JP6776920B2 - Manufacturing method of plated model, and photosensitive composition for manufacturing plated model - Google Patents

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, there has been an increasing demand for high-density mounting of wiring for semiconductor elements and display elements such as liquid crystal displays and touch panels, and connection terminals such as bumps, so miniaturization is progressing.

Generally, wiring, bumps, and the like 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.
Therefore, with the miniaturization of wiring, bumps, etc., the resist pattern used in the manufacture thereof also needs to be miniaturized.

Japanese Unexamined Patent Publication No. 2006-285035

However, when the resist pattern is made finer, 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 by pushing the plating solution, and therefore the plating model becomes thicker. It has become difficult to ignore the problem that a plated molded product having a desired shape cannot be manufactured. Especially in the case of gold plating, since the plating solution strongly pushes the resist, there is a big problem of thickening of the plated model. 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, it is necessary to peel off the resist from the substrate after the plated model is manufactured by plating. Therefore, it is desired that the resist is easily peeled off from the substrate. At that time, if the resist has a hardness such that it is not deformed by pushing, it tends to be difficult to peel the resist from the substrate.

That is, the hardness required for the resist so that it is not deformed by pushing and the ease of peeling from the substrate are antinomy performances.
The present invention is to form a method for producing a plated model that can produce an appropriate plated model even in the case of gold plating that requires strong pressing, and to form a resist suitable for producing such a plated product. It is an object of the present invention to provide a resist composition capable of plating.

The present invention that achieves the above object comprises 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 at least one photoradical polymerization initiator (C1) selected from the photoradical polymerization initiator (C1) represented by 1) and the photoradical polymerization initiator (C2) represented by the following formula (2). Step of applying a substance on a base material to form a coating film (1),

（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 formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ independently represent an alkyl group, an aralkyl group, or an aryl group;
X indicates an oxygen atom or a sulfur atom;
n indicates 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 formula (2), the two R ^21s independently represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ^21s is a hydroxyl group;
The two R ²² and the 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 of exposing the coating film (2)
Step of developing the coating film after exposure to form a resist pattern (3),
A step of plating the base material using the resist pattern as a mask (4) and a step of removing the resist pattern from the base material (5).
It is a method for manufacturing a plated model, which is characterized by having.

In the method for producing a plated model, it is preferable that the photoradical polymerization initiator (B) contains the photoradical polymerization initiator (C1).
In the method for producing a plated molded product, the photosensitive composition contains 100 to 5,000 parts by mass of the photoradical polymerization initiator (B) with respect to 100 parts by mass of the photoradical polymerization initiator (B). It is preferable to do so.

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 molded product, 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). Is preferable.
As a method for producing the plated model, an embodiment in which the plating process is a gold plating process can be mentioned.

In addition, the present invention that achieves the above object comprises 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. It contains at least one photoradical polymerization initiator (C) selected from the photoradical polymerization initiator (C1) represented by the formula (1) and the photoradical polymerization initiator (C2) represented by the following formula (2). It is a photosensitive composition for producing a plated model, which is characterized by the above.

（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 formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ independently represent an alkyl group, an aralkyl group, or an aryl group;
X indicates an oxygen atom or a sulfur atom;
n indicates 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 formula (2), the two R ^21s independently represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ^21s is a hydroxyl group;
The two R ²² and the 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. )

By using the photosensitive composition for manufacturing a plated model of the present invention, even in the case of gold plating that requires strong pressing, a resist that is not deformed by pressing the plating solution and is easily peeled off from the substrate after completion of plating is formed. can do.

In the method for producing a plated model of the present invention, by using the photosensitive composition for producing a plated model, the resist formed does not deform when the plating solution is pushed in, so that a desired appropriate plating model is desired. A product can be manufactured, and the resist can be easily peeled off from the substrate after plating is completed.

