JP2018127648A - Method for producing plating product and photosensitive composition for producing plating product - Google Patents

Abstract

SOLUTION: The method for producing the plating product comprises the steps of (1) coating a photosensitive composition, which contains a compound (A) having at least one ethylenically unsaturated double bond in a molecule, a photo-radical polymerization initiator (B) having oxime ester structure and a photo-radical polymerization initiator (C ) having specific structure, on a substrate to form a coating film, (2) exposing the coating film, (3) developing the coating film after exposure to form a resist pattern, (4) performing a plating process on the substrate using the resist pattern as a mask, and (5) removing the resist pattern from the substrate.EFFECT: The method for producing the plating product according to the present invention makes it possible to produce the desired proper plating product and further, makes it possible to easily peel off a resist from a substrate after completion of plating since the photosensitive composition is used and thereby the formed resist does not deform when a plating solution is pushed in.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a plated model and a photosensitive composition for producing a plated model.

  In recent years, connection terminals such as wiring and bumps of semiconductor elements and display elements such as liquid crystal displays and touch panels have been increasingly miniaturized due to an increasing demand for high-density mounting.

In general, wiring and bumps are plated objects, and as described in Patent Document 1, a resist pattern is formed on a substrate having a metal foil such as copper, and plating is performed using the resist pattern as a mask. Manufactured by doing.
For this reason, with the miniaturization of wiring, bumps and the like, the resist pattern used for the manufacture thereof has also become necessary to be miniaturized.

JP 2006-285035 A

  However, when the resist pattern is miniaturized, the width between the resist patterns is narrowed. Therefore, when the plating solution is filled between the resist patterns in the plating process, the resist is deformed due to the pushing of the plating solution, and thus the plated model is thickened. The problem that it is generated and a plated shaped article having a desired shape cannot be manufactured cannot be ignored. In particular, in the case of gold plating, the plating solution strongly pushes the resist, so the problem of the thickness of the plated model is large. For this reason, the resist is required to have a hardness that does not cause deformation due to the pressing of the plating solution.

  On the other hand, after a plated model is manufactured by plating, it is necessary to peel the resist from the substrate. For this reason, it is desirable that the resist be easily peeled from the substrate. At that time, if the resist has a hardness that does not cause deformation by pressing, it tends to be difficult to remove the resist from the substrate.

In other words, the hardness required for the resist that does not cause deformation due to indentation and the ease of peeling from the substrate are in a trade-off relationship.
The present invention provides a method for manufacturing a plated model that can manufacture an appropriate plated model, even in the case of gold plating that requires strong indentation, and a resist that is suitable for manufacturing such a model. An object of the present invention is to provide a resist composition that can be used.

  The present invention that achieves the above object includes a compound (A) having at least one ethylenically unsaturated double bond in one molecule, a photoradical polymerization initiator (B) having an oxime ester structure, and the following formula ( A photosensitive composition containing a photoradical polymerization initiator (C1) shown in 1) and at least one photoradical polymerization initiator (C) selected from the photoradical polymerization initiator (C2) shown in the following formula (2) A step (1) of applying a product on a substrate to form a coating film;

（式（１）中、Ｒ¹¹は、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し；
Ｒ¹²およびＲ¹³はそれぞれ独立に、アルキル基、アラルキル基、またはアリール基を示し；
Ｘは、酸素原子または硫黄原子を示し；
ｎは、０または１を示し；
Ｒ¹⁴は、置換基として水酸基、カルボキシル基およびスルホ基から選ばれる少なくとも１種の基を有する置換炭化水素基を示す。）

(In the formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
X represents an oxygen atom or a sulfur atom;
n represents 0 or 1;
R ¹⁴ represents a substituted hydrocarbon group having at least one group selected from a hydroxyl group, a carboxyl group and a sulfo group as a substituent. )

（式（２）中、２つのＲ²¹はそれぞれ独立に、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し、２つのＲ²¹のうち少なくとも１つは水酸基であり；
２つのＲ²²および２つのＲ²³はそれぞれ独立に、アルキル基、アラルキル基、又はアリール基を示し；
Ｙは、アルカンジイル基、酸素原子、または硫黄原子を示し；
ｍは、０または１の整数を示す。）

(In the formula (2), two R ²¹ each independently represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ²¹ is a hydroxyl group;
Two R ²² and two R ²³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
Y represents an alkanediyl group, an oxygen atom, or a sulfur atom;
m represents an integer of 0 or 1. )

Step (2) of exposing the coating film
A step (3) of developing the exposed coating film to form a resist pattern;
Step (4) of performing a plating process on the base material using the resist pattern as a mask and Step (5) of removing the resist pattern from the base material
It is a manufacturing method of the plated modeling thing characterized by having.

In the method for producing a plated model, the photo radical polymerization initiator (B) preferably contains the photo radical polymerization initiator (C1).
In the method for producing a plated model, the photosensitive composition contains 100 to 5,000 parts by mass of the radical photopolymerization initiator (B) with respect to 100 parts by mass of the radical photopolymerization initiator (B). It is preferable to do.

