of the photosensitive resin composition layer was dissolved and removed by spraying for 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 means the minimum time required for the unexposed portion of the photosensitive resin composition layer to be completely dissolved and removed.

<Evaluation of sensitivity>
For the evaluation of the sensitivity, a laminated substrate 15 minutes after the above <laminate> was used.
A mask pattern of 10 lines of line / space = 40 μm / 40 μm was directly drawn and exposed on the laminated substrate, 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.
The resist top width is 39.0 μm and the exposure amount is 28 mJ or less: Sensitivity "○ (good)"
The resist top width is 39.0 μm and the exposure amount exceeds 28 mJ: Sensitivity “× (defective)”
Here, the measurement location of the resist line was set to the position of the fifth line from the end of the ten lines and 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 influence of the diffusion of the developing solution and the 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 set so that 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 the evaluation of the resolution, a laminated substrate 15 minutes after the above <laminate> was used.
Patterns of various sizes of lines / space = 1/1 were directly drawn and exposed on the laminated substrate, and then developed by the method described in <Development> above.
With respect to the obtained pattern, the minimum pattern width formed was observed with an 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 “△ (possible)”
When the minimum pattern width exceeds 24 μm: Resolution “× (defective)”

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

<Tending property>
The tenting property was evaluated by observing the laminated substrate after the above <laminating> obtained by using the substrate having through holes.
The number of holes in which the photosensitive resin composition layer (tent film) formed on the through holes was broken was measured, the ratio to all the holes (tent film tear rate) was calculated, and the evaluation was made according to the following criteria.
When the tent film tear rate is less than 0.1%: Tenting property "◎ (extremely good)"
When the tent film tear rate is 0.1% or more and less than 2%: Tenting property "○ (good)"
When the tent film tear rate is 2% or more: Tenting property "x (defective)"

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

<Vertical and horizontal difference in wiring width>
For the evaluation of the vertical and horizontal differences in the wiring width, a laminated substrate 15 minutes after the above <laminate> was used.
An exposure pattern in which 10 patterns of 10 lines having a line / space = 50 μm / 30 μm were arranged in tiles in the MD direction and the TD direction was directly drawn and exposed on the laminated substrate.
After 15 minutes have passed from the exposure, the support is peeled off from the photosensitive resin composition layer, and a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is used using an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film). Was sprayed for twice the minimum development time to dissolve and remove the unexposed portion of the photosensitive resin composition layer. After development, it was washed with pure water for 1.5 times the development time.
Next, without drying the substrate having this line / space pattern after washing with water, the direction of the line / space of the substrate is orthogonal to the transport direction (MD), and the copper chloride vacuum etching apparatus (manufactured by Fuji Kiko, input port width 750 mm). , Tank length 2.6 m), 14 rows in the etching solution piping MD direction (pipe interval about 18 cm), number of spray nozzles per pipe 14 in the TD direction (slit nozzles, injection direction is parallel to the TD direction) , Nozzle spacing approx. 14 cm, distance from substrate approx. 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 at a line speed of 2.2 m / min for 71 seconds under the conditions of 15 MPa and an etching solution temperature of 48 ° C.

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

Examples 1 to 23 and Comparative Examples 1 to 8
Table 1 shows the compositions of the photosensitive resin compositions used in Examples and Comparative Examples.
The details of each component name shown in Table 1 are shown in Table 2. The blending amount of each component in Table 1 is a mass part in terms of solid content.
The evaluation results performed using each composition are shown in Table 1.

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

<Measurement of weight average molecular weight>
The weight average molecular weight of the polymer is gel permeation chromatography (GPC) manufactured by Nippon Kogaku Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK, KF-807, KF-806M, KF-806M, KF-802.5) 4 series, moving layer solvent: tetrahydrofuran, using a polystyrene standard sample (using a calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK), converted to polystyrene Obtained as a value.

(2) Preparation method of evaluation sample <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 applied on a polyethylene terephthalate film (manufactured by Teijin DuPont Film Co., Ltd., GR-16) having a thickness of 16 μm as a support using a bar coater, and then heated to 95 ° C. A photosensitive resin layer having a thickness of 33 μm was formed on the support by heating and drying in a temperature-controlled dryer for 4 minutes.
Next, a polyethylene film (GF-18 manufactured by Tamapoli Co., Ltd.) having a thickness of 19 μm, which is a protective layer, was attached onto the surface of the photosensitive resin layer on the opposite side to the support to obtain a photosensitive element.

