JP6733553B2 - Photosensitive resin composition, photosensitive element, resist pattern forming method, and structure manufacturing method - Google Patents

Description

The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a structure.

In the field of manufacturing a printed wiring board, which is one of structures having a conductor circuit, a photosensitive resin composition is widely known as a resist material used for etching or plating.

The printed wiring board is, for example, one in which a plurality of wiring layers are formed on a core board, and a copper clad laminate serving as the core board, an interlayer insulating material provided between the wiring layers, and a solder provided on the outermost surface. And a resist. A semiconductor element is usually mounted on a printed wiring board via a die bonding material or an underfill material. Further, if necessary, the entire surface may be sealed with a transfer sealing material, and a metal cap (lid) for improving heat dissipation may be attached. In recent years, there has been no end to the miniaturization of semiconductor devices, and miniaturization of semiconductor devices and multilayer printed wiring boards is increasing. In addition, mounting forms such as package-on-package in which semiconductor devices are stacked on top of semiconductor devices are also actively used, and it is expected that the mounting density of semiconductor devices will be further increased in the future.

Vias (openings) for electrically connecting the upper and lower wiring layers must be provided in the interlayer insulating material of the printed wiring board. If the number of pins of the flip chip mounted on the printed wiring board increases, it is necessary to provide openings of the number corresponding to the number of pins. However, in the conventional printed wiring board, the mounting density is low, and the number of pins of the semiconductor element to be mounted is designed to be about several thousand to ten thousand pins, so it is necessary to provide openings with a small diameter and a narrow pitch. There wasn't.

However, as the miniaturization of semiconductor elements progresses and the number of pins increases from tens of thousands to hundreds of thousands of pins, the opening formed in the interlayer insulating material of the printed wiring board also becomes narrower according to the number of pins of the semiconductor element. The need is growing. Recently, for example, as in the method shown in FIG. 1, development of a printed wiring board in which an opening is formed by laser using a thermosetting resin material is underway (for example, see Patent Documents 1 to 4 below).

FIG. 1 is a schematic diagram showing a conventional method for manufacturing a multilayer printed wiring board. The multilayer printed wiring board 100 shown in FIG. 1(f) has a wiring pattern on the surface and inside. The multilayer printed wiring board 100 is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil and the like and forming a wiring pattern by an etching method or a semi-additive method as appropriate.

The multilayer printed wiring board is manufactured, for example, as follows. First, the interlayer insulating layers 103 are formed on both surfaces of the copper clad laminate 101 having the wiring pattern 102 on the surface (see FIG. 1A). As a method for forming the interlayer insulating layer 103, the thermosetting resin composition may be printed using a screen printer or a roll coater, or a film made of the thermosetting resin composition may be prepared in advance and a laminator may be used. The lever film can also be attached to the surface of the printed wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser at a portion that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by desmearing (FIG. 1B). reference). Next, the seed layer 105 is formed by the electroless plating method (see FIG. 1C). Further, a photosensitive resin composition is laminated on the seed layer 105 to form a photosensitive resin composition layer (photosensitive resin composition layer forming step). Then, an actinic ray is irradiated to a predetermined portion of the photosensitive resin composition layer to cure the exposed portion (exposure step). Then, the unexposed portion is removed (developed) to form a pattern (resist pattern) 106 of the photosensitive resin layer made of a cured product of the photosensitive resin composition (developing step, see FIG. 1D). Next, the wiring pattern (circuit) 107 is formed by electrolytic plating (circuit forming step). Then, the cured product (pattern of the photosensitive resin layer) 106 of the photosensitive resin composition is peeled and removed by the peeling liquid (peeling treatment step). Further, the seed layer 105 is removed by etching (see FIG. 1(e)). By repeating the above process and forming the solder resist 108 on the outermost surface, the multilayer printed wiring board 100 can be manufactured (see FIG. 1F). In the multilayer printed wiring board 100 thus obtained, the semiconductor element is mounted at the corresponding location, and electrical connection can be secured.

However, in the multilayer printed wiring board 100 manufactured by the method shown in FIG. 1, in addition to the introduction of new equipment such as a laser, a large opening with a via diameter of 100 μm or more (for example, a cylindrical opening). In this case, the throughput decreases as the number of laser shots increases, and in the case of a minute opening with a via diameter of 60 μm or less (for example, a cylindrical opening), the laser used according to the opening diameter is selected. There are problems that it is necessary to use properly and it is difficult to provide a special shape. In addition, when forming an opening using a laser, it is necessary to form each opening one by one, so it takes time when a large number of minute openings need to be provided, and a resin is formed around the opening. However, there is also a problem that the reliability of the obtained multilayer printed wiring board decreases unless the residue is removed.

Therefore, in order to solve the above-mentioned problems, various photosensitive resin compositions have been conventionally studied (for example, refer to Patent Documents 5 and 6 below). In such a technique, a photosensitive resin composition that swells in an alkaline aqueous solution is used to form an opening that exposes a conductor circuit, and the photosensitive resin composition has an opening forming portion that is removed to form an opening. A resin layer is formed, and then the opening forming portion is swollen and peeled with an alkaline aqueous solution to remove the resin layer, thereby forming an opening.

Japanese Patent Laid-Open No. 08-279678 JP, 11-054913, A JP 2001-217543 A JP, 2003-017848, A International Publication No. 2013/054790 JP, 11-274727, A

However, in the photosensitive resin composition used in the technique described in Patent Document 5 or 6, when a finer opening (for example, a cylindrical opening having a diameter of 30 μm or less) is formed, the fine opening forming portion is alkaline. Since the aqueous solution is difficult to permeate, there is a problem that it is difficult to remove the opening forming portion due to swelling and peeling of the alkaline aqueous solution.

As described above, the photosensitive resin composition for obtaining the resin layer in which the opening is formed is excellent in the opening property even when the fine opening (for example, the opening having a diameter of 30 μm or less) is formed. Is required.

The present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a photosensitive resin composition having excellent openability even when forming a fine opening. Another object of the present disclosure is to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a structure.

As a result of repeated intensive studies to solve the above problems, the present inventors have used a binder polymer, a specific photopolymerizable compound, and a photopolymerization initiator in combination, whereby a photosensitive resin having excellent opening properties is obtained. It has been found that a composition is obtained.

［式（１）中、Ｒ^１１は、炭素数１〜２０のアルキレン基、炭素数１〜１０のシクロアルキレン基、又は、フェニレン基を示し、Ｒ^１２及びＲ^１３は、各々独立に水素原子又はメチル基を示し、Ｘ^１１及びＸ^１２は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含むオキシアルキレン基又はポリオキシアルキレン基を示し、Ｘ^１１及びＸ^１２に含まれるオキシエチレン基及びオキシプロピレン基の総数が１２〜８０である。］The photosensitive resin composition according to the first embodiment of the present disclosure contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerizable compound has the following general formula (1). And a compound having one ethylenically unsaturated bond in the molecule.

[In the formula (1), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and R ¹² and R ¹³ are each independently a hydrogen atom or A methyl group, X ¹¹ and X ¹² each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group; and X ¹¹ and X ¹² The total number of oxyethylene groups and oxypropylene groups contained in is 12 to 80. ]

［式（２）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、各々独立に炭素数１〜２０のアルキレン基を示し、Ｒ^２４、Ｒ^２５及びＲ^２６は、各々独立に水素原子又はメチル基を示し、Ｘ^２１、Ｘ^２２及びＸ^２３は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含むオキシアルキレン基又はポリオキシアルキレン基を示し、Ｘ^２１、Ｘ^２２及びＸ^２３に含まれるオキシエチレン基及びオキシプロピレン基の総数が１５〜１２０である。］ The photosensitive resin composition according to the second embodiment of the present disclosure contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerizable compound has the following general formula (2). And a compound having one ethylenically unsaturated bond in the molecule.

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group. X ²¹ , X ²² and X ²³ each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X ²¹ , X ²² And the total number of oxyethylene groups and oxypropylene groups contained in X ²³ is 15 to 120. ]

The photosensitive resin composition according to the present disclosure has excellent openability (removability) even when forming a fine opening (for example, a cylindrical opening having a diameter of 30 μm or less). The photosensitive resin composition according to the present disclosure can form openings while suppressing the generation of residues derived from the photosensitive resin composition. According to the photosensitive resin composition of the present disclosure, it is possible to obtain a resist pattern having excellent openability, and to obtain a structure having fine openings and excellent reliability sufficiently efficiently. be able to.

Further, according to the photosensitive resin composition according to the present disclosure, not only can a cylindrical opening be suitably formed, but also an opening of another shape (for example, a line can be formed while suppressing the generation of a residue derived from the photosensitive resin composition). It is also possible to form a line-shaped opening) for obtaining a conductor pattern having a rectangular shape.

［式（３）中、Ｒ^３１は、炭素数１〜５のアルキル基、ハロゲン原子又は水酸基を示し、Ｒ^３２は、水素原子又はメチル基を示し、Ｒ^３３は、水素原子、メチル基又はハロゲン化メチル基を示し、Ａは、炭素数２〜４のアルキレン基を示し、ｍは、１〜４の整数を示し、ｎは、０〜４の整数を示す。なお、ｎが２以上の場合、複数存在するＲ^３１は同一でも異なっていてもよい。］The compound having one ethylenically unsaturated bond in the molecule may include a compound represented by the following general formula (3).

[In the formula (3), R ³¹ represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, R ³² represents a hydrogen atom or a methyl group, and R ³³ represents a hydrogen atom, a methyl group or a halogen. A methyl group, A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 4, and n represents an integer of 0 to 4. When n is 2 or more, a plurality of R ^{31 s} may be the same or different. ]

The binder polymer may have a structural unit derived from (meth)acrylic acid alkyl ester.

The acid value of the binder polymer may be 60 to 250 mg KOH/g. The weight average molecular weight of the binder polymer may be 10,000 to 100,000.

The photopolymerization initiator may include a 2,4,5-triarylimidazole dimer.

The photosensitive resin composition according to the present disclosure may further contain a sensitizing dye.

The photosensitive resin composition according to the present disclosure may further contain a hydrogen donor.

The photosensitive element according to the present disclosure includes a support, and a photosensitive resin layer formed on the support using the photosensitive resin composition according to the present disclosure.