In the method for producing a plated model, it is preferable that the photosensitive composition further contains an alkali-soluble resin (D).
In the method for producing a plated model, the photosensitive composition contains 0.01 to 10 parts by mass of the radical photopolymerization initiator (B) with respect to 100 parts by mass of the alkali-soluble resin (D). Is preferred.
Examples of the method for producing the plated model include an embodiment in which the plating process is a gold plating process.

  In addition, the present invention for achieving the above object includes a compound (A) having at least one ethylenically unsaturated double bond in one molecule, a radical photopolymerization initiator (B) having an oxime ester structure, Containing at least one photoradical polymerization initiator (C) selected from a photoradical polymerization initiator (C1) represented by the formula (1) and a photoradical polymerization initiator (C2) represented by the following formula (2): Is a photosensitive composition for producing a plated model.

（式（１）中、Ｒ¹¹は、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し；
Ｒ¹²およびＲ¹³はそれぞれ独立に、アルキル基、アラルキル基、またはアリール基を示し；
Ｘは、酸素原子または硫黄原子を示し；
ｎは、０または１を示し；
Ｒ¹⁴は、置換基として水酸基、カルボキシル基およびスルホ基から選ばれる少なくとも１種の基を有する置換炭化水素基を示す。）

(In the formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
X represents an oxygen atom or a sulfur atom;
n represents 0 or 1;
R ¹⁴ represents a substituted hydrocarbon group having at least one group selected from a hydroxyl group, a carboxyl group and a sulfo group as a substituent. )

（式（２）中、２つのＲ²¹はそれぞれ独立に、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し、２つのＲ²¹のうち少なくとも１つは水酸基であり；
２つのＲ²²および２つのＲ²³はそれぞれ独立に、アルキル基、アラルキル基、又はアリール基を示し；
Ｙは、アルカンジイル基、酸素原子、または硫黄原子を示し；
ｍは、０または１を示す。）

(In the formula (2), two R ²¹ each independently represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ²¹ is a hydroxyl group;
Two R ²² and two R ²³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
Y represents an alkanediyl group, an oxygen atom, or a sulfur atom;
m represents 0 or 1. )

  Using the photosensitive composition for producing a plated article of the present invention, even in the case of gold plating that requires strong indentation, a resist that is not easily deformed by the indentation of the plating solution and that is easily peeled off from the substrate after the plating is completed is formed. can do.

  The method for producing a plated model according to the present invention uses the photosensitive composition for producing a modeled plating, so that the resist to be formed is not deformed when the plating solution is pushed in. In addition, the resist can be easily peeled off from the substrate after the plating is completed.

[Photosensitive composition for producing a plated model]
The photosensitive composition for producing a plated article of the present invention includes a compound (A) having at least one ethylenically unsaturated double bond in one molecule, and a photo radical polymerization initiator (B) having an oxime ester structure. And at least one photoradical polymerization initiator (C) selected from a photoradical polymerization initiator (C1) represented by the following formula (1) and a photoradical polymerization initiator (C2) represented by the following formula (2): It may contain an alkali-soluble resin (D), and may further contain other components depending on the purpose.

  The photosensitive composition for producing a plated article of the present invention is deformed by using a combination of the photo radical polymerization initiator (B) and the photo radical polymerization initiator (C) as a photo radical polymerization initiator. This realizes a high level of resist performance that has a trade-off relationship between hardness and ease of peeling from the substrate, and makes it possible to produce an appropriate plated model even in gold plating and the like.

  In the present invention, the (meth) acryloyl group is a generic name for acryloyl group and methacryloyl group, and the (meth) acryloyloxy group is a generic name for acryloyloxy group and methacryloyloxy group, and (meth) acrylate. Is a general term for acrylate and methacrylate.

[Compound (A) having at least one ethylenically unsaturated double bond in one molecule]
The compound (A) is a component that undergoes radical polymerization by active species generated from a photoradical polymerization initiator upon exposure, and has at least one ethylenically unsaturated double bond in one molecule.
As the compound (A), a (meth) acrylate compound having a (meth) acryloyl group and a compound having a vinyl group are preferable. The (meth) acrylate compound is classified into a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound, and any compound may be used.

Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl amyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, Allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, glycerol (meth) acrylate, ethylene glycol monomethyl Ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, E Bruno carboxymethyl polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decadienyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] Decanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decenyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, cyclohexyl (meth) acrylate, acrylic acid amide, methacrylic acid amide , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, tert-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Examples thereof include relate and 7-amino-3,7-dimethyloctyl (meth) acrylate.

  Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO (propylene oxide) modified tri (meth) acrylate, and tetramethylolpropane. Tetra (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tris (2-hydroxyethyl) i Epoxy with cyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A diglycidyl ether added with (meth) acrylic acid ( Meth) acrylate, bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxymethyl ethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyester Meth) acrylate (trifunctional or higher), and the like reaction product of phthalic acid and epoxy acrylate.