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

<Laminate>
The roll temperature was adjusted by a hot roll laminator (AL-70, manufactured by Asahi Kasei Corporation) while peeling off the polyethylene film of the photosensitive element obtained in each example or comparative example on the substrate prepared and preheated to 60 ° C. Laminating was performed under the conditions of 105 ° C., an air pressure of 0.35 MPa, and a laminating speed of 1.5 m / min.

<Exposure>
Illuminance using a direct drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-purple diode, main wavelength 405 ± 5 nm) using a Stowfa 41-step 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 the Stowfa 41-step step tablet.

<Development>
After peeling the support from the photosensitive resin layer after exposure, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. was used with an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film) for a minimum developing time of 2. The unexposed portion of the photosensitive resin layer was dissolved and removed by spraying for twice as long. 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 is the minimum time required for the unexposed portion of the photosensitive resin layer to be completely dissolved and removed.

<Etching>
A cupric chloride etching solution (copper chloride) at 50 ° C. was used on the evaluation substrate on which the resist pattern was formed by development, using a copper chloride etching device (copper chloride etching device manufactured by Tokyo Kakoki Co., Ltd.). By spraying (concentration 250 g / L, HCl concentration 3 mol / L) for 60 seconds, the copper foil in the portion not covered by the resist pattern on the copper-clad laminate was dissolved and removed.

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

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

(Ii) Sensitivity test Using the photosensitive elements obtained in each example and comparative example, laminating and exposure were performed according to the above method, and 14 steps in the Stoufa 41-step step tablet according to each exposure amount and the number of steps remaining after development. The exposure amount (mj / cm ² , 14 / 41ST exposure amount) corresponding to the above was examined and evaluated according to the following criteria.
Sensitivity "○" (good): When the 14 / 41ST exposure amount is 25 mj / cm ² or less Sensitivity "x" (poor): When the 14 / 41ST exposure amount exceeds 25 mj / cm ² .

(Iii) Resolution test After laminating according to the above method using the photosensitive elements obtained in each example and comparative example, the line / space was set to 1/1 using the sample 15 minutes later, and further. Direct drawing exposure was performed according to the above method. Then, development was performed according to the above method.
Furthermore, the minimum mask line width in which the cured resist line was normally formed was investigated 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 “×” (bad): The minimum line width is When it is 30 μm or more

(Iv) Adhesion Test After laminating according to the above method using the photosensitive elements obtained in each Example and Comparative Example, direct drawing exposure was performed according to the above method using a sample 15 minutes after. Then, it was developed according to the above method.
Further, when the line / space = X / 200, the minimum mask line width normally formed as X was examined 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 “×” (defective): Minimum When the line width is 30 μm or more

Examples 1 to 6 and Comparative Examples 1 to 5
The compositions of the photosensitive resin compositions used in Examples and Comparative Examples are shown in Table 3, and the details of each component name in Table 3 are shown in Table 4. The blending amount of each component in Table 4 is a mass part in terms of solid content.
The evaluation results performed using each composition are also shown in Table 4.

<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 an example.
The measurement of the physical property values of the polymer and the monomer, and the method of preparing the evaluation sample of Examples and Comparative Examples will be described, and then the evaluation method of the obtained sample and the evaluation result thereof will be shown.

(1) Measurement or calculation of physical property values <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 Nippon Kogaku Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex® manufactured by Showa Denko KK) (registered trademark). KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving layer solvent: tetrahydrofuran, polystyrene standard sample (using calibration curve by Showa Denko Corporation's Chromatography STANDARD SM-105) Obtained as polystyrene conversion.
Further, 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>
As used herein, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in the molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.

(2) Method for preparing evaluation samples The evaluation samples in Examples 1 to 12 and Comparative Examples 1 to 5 were prepared as follows.

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

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

<Board surface preparation>
Jet scrub polishing of 0.4 mm thick copper-clad laminate with 35 μm rolled copper foil laminated using a grinding material (Sacron R (registered trademark # 220) manufactured by Nippon Carlit Co., Ltd.) at a spray pressure of 0.2 MPa. By doing so, an evaluation substrate was produced.

<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was placed on a copper-clad laminate that had been surface-prepared and preheated to 60 ° C with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). Specimens were 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 (manufactured by Via Mechanics, Ltd., DE-1DH, main wavelength 405 nm).

<Development>
After peeling the polyethylene terephthalate film from the photosensitive resin laminate, use a developing device manufactured by Fuji Kiko Co., Ltd. with a full cone type nozzle at a developing spray pressure of 0.15 MPa and 1 mass% Na ₂ CO at 30 ° C. The _three aqueous solutions were sprayed for a predetermined time to develop, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved 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 step was performed with a flat type nozzle at a washing spray pressure of 0.15 MPa for the same time as the developing step.