A method for forming a resist pattern according to the present disclosure includes a step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to the present disclosure or the photosensitive element according to the present disclosure, and the photosensitive resin. An exposure step of irradiating a predetermined portion of the layer with an actinic ray to cure the predetermined portion, and removing a portion of the photosensitive resin layer other than the predetermined portion from the substrate, thereby forming the photosensitive resin composition. And a developing step of forming a resist pattern made of a cured product on the substrate.

In the method for forming a resist pattern according to the present disclosure, the wavelength of the actinic ray may be in the range of 340 to 430 nm.

A method for manufacturing a structure according to the present disclosure is a structure in which an opening is provided in an insulating layer formed on a surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. And a photosensitive element according to the present disclosure is used to form a first photosensitive resin layer on the substrate so as to cover a conductor circuit. A step of forming a photosensitive resin layer, a first patterning step of patterning the first photosensitive resin layer by subjecting the first photosensitive resin layer to an exposure process and a development process, and covering the pattern of the first photosensitive resin layer. A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate, and a step of removing a part of the thermosetting resin layer to form a predetermined portion of the pattern of the first photosensitive resin layer by the heat treatment. A pattern exposing step of exposing from the curable resin layer and the predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer are removed, and an opening exposing the conductor circuit is formed by the heat treatment. An opening forming step of forming the curable resin layer. According to the method for manufacturing a structure according to the present disclosure, it is possible to sufficiently efficiently manufacture a structure having fine openings and excellent reliability.

The method for manufacturing a structure according to the present disclosure may further include a thermosetting step of thermosetting the thermosetting resin layer as a step between the thermosetting resin layer forming step and the pattern exposing step.

In the method for manufacturing a structure according to the present disclosure, a seed layer serving as a base of the wiring portion is formed by electroless plating so as to cover at least a part of the thermosetting resin layer after forming the opening. Seed layer forming step, and second patterning step of forming a second photosensitive resin layer so as to cover the seed layer, and then subjecting the second photosensitive resin layer to exposure and development processing for patterning. And a wiring portion patterning step of patterning the wiring portion by forming the wiring portion by an electrolytic plating method so as to cover at least a part of the seed layer, and then peeling off the pattern of the second photosensitive resin layer. And a seed layer removing step of removing the seed layer in the region where the wiring portion is not formed.

According to the present disclosure, it is possible to provide a photosensitive resin composition having excellent openability even when forming fine openings. Further, according to the present disclosure, it is possible to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a structure.

It is a schematic diagram which shows the manufacturing method of the conventional multilayer printed wiring board.

Hereinafter, modes for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments.

In addition, in this specification, "(meth)acrylic acid" means at least one of acrylic acid and methacrylic acid, and "(meth)acrylate" means at least one of acrylate and methacrylate. The “(poly)oxyalkylene group” means at least one of an oxyalkylene group and a polyoxyalkylene group in which two or more alkylene groups are linked by an ether bond. The “(poly)oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The “(poly)oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. "EO-modified" means a compound having a (poly)oxyethylene group, "PO-modified" means a compound having a (poly)oxypropylene group, and "EO-PO". "Modified" means a compound having both a (poly)oxyethylene group and a (poly)oxypropylene group. Note that "oxyalkylene _{group", (- C p H 2p -O-} ) group represented by: a (p 1 or more integer), the term "oxyethylene group", _(- C 2 _{H 4} a group represented by -O-), a "oxypropylene _{group", (-} a group represented by _C 3 H 6 -O-).

In the present specification, the term “process” is included in this term as long as the intended purpose of the process is achieved not only as an independent process but also when it cannot be clearly distinguished from other processes. Be done.

The numerical range indicated by "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. The content of each component in the composition means the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.

The term “layer” includes not only the structure of the shape formed on the entire surface but also the structure of the shape partially formed when observed as a plan view.

The term "laminate" refers to stacking layers, two or more layers may be joined and two or more layers may be removable.

<Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment (first embodiment and second embodiment) has (A) a binder polymer (hereinafter also referred to as “(A) component”) and (B) photopolymerizable. It contains a compound (hereinafter, also referred to as “(B) component”) and a (C) photopolymerization initiator (hereinafter, also referred to as “(C) component”). In the photosensitive resin composition according to the first embodiment, the component (B) contains a compound represented by the following general formula (1) and a compound having one ethylenically unsaturated bond in the molecule. .. In the photosensitive resin composition according to the second embodiment, the component (B) contains a compound represented by the following general formula (2) and a compound having one ethylenically unsaturated bond in the molecule. .. In the present embodiment, the component (B) may include both the compound represented by the following general formula (1) and the compound represented by the following general formula (2). That is, in the photosensitive resin composition according to the present embodiment, the component (B) is selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). And a compound having one ethylenically unsaturated bond in the molecule. The photosensitive resin composition according to the present embodiment may further contain other components, if necessary.

［式（１）中、Ｒ^１１は、炭素数１〜２０のアルキレン基、炭素数１〜１０のシクロアルキレン基、又は、フェニレン基を示し、Ｒ^１２及びＲ^１３は、各々独立に水素原子又はメチル基を示し、Ｘ^１１及びＸ^１２は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含む（ポリ）オキシアルキレン基（オキシアルキレン基又はポリオキシアルキレン基）を示し、Ｘ^１１及びＸ^１２に含まれるオキシエチレン基及びオキシプロピレン基の総数（分子内の総数）が１２〜８０である。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。］

[In the formula (1), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and R ¹² and R ¹³ are each independently a hydrogen atom or Represents a methyl group, and X ¹¹ and X ¹² each independently include at least one selected from the group consisting of an oxyethylene group and an oxypropylene group (poly)oxyalkylene group (oxyalkylene group or polyoxyalkylene group) The total number of oxyethylene groups and oxypropylene groups contained in X ¹¹ and X ¹² (total number in the molecule) is 12 to 80. When both the oxyethylene group and the oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. ]

［式（２）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、各々独立に炭素数１〜２０のアルキレン基を示し、Ｒ^２４、Ｒ^２５及びＲ^２６は、各々独立に水素原子又はメチル基を示し、Ｘ^２１、Ｘ^２２及びＸ^２３は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含む（ポリ）オキシアルキレン基（オキシアルキレン基又はポリオキシアルキレン基）を示し、Ｘ^２１、Ｘ^２２及びＸ^２３に含まれるオキシエチレン基及びオキシプロピレン基の総数（分子内の総数）が１５〜１２０である。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。］

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group. In the formula, X ²¹ , X ²² and X ²³ each independently represent a (poly)oxyalkylene group (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of oxyethylene groups and oxypropylene groups. The total number of oxyethylene groups and oxypropylene groups contained in X ²¹ , X ²² and X ²³ (total number in molecule) is 15 to 120. When both the oxyethylene group and the oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. ]

((A): Binder polymer)
First, the binder polymer will be described.

The binder polymer is not particularly limited, but may be soluble in an alkaline aqueous solution from the viewpoint of further improving the developability. The component (A) may have a structural unit derived from a polymerizable monomer described below, and can be produced, for example, by radically polymerizing the polymerizable monomer described below.

Examples of the polymerizable monomer (monomer) include (meth)acrylic acid; (meth)acrylic acid alkyl ester, (meth)acrylic acid cycloalkyl ester, benzyl (meth)acrylic acid, and benzyl (meth)acrylic acid derivative. Furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-bromo(meth ) Acrylic acid, (meth)acrylic acid ester such as α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, β-styryl(meth)acrylic acid; styrene; vinyltoluene, α-methylstyrene, etc. Styrene derivatives such as compounds substituted at the α-position or the aromatic ring; acrylamide such as diacetone acrylamide; acrylonitrile; esters of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic acid Maleic acid monoesters such as monomethyl, monoethyl maleate and monoisopropyl maleate; fumaric acid; cinnamic acid; α-cyanocinnamic acid; itaconic acid; crotonic acid; propiolic acid. The polymerizable monomers may be used alone or in any combination of two or more.

The component (A) has a structural unit derived from an alkyl (meth)acrylate ester from the viewpoint of further improving the opening property of the photosensitive resin layer by the alkaline aqueous solution during the exposure of the conductor circuit and the formation of the opening. Good. For example, the component (A) may be obtained by radically polymerizing an alkyl (meth)acrylate ester.

Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate and (meth) ) Dodecyl acrylate may be mentioned. The (meth)acrylic acid alkyl ester can be used alone or in any combination of two or more kinds.

When the component (A) has a structural unit derived from a (meth)acrylic acid alkyl ester, the content of the structural unit is more than that of the structural unit constituting the component (A) from the viewpoint of further excellent adhesiveness and opening property. It may be 30 to 85% by mass, 40 to 80% by mass, or 50 to 75% by mass, based on the total mass of the solid content. This content may be 30% by mass or more, 40% by mass or more, or 50% by mass or more from the viewpoint of further excellent adhesion. Further, this content may be 85% by mass or less, 80% by mass or less, or 75% by mass or less, from the viewpoint of further excellent openability.

When the component (A) has a structural unit derived from (meth)acrylic acid, the content of the structural unit is such that the solid content of the structural unit constituting the component (A) is more excellent in adhesiveness and openability. It may be 5 to 80% by mass, 10 to 70% by mass, or 15 to 60% by mass based on the total mass. This content may be 5% by mass or more, 10% by mass or more, and 15% by mass or more from the viewpoint of further excellent developability and openability. Further, this content may be 80% by mass or less, 70% by mass or less, or 60% by mass or less from the viewpoint of further excellent adhesion.

The component (A) may have a structural unit derived from benzyl (meth)acrylate or a derivative thereof, from the viewpoint of further improving the opening property and the adhesiveness. When the component (A) has a structural unit derived from benzyl (meth)acrylate or a derivative thereof, the content of the structural unit is 5 based on the total solid mass of the structural units constituting the component (A). -60 mass%, 10-55 mass%, and 20-50 mass% may be sufficient. This content may be 5% by mass or more, 10% by mass or more, and 20% by mass or more from the viewpoint of further excellent adhesion. Further, this content may be 60% by mass or less, 55% by mass or less, or 50% by mass or less from the viewpoint of further excellent openability.

The acid value of the component (A) may be 60 to 250 mgKOH/g, 100 to 250 mgKOH/g, or 100 to 230 mgKOH/g from the viewpoint of further excellent developability and developer resistance. It may be present or may be 130 to 230 mg KOH/g. When carrying out the solvent development, a small amount of a polymerizable monomer (monomer) having a carboxyl group such as (meth)acrylic acid may be adjusted. The acid value of the component (A) can be measured with reference to the measuring method of Examples described later.