As the compound (A), a commercially available compound can be used as it is. Examples of commercially available compounds include Aronix M-210, M-309, M-310, M-320, M-400, M-7100, M-8030, M-8060, Same M-8100, Same M-9050, Same M-240, Same M-245, Same M-6100, Same M-6200, Same M-6250, Same M-6300, Same M-6400, Same M-6500 ( As described above, manufactured by Toagosei Co., Ltd.), KAYARAD R-551, R-712, TMPTA, HDDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-604, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote # 295, 300, 260, 312 and 335H P, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
These compounds (A) may be used individually by 1 type, and may use 2 or more types together.

[Photoradical polymerization initiator having oxime ester structure (B)]
The photoradical polymerization initiator (B) having an oxime ester structure is a compound that generates radicals by light irradiation and initiates radical polymerization of the compound (A). The radical photopolymerization initiator (B) has a function of generating active species in a large quantity and a large amount and suppressing inhibition by oxygen in the air.

  The photoradical polymerization initiator (B) having an oxime ester structure may have geometric isomers due to the double bond of oxime, but these are not distinguished and both are included in the photoradical polymerization initiator (B). It is.

  Examples of the photo radical polymerization initiator (B) include WO 2010/14683, JP 2011-132215, JP 2008-506749, JP 2009-519904, and JP 2009-519991. Mention may be made of the described radical photopolymerization initiators.

  Specific examples of the photo radical polymerization initiator (B) include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] ethane-1-imine, and N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa) Cyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, ethanone, 1- [9-ethyl-6- (2-methylbenzo) Le) -9H- carbazol-3-yl] -, 1- (O- acetyloxime) and the like.

  The oxime ester structure possessed by the radical photopolymerization initiator (B) is preferably a structure represented by the following formula (3).

式（３）中、Ｒ⁴は置換基を有してもよいアルキル基又は置換基を有してもよいアリール基を示す。

In formula (3), R ⁴ represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

  Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, and examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a pyrenyl group.

  Two organic groups are bonded to the leftmost carbon atom of the formula (3). Examples of the organic group include an alkyl group and a group having an aryl group such as a phenylcarbazole group and a phenylthiobenzoyl group.

  When the radical photopolymerization initiator (B) has a structure represented by the formula (3) as an oxime ester structure, oxygen inhibition can be efficiently eliminated, so that a resist pattern with excellent resolution can be formed.

  Suitable examples of the radical photopolymerization initiator (B) include a compound having a structure in which an oxime ester structure is bonded to a phenylcarbazole group and a compound represented by the following formula (4).

式（３）で表わされるオキシムエステル構造がカルバゾール基に結合してなる構造を有する化合物としては、例えば下記式（５）および（６）で表わされる化合物を挙げることができる。

Examples of the compound having a structure in which the oxime ester structure represented by the formula (3) is bonded to a carbazole group include compounds represented by the following formulas (5) and (6).

光ラジカル重合開始剤（Ｂ）は１種単独で用いてもよく、２種以上を併用してもよい。

A radical photopolymerization initiator (B) may be used individually by 1 type, and may use 2 or more types together.

  Content of radical photopolymerization initiator (B) in this photosensitive composition is 0.005-10 mass% in solid content, Preferably it is 0.05-5 mass%. When the content of the radical photopolymerization initiator (B) is within the above range, it is possible to form a resist that is excellent in resolution, is not deformed by the indentation of the plating solution, and is easily peeled off. Here, the “solid content” means all components other than the solvent.

  When the photosensitive composition of this invention contains the alkali-soluble resin (D) mentioned later, content of radical photopolymerization initiator (B) is 0.00 with respect to 100 mass parts of alkali-soluble resin (D). It is preferable that it is 01-10 mass parts, and it is more preferable that it is 0.1-5 mass parts. When the content of the photo-radical polymerization initiator (B) with respect to the alkali-soluble resin (D) is within the above range, it is possible to form a resist that is excellent in resolution, is not deformed by the indentation of the plating solution, and is easily peeled off. .

[Photoradical polymerization initiator (C)]
The radical photopolymerization initiator (C) is a compound that generates radicals upon irradiation with light and initiates radical polymerization of the compound (A) together with the radical photopolymerization initiator (B).
The photoradical polymerization initiator (C) is at least one selected from a photoradical polymerization initiator (C1) represented by the following formula (1) and a photoradical polymerization initiator (C2) represented by the following formula (2). That is, the photoradical polymerization initiator (C) is a photoradical polymerization initiator (C1) or a photoradical polymerization initiator (C2), or a photoradical polymerization initiator (C1) and a photoradical polymerization initiator (C2). .