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

The photosensitive composition for producing a plated molded product of the present invention is deformed by using the photoradical polymerization initiator (B) and the photoradical polymerization initiator (C) in combination as the photoradical polymerization initiator. It realizes the performance of the resist, which has a trade-off relationship of hardness and ease of peeling from the substrate, at a high level, and enables the production of an appropriate plated model even in gold plating and the like.

In the present invention, the (meth) acryloyl group is a general term for an acryloyl group and a meta-acryloyl group, and the (meth) acryloyloxy group is a general term for an acryloyloxy group and a metaacryloyloxy group, and is a (meth) acrylate. Is a general term for acrylate and methacrylate.

[Compound (A) having at least one ethylenically unsaturated double bond in one molecule]
Compound (A) is a component that radically polymerizes with an 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, and 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, stearyl (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 (Meta) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxyethyl 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, methacrylate amide, diacetone (meth) acrylamide, iso Butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, tert-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylami Examples thereof include noethyl (meth) acrylate 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 (Meta) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxy) Ethyl) isocyanurate tri (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, epoxy (meth) acrylate in which (meth) acrylic acid is added to diglycidyl ether of bisphenol A, bisphenol A di (meth) acryloyl. Oxyethyl ether, bisphenol A di (meth) acryloyloxymethyl ethyl ether, bisphenol A di (meth) acryloyloxyethyl oxyethyl ether, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Examples thereof include meta) acrylate, dipentaerythritol hexa (meth) acrylate, polyester (meth) acrylate (trifunctional or higher), and a 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, and 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 mentioned above, 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 (all manufactured by Nippon Kayaku Co., Ltd.), Viscort # 295, 300, 260, 312, 335HP, 360, 360. GPT, 3PA, 400 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like can be mentioned.
These compounds (A) may be used alone or in combination of two or more.

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

The photoradical polymerization initiator (B) having an oxime ester structure may contain geometric isomers due to the double bond of the oxime, but these are not distinguished and all of them are contained in the photoradical polymerization initiator (B). Is done.

Examples of the photoradical polymerization initiator (B) include WO2010 / 146883A, Japanese Patent Application Laid-Open No. 2011-132215, Japanese Patent Application Laid-Open No. 2008-506749, Japanese Patent Application Laid-Open No. 2009-519904, and Japanese Patent Application Laid-Open No. 2009-519991. The photoradical polymerization initiator described is mentioned.

Specific examples of the photoradical polymerization initiator (B) include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and 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-carbazole-3-yl] ethane-1-imine, and N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa) Cyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]- , 1- (O-acetyloxime) and the like.

As the oxime ester structure of the photoradical polymerization initiator (B), a structure represented by the following formula (3) is preferable.

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, a propyl group and the like, and examples of the aryl group include a phenyl group, a naphthyl group, an anthrasenyl group, a fluorenyl group and a pyrenyl group.

Two organic groups are bonded to the carbon atom at the left end 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 photoradical polymerization 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 having excellent resolution can be formed.

Examples of the suitable photoradical polymerization initiator (B) include a compound having an oxime ester structure 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。

The photoradical polymerization initiator (B) may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator (B) in the photosensitive composition is 0.005 to 10% by mass, preferably 0.05 to 5% by mass in the solid content. When the content of the photoradical polymerization initiator (B) is within the above range, it is possible to form a resist which has excellent resolution and is not deformed by pushing the plating solution and can be easily peeled off. Here, the "solid content" refers to all components other than the solvent.

When the photosensitive composition of the present invention contains the alkali-soluble resin (D) described later, the content of the photoradical polymerization initiator (B) is 0. 0 with respect to 100 parts by mass of the alkali-soluble resin (D). It is preferably 01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. When the content of the photoradical polymerization initiator (B) with respect to the alkali-soluble resin (D) is within the above range, it is possible to form a resist which has excellent resolution and is not deformed by pushing the plating solution and can be easily peeled off. ..

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

R ¹² and R ¹³ independently represent an alkyl group, an aralkyl group, or an aryl group, respectively. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, a pyrenyl group and the like. Examples of the aralkyl group include a group formed 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 can be directly formed by a single bond. It may be attached to any of the atoms.