The weight average molecular weight (Mw) of the component (A) is, when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), further excellent in developability and developer resistance, It may be 10,000 to 100,000, 20,000 to 80,000, or 25,000 to 70,000. The weight average molecular weight of the component (A) may be 100,000 or less, 80,000 or less, or 70,000 or less from the viewpoint of further excellent developability. The weight average molecular weight of the component (A) may be 10,000 or more, 20,000 or more, or 25,000 or more, from the viewpoint of further excellent developer resistance. The weight average molecular weight can be measured with reference to the measuring method of Examples described later.

As the component (A), one kind of binder polymer may be used alone, or two or more kinds of binder polymers may be used in arbitrary combination. When two or more kinds of binder polymers are used in combination, for example, two or more kinds of binder polymers composed of different copolymerization components (binder polymers containing different monomer units as copolymerization components) and two kinds of different weight average molecular weights. The above binder polymers and two or more kinds of binder polymers having different dispersities are included. Further, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

The content of the component (A) may be in the following range based on 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of further excellent film forming property, sensitivity and adhesion. The content of the component (A) may be 30 parts by mass or more, 40 parts by mass or more, and 50 parts by mass or more. The content of the component (A) may be 70 parts by mass or less, or 65 parts by mass or less. From these viewpoints, the content of the component (A) may be 30 to 70 parts by mass, 40 to 70 parts by mass, or 50 to 65 parts by mass.

((B): Photopolymerizable compound)
Next, the photopolymerizable compound will be described.

The photosensitive resin composition according to the first embodiment has, as the component (B), a urethane di(meth)acrylate having a total number of structural units of oxyethylene groups and oxypropylene groups per functional group of 6 to 40, and It contains a compound having one (only one) ethylenically unsaturated bond in the molecule. As used herein, the functional group means a (meth)acryloyl group.

Urethane di(meth)acrylate contains the compound represented by the said General formula (1). The photosensitive resin composition according to the first embodiment contains the compound represented by the general formula (1) and the compound having one ethylenically unsaturated bond in the molecule, thereby exposing the conductor circuit. In addition, the opening property can be improved when forming the opening (for example, the opening formed in the photosensitive resin layer by the alkaline aqueous solution).

In the general formula (1), X ¹¹ and X ¹² may each independently be an oxyethylene group and an oxypropylene group, or may be an oxyalkylene group other than the oxyethylene group and the oxypropylene group. It may be. Examples of the oxyalkylene group other than the oxyethylene group and the oxypropylene group include an oxybutylene group. When an oxyalkylene group other than the oxyethylene group and the oxypropylene group is present, the oxyalkylene group and the oxyethylene group and/or the oxypropylene group may be present randomly or may form a block. ..

The compound represented by the general formula (1) may be, for example, a compound represented by the following general formula (1a).

［式（１ａ）中、Ｒ^１１は、式（１）と同様に、炭素数１〜２０のアルキレン基、炭素数１〜１０のシクロアルキレン基、又は、フェニレン基を示し、Ｒ^１２及びＲ^１３は、式（１）と同様に、各々独立に水素原子又はメチル基を示し、Ａ^１Ｏ及びＢ^１Ｏは、各々独立にオキシエチレン基又はオキシプロピレン基を示し、（Ａ^１Ｏ）_ａ１、（Ｂ^１Ｏ）_ｂ１、（Ａ^１Ｏ）_ｃ１及び（Ｂ^１Ｏ）_ｄ１は、各々（ポリ）オキシエチレン基又は（ポリ）オキシプロピレン基を示す。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。ａ１、ｂ１、ｃ１及びｄ１は、対応する構造単位の構造単位数を示し、ａ１、ｂ１、ｃ１及びｄ１は、単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。ａ１＋ｂ１＋ｃ１＋ｄ１は、１２〜８０である。ａ１、ｂ１、ｃ１及びｄ１は、各々独立に０〜８０の数値を採り得る。］

[In the formula (1a), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, as in the formula (1), and R ¹² and R ¹³ Are each independently a hydrogen atom or a methyl group, as in the formula (1), A ¹ O and B ¹ O are each independently an oxyethylene group or an oxypropylene group, and (A ¹ O) _a1 , (B ¹ O) _b1 , (A ¹ O) _c1 and (B ¹ O) _d1 each represent a (poly)oxyethylene group or a (poly)oxypropylene group. When both the oxyethylene group and the oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. a1, b1, c1 and d1 represent the number of structural units of the corresponding structural unit, a1, b1, c1 and d1 represent integer values in a single molecule, and the average as an aggregate of a plurality of types of molecules. Indicates a rational number that is a value. Hereinafter, the same applies to the number of structural units of the structural unit. a1+b1+c1+d1 is 12 to 80. Each of a1, b1, c1 and d1 can independently take a numerical value of 0 to 80. ]

In General Formula (1) and General Formula (1a), R ¹¹ represents an alkylene group having 2 to 18 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or a phenylene group from the viewpoint of further improving the adhesion. Or an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 1 to 7 carbon atoms, or a phenylene group, an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 3 to 6 carbon atoms. It may be a cycloalkylene group or a phenylene group. R ¹² and R ¹³ may be methyl groups from the viewpoint of further improving the adhesiveness. a1+b1+c1+d1 may be 12 to 70 or 12 to 60 from the viewpoint of further improving the developability, opening property and flexibility.

Here, the flexibility will be described. When a resist pattern is formed on a thin substrate having a thickness of 0.5 mm or less, if the resist pattern is peeled off from the substrate due to bending of the substrate or the like, it may cause a short circuit of a circuit (copper wiring or the like) pattern in a subsequent process. Therefore, it is desirable that the formed resist pattern have excellent flexibility. When these characteristics are poor, the resist pattern is likely to be chipped, which causes a short circuit of a circuit (copper wiring or the like) pattern in the subsequent steps.

Examples of the compound represented by the general formula (1) or the general formula (1a) include a compound represented by the following formula (A) (UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name): (EO ) (PO)-modified urethane dimethacrylate (ethylene oxide average 2 mol, propylene oxide average 18 mol adduct) is commercially available. The compounds represented by the general formula (1) or the general formula (1a) can be used alone or in any combination of two or more kinds.

The photosensitive resin composition according to the second embodiment has, as the component (B), an isocyanurate-derived tri(meth)acrylate in which the total number of structural units of oxyethylene groups and oxypropylene groups per functional group is 5 to 40. , And a compound having one (only one) ethylenically unsaturated bond in the molecule. As used herein, the functional group means a (meth)acryloyl group.

The isocyanurate-derived tri(meth)acrylate includes the compound represented by the above general formula (2). The isocyanurate-derived tri(meth)acrylate can also be said to be a tri(meth)acrylate having a skeleton derived from isocyanurate. The photosensitive resin composition according to the second embodiment contains the compound represented by the general formula (2) and the compound having one ethylenically unsaturated bond in the molecule, thereby exposing the conductor circuit. In addition, the opening property can be improved when forming the opening (for example, the opening formed in the photosensitive resin layer by the alkaline aqueous solution).

In the general formula (2), X ²¹ , X ²² and X ²³ may each independently be an oxyethylene group or an oxypropylene group, and may be an oxyalkylene group other than an oxyethylene group and an oxypropylene group. It may be an aspect including. Examples of the oxyalkylene group other than the oxyethylene group and the oxypropylene group include an oxybutylene group. When an oxyalkylene group other than the oxyethylene group and the oxypropylene group is present, the oxyalkylene group and the oxyethylene group and/or the oxypropylene group may be present randomly or may form a block. ..

The compound represented by the general formula (2) may be, for example, a compound represented by the following general formula (2a).

［式（２ａ）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、各々独立に炭素数１〜２０のアルキレン基を示し、Ｒ^２１、Ｒ^２２及びＲ^２３は、無置換であってもよく、置換されていてもよく、当該置換基は、互いに同一であっても異なっていてもよく、Ｒ^２４、Ｒ^２５及びＲ^２６は、各々独立に水素原子又はメチル基を示し、Ａ^２Ｏ及びＢ^２Ｏは、各々独立にオキシエチレン基又はオキシプロピレン基を示し、（Ａ^２Ｏ）_ａ２、（Ｂ^２Ｏ）_ｂ２、（Ａ^２Ｏ）_ｃ２、（Ｂ^２Ｏ）_ｄ２、（Ａ^２Ｏ）_ｅ２及び（Ｂ^２Ｏ）_ｆ２は、各々（ポリ）オキシエチレン基又は（ポリ）オキシプロピレン基を示す。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。ａ２、ｂ２、ｃ２、ｄ２、ｅ２及びｆ２は、対応する構造単位の構造単位数を示し、ａ２、ｂ２、ｃ２、ｄ２、ｅ２及びｆ２は、単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。ａ２＋ｂ２＋ｃ２＋ｄ２＋ｅ２＋ｆ２は、１５〜１２０である。ａ２、ｂ２、ｃ２、ｄ２、ｅ２及びｆ２は、各々独立に０〜１２０の数値を採り得る。］

[In the formula (2a), R ²¹ , R ²² and R ²³ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ²¹ , R ²² and R ²³ may be unsubstituted or substituted. And the substituents may be the same or different from each other, and R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group, and A ² O and B ² O's each independently represent an oxyethylene group or an oxypropylene group, and are (A ² O) _a2 , (B ² O) _b2 , (A ² O) _c2 , (B ² O) _d2 , (A ² O) _e2. And (B ² O) _f2 each represent a (poly)oxyethylene group or a (poly)oxypropylene group. When both the oxyethylene group and the oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. a2, b2, c2, d2, e2 and f2 represent the number of structural units of the corresponding structural unit, and a2, b2, c2, d2, e2 and f2 represent integer values in a single molecule, and plural types A rational number, which is the average value, is shown as the aggregate of numerator of. Hereinafter, the same applies to the number of structural units of the structural unit. a2+b2+c2+d2+e2+f2 is 15 to 120. Each of a2, b2, c2, d2, e2 and f2 can independently take a numerical value of 0 to 120. ]

In the general formula (2) and the general formula (2a), R ²¹ , R ²² and R ²³ may be an alkylene group having 2 to 18 carbon atoms and 2 carbon atoms from the viewpoint of further improving the adhesiveness. It may be an alkylene group having 15 to 15 carbon atoms, or an alkylene group having 2 to 10 carbon atoms. R ²⁴ , R ²⁵ and R ²⁶ may be methyl groups from the viewpoint of further improving the adhesiveness. a2+b2+c2+d2+e2+f2 may be 15 to 100 or 15 to 90 from the viewpoint of further improving the developability, the opening property and the flexibility.