式（１）中、Ｒ¹¹は、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示す。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。

In the formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

R ¹² and R ¹³ each independently represents an alkyl group, an aralkyl group, or an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a pyrenyl group. Examples of the aralkyl group include a group obtained by substituting one of the hydrogen atoms of the alkyl group with the aryl group.

X represents an oxygen atom or a sulfur atom.
n represents 0 or 1. That is, R ¹⁴ may be bonded to any of the five carbon atoms to which the benzene ring can be bonded via an oxygen atom or a sulfur atom, and the five carbons to which the benzene ring can be bonded directly by a single bond. It may be bonded to any atom.

R ¹⁴ represents a substituted hydrocarbon group having at least one group selected from a hydroxyl group, a carboxyl group and a sulfo group as a substituent. As R ¹⁴ , for example, — (CH ₂ ) _a —OH, — (CH ₂ ) _b —COOH, — (CH ₂ ) _c —SO ₃ H (a, b, and c each independently represents an integer of 1 or more. Show).

式（２）中、２つのＲ²¹はそれぞれ独立に、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し、２つのＲ²¹のうち少なくとも１つは水酸基である。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。

In formula (2), two R ^{21 s} independently represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ²¹ is a hydroxyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

Two R ²² and two R ²³ each independently represent an alkyl group, an aralkyl group, or an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, and a pyrenyl group. Examples of the aralkyl group include a group obtained by substituting one of the hydrogen atoms of the alkyl group with the aryl group.

  Y represents an alkanediyl group, an oxygen atom, or a sulfur atom. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-2,2-diyl group, and a propane-1,3-diyl group.

  m represents 0 or 1. That is, the two benzene rings included in the formula (2) may be bonded to any one of the five carbon atoms to which each benzene ring can be bonded via an oxygen atom or a sulfur atom, and are directly bonded to a single bond. May be bonded at any of the five carbon atoms to which each benzene ring can be bonded.

  The photoradical polymerization initiator (C) preferably contains a photoradical polymerization initiator (C1). That is, the photoradical polymerization initiator (C) is preferably a photoradical polymerization initiator (C1), or a photoradical polymerization initiator (C1) and a photoradical polymerization initiator (C2). When the radical photopolymerization initiator (C) contains the radical photopolymerization initiator (C1), it is possible to form a resist that is excellent in resolution, is not deformed by the indentation of the plating solution, and is easily peeled off.

  Examples of the photo radical polymerization initiator (C1) include 2-methyl-1- [4- (2-hydroxyethylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- ( 3-hydroxypropylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (4-hydroxybutylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl- 1- [4- (5-hydroxyheptylthio) phenyl] -2-morpholinopropan-1-one, and 2-methyl-1- [4- (5-hydroxyhexylthio) phenyl] -2-morpholinopropane-1 -ON.

  Examples of the photo radical polymerization initiator (C2) include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl-propan-1-one, 4,4′-bis- (α-morpholinoisobutyroyl) -diphenyl disulfide, 1,2′-bis- [4- (α-morpholinoisobutyroyl) -phenylthio] -ethane, bis- [4- (α -Morpholinoisobutyroyl) -phenylthio] -methane, 2,2'-bis [4- (α-morpholinoisobutyroyl) -phenylthio] -diethyl sulfide, 1,4-bis- [4- (α-morpholinoiso) Butyroyl) -phenylthio] -benzene and 2-methyl-1- [3,5-bis- (methylthio) -2-methoxyphenyl] -2-morpholinopropane- - it can be mentioned on.

  Among these, as the radical photopolymerization initiator (C), the radical photopolymerization initiator (C1) is excellent in resolution, and it is possible to form a resist that is not deformed and easily peeled off by pressing the plating solution. preferable.

  The radical photopolymerization initiator (C) is preferably contained in an amount of 100 to 5,000 parts by mass, and 300 to 3,000 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator (B). More preferably.

[Alkali-soluble resin (D)]
By containing the alkali-soluble resin (D), the photosensitive composition for producing a plated shaped article of the present invention can impart resistance to a plating solution to a resist, and development can be performed with an alkaline developer. . The alkali-soluble resin (D) is a resin having a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible. For example, JP 2008-276194 A, JP 2003-241372 A, JP 2009-531730 A, WO 2010/001691, JP 2011-123225 A, JP 2009-222923 A, and Special Examples include alkali-soluble resins described in Kaikai 2006-243161.

  The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography of the alkali-soluble resin (D) is usually 1,000 to 1,000,000, preferably 2,000 to 50,000. Preferably it exists in the range of 3,000-20,000.

  Content of alkali-soluble resin (D) is 100-300 mass parts normally with respect to 100 mass parts of compounds (A), Preferably it is 150-250 mass parts. When content of alkali-soluble resin (D) exists in the said range, formation of the resist excellent in plating solution tolerance is attained.