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. For R ¹⁴ , for example, − (CH ₂ ) _a −OH, − (CH ₂ ) _b −COOH, − (CH ₂ ) _c −SO ₃ H (a, b, and c are integers of 1 or more independently. (Show) can be mentioned.

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

The two R ²² and the 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, a propyl group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, a pyrenyl group and the like. Examples of the aralkyl group include a group formed 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, a propane-1,3-diyl group and the like.

m represents 0 or 1. That is, the two benzene rings contained in the formula (2) may be bonded at any of the five carbon atoms that can be bonded to each benzene ring via an oxygen atom or a sulfur atom, and may be directly bonded. Therefore, they may be bonded at any of the five bondable carbon atoms of each benzene ring.

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 photoradical polymerization initiator (C) contains the photoradical polymerization initiator (C1), it is possible to form a resist which has excellent resolution and is not deformed by pushing the plating solution and can be easily peeled off.

Examples of the photoradical polymerization initiator (C1) include 2-methyl-1- [4- (2-hydroxyethylthio) phenyl] -2-morpholinopropane-1-one and 2-methyl-1- [4-(. 3-Hydroxypropylthio) Phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (4-hydroxybutylthio) phenyl] -2-morpholinopropane-1-one, 2-methyl- 1- [4- (5-Hydroxyheptylthio) phenyl] -2-morpholinopropane-1-one, and 2-methyl-1- [4- (5-hydroxyhexylthio) phenyl] -2-morpholinopropane-1 -Can be turned on.

Examples of the photoradical polymerization initiator (C2) include 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl-propane-1-one. 4,4'-bis- (α-morpholinoisobutyroyl) -diphenyldisulfide, 1,2'-bis- [4- (α-morpholinoisobutyroyl) -phenylthio] -ethane, bis- [4- (α) -Molholinoisobutyroyl) -phenylthio] -methane, 2,2'-bis [4- (α-morpholinoisobutyroyl) -phenylthio] -diethylsulfide, 1,4-bis- [4- (α-morpholinoiso) Butyroyl) -phenylthio] -benzene, and 2-methyl-1- [3,5-bis- (methylthio) -2-methoxyphenyl] -2-morpholinopropane-1-one can be mentioned.

Among these, as the photoradical polymerization initiator (C), the photoradical polymerization initiator (C1) has excellent resolution, and it is possible to form a resist that is not deformed by pushing the plating solution and is easily peeled off. preferable.

The photoradical polymerization initiator (C) is preferably contained in an amount of 100 to 5,000 parts by mass, preferably 300 to 3,000 parts by mass, based on 100 parts by mass of the photoradical polymerization initiator (B). It is more preferable to have.

[Alkali-soluble resin (D)]
By containing the alkali-soluble resin (D), the photosensitive composition for producing a plated molded product of the present invention can impart resistance to the plating solution to the resist and can be developed with an alkaline developer. .. The alkali-soluble resin (D) is a resin having a property of being dissolved in an alkaline developer to the extent that the desired development treatment can be performed. For example, JP-A-2008-276194, JP-A-2003-241372, JP-A-2009-531730, WO2010 / 001691, JP-A-2011-123225, JP-A-2009-222923, and Examples thereof include alkali-soluble resins described in Japanese Patent Publication No. 2006-243161.

The polystyrene-equivalent 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. It is preferably in the range of 3,000 to 20,000.

The content of the alkali-soluble resin (D) is usually 100 to 300 parts by mass, preferably 150 to 250 parts by mass with respect to 100 parts by mass of the compound (A). When the content of the alkali-soluble resin (D) is within the above range, it is possible to form a resist having excellent resistance to the plating solution.

The alkali-soluble resin (D) preferably has a phenolic hydroxyl group in that the resistance to the plating solution of the resist is improved. As the alkali-soluble resin (D) having a phenolic hydroxyl group, an alkali-soluble resin (D') having a structural unit represented by the following formula (6) (hereinafter, also referred to as “structural unit (6)”) is preferable.