Examples of the compound represented by the general formula (2) or the general formula (2a) include a compound represented by the following formula (B) (UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name): (EO ) Modified isocyanurate derived trimethacrylates (ethylene oxide average 27 mol adduct)) are commercially available. The compounds represented by the general formula (2) or the general formula (2a) can be used alone or in any combination of two or more kinds.

In the photosensitive resin composition according to the present embodiment, the content (total amount) of at least one selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2). May be in the following range with respect to 100 parts by mass of the component (B) from the viewpoint of further excellent openability. The content may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, and 50 parts by mass or more. The content is less than 100 parts by mass, may be 95 parts by mass or less, may be 90 parts by mass or less, and may be 85 parts by mass or less. From these viewpoints, the content may be 10 parts by mass or more and less than 100 parts by mass, 20 parts by mass or more and less than 100 parts by mass, or 30 parts by mass or more and less than 100 parts by mass. It may be 20 to 95 parts by mass, 30 to 90 parts by mass, or 50 to 85 parts by mass.

In the photosensitive resin composition according to the first embodiment, the content of the compound represented by the general formula (1) is as follows with respect to 100 parts by mass of the component (B) from the viewpoint of further excellent openability. It may be a range. The content of the compound represented by the general formula (1) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, and 50 parts by mass or more. It may be. The content of the compound represented by the general formula (1) is less than 100 parts by mass, may be 95 parts by mass or less, may be 90 parts by mass or less, or may be 85 parts by mass or less. Good. From these viewpoints, the content of the compound represented by the general formula (1) may be 10 parts by mass or more and less than 100 parts by mass, 20 parts by mass or more and less than 100 parts by mass, and 30 parts by mass. The amount may be from 100 parts by mass to less than 100 parts by mass, 20 to 95 parts by mass, 30 to 90 parts by mass, or 50 to 85 parts by mass.

In the photosensitive resin composition according to the second embodiment, the content of the compound represented by the general formula (2) is the following with respect to 100 parts by mass of the component (B) from the viewpoint of further excellent openability. It may be a range. The content of the compound represented by the general formula (2) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, and 50 parts by mass or more. It may be. The content of the compound represented by the general formula (2) is less than 100 parts by mass, may be 95 parts by mass or less, may be 90 parts by mass or less, or may be 85 parts by mass or less. Good. From these viewpoints, the content of the compound represented by the general formula (2) may be 10 parts by mass or more and less than 100 parts by mass, 20 parts by mass or more and less than 100 parts by mass, and 30 parts by mass. The amount may be from 100 parts by mass to less than 100 parts by mass, 20 to 95 parts by mass, 30 to 90 parts by mass, or 50 to 85 parts by mass.

Examples of the compound having one ethylenically unsaturated bond in the molecule include fumaric acid compounds. The compounds having one ethylenically unsaturated bond in the molecule can be used alone or in combination of two or more kinds.

The compound having one ethylenically unsaturated bond in the molecule may include a compound represented by the following general formula (3) from the viewpoint of further excellent adhesiveness.

［式（３）中、Ｒ^３１は、炭素数１〜５のアルキル基、ハロゲン原子又は水酸基を示し、Ｒ^３２は、水素原子又はメチル基を示し、Ｒ^３３は、水素原子、メチル基又はハロゲン化メチル基を示し、Ａは、炭素数２〜４のアルキレン基を示し、ｍは、１〜４の整数を示し、ｎは、０〜４の整数を示す。なお、ｎが２以上の場合、複数存在するＲ^３１は同一でも異なっていてもよい。］

[In the formula (3), R ³¹ represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, R ³² represents a hydrogen atom or a methyl group, and R ³³ represents a hydrogen atom, a methyl group or a halogen. A methyl group, A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 4, and n represents an integer of 0 to 4. When n is 2 or more, a plurality of R ^{31 s} may be the same or different. ]

In the general formula (3), R ³² may be a methyl group from the viewpoint of further improving the adhesiveness. R ³³ may be a halogenated methyl group from the viewpoint of easy availability. A may be a propylene group from the viewpoint of further improving the adhesiveness, or may be an ethylene group from the viewpoint of further improving the developability. m may be 1 from the viewpoint of further improving the adhesiveness. n may be 0 or 1, or 0, from the viewpoint of further improving the developability.

Examples of commercially available compounds represented by the general formula (3) include FA-MECH (manufactured by Hitachi Chemical Co., Ltd., γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate). Are listed.

Examples of commercially available compounds having one ethylenically unsaturated bond in the molecule other than the compound represented by the general formula (3) include M-114 (Toagosei Co., Ltd., 4-normalnonylphenoxy). Octaethyleneoxy acrylate) and the like.

The content of the compound having one ethylenically unsaturated bond in the molecule may be in the following range with respect to 100 parts by mass of the component (B) from the viewpoint of more excellent openability. The content of the compound having one ethylenically unsaturated bond in the molecule is more than 0 parts by mass, 5 parts by mass or more, 10 parts by mass or more, and 15 parts by mass or more. May be. The content of the compound having one ethylenically unsaturated bond in the molecule may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, and 50 parts by mass. It may be equal to or less than a part. From these viewpoints, the content of the compound having one ethylenically unsaturated bond in the molecule may be more than 0 parts by mass and 90 parts by mass or less, or 5 to 80 parts by mass, or 10 ˜70 parts by mass, or 15 to 50 parts by mass.

The component (B) is a photopolymerizable compound other than the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound having one ethylenically unsaturated bond in the molecule. Any compound can be used without particular limitation as long as it can contain a compound and can be photocrosslinked. The component (B) is a compound having an ethylenically unsaturated bond (a compound represented by the general formula (1), a compound represented by the general formula (2), and one ethylenically unsaturated bond in the molecule). (Excluding compounds that have). Examples of the compound having an ethylenically unsaturated bond include a compound having two ethylenically unsaturated bonds in the molecule and a compound having three ethylenically unsaturated bonds in the molecule. The photopolymerizable compound other than the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound having one ethylenically unsaturated bond in the molecule may be used alone or Two or more types can be used in combination.

Examples of the compound having two ethylenically unsaturated bonds in the molecule include EO-modified urethane di(meth)acrylate other than the compound represented by the general formula (1), bisphenol type di(meth)acrylate, polyethylene glycol di( (Meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane, and 2,2-bis(4-( Methacryloxypolyethoxypolypropoxy)phenyl)propane. The compound having two ethylenically unsaturated bonds in the molecule can be used alone or in combination of two or more kinds.

Examples of the compound having three ethylenically unsaturated bonds in the molecule include EO-modified isocyanurate-derived tri(meth)acrylate other than the compound represented by the general formula (2), and the general formula (2). PO-modified isocyanurate-derived tri(meth)acrylate other than the compound, EO/PO-modified isocyanurate-derived tri(meth)acrylate other than the compound represented by the general formula (2), trimethylolpropane tri(meth)acrylate, EO-modified Trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO/PO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified pentaerythritol tri(meth)acrylate , PO-modified pentaerythritol tri(meth)acrylate, EO/PO-modified pentaerythritol tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, EO-modified tetramethylolmethane tri(meth)acrylate, PO-modified tetramethylolmethane tri( Examples thereof include (meth)acrylate and EO/PO-modified tetramethylolmethane tri(meth)acrylate. Among them, commercially available products include A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., tetramethylolmethane triacrylate), TMPT21E, TMPT30E (manufactured by Hitachi Chemical Co., Ltd., EO-modified trimethylolpropane trimethacrylate). ) And the like. The compounds having three ethylenically unsaturated bonds in the molecule can be used alone or in combination of two or more kinds.

The content of the component (B) may be in the following range based on 100 parts by mass of the total amount of the components (A) and (B). The content of the component (B) may be 30 parts by mass or more, may be 35 parts by mass or more, and may be 40 parts by mass or more, from the viewpoint that sensitivity and adhesion tend to be more excellent. May be The content of the component (B) may be 70 parts by mass or less, may be 60 parts by mass or less, and may be 50 parts by mass or less from the viewpoint that the developability tends to be more excellent. May be. From these viewpoints, the content of the component (B) may be 30 to 70 parts by mass, 30 to 60 parts by mass, 35 to 50 parts by mass, or 40 to 50 parts by mass. It may be part by mass.

((C): Photopolymerization initiator)
Next, the photopolymerization initiator will be described.

The component (C) is not particularly limited as long as it can polymerize the component (B) by irradiation with actinic rays or the like, and can be appropriately selected from photopolymerization initiators usually used.

Examples of the component (C) include benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and 2-methyl-1-[4-(methylthio)phenyl]-2-. Aromatic ketones such as morpholino-1-propanone; quinones such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyldimethylketal; 2-(o-chlorophenyl )-4,5-Diphenylimidazole dimer (for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2- (O-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4, 2,4,5-triarylimidazole dimers such as 5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; 9-phenylacridine, 1,7- Examples include acridine derivatives such as bis(9,9′-acridinyl)heptane; N-phenylglycine; N-phenylglycine derivatives. The component (C) can be used alone or in combination of two or more kinds.

Further, the substituents of the two aryl groups of 2,4,5-triarylimidazole may give the same and symmetrical compounds, or differently give asymmetric compounds. Further, the component (C) may contain a 2,4,5-triarylimidazole dimer from the viewpoint of further improving the adhesiveness and the sensitivity. When the component (C) contains a 2,4,5-triarylimidazole dimer, its content may be 10 to 100 parts by mass based on 100 parts by mass of the solid content of the component (C). , 30 to 100 parts by mass, or 50 to 100 parts by mass. When the content of the 2,4,5-triarylimidazole dimer in the component (C) is 10 parts by mass or more, the sensitivity and the adhesiveness tend to be further improved.