  The alkali-soluble resin (D) preferably has a phenolic hydroxyl group from the viewpoint of improving the plating solution resistance of the resist. The alkali-soluble resin (D) having a phenolic hydroxyl group is preferably an alkali-soluble resin (D ′) having a structural unit represented by the following formula (6) (hereinafter also referred to as “structural unit (6)”).

式（６）中、Ｒ⁶は水素原子またはメチル基を表す。

In the formula (6), R ⁶ represents a hydrogen atom or a methyl group.

  By using the alkali-soluble resin (D ′) having the structural unit (6), a resist pattern that does not easily swell in the plating step can be obtained. As a result, the resist pattern does not float or peel off from the substrate, preventing the plating solution from seeping out to the interface between the substrate and the resist pattern even when the plating process is performed for a long time. it can. Also, the resolution can be improved.

  Content of the structural unit (6) in alkali-soluble resin (D ') which has a structural unit (6) is 1-40 mass% normally, Preferably it exists in the range of 10-30 mass%. The molecular weight of the alkali-soluble resin (D ′) can be sufficiently increased by using the monomer having the content of the structural unit (6) in the above-described range, that is, the monomer that leads to the structural unit (6). it can. In addition, a resist pattern that hardly swells in the plating step can be obtained.

  The alkali-soluble resin (D ′) having the structural unit (6) is, for example, a hydroxyl group-containing aromatic vinyl compound such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, p-isopropenylphenol (hereinafter referred to as “single”). (Also referred to as “mer (6 ′)”) as a part of the raw material monomer. These monomers (6 ′) may be used alone or in combination of two or more.

  Among these monomers (6 ′), p-hydroxystyrene and p-isopropenylphenol are preferable in that a resin composition capable of forming a resist pattern excellent in long-term plating treatment resistance is obtained. Propenylphenol is more preferred.

  The alkali-soluble resin (D ′) having the structural unit (6) is further derived from another monomer copolymerizable with the monomer (6 ′) (hereinafter also referred to as “monomer (I)”). May have a structural unit.

Examples of the monomer (I) include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene;
Heteroatom-containing alicyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam;
Phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxytripropylene glycol (meth) acrylate , Phenoxytetrapropylene glycol (meth) acrylate, Lauroxydiethylene glycol (meth) acrylate, Lauroxytriethylene glycol (meth) acrylate, Lauroxytetraethylene glycol (meth) acrylate, Lauroxydipropylene glycol (meth) acrylate, Lauroxytri Propylene glycol (meth) acrylate, Lauroxy Having a glycol structure, such as tiger propylene glycol (meth) acrylate (meth) acrylic acid derivatives;
Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile;
Conjugated diolefins such as 1,3-butadiene and isoprene;
Carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) (Meth) acrylic acid esters such as acrylate;
p-hydroxyphenyl (meth) acrylamide etc. are mentioned. These monomers (I) may be used individually by 1 type, and may use 2 or more types together.

  Among these monomers (I), styrene, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tricyclodecanyl (meth) acrylate, benzyl ( Preferred are meth) acrylate, isobornyl (meth) acrylate, p-hydroxyphenyl (meth) acrylamide and the like.

The alkali-soluble resin (D ′) can be produced, for example, by radical polymerization. Examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.
Alkali-soluble resin (D) may be used individually by 1 type, and may use 2 or more types together.

[Other ingredients]
The photosensitive composition for producing a plated article of the present invention includes, as other components, a photoradical polymerization initiator other than the photoradical polymerization initiators (B) and (C), a polymerization inhibitor, a solvent, a surfactant, and an adhesive. You may contain an adjuvant, a sensitizer, an inorganic filler, etc. in the range which does not impair the objective and characteristic of this invention.

(solvent)
By containing a solvent, the photosensitive composition for producing a plated model according to the present invention improves handling properties, facilitates adjustment of viscosity, and improves storage stability.
As a solvent,
Alcohols such as methanol, ethanol, propylene glycol;
Cyclic ethers such as tetrahydrofuran and dioxane;
Glycols such as ethylene glycol and propylene glycol;
Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether;
Alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Ethyl acetate, butyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3 Esters such as ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl lactate;
N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone , Caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and the like.

A solvent may be used individually by 1 type and may use 2 or more types together.
The amount of the solvent used may be such that when the resist pattern having a film thickness of 0.1 to 100 μm is formed, the solid content of the photosensitive composition for manufacturing a plated article is 5 to 80% by mass. Solid content means the component except a solvent among all the components contained in a composition.

[Method for producing photosensitive composition for producing plated shaped article]
The photosensitive composition for producing a plated article of the present invention can be produced by uniformly mixing the above components. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

  Moreover, the composition which consists of a component which does not contain a phosphorus atom is preferable for the photosensitive composition for plating molded article manufacture of this invention. In particular, the photoradical polymerization initiators other than the photoradical polymerization initiators (B) and (C) mentioned as the photoradical polymerization initiator (B), photoradical polymerization initiator (C), and other components contain phosphorus atoms Preferably not.