式（６）中、Ｒ⁶は水素原子またはメチル基を表す。

In 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 base material, so that the plating solution can be prevented from seeping out to the interface between the base material and the resist pattern even when the plating process is performed for a long time. it can. In addition, the resolution can be improved.

The content of the structural unit (6) in the alkali-soluble resin (D') having the structural unit (6) is usually in the range of 1 to 40% by mass, preferably 10 to 30% by mass. The content of the structural unit (6) is in the above range, that is, the molecular weight of the alkali-soluble resin (D') can be sufficiently increased by using the monomer leading to the structural unit (6) in such an amount. it can. In addition, a resist pattern that does not easily swell in the plating process 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, or p-isopropenylphenol (hereinafter, "single"). It can be obtained by polymerizing using a "quantity (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, and p-isopropenylphenol is preferable in that a resin composition capable of forming a resist pattern excellent in long-term plating resistance can be obtained. Propenylphenol is more preferred.

The alkali-soluble resin (D') having the structural unit (6) is further derived from another monomer (hereinafter, also referred to as "monomer (I)") copolymerizable with the monomer (6'). It may have a structural unit to be used.

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 (Meta) acrylic acid derivatives having a glycol structure such as propylene glycol (meth) acrylate and lauroxytetrapropylene glycol (meth) acrylate;
Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile;
Conjugate diolefins such as 1,3-butadiene and isoprene;
Carboxylic acid-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 ( Meta) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) (Meta) acrylic acid esters such as acrylates;
Examples thereof include p-hydroxyphenyl (meth) acrylamide. These monomers (I) may be used alone or in combination of two or more.

Among these monomers (I), styrene, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tricyclodecanyl (meth) acrylate, benzyl ( Preferables include meta) acrylate, isobornyl (meth) acrylate, and p-hydroxyphenyl (meth) acrylamide.

The alkali-soluble resin (D') can be produced, for example, by radical polymerization. In addition, examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a massive polymerization method.
The alkali-soluble resin (D) may be used alone or in combination of two or more.

[Other ingredients]
The photosensitive composition for producing a plated molded product of the present invention has, 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. Auxiliary agents, sensitizers, inorganic fillers and the like may be contained within a range that does not impair the object and properties of the present invention.

(solvent)
By containing a solvent, the photosensitive composition for producing a plated model of the present invention improves handleability, facilitates viscosity adjustment, and improves storage stability.
As a solvent
Alcohols such as methanol, ethanol and propylene glycol;
Cyclic ethers such as tetrahydrofuran and dioxane;
Glycos such as ethylene glycol and propylene glycol;
Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 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, methylethyl 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-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone , Caproic acid, capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate and the like.

The solvent may be used alone or in combination of two or more.
When forming a resist pattern having a film thickness of 0.1 to 100 μm, the amount of the solvent used may be such that the solid content of the photosensitive composition for producing the plated model is 5 to 80% by mass. The solid content means a component of all the components contained in the composition excluding the solvent.

[Manufacturing method of photosensitive composition for manufacturing plated shaped objects]
The photosensitive composition for producing a plated model of the present invention can be produced by uniformly mixing the above components. Further, in order to remove dust, each component may be uniformly mixed, and then the obtained mixture may be filtered with a filter or the like.

Further, in the photosensitive composition for producing a plated model of the present invention, a composition composed of a phosphorus atom-free component is preferable. In particular, the photoradical polymerization initiators (B), the photoradical polymerization initiators (C), and other photoradical polymerization initiators (B) and (C) other than the photoradical polymerization initiators (C) contain phosphorus atoms. It is preferable not to have it.

By not containing a photoradical polymerization initiator or the like that produces a component such as a phosphorus compound that adversely affects the plating solution as a decomposition product, it is possible to produce a plated molded product without adversely affecting the plating solution.