The content of the component (C) may be in the following range based on 100 parts by mass of the total amount of the components (A) and (B). The content of the component (C) may be 0.1 parts by mass or more, 1 part by mass or more, or 2 parts by mass or more, from the viewpoint that the sensitivity and the adhesiveness tend to be further improved. It may be present or may be 3 parts by mass or more. The content of the component (C) may be 10 parts by mass or less, may be 6 parts by mass or less, and may be 5 parts by mass from the viewpoint that the shape of the opening forming portion tends to be more excellent. It may be the following. From these viewpoints, the content of the component (C) may be 0.1 to 10 parts by mass, 1 to 10 parts by mass, 2 to 6 parts by mass, or 3 It may be up to 5 parts by mass.

((D): Sensitizing dye)
The photosensitive resin composition according to this embodiment may further contain (D) a sensitizing dye (hereinafter, also referred to as “component (D)”).

Examples of the component (D) include dialkylaminobenzophenone compounds (4,4′-bis(diethylamino)benzophenone and the like), pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazoles. Examples thereof include compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds. The component (D) can be used alone or in combination of two or more kinds.

As the component (D), a sensitizing dye having an absorption maximum at 340 to 430 nm can be used. In particular, when exposing the photosensitive resin layer using an actinic ray of 340 to 430 nm, the component (D) is a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, from the viewpoint of further improving the sensitivity and the adhesion. It may contain at least one sensitizing dye selected from the group consisting of a coumarin compound, a triarylamine compound, a thioxanthone compound and an aminoacridine compound, and among them, a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound and a triarylamine compound are included. You may include at least 1 sort(s) selected from the group consisting of.

When the photosensitive resin composition contains the component (D), the content of the component (D) may be in the following range based on 100 parts by mass of the total amount of the components (A) and (B). .. The content of the component (D) may be 0.01 parts by mass or more, or may be 0.05 parts by mass or more, from the viewpoint that sensitivity and adhesion tend to be more excellent. It may be 0.1 part by mass or more. The content of the component (D) may be 10 parts by mass or less, may be 5 parts by mass or less, or 3 parts by mass from the viewpoint that the resist shape in the opening forming portion tends to be more excellent. 1 part by mass or less, 1 part by mass or less, 0.5 parts by mass or less, or 0.3 parts by mass or less. From these viewpoints, the content of the component (D) may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass. , 0.1 to 1 part by mass, 0.1 to 0.5 part by mass, or 0.1 to 0.3 part by mass.

((E): Hydrogen donor)
The photosensitive resin composition according to the present embodiment may further contain (E) hydrogen donor (hereinafter also referred to as “(E) component”). The component (E) can give hydrogen during the reaction in the exposed area. When the photosensitive resin composition according to the present embodiment further contains the component (E), the contrast between the exposed portion and the unexposed portion (also referred to as “imaging property”) can be further improved.

Examples of the component (E) include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane and leuco crystal violet. The component (E) can be used alone or in combination of two or more kinds.

When the photosensitive resin composition contains the component (E), the content of the component (E) may be in the following range based on 100 parts by mass of the total amount of the components (A) and (B). .. The content of the component (E) may be 0.01 parts by mass or more, may be 0.05 parts by mass or more, and may be 0.1, from the viewpoint that the sensitivity tends to be more excellent. The amount may be not less than mass part, or may be not less than 0.2 part by mass. The content of the component (E) may be 10 parts by mass or less, or may be 5 parts by mass or less, from the viewpoint that the component (E) tends to be less likely to precipitate as a foreign substance after the film is formed. It may be 2 parts by mass or less, 1 part by mass or less, or 0.5 parts by mass or less. From these viewpoints, the content of the component (E) may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 2 parts by mass. The amount may be 0.2 to 1 part by mass, or 0.2 to 0.5 part by mass.

(Other ingredients)
The photosensitive resin composition according to the present embodiment is, if necessary, a photopolymerizable compound (oxetane compound etc.) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye (malachite). Green, etc.), photo-coloring agents (tribromophenyl sulfone, leuco crystal violet, etc.), thermal color inhibitors, plasticizers (p-toluene sulfonamide, etc.), pigments, fillers, defoamers, flame retardants, stabilizers, It may further contain an adhesion-imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent and the like. These may be used alone or in combination of two or more. The content thereof may be 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).

[Solution of photosensitive resin composition]
The photosensitive resin composition according to the present embodiment may contain a solvent described below in order to adjust the viscosity, if necessary. For example, the photosensitive resin composition according to the present embodiment can be dissolved in a solvent and used as a solution (coating liquid) having a solid content of 30 to 60% by mass. Examples of the solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and mixed solvents thereof.

The photosensitive resin composition according to the present embodiment can be used to form a photosensitive resin layer by applying a coating liquid on the surface of a support, a substrate, or the like of a photosensitive element described below and drying the coating liquid.

Although the thickness of the photosensitive resin layer varies depending on its use, it may be 2 to 50 μm after being dried. The surface of the photosensitive resin layer may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

<Photosensitive element>
The photosensitive element according to the present embodiment includes a support and a photosensitive resin layer formed on the support using the photosensitive resin composition according to the present embodiment. A photosensitive resin layer can be formed on a support by using the photosensitive resin composition by coating the support on the support and drying the composition. In this way, the photosensitive element according to the present embodiment including the support and the photosensitive resin layer formed on the support is obtained. The photosensitive resin layer can include the above-mentioned photosensitive resin composition. The photosensitive resin composition coated on the support may be the coating liquid described above.

As the support, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate (PET), polypropylene, polyethylene and polyester can be used.

The photosensitive element may optionally include a protective layer that covers the surface of the photosensitive resin layer opposite to the support.

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

As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene and polyester can be used. Examples of commercially available products include Alfan MA-410, E-200C manufactured by Oji Paper Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and PS series such as PS-25 manufactured by Teijin DuPont Films Co., Ltd. Examples thereof include polyethylene terephthalate film. The protective layer may be the same as the support.

Specifically, the photosensitive element can be manufactured as follows, for example. The photosensitive element includes a step of preparing a coating liquid containing the photosensitive resin composition according to the present embodiment, a step of coating the coating liquid on a support to form a coating layer, and drying the coating layer. It can be manufactured by a manufacturing method including a step of forming a photosensitive resin layer.

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

The drying of the coating layer is not particularly limited as long as at least a part of the solvent can be removed from the coating layer. The coating layer may be dried, for example, at 70 to 150° C. for 1 to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive resin layer may be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in a subsequent step.

Further, the thickness (after drying) of the photosensitive resin layer can be appropriately adjusted as necessary. The thickness (after drying) of the photosensitive resin layer may be, for example, 2 to 50 μm. When the thickness is 2 μm or more, it is easy to industrially form the photosensitive resin layer.

The transmittance of the photosensitive resin layer with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays having a wavelength of 365 nm. When this transmittance is 5% or more, sufficient adhesion tends to be easily obtained. When this transmittance is 75% or less, sufficient adhesion tends to be easily obtained. The transmittance can be measured by a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

The photosensitive element may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer and the like.

The obtained photosensitive element may be stored in a sheet form, or may be wound on a winding core and stored. When wound in a roll, the support may be wound outside. Examples of the core include polyethylene, polypropylene, polystyrene, polyvinyl chloride, plastic such as ABS resin (acrylonitrile-butadiene-styrene copolymer), and the like. An end face separator may be installed on the end face of the roll-shaped photosensitive element roll thus obtained from the viewpoint of end face protection, or a moisture-proof end face separator may be installed from the viewpoint of edge fusion resistance. The packaging method may be a method of wrapping in a black sheet having low moisture permeability and packaging.

<Method of forming resist pattern>
A resist pattern can be formed using the photosensitive resin composition or the photosensitive element. The method for forming a resist pattern according to the present embodiment includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate by using the photosensitive resin composition or the photosensitive element, and (ii) ) An exposure step of irradiating a predetermined portion of the photosensitive resin layer with an actinic ray to expose and cure the predetermined portion, and (iii) removing a portion other than the predetermined portion of the photosensitive resin layer from the substrate. And a developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate.

(I) Photosensitive resin layer forming step First, a photosensitive resin layer is formed on a substrate using a photosensitive resin composition or a photosensitive element. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

Examples of the method for forming the photosensitive resin layer on the substrate include, for example, a method in which the photosensitive resin composition is applied on the substrate and then dried, and the photosensitive resin layer in the above-described photosensitive element is transferred onto the substrate. The method of (laminating) is mentioned.

The application of the photosensitive resin composition onto the substrate can be carried out by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating or bar coating.

When a photosensitive element is used, lamination of the photosensitive resin layer onto the substrate is performed by, for example, removing the protective layer of the photosensitive element and then pressure-bonding to the substrate while heating the photosensitive resin layer of the photosensitive element. It is done by As a result, a laminated body including the substrate, the photosensitive resin layer, and the support, which are sequentially laminated, is obtained.

The laminating conditions can be appropriately adjusted as necessary. Lamination may be performed under reduced pressure from the viewpoint of further improving the adhesiveness and the followability. The heating of the photosensitive resin layer and/or the substrate at the time of pressure bonding may be performed at a temperature of 70 to 130°C. The pressure bonding may be performed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf/cm ² ). There are no particular restrictions on these conditions. If the photosensitive resin layer is heated to 70 to 130° C., it is not necessary to preheat the substrate in advance. In order to further improve the stackability, the substrate may be preheated within the above temperature range.

(Ii) Exposure Step Next, a predetermined portion of the photosensitive resin layer on the substrate is irradiated with an actinic ray to expose the predetermined portion and cure it. At this time, when the support existing on the photosensitive resin layer is transparent to the actinic ray, the actinic ray can be irradiated through the support. When the support has a light-shielding property, the photosensitive resin layer is irradiated with actinic rays after the support is removed.

Examples of the exposure method include a method (mask exposure method) of irradiating an image with an actinic ray through a negative or positive mask pattern called an artwork. Further, a method of irradiating an actinic ray imagewise by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method and a DLP (Digital Light Processing) exposure method may be adopted.

A known light source can be used as the light source of the actinic ray. Examples of the light source of actinic rays include ultraviolet rays and visible light such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers (argon lasers, etc.), solid-state lasers (YAG lasers, etc.), semiconductor lasers, etc. Those that radiate effectively are used.

The wavelength of the actinic ray (exposure wavelength) may be 340 to 430 nm or 350 to 420 nm from the viewpoint of more reliably obtaining the effect of the present embodiment.