  By not including a radical photopolymerization initiator or the like that generates a component such as a phosphorus compound that adversely affects the plating solution as a decomposition product, a plated model can be produced without adversely affecting the plating solution.

[Method of manufacturing plated model]
The method for producing a plated article of the present invention includes a compound (A) having at least one ethylenically unsaturated double bond in one molecule, a photo radical polymerization initiator (B) having an oxime ester structure, Photosensitivity containing at least one photoradical polymerization initiator (B) selected from a photoradical polymerization initiator (C1) represented by the formula (1) and a photoradical polymerization initiator (C2) represented by the following formula (2): A step (1) of forming a coating film by applying a functional composition on a substrate;

（式（１）中、Ｒ¹¹は、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し；
Ｒ¹²およびＲ¹³はそれぞれ独立に、アルキル基、アラルキル基、またはアリール基を示し；
Ｘは、酸素原子または硫黄原子を示し；
ｎは、０または１を示し；
Ｒ¹⁴は、置換基として水酸基、カルボキシル基またはスルホ基を有する置換炭化水素基を示す。）

(In the formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
X represents an oxygen atom or a sulfur atom;
n represents 0 or 1;
R ¹⁴ represents a substituted hydrocarbon group having a hydroxyl group, a carboxyl group or a sulfo group as a substituent. )

（式（２）中、２つのＲ²¹はそれぞれ独立に、水酸基、モルホリノ基、アミノ基、またはアルコキシ基を示し、２つのＲ²¹のうち少なくとも１つは水酸基であり；
２つのＲ²²および２つのＲ²³はそれぞれ独立に、アルキル基、アラルキル基、又はアリール基を示し；
Ｙは、アルカンジイル基を示し；
ｍは、０または１の整数を示す。）

(In the formula (2), two R ²¹ each independently represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ²¹ is a hydroxyl group;
Two R ²² and two R ²³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
Y represents an alkanediyl group;
m represents an integer of 0 or 1. )

Step (2) of exposing the coating film
A step (3) of developing the exposed coating film to form a resist pattern;
Step (4) of performing a plating process on the base material using the resist pattern as a mask and Step (5) of removing the resist pattern from the base material
Have

  The photosensitive composition used in the method for manufacturing a plated model according to the present invention is the photosensitive composition for manufacturing a plated model. The method for producing a plated model according to the present invention can be carried out according to a conventionally known method for producing a plated model, except that the photosensitive composition for producing a modeled product is used as the photosensitive composition.

[Step (1)]
In the step (1), the photosensitive composition is applied onto a substrate to form a coating film.
The substrate is not particularly limited as long as it can form the coating film. For example, a semiconductor substrate, a glass substrate, a silicon substrate and a semiconductor plate, a glass plate, and various metal films on the surface of the silicon plate. The board | substrate etc. which are formed and can be mentioned. There is no restriction | limiting in particular in the shape of a base material. Even if it is flat form, the shape formed by providing a recessed part (hole) in a flat plate like the base material (silicon wafer) used by the below-mentioned Example may be sufficient. In the case of a substrate having a recess and further having a copper film on the surface, a copper film may be provided on the bottom of the recess as in the TSV structure.

  The coating method of the photosensitive composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an ink jet method can be employed, and in particular, a spin coating method. Is preferred. In the case of the spin coating method, the rotation speed is usually 800 to 3000 rpm, preferably 800 to 2000 rpm, and the rotation time is usually 1 to 300 seconds, preferably 5 to 200 seconds. After spin-coating the photosensitive composition, the obtained coating film is dried by heating at, for example, 50 to 250 ° C. for about 1 to 30 minutes.

  The film thickness of a coating film is 0.1-100 micrometers normally, Preferably it is 1-80 micrometers, More preferably, it is 10-70 micrometers, More preferably, it is 30-60 micrometers. Since the influence of oxygen inhibition appears more conspicuously as it is a thin film, when manufacturing a plated modeling thing, it is preferable to use in the above-mentioned range.

[Step (2)]
In the step (2), the coating film is exposed. That is, the coating film is selectively exposed so that a resist pattern is obtained in step (3) and subsequent steps.
In the exposure, the coating film is usually exposed through a desired photomask using, for example, a contact aligner, a stepper or a scanner. As exposure light, light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is used. The exposure amount varies depending on the type of component in the coating film, the blending amount, the thickness of the coating film, and the like, but is usually 100 to 10,000 mJ / cm ² when i-line is used for exposure light.

  In addition, heat treatment can be performed after the exposure. The conditions for the heat treatment after the exposure are appropriately determined depending on the type of component in the coating film, the blending amount, the thickness of the coating film, and the like, but are usually 70 to 180 ° C. and 1 to 60 minutes.

[Step (3)]
In step (3), the exposed coating film is developed to form a resist pattern.
Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. An aqueous solution of 0] -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

  The development time varies depending on the type of each component in the composition, the mixing ratio, the thickness of the coating film, etc., but is usually 30 to 600 seconds. The developing method may be any of a liquid piling method, a dipping method, a paddle method, a spray method, a shower developing method, and the like.