(3) Sample evaluation method <tentability>
A 0.6 mm thick double-sided copper-clad laminate having a through hole having a width of 2.0 mm and a length of 15 mm was surface-treated with a jet scrub grinding machine. Both sides were laminated by the method described in the above <lamination>, and both sides were exposed on the entire surface by a direct drawing type exposure apparatus (manufactured by Via Mechanics, Ltd., DE-1DH, main wavelength 405 nm). When developed by the method described in <Development> above, the number of torn tent holes was measured, the tear rate for all tent holes was calculated, and the ranking was made according to the following criteria.
◎ ◎ (best): The film tear rate after development is 2% or less.
⊚ (extremely good): The film tear rate after development exceeds 2% and is 4% or less.
◯ (Good): The film tear rate after development exceeds 4% and is 10% or less.
X (defective): The film tear rate after development exceeds 10%.

<Contact angle (remaining water short circuit defect suppression property)>
In the evaluation of the contact angle (water residue short-circuit defect suppression property), after laminating by the method described in the above <lamination>, the entire surface is developed by the method described in the above <exposure>, and then in the above <development>. Development was performed by the method described.
Within 30 minutes after development, the sample was subjected to contact angle measurement.
The contact angle is measured according to the static drip method of JIS R3257, and is 0 on the cured film in an environment of temperature 23 ° C. and humidity 50 RH% using an optical microscope type contact angle meter "LSE-B100" manufactured by Nick Co., Ltd. After dropping 5.5 μL of pure water, the 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 the defective short circuit of residual water.
⊚ (extremely 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 (defective): 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 an example.
(1) Measurement of raw material property values <Measurement of weight average molecular weight>
The weight average molecular weight of the polymer is gel permeation chromatography (GPC) manufactured by Nippon Kogaku Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK, KF-807, KF-806M, KF-806M, KF-802.5) 4 series, moving layer solvent: tetrahydrofuran, using a polystyrene standard sample (using a calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK), converted to polystyrene Obtained as a value.

<Acid equivalent>
As used herein, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

(2) Preparation method and analysis of evaluation sample <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 content concentration of 56% by mass. The numbers in each component column in Table 8 are the amounts (parts by mass) of each component used to prepare the composition.
The obtained photosensitive resin composition is uniformly applied onto a support, a polyethylene terephthalate film having a thickness of 16 μm (GR-16 manufactured by Teijin DuPont Film Co., Ltd., haze value 2.7%) using a bar coater. Then, it was heated and dried in a dryer whose temperature was adjusted to 95 ° C. for 3 minutes and 20 seconds to form a photosensitive resin layer having a thickness of 33 μm on the support.
Next, a polyethylene film (GF-18 manufactured by Tamapoli Co., Ltd.) having a thickness of 19 μm, which is a protective layer, was attached onto the surface of the photosensitive resin layer on the opposite side to the support to obtain a photosensitive element.

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

<Laminate>
While peeling off the polyethylene film of the photosensitive element obtained in each example or comparative example on the substrate after surface preparation, a hot roll laminator (AL-70 manufactured by Asahi Kasei Corporation) was used to roll temperature 105 ° C. and air pressure. Laminating was performed under the conditions of 0.35 MPa and a laminating speed of 1.5 m / min.

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

<Development>
After peeling the support from the photosensitive resin layer after exposure, a 0.8 mass% Na ₂ CO ₃ aqueous solution at 29 ° C. is used for a minimum development time using an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film). The unexposed portion of the photosensitive resin layer was dissolved and removed by spraying for 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 warm air drying treatment to obtain a substrate having a cured film for evaluation.
The minimum development time refers to the minimum time required for the unexposed portion of the photosensitive resin layer to be completely dissolved and removed, and refers to the concentration or temperature of the developer, the direction or amount of spray, the pressure, and the oscillation. It changes depending on the frequency and so on.
Here, the minimum development time was ranked as follows:
◯: The minimum development time exceeds 30 seconds.
X: Minimum development time is 30 seconds or less.

<Evaluation of sensitivity>
For the evaluation of the sensitivity, a laminated substrate 15 minutes after the above <laminate> was used.
A mask pattern of 10 lines of line / space = 40 μm / 40 μm was directly drawn and exposed on the laminated substrate, 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 used as the evaluation of sensitivity.
Here, the measurement location of the resist line was set to the position of the fifth line from the end of the ten lines and 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 the 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 set so that the resist top width was 39 μm with respect to the mask pattern of line / space = 40 μm / 40 μm. Here, the sensitivities were ranked according to the amount of exposure as follows:
◯: The exposure amount having a line width of 39 μm is 28 mJ / cm ² or less.
X: The exposure amount having a line width of 39 μm exceeds 28 mJ / cm ² .