(Iii) Developing Step In the developing step, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate by removing a portion of the photosensitive resin layer other than the predetermined portion from the substrate. When the support is present on the photosensitive resin layer, the support is removed, and then the portion (unexposed portion) other than the predetermined portion (exposed portion) is removed (developed). The developing method includes wet development and dry development, but wet development is widely used.

In the case of wet development, development is performed by a known development method using a developing solution corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking dipping and the like. From the viewpoint of further improving the resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.

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

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

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

Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and γ-butyrolactone. Water may be added to these organic solvents in the range of 1 to 20% by mass to prevent ignition, to prepare an organic solvent developer.

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

<Method of manufacturing structure>
The photosensitive resin composition according to the present embodiment and the photosensitive element according to the present embodiment are suitably used for manufacturing a structure (for example, a printed wiring board) for mounting a semiconductor element, and particularly, a high density It is preferably used for manufacturing a package substrate and more preferably used for manufacturing a structure (structure having a conductor circuit). In particular, in addition to manufacturing a printed wiring board for mounting a flip-chip type semiconductor device, a method for rewiring a substrateless package such as a coreless board, WLP (Wafer Level Package), and eWLB (embedded Wafer Level Ball Grid Array) is used. Can also be preferably used. Above all, the size of the semiconductor element to be mounted is large, and it is particularly suitable for a printed wiring board for electrically connecting to tens of thousands of bumps arranged in an area array on the surface of the semiconductor element.

The structure according to the present embodiment is a structure in which an opening is provided in an insulating layer formed on the surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. The photosensitive resin composition according to the present embodiment and the photosensitive element according to the present embodiment are provided with an opening in an insulating layer formed on the surface of a substrate having a conductor circuit and are connected to the conductor circuit. It can be used in a method of manufacturing a structure having a wiring part formed in the opening. The insulating layer is, for example, a thermosetting resin layer and/or a photosensitive resin layer. The method for manufacturing a structure according to the present embodiment uses the photosensitive resin composition according to the present embodiment or the photosensitive element according to the present embodiment to form a first photosensitive film on a substrate so as to cover a conductor circuit. Of a photosensitive resin layer for forming a photosensitive resin layer, a first patterning step of patterning a first photosensitive resin layer by exposing and developing the first photosensitive resin layer, and a pattern of the first photosensitive resin layer A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover the substrate, and removing a part of the thermosetting resin layer to heat a predetermined portion of the pattern of the first photosensitive resin layer. A pattern exposing step of exposing from the curable resin layer and a predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer are removed to form an opening for exposing the conductor circuit in the thermosetting resin layer. And a step of forming an opening. The photosensitive resin composition according to this embodiment and the photosensitive element according to this embodiment can be used in a method for manufacturing such a structure. That is, according to the present disclosure, the multilayer printed wiring board shown in FIG. 1 can be manufactured without using a laser. As a method for manufacturing the structure, the manufacturing method described in Patent Document 5 may be used. In this specification, a flexible substrate or a rigid substrate may be used as the “substrate having a conductor circuit”. Further, the "conductor circuit" can be said to be a "conductor pattern" or a "wiring pattern". The shape of the opening is not particularly limited, and may be, for example, an elliptical shape, a polygonal shape, an irregular shape, or another shape in addition to the circular shape and the linear shape. When the line-shaped opening forming portion is formed using the stripping solution, the stripping solution penetrates more than when the opening forming portion having a circular shape, an elliptical shape, a polygonal shape, or an irregular shape is formed. Tends to be easy. In addition, the multilayer printed wiring board that can be manufactured according to the present disclosure includes an insulating layer that is formed so as to cover the conductor circuit, on the substrate that includes the conductor circuit (wiring pattern). Further, the insulating layer has an opening formed so that at least a part of the conductor circuit on the substrate is exposed, and a conductor pattern can be formed in the opening.

In this method for manufacturing a structure, various openings can be easily formed by patterning the first photosensitive resin layer in the first patterning step according to the shape of the opening formed in the thermosetting resin layer. Can be formed. Further, in the method of manufacturing this structure (for example, a printed wiring board), unlike the case where the openings are formed by a laser, a plurality of openings can be formed at the same time, and the residue of resin around the openings can be reduced. Therefore, even when the number of pins of the semiconductor element increases and it becomes necessary to provide a large number of fine openings, a structure having excellent reliability (for example, a printed wiring board) can be efficiently manufactured. Further, even when forming an opening having a diameter of 30 μm or less or forming a large opening having a diameter of 100 μm or more, it is possible to more efficiently form an opening having excellent insulation reliability. it can.

In addition, in the method for manufacturing the structure, the thermosetting resin layer is heat-treated as a step between the thermosetting resin layer forming step and the pattern exposing step (for example, a step immediately after the thermosetting resin layer forming step). It may further include a heat curing step of curing. In this case, for example, part of the thermosetting resin layer after thermosetting is removed in the pattern exposing step, and the first photosensitive resin layer exposed from the thermosetting resin layer is removed in the opening forming step. To do. Examples of methods for removing a part of the thermosetting resin layer after thermosetting include mechanical polishing, plasma treatment, wet blasting, sand blasting, chemical polishing and the like. Examples of methods for removing the first photosensitive resin layer exposed from the thermosetting resin layer include chemical treatment (also referred to as “desmear treatment”), plasma treatment, wet blasting, and sand blasting.

The method of removing a part of the thermosetting resin layer after the thermosetting may be mechanical polishing, and the method of removing the first photosensitive resin layer exposed from the thermosetting resin layer may be a chemical solution treatment. .. By removing a part of the thermosetting resin layer after thermosetting by mechanical polishing, the first photosensitive resin layer can be exposed more quickly, and the residue around the opening can be more reliably reduced. By removing the first photosensitive resin layer exposed from the thermosetting resin layer by the chemical treatment, the residue around the opening can be reduced more reliably. Further, the method of removing a part of the thermosetting resin layer after the thermosetting and the method of removing the first photosensitive resin layer exposed from the thermosetting resin layer may be a chemical treatment. .. In this case, the first photosensitive resin layer can be exposed more quickly, and the residue around the opening can be reduced more reliably. Further, the chemical solution used for the chemical solution treatment can be peeled off by using an aqueous solution which is more alkaline than the alkaline aqueous solution used for the development. Examples of the strongly alkaline aqueous solution include sodium permanganate aqueous solution, sodium hydroxide aqueous solution, and potassium permanganate aqueous solution. Further, as the chemical solution used for the chemical solution treatment, a developing solution comprising water or an alkaline aqueous solution and one or more kinds of organic solvents can be preferably used. Examples of the base of the alkaline aqueous solution include tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol and the like. Examples of the organic solvent used together include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether and the like. A single base or a combination of two or more bases can be used. These chemicals can be used alone or in combination of two or more as a mixed solution.

Further, a method of removing a part of the thermosetting resin layer after the thermosetting and a method of removing the first photosensitive resin layer exposed from the thermosetting resin layer include plasma treatment, wet blasting and sand blasting. It may be at least one selected from the group consisting of In this case, the first photosensitive resin layer can be exposed more quickly, and the residue around the opening can be reduced more reliably.

Further, in the heat curing step, heat curing may be performed in an inert gas atmosphere. By performing thermosetting in an inert gas atmosphere, it is possible to suppress copper oxidation on the surface of the conductor circuit in the thermosetting process.

Further, the method for manufacturing a structure includes a seed layer forming step of forming a seed layer as a base of a wiring portion by electroless plating so as to cover at least a part of the thermosetting resin layer after forming the opening. A second patterning step of forming a second photosensitive resin layer so as to cover the seed layer, and then subjecting the second photosensitive resin layer to exposure and development processing for patterning, and at least one of the seed layers. A wiring portion patterning step of patterning the wiring portion by peeling the second photosensitive resin layer by a peeling process after forming the wiring portion by electrolytic plating so as to cover the portion, and a region where the wiring portion is not formed And a seed layer removing step of removing the seed layer. By forming the seed layer, the wiring portion can be formed by the electrolytic plating method, and the wiring portion can be selectively patterned.

Moreover, in the photosensitive resin layer forming step, the thickness T ₁ of the first photosensitive resin layer may be 2 to 50 μm. When the thickness T ₁ of the first photosensitive resin layer is 2 μm or more, the photosensitive resin composition used for forming the first photosensitive resin layer can be easily formed, so that the structure (for example, a printed wiring board) can be formed. The photosensitive resin layer of the photosensitive element used for manufacturing (1) can be easily formed. When the thickness T ₁ of the first photosensitive resin layer is 50 μm or less, it becomes easy to form a fine pattern on the first photosensitive resin layer.

Further, in the thermosetting resin layer forming step, the thickness T ₂ of the thermosetting resin layer may be ₂ to 50 μm. When the thickness T ₂ of the thermosetting resin layer is 2 μm or more, the thermosetting resin composition used for forming the thermosetting resin layer can be easily formed, so that a structure (for example, a printed wiring board) is manufactured. The film-shaped thermosetting resin composition used for can be easily produced. When the thickness T ₂ of the thermosetting resin layer is 50 μm or less, it becomes easy to form a fine pattern on the thermosetting resin layer.

Further, the structure according to the present embodiment is a structure (structure having a conductor circuit) manufactured by the above-described method for manufacturing a structure, and the diameter of the opening of the thermosetting resin layer is 30 μm or less. It may be. The structure manufactured by the above-described manufacturing method can have fine openings in the insulating layer and have excellent reliability, as compared with the conventional structure shown in FIG. Further, since the diameter of the opening of the thermosetting resin layer in the structure is 30 μm or less, it is suitable for mounting a semiconductor element having a large number of pins whose number is from tens of thousands to hundreds of thousands. It will be a thing.

Further, the thermosetting resin composition used in the above-mentioned method for producing a structure is not particularly limited as long as it can be cured by heat. The thermosetting resin composition may be, for example, a resin composition containing at least one selected from the group consisting of an epoxy resin, a phenol resin, a cyanate ester resin, a polyamideimide resin, and a thermosetting polyimide resin. Further, the thermosetting resin composition may contain an inorganic filler having a maximum particle size of 5 μm or less and an average particle size of 1 μm or less when dispersed in the thermosetting resin composition. By forming a thermosetting resin layer using such a thermosetting resin composition, the surface of the opening formed in the thermosetting resin layer becomes smooth, and a seed layer can be easily formed on the opening. Incidentally, the maximum particle size of the inorganic filler in the state of being dispersed in the thermosetting resin composition refers to that measured using the microtrack method or nanotrack method, for example, dynamic light scattering nanotrack particle size distribution The average value of the respective values measured using a total of "UPA-EX150" (manufactured by Nikkiso Co., Ltd.) and a laser diffraction/scattering type microtrack particle size distribution meter "MT-3100" (manufactured by Nikkiso Co., Ltd.).