  The resist pattern can be further cured by performing additional exposure (hereinafter referred to as “post-exposure”) or heating the resist pattern produced as described above, depending on the application.

The post-exposure can be performed by the same method as the above exposure. The exposure amount is not particularly limited, but is preferably 100 to 10,000 mJ / cm ² when using a high-pressure mercury lamp. For heating, using a heating device such as a hot plate or oven, heat treatment is performed at a predetermined temperature, for example, 60 to 100 ° C. for a predetermined time, for example, 5 to 30 minutes on the hot plate, and 5 to 60 minutes in the oven. do it. By this post-treatment, a cured film having a pattern with even better characteristics can be obtained.
The resist pattern may be washed with running water or the like. Then, you may air dry using an air gun etc., and you may make it dry under heating, such as a hotplate and oven.

[Step (4)]
In step (4), the substrate is plated using the resist pattern as a mask. The plating process can be performed according to a conventional method.
Since the resist pattern is formed using the photosensitive composition for producing a plated article as a photosensitive composition, the resist pattern is deformed by indentation of the plating solution even in the case of gold plating which has high strength and requires strong indentation. There is nothing to do. For this reason, the manufacturing method of the plating model of this invention can manufacture a desired appropriate plating model.

[Step (5)]
In step (5), the resist pattern is removed from the substrate. The removal of the resist pattern can be performed according to a conventional method.
In the method for producing a plated model according to the present invention, the resist pattern can be easily peeled off and removed from the substrate by using the photosensitive composition for producing a plated model as the photosensitive composition.
A plated model can be manufactured through the above steps (1) to (5). A bump etc. are mentioned as a plating modeling thing manufactured.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.

Method for measuring weight average molecular weight (Mw) of polymer The weight average molecular weight (Mw) was measured by gel permeation chromatography under the following conditions.
Column: Tosoh column TSK-M and TSK2500 connected in series Solvent: Tetrahydrofuran Temperature: 40 ° C
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8220-GPC”

1. Production of photosensitive composition [Examples 1A to 4A and Comparative Examples 1A to 2A] Production of photosensitive composition The components and amounts shown in Table 1 below were mixed and filtered through a capsule filter (pore size 10 μm). Photosensitive compositions of Examples 1A to 4A and Comparative Examples 1A to 2A were produced. The details of each component shown in Table 1 are as follows.
A1: Polyester acrylate (trade name “Aronix M-8060”, manufactured by Toagosei Co., Ltd.)
A2: Trimethylolpropane triacrylate A3: Reaction product of phthalic acid and epoxy acrylate (trade name “Denacol DA-721”, manufactured by Nagase ChemteX Corporation)
B1: Compound represented by the following formula (4)

Ｂ２：エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−，１-（Ｏ−アセチルオキシム）（商品名「ＩＲＧＡＣＵＲＥ ＯＸＥ０２」、ＢＡＳＦ（株）製）
Ｃ１：２−メチル−１−［４−（２−ヒドロキシエチルチオ）フェニル］−２−モルホリノプロパン−１−オン
Ｄ１：下記式（７）に示す構造単位を有する重合体であるアルカリ可溶性樹脂（Ｍｗ：９，５００、ａ／ｂ／ｃ／ｄ：１０／２５／５３／１２（重量比））

B2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name “IRGACURE OXE02”, BASF Corp. Made)
C1: 2-methyl-1- [4- (2-hydroxyethylthio) phenyl] -2-morpholinopropan-1-one D1: an alkali-soluble resin which is a polymer having a structural unit represented by the following formula (7) ( Mw: 9,500, a / b / c / d: 10/25/53/12 (weight ratio))

Ｅ１：プロピレングリコールモノメチルエーテルアセテート
Ｆ１：ジフェニル（２，４，６−トリメチルベンゾイル）ホスフィンオキシド（光ラジカル重合開始剤、商品名「ＬＵＣＩＲＩＮ ＴＰＯ」、ＢＡＳＦ（株）製）
Ｆ２：２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン（光ラジカル重合開始剤、商品名「ＩＲＧＡＣＵＲＥ６５１」、ＢＡＳＦ（株）製）
Ｆ３：ジメチルメチル（ポリエチレンオキサイドアセテート）シロキサン（ＣＡＳ番号：７０９１３−１２−４、界面活性剤）

E1: Propylene glycol monomethyl ether acetate F1: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (photo radical polymerization initiator, trade name “LUCIRIN TPO”, manufactured by BASF Corporation)
F2: 2,2-dimethoxy-1,2-diphenylethane-1-one (photo radical polymerization initiator, trade name “IRGACURE651”, manufactured by BASF Corporation)
F3: Dimethylmethyl (polyethylene oxide acetate) siloxane (CAS number: 70913-12-4, surfactant)

2. Manufacture and Evaluation of Plated Model [Examples 1B to 4B and Comparative Examples 1B to 2B]
In Examples 1B to 4B and Comparative Examples 1B to 2B, Examples 1A to 4A and Comparative Examples 1A to 1B were used by using a spin coater on a gold sputtered film of a substrate provided with a copper sputtered film on a silicon wafer, respectively. The photosensitive composition produced in 2A was applied and heated on a hot plate at 110 ° C. for 300 seconds to form a coating film (1) having a thickness of 28 μm.