[Manufacturing method of plated model]
The method for producing a plated model of the present invention comprises 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. Photosensitivity containing at least one photoradical polymerization initiator (C1) selected from the photoradical polymerization initiator (C1) represented by the formula (1) and the photoradical polymerization initiator (C2) represented by the following formula (2). Step (1) of applying the sex composition onto 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、カルボキシル基またはスルホ基を有する置換炭化水素基を示す。）

(In formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ independently represent an alkyl group, an aralkyl group, or an aryl group;
X indicates an oxygen atom or a sulfur atom;
n indicates 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 formula (2), the two R ^21s independently represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ^21s is a hydroxyl group;
The two R ²² and the two R ²³ each independently represents an alkyl group, an aralkyl group, or an aryl group;
Y indicates an alkanediyl group;
m represents an integer of 0 or 1. )

Step of exposing the coating film (2)
Step of developing the coating film after exposure to form a resist pattern (3),
A step of plating the base material using the resist pattern as a mask (4) and a step of removing the resist pattern from the base material (5).
Have.

The photosensitive composition used in the method for producing a plated model of the present invention is the photosensitive composition for producing a plated model. The method for producing a plated model of 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 plated model 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 base material is not particularly limited as long as it is a base material capable of forming the coating film. For example, a semiconductor substrate, a glass substrate, a silicon substrate and a semiconductor plate, a glass plate, various metal films on the surface of the silicon plate, etc. Examples thereof include a substrate provided and formed. The shape of the base material is not particularly limited. It may have a flat plate shape or a shape in which a recess (hole) is provided in the flat plate as in the base material (silicon wafer) used in the examples described later. In the case of a base material having a recess and a copper film on the surface, a copper film may be provided at 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, and an inkjet method can be adopted, and in particular, a spin coating method. Is preferable. 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 heat-dried at, for example, 50 to 250 ° C. for about 1 to 30 minutes.

The film thickness of the coating film is usually 0.1 to 100 μm, preferably 1 to 80 μm, more preferably 10 to 70 μm, and further preferably 30 to 60 μm. The thinner the film, the more pronounced the effect of oxygen inhibition, so it is preferable to use it within the above range when producing a plated model.

[Step (2)]
In the step (2), the coating film is exposed. That is, the coating film is selectively exposed so that a resist pattern can be obtained in the step (3) and subsequent steps.
The exposure is usually done through a desired photomask, for example using a contact aligner, stepper or scanner, on the coating. As the 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 when i-line is used for the exposure light, it is usually 100 to 10,000 mJ / cm ² .

It is also possible to perform heat treatment after exposure. The conditions for the heat treatment after the exposure are appropriately determined depending on the type of the component in the coating film, the blending amount, the thickness of the coating film, and the like, but are usually 70 to 180 ° C. for 1 to 60 minutes.

[Step (3)]
In the step (3), the coating film after exposure is developed to form a resist pattern.
Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, and the like. 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 above-mentioned aqueous solution of alkalis can also be used as a developing solution.

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

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

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

[Step (4)]
In the step (4), the resist pattern is used as a mask to perform a plating treatment on the base material. The plating process can be performed according to a conventional method.
Since the resist pattern is formed by using the photosensitive composition for manufacturing a plated model as a photosensitive composition, the resist pattern is deformed by pressing the plating solution even in the case of gold plating having high strength and requiring strong pressing. There is nothing to do. Therefore, the method for producing a plated model of the present invention can produce a desired and appropriate plated model.

[Step (5)]
In step (5), the resist pattern is removed from the substrate. The resist pattern can be removed according to a conventional method.
In the method for producing a plated model of the present invention, the resist pattern can be easily peeled off from the substrate and removed by using the photosensitive composition for producing a plated model as the photosensitive composition.
By the above steps (1) to (5), a plated model can be manufactured. Examples of the plated model to be manufactured include bumps and the like.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" is used to mean "parts by mass" in the following examples and the like.