Hereinafter, the objects and advantages of the present disclosure will be described more specifically with reference to Examples, but the present disclosure is not limited to the following Examples.

<Synthesis of Binder Polymer (A-1)>
Obtained by mixing 54 g of methacrylic acid which is a polymerizable monomer (monomer), 150 g of methyl methacrylate and 96 g of ethyl acrylate (mass ratio 18/50/32) with 2.5 g of azobisisobutyronitrile. The solution was designated as "solution a".

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

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

The solution a was added dropwise to the above mixed solution in the flask over a period of 4 hours at a constant dropping rate, and then stirred at 80° C. for 2 hours. Next, the above solution b was added dropwise to the solution in the flask over a period of 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80° C. for 3 hours. Further, the solution in the flask was heated to 90° C. over 30 minutes, stirred at 90° C. for 2 hours, stopped stirring, and cooled to room temperature to obtain a solution of the binder polymer (A-1). In the present specification, room temperature refers to 25°C.

The binder polymer (A-1) had a nonvolatile content (solid content) of 44.6% by mass, a weight average molecular weight of 50,000 and an acid value of 117 mgKOH/g.

(Measurement method of weight average molecular weight)
The weight average molecular weight was derived by measuring it by gel permeation chromatography (GPC) and converting it using a calibration curve of standard polystyrene. The conditions of GPC are shown below.
(GPC condition)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (above, Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran (hereinafter also referred to as "THF")
Sample concentration: 120 mg of a binder polymer solution having a solid content of 44.6% by mass was collected and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40°C
Injection volume: 200 μL
Pressure: 49 Kgf/cm ² (4.8 MPa)
Flow rate: 2.05 mL/min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

(Method of measuring acid value)
About 1 g of the synthesized binder polymer was weighed in an Erlenmeyer flask. Next, a mixed solvent (mass ratio: toluene/methanol=70/30) was added to dissolve the binder polymer. After that, an appropriate amount of phenolphthalein solution was added as an indicator and titrated with 0.1N potassium hydroxide aqueous solution, and the acid value was measured by the following formula.
x=10×Vf×56.1/(Wp×I)
In the formula, x represents an acid value (mgKOH/g), Vf represents a titration amount (mL) of a 0.1 N KOH aqueous solution, Wp represents a measured resin solution mass (g), and Ip Indicates the ratio (mass %) of the non-volatile content in the measured resin solution.

<Synthesis of Binder Polymers (A-2) and (A-3)>
As the polymerizable monomer (monomer), the materials shown in Table 1 were used in the mass ratios shown in Table 1, and the binder polymer (A-2) was obtained in the same manner as in the case of obtaining the solution of the binder polymer (A-1). ) And the solution of (A-3) were obtained.

<Preparation of Photosensitive Resin Composition (Coating Liquid)>
The photosensitive resin compositions (coating liquids) of Examples and Comparative Examples were prepared by mixing the components shown in Tables 2 to 5 in the blending amounts (parts by mass) shown in Tables 2 to 5. The blending amount of the binder polymer in the table is the mass (solid content) of the nonvolatile content. Details of each component shown in Tables 2 to 5 are as follows.

(A) Binder polymer The binder polymers (A-1) to (A-3) synthesized as described above were used.

(B) Photopolymerizable compound UA-13: (EO)(PO)-modified urethane dimethacrylate (ethylene oxide average 2 mol, propylene oxide average 18 mol adduct) (Shin-Nakamura Chemical Co., Ltd., trade name)
UA-7100: (EO)-modified isocyanurate-derived trimethacrylate (ethylene oxide average 27 mol adduct) (Shin-Nakamura Chemical Co., Ltd., trade name)
FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (trade name, manufactured by Hitachi Chemical Co., Ltd.)
-M-114: 4-normalnonylphenoxyoctaethyleneoxy acrylate (trade name, manufactured by Toagosei Co., Ltd.)
-UA-11: (EO) modified urethane dimethacrylate (ethylene oxide average 10 mol adduct) (Shin-Nakamura Chemical Co., Ltd., trade name)
-UA-21: (EO)-modified isocyanurate-derived trimethacrylate (ethylene oxide average 12 mol adduct) (Shin-Nakamura Chemical Co., Ltd., trade name)
TMPT-9EO: (EO) modified trimethylolpropane trimethacrylate (ethylene oxide average 9 mol adduct) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
TMPT-21EO: (EO) modified trimethylolpropane trimethacrylate (ethylene oxide average 21 mol adduct) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
FA-024M: a vinyl compound (trade name, manufactured by Hitachi Chemical Co., Ltd.) in which R ⁴¹ and R ^{42 are} methyl groups, r4=6 (average value), and s41+s42=12 (average value) in the following general formula (4). )
9G: Polyethylene glycol dimethacrylate (ethylene oxide average 9 mol adduct) (Shin-Nakamura Chemical Co., Ltd., trade name)

(C) Photopolymerization initiator B-CIM: 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole (Hampford, trade name )

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

(E) Hydrogen donor LCV: Leuco Crystal Violet (Yamada Chemical Co., Ltd., trade name)

Dye MKG: Malachite Green (Osaka Organic Chemical Industry Co., Ltd., trade name)

<Preparation of printed wiring board having conductor circuit>
(Production of photosensitive element)
Each of the photosensitive resin compositions obtained above was applied onto a polyethylene terephthalate film (manufactured by Teijin Limited, trade name “HTF-01”) having a thickness of 16 μm (supporting film) so that the thickness would be uniform. did. Next, using a hot air convection dryer, the film was dried at 70° C. for 1 minute and then at 110° C. for 1 minute to form a photosensitive resin layer having a film thickness after drying of 25 μm. Further, a polyethylene film (manufactured by Tama Poly Co., Ltd., trade name "NF-15") (protective layer) was attached on the photosensitive resin layer, and the support film, the photosensitive resin layer, and the protective layer were laminated in order. As the photosensitive element, the photosensitive elements according to the example and the comparative example were obtained.

(Formation of photosensitive resin layer)
First, a copper-clad laminate (trade name "MCL-E-679FG" manufactured by Hitachi Chemical Co., Ltd.) having 18 μm-thick copper foil adhered on both sides was prepared. The thickness of the copper clad laminate was 400 μm. The copper surface was roughened with a CZ treatment liquid (manufactured by Mec Co., Ltd., trade name "Mec Etch Bond CZ-8100"). After heating this roughened copper substrate (hereinafter, simply referred to as “substrate”) to 80° C., each of the photosensitive elements according to Examples and Comparative Examples was laminated on the copper surface of the substrate ( Laminated). Lamination was performed under conditions of a temperature of 120° C. and a laminating pressure of 0.39 MPa while the protective layer was removed and the photosensitive resin layer of each photosensitive element was in close contact with the copper surface of the substrate. Then, it was cooled to room temperature to obtain a laminated substrate A in which the photosensitive resin layer and the supporting film were laminated on the copper surface of the substrate.

(Formation of photosensitive resin layer pattern)
Next, the laminated substrate A is divided into two regions, and a circular pattern having a diameter of 30 μmφ, 40 μmφ, and 50 μmφ is arranged at a pitch of 40 μm, 80 μm, and 100 μm on the support film in one region, respectively. A photo tool made of PET was placed. The distance between the centers of two adjacent circular patterns is called "pitch". The exposure is performed using a parallel light exposure machine (manufactured by Oak Co., Ltd., trade name “EXM-1201”) using a short arc UV lamp (manufactured by Oak Co., Ltd., trade name “AHD-5000R”) as a light source. The photosensitive resin layer was exposed through a phototool made of PET and a supporting film with an exposure amount (energy amount) that the diameter of a circular pattern of 30 μmφ after development was obtained as designed. An ultraviolet illuminometer (trade name “UV-350SN type” manufactured by Oak Manufacturing Co., Ltd.) to which a probe compatible with 365 nm was applied was used for measuring the illuminance.

After the exposure, the support film was peeled off from the laminated substrate A to expose the photosensitive resin layer. Then, an unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution at 30° C. and 0.2 MPa using a developing machine (manufactured by HMS). The development time was twice the minimum development time of each photosensitive resin composition. In this way, a laminated substrate B was obtained by forming a cured film composed of a cured product pattern (photosensitive resin layer pattern) of the photosensitive resin composition on the copper surface of the substrate. The shortest development time is a value obtained by the following measurement. First, the laminated substrate A was cut into a size of 30 mm×30 mm to prepare a test piece. After peeling the support film from the test piece, spray development is performed at a pressure of 0.2 MPa using a 1% by mass sodium carbonate aqueous solution at 30° C., and it is possible to visually confirm that the unexposed portion of 1 mm or more has been removed. Was set as the shortest development time.

(Preparation of thermosetting film type resin composition)
As a thermosetting resin composition used for forming a thermosetting resin layer (interlayer insulating layer) of a printed wiring board, 70 parts by mass of an epoxy resin, 30 parts by mass of a curing agent (solid content), and an inorganic filler component were used. A thermosetting resin composition solution was prepared by mixing. The inorganic filler component was blended so as to be 30% by mass with respect to the resin component.

As the epoxy resin, a biphenylaralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name “NC-3000H”) was used.

As the curing agent, a solution of the curing agent obtained as described below was used. In a reaction vessel having a thermometer, a stirrer, and a water content meter with a reflux condenser and capable of heating and cooling and having a volume of 2 L, bis(4-aminophenyl)sulfone: 26.40 g and 2,2′- Bis[4-(4-maleimidophenoxy)phenyl]propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g were added and reacted at 140° C. for 5 hours. As a result, a solution of a curing agent having a sulfone group in the molecular main chain and an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

As the inorganic filler component, a silica filler having an average particle diameter of 50 nm and subjected to silane coupling treatment with vinylsilane was used. Regarding the dispersion state, a dynamic light scattering nanotrack particle size distribution meter “UPA-EX150” (manufactured by Nikkiso Co., Ltd.) and a laser diffraction scattering type microtrack particle size distribution meter “MT-3100” (manufactured by Nikkiso Co., Ltd.) were used. It was confirmed that the maximum particle size was 1 μm or less.