  The coating film (1) was exposed through a pattern mask using a stepper (manufactured by Nikon Corporation, model “NSR-i10D”). The coated film (1) after exposure is immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide solution for 40 seconds, this immersion is performed twice, the coated film (1) is developed, and a resist pattern ( Resist width: 10 μm, distance between resist patterns: 10 μm, height: about 28 μm). When the obtained resist pattern was observed with an electron microscope, the vertical cross-sectional shape was rectangular.

Subsequently, gold plating was performed using this resist pattern as a mask. The gold plating solution was used under the product name “MICROFABAu 2151” (manufactured by EEJA). After gold plating, the resist pattern is removed by immersing in a resist stripping solution (dimethylsulfoxide / water / isopropyl alcohol / tetramethylammonium hydroxide = 95/2/2/1 (mass%) solution) at 30 ° C. A gold-plated shaped article was manufactured. The time required to remove the resist pattern with the resist stripper was defined as “resist strippability”. Measure the width of the manufactured gold-plated shaped object, and take the length obtained by subtracting the distance between resist patterns (10 μm) from this width as the deformation of the resist due to the indentation of the gold plating solution. The ratio (increase ratio) was evaluated as “resist indentation resistance” according to the following evaluation criteria. The evaluation results are shown in Table 2.
"Removability of resist"
A: The time required for peeling is less than 90 seconds.
B: Time required for peeling is 90 to 110 seconds.
C: The time required for peeling is longer than 110 seconds.
"Resist indentation resistance"
A: The increase rate is less than 5%.
B: The increase rate is 5 to 10%.
C: The increase rate is larger than 10%.

Claims (7)

Compound (A) having at least one ethylenically unsaturated double bond in one molecule, photoradical polymerization initiator (B) having an oxime ester structure, and photoradical polymerization initiator represented by the following formula (1) A photosensitive composition containing (C1) and at least one photoradical polymerization initiator (C) selected from the photoradical polymerization initiator (C2) represented by the following formula (2) is coated on a substrate. Step (1) of forming a coating film,

(In the formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
X represents an oxygen atom or a sulfur atom;
n represents 0 or 1;
R ¹⁴ represents a substituted hydrocarbon group having at least one group selected from a hydroxyl group, a carboxyl group and a sulfo group as a substituent. )

(In the formula (2), two R ²¹ each independently represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ²¹ is a hydroxyl group;
Two R ²² and two R ²³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
Y represents an alkanediyl group, an oxygen atom, or a sulfur atom;
m represents 0 or 1. )
Step (2) of exposing the coating film,
A step (3) of developing the exposed coating film to form a resist pattern;
Step (4) of performing a plating process on the base material using the resist pattern as a mask and Step (5) of removing the resist pattern from the base material
The manufacturing method of the plating molded article characterized by having.   The manufacturing method of the plating molded article of Claim 1 in which the said radical photopolymerization initiator (C) contains the said radical photopolymerization initiator (C1).   The photosensitive composition contains 100 to 5,000 parts by mass of the photo radical polymerization initiator (C) with respect to 100 parts by mass of the photo radical polymerization initiator (B). The manufacturing method of the plating molded article of crab.   The method for producing a plated model according to claim 1, wherein the photosensitive composition further contains an alkali-soluble resin (D).   The plating model according to claim 4, wherein the photosensitive composition contains 0.01 to 10 parts by mass of the photoradical polymerization initiator (B) with respect to 100 parts by mass of the alkali-soluble resin (D). Manufacturing method.   The method of manufacturing a plated article according to claim 1, wherein the plating process is a gold plating process. Compound (A) having at least one ethylenically unsaturated double bond in one molecule, photoradical polymerization initiator (B) having an oxime ester structure, and photoradical polymerization initiator represented by the following formula (1) (C1) and at least one photoradical polymerization initiator (C) selected from photoradical polymerization initiators (C2) represented by the following formula (2): Composition.

(In the formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
X represents an oxygen atom or a sulfur atom;
n represents 0 or 1;
R ¹⁴ represents a substituted hydrocarbon group having at least one group selected from a hydroxyl group, a carboxyl group and a sulfo group as a substituent. )

(In the formula (2), two R ²¹ represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ²¹ is a hydroxyl group;
Two R ²² and two R ²³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
Y represents an alkanediyl group, an oxygen atom, or a sulfur atom;
m represents 0 or 1. )