<Evaluation of resolution>
For the evaluation of the resolution, a laminated substrate 15 minutes after the above <laminate> was used.
Patterns of various sizes of lines / space = 1/1 were directly drawn and exposed on the laminated substrate, and then developed by the method described in <Development> above.
With respect to the obtained pattern, the minimum pattern width formed was observed with an optical microscope, and the resolution was evaluated according to the following criteria.
◯: 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 laminated substrate 15 minutes after the above <laminate> was used.
Patterns of independent lines of various sizes were directly drawn and exposed on the laminated substrate, and then developed by the method described in <Development> above.
The obtained pattern was observed with an optical microscope, and the 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 collapsed, the line pattern is meandering, or the line pattern does not exist on the substrate. say.
◯: 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 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. Then, the developer was allowed to stand for one day, and the generation of agglomerates was observed. When a large amount of agglomerates are generated, powdery substances or oily substances are observed on the bottom surface and the side surface of the spray device. In a composition having good developer cohesiveness, the above-mentioned agglomerates do not occur at all. The cohesiveness was ranked as follows based on the state of cohesiveness:
◯: No agglomerates are generated.
Δ: Aggregates are seen on the bottom or a part of the side surface of the spray device.
X: Aggregates are seen throughout the spraying device.

<Evaluation of peelability>
Using a substrate 15 minutes after the treatment described in the above <laminate>, a rectangular pattern of 4 cm × 6 cm was directly drawn and exposed to the laminated substrate, and then developed by the method described in the above <development>.
The cured resist on the obtained substrate was immersed in 3% by mass NaOH at 50 ° C., and the time until the resist was completely peeled off from the substrate was measured and used as the peeling time.
Here, the peelability was ranked as follows:
◯: It takes 40 seconds or less to completely peel off.
X: It takes more than 40 seconds to completely peel off.

Examples 1 to 7 and Comparative Examples 1 to 4
The compositions of the photosensitive resin compositions used in Examples and Comparative Examples are shown in Table 8, and the details of each component name shown in Table 8 are shown in Table 9. The blending amount of each component in Table 8 is a mass part in terms of solid content.
The evaluation results performed using each composition are also shown in Table 8.

Claims (11)

(A) Alkali-soluble polymer;
(B) Ethylene unsaturated bond-containing compound; and (C) Photopolymerization initiator;
A photosensitive resin composition containing
The (A) alkali-soluble polymer is a structural unit of (meth) acrylic acid of 10% by mass to 24% by mass and 35% by mass based on the total mass of the monomers constituting the (A) alkali-soluble polymer. The photosensitive resin composition containing up to 90% by mass of a structural unit of styrene and having the weight average molecular weight of the (B) ethylenically unsaturated bond-containing compound of 1,200 or more. The photosensitive resin composition according to claim 1, wherein the (B) ethylenically unsaturated bond-containing compound has a weight average molecular weight of 1,300 or more. Of the ethylenically unsaturated bond-containing compound (B), 40% by mass or more is the following general formula (II):

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

{In the formula, R ₅ , R ₆ and R ₇ each independently represent 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. Independently, if m 2 + m 3 + m 4 is an integer from 0 to 40, m ₂ + m ₃ + m ₄ is 1 to 40, and m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of X's are identical to each other. May be present or different}
The photosensitive resin composition according to claim 1 or 2, which comprises a tri (meth) acrylate compound represented by. The ethylenically unsaturated bond-containing compound (B) has the following general formula (IV):

{In the formula, R ₈ and R ₉ 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 is an integer of 0 to 40 independently, and s + t ≧ 1}
The photosensitive resin composition according to claim 1 or 2, which comprises a urethane di (meth) acrylate compound represented by. The photosensitive resin composition according to any one of claims 1 to 7, wherein the alkali-soluble polymer (A) further contains a structural unit of butyl (meth) acrylate. The photosensitive resin composition according to any one of claims 1 to 8, which is used for direct imaging exposure. Laminating step of laminating a photosensitive resin layer made of the photosensitive resin composition according to any one of claims 1 to 9 on a support;
An exposure step for exposing the photosensitive resin layer; and a developing step for developing the exposed photosensitive resin layer;
A method for forming a resist pattern including. Laminating step of laminating a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 9 on a substrate;
An exposure step for exposing the photosensitive resin layer;
A developing 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 a substrate on which the resist pattern is formed; and a peeling step of peeling off the resist pattern;
Manufacturing method of wiring board including.