The solution of the thermosetting resin composition obtained as described above is uniformly applied onto a polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) having a thickness of 16 μm, which is a supporting layer, to obtain thermosetting properties. A resin composition layer was formed. Then, the thermosetting resin composition layer was dried at 100° C. for about 10 minutes using a hot air convection dryer to obtain a film thermosetting resin composition. The film thickness of the film thermosetting resin composition was adjusted to 10 to 90 μm.

Then, a polyethylene film (Tama Poly Co., Ltd., trade name "NF-15") is provided on the surface opposite to the side in contact with the support layer so that dust or the like does not adhere to the thermosetting resin composition layer. This was laminated as a protective film to obtain a thermosetting film type resin composition.

(Aperture formation)
A thermosetting resin layer was formed on the laminated substrate B by using the obtained thermosetting film type resin composition. Specifically, first, only the protective film of the thermosetting film type resin composition comprising the thermosetting resin composition is peeled off, and heat is applied to both surfaces of the laminated substrate B (on the photosensitive resin layer pattern and the conductor circuit). The curable resin composition was placed. The thermosetting resin composition was laminated on the surface of the laminated substrate B using a press type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.). Regarding the press conditions, the hot plate temperature of the press was 80° C., the evacuation time was 20 seconds, the laminating press time was 30 seconds, the atmospheric pressure was 4 kPa or less, and the pressure bonding was 0.4 MPa. Then, the thermosetting resin layer was thermoset in a clean oven at a predetermined temperature for a predetermined time.

Then, the thermosetting resin layer was ground by plasma treatment (plasma ashing) under the conditions shown in Table 6 to form an exposed portion in the photosensitive resin layer pattern. Then, along the steps shown in Table 7, the exposed portion of the photosensitive resin layer pattern is removed, and a part of the thermosetting resin layer and the photosensitive resin layer is opened to form a via, thereby forming a via. Got

<Evaluation of openness>
The openability of the via (removability of the cylindrical resist) was evaluated by observing vias having a diameter of 30 μmφ, 40 μmφ, and 50 μmφ with an electron microscope (SEM) based on the following criteria. The evaluation results are shown in Tables 8-11.
A: There is no residue derived from the photosensitive resin composition on the copper surface, and it can be peeled and removed.
B: Residue derived from the photosensitive resin composition is generated in less than 50% of the volume in the via formation portion (opening portion).
C: 50% or more of the volume of the residue derived from the photosensitive resin composition is generated in the via formation portion (opening portion).

<Evaluation of flexibility>
An FPC board (trade name: F-30VC1, substrate thickness: 25 μm, copper thickness: 18 μm, manufactured by Nikkan Kogyo Co., Ltd.) was heated to 80° C., and the photosensitive element according to the example and the comparative example was placed on the copper surface. The photosensitive resin composition layer and the supporting film were laminated at a speed of 1.5 m/min using a heat roll at 110° C. while peeling off the protective film so that the photosensitive resin composition layer faced the FPC substrate side. The FPC board on which the photosensitive resin composition layer and the supporting film were laminated was used as a test piece for evaluating flexibility. For the above test piece, a parallel light exposure machine (manufactured by Oak Co., Ltd., trade name “EXM-1201”) using a short arc UV lamp (manufactured by Oak Co., Ltd., trade name “AHD-5000R”) is used. Then, the 41-step step tablet was exposed to light with an energy amount of 20 steps after the development, and the photosensitive resin composition layer was photocured. Then, the supporting film was peeled off and then developed to obtain a substrate for flexural evaluation in which a resist pattern was laminated on the FPC substrate.

Flexibility was evaluated by a mandrel test. The flexural evaluation substrate was cut into a strip having a width of 2 cm and a length of 10 cm, and rubbed against a cylindrical rod at 180° for 5 reciprocations. After that, the minimum diameter (mm) of the cylinder that was not peeled off between the FPC board and the resist pattern was obtained. The smaller the diameter of the cylinder, the better the flexibility. The results are shown in Tables 8-11.

<Adhesion evaluation>
Adhesion was evaluated using the photosensitive resin compositions of Examples 2, 7, 12, and 14. Similar to the above (Formation of photosensitive resin layer pattern), using a PET photo tool having a design in which circular patterns having diameters of 30 μmφ, 40 μmφ, and 50 μmφ are arranged at 40 μm, 80 μm, and 100 μm pitches, respectively. A columnar resist (also called a post) was formed. It was observed with an electron microscope (SEM), and the ratio of the post remaining after development (that is, the formability of the post) was evaluated based on the following criteria as an index of adhesion. The results are shown in Tables 12 and 13.
A: Posts are formed in 90% or more of the entire opening of the mask design.
B: Posts are formed in 50% or more and less than 90% of the entire opening of the mask design.
C: Posts are formed in less than 50% of the entire opening of the mask design.

As is clear from Tables 8 to 11, it was found that by using the photosensitive resin composition of the example, the opening property was good and the flexibility was excellent even when the via diameter was 30 μm or less. On the other hand, the opening property of the via obtained using the photosensitive resin composition of the comparative example was inferior to that of the example. Further, it was found that the use of the photosensitive resin composition of Example 2 was superior to the case of using the photosensitive resin composition of Example 7 in forming the cylindrical resist. Moreover, it was found that the use of the photosensitive resin composition of Example 12 was superior in the formability of the cylindrical resist as compared with the case of using the photosensitive resin composition of Example 14.

Further, a printed wiring board was prepared in the same manner as in the above evaluation except that the diameter of the via was changed to 100 μm, and the same evaluation as above was performed. Further, a printed wiring board was prepared in the same manner as the above evaluation except that the diameter of the via was changed to 200 μm, and the same evaluation as above was performed. In all cases, it was found that when the photosensitive resin compositions of Examples 1 to 14 were used, the opening property was good and the throughput was excellent even if the roughening time was shortened to one third.

100... Multilayer printed wiring board, 101... Copper clad laminated board, 102... Wiring pattern, 103... Interlayer insulating layer, 104... Opening, 105... Seed layer, 106... Wiring pattern, 107... Wiring pattern, 108... Solder resist.

Claims (15)

Contains a binder polymer (excluding a binder polymer having a weight average molecular weight of 80,000) , a photopolymerizable compound, and a photopolymerization initiator,
A photosensitive resin composition, wherein the photopolymerizable compound comprises a compound represented by the following general formula (1) and a compound having one ethylenically unsaturated bond in the molecule.

[In the formula (1), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and R ¹² and R ¹³ are each independently a hydrogen atom or A methyl group, X ¹¹ and X ¹² each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group; and X ¹¹ and X ¹² The total number of oxyethylene groups and oxypropylene groups contained in is 12 to 80. ] Contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator,
A photosensitive resin composition, wherein the photopolymerizable compound comprises a compound represented by the following general formula (2) and a compound having one ethylenically unsaturated bond in the molecule.

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group. X ²¹ , X ²² and X ²³ each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X ²¹ , X ²² And the total number of oxyethylene groups and oxypropylene groups contained in X ²³ is 15 to 120. ] The photosensitive resin composition according to claim 1 or 2, wherein the compound having one ethylenically unsaturated bond in the molecule includes a compound represented by the following general formula (3).

[In the formula (3), R ³¹ represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, R ³² represents a hydrogen atom or a methyl group, and R ³³ represents a hydrogen atom, a methyl group or a halogen. A methyl group, A represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 4, and n represents an integer of 0 to 4. When n is 2 or more, a plurality of R ^{31 s} may be the same or different. ] The photosensitive resin composition according to any one of claims 1 to 3, wherein the binder polymer has a structural unit derived from an alkyl (meth)acrylate. The photosensitive resin composition according to claim 1, wherein the binder polymer has an acid value of 60 to 250 mgKOH/g. The photosensitive resin composition according to any one of claims 1 to 5, wherein the binder polymer has a weight average molecular weight of 10,000 to 100,000. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator contains a 2,4,5-triarylimidazole dimer. The photosensitive resin composition according to claim 1, further containing a sensitizing dye. The photosensitive resin composition according to claim 1, further containing a hydrogen donor. A photosensitive element comprising a support and a photosensitive resin layer formed on the support using the photosensitive resin composition according to claim 1. Forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 9 or the photosensitive element according to claim 10.
An exposure step of irradiating a predetermined portion of the photosensitive resin layer with an actinic ray to cure the predetermined portion;
A developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate by removing a portion other than the predetermined portion of the photosensitive resin layer from the substrate, the resist Pattern formation method. The method for forming a resist pattern according to claim 11, wherein the wavelength of the actinic ray is in the range of 340 to 430 nm. A method of manufacturing a structure, wherein an opening is provided in an insulating layer formed on a surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening,
The 1st photosensitive resin on the said board|substrate so that a conductor circuit may be covered using the photosensitive resin composition as described in any one of Claims 1-9, or the photosensitive element of Claim 10. A photosensitive resin layer forming step of forming a layer,
A first patterning step of patterning by subjecting the first photosensitive resin layer to an exposure treatment and a development treatment;
A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover the pattern of the first photosensitive resin layer;
A pattern exposing step of removing a part of the thermosetting resin layer to expose a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer;
An opening forming step of removing the predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit; A method of manufacturing a structure, comprising: The method for manufacturing a structure according to claim 13, further comprising a thermosetting step of thermosetting the thermosetting resin layer as a step between the thermosetting resin layer forming step and the pattern exposing step. A seed layer forming step of forming a seed layer as a base of the wiring portion by an electroless plating method so as to cover at least a part of the thermosetting resin layer after forming the opening;
A second patterning step of patterning the second photosensitive resin layer by exposing and developing the second photosensitive resin layer after forming the second photosensitive resin layer so as to cover the seed layer;
A wiring part patterning step of patterning the wiring part by peeling the pattern of the second photosensitive resin layer after forming the wiring part by electrolytic plating so as to cover at least a part of the seed layer;
The method for manufacturing a structure according to claim 13, further comprising: a seed layer removing step of removing a seed layer in a region where the wiring portion is not formed.

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