Method for Measuring Weight Average Molecular Weight (Mw) of Polymer The weight average molecular weight (Mw) was measured by a gel permeation chromatography method under the following conditions.
-Column: Tosoh column TSK-M and TSK2500 are connected in series.-Solvent: Tetrahydrofuran-Temperature: 40 ° C.
-Detection method: Refractive index method-Standard substance: Polystyrene-GPC device: Tosoh, device name "HLC-8220-GPC"

1. 1. Production of Photosensitive Compositions [Examples 1A to 4A and Comparative Examples 1A to 2A] Production of Photosensitive Compositions The components and amounts shown in Table 1 below are mixed and filtered through a capsule filter (pore size 10 μm). Photosensitive compositions of Examples 1A-4A and Comparative Examples 1A-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: Reactant 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: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (trade name "IRGACURE OXE02", BASF Limited Made)
C1: 2-Methyl-1- [4- (2-hydroxyethylthio) phenyl] -2-morpholinopropane-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 (photoradical polymerization initiator, trade name "LUCIRIN TPO", manufactured by BASF Co., Ltd.)
F2: 2,2-dimethoxy-1,2-diphenylethane-1-one (photoradical polymerization initiator, trade name "IRGACURE651", manufactured by BASF Limited)
F3: Dimethylmethyl (polyethylene oxide acetate) siloxane (CAS number: 70913-12-4, surfactant)

2. Production of plated model and evaluation thereof [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 1A to 4A, respectively, using a spin coater on a gold sputtered film of a substrate having a copper sputtered film on a silicon wafer. 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 film thickness of 28 μm.

The coating film (1) was exposed using a stepper (manufactured by Nikon Corporation, model "NSR-i10D") via a pattern mask. The exposed coating film (1) is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds, and this immersion is performed twice to develop the coating film (1), and a resist pattern (resist pattern (1)) is formed on the substrate. The resist width: 10 μm, the distance between resist patterns: 10 μm, and the height: about 28 μm) were formed. When the obtained resist pattern was observed with an electron microscope, its vertical cross-sectional shape was rectangular.

Next, gold plating was performed using this resist pattern as a mask. The gold plating solution was used under the product name "MICROFABAu2151" (manufactured by EEJA Co., Ltd.). After gold plating, the resist pattern is removed by immersing in a resist stripping solution (a solution containing dimethyl sulfoxide / water / isopropyl alcohol / tetramethylammonium hydroxide = 95/2/2/1 (mass%)) at 30 ° C. , Manufactured a gold-plated model. The time required to remove the resist pattern with the resist stripping solution was defined as "resist stripping property". The width of the manufactured gold-plated model is measured, and the length obtained by subtracting the distance between resist patterns (10 μm) from this width is regarded as the deformation of the resist due to the pushing of the gold plating solution, and the length is the distance between the resist patterns. The ratio (increase rate) 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: The time required for peeling is 90 to 110 seconds.
C: The time required for peeling is longer than 110 seconds.
"Resist push resistance"
A: The rate of increase is less than 5%.
B: The rate of increase is 5 to 10%.
C: The rate of increase is greater than 10%.

Claims (7)

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 a photoradical polymerization initiator represented by the following formula (1). A photosensitive composition containing at least one photoradical polymerization initiator (C) selected from (C1) and the photoradical polymerization initiator (C2) represented by the following formula (2) is applied onto a substrate. Step of forming a coating film (1),

(In formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ independently represent an alkyl group, an aralkyl group, or an aryl group;
X indicates an oxygen atom or a sulfur atom;
n indicates 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 formula (2), the two R ^21s independently represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ^21s is a hydroxyl group;
The two R ²² and the 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,
Step of developing the coating film after exposure to form a resist pattern (3),
A step of plating the base material using the resist pattern as a mask (4) and a step of removing the resist pattern from the base material (5).
A method for producing a plated model, which comprises. The method for producing a plated model according to claim 1, wherein the photoradical polymerization initiator (C) contains the photoradical polymerization initiator (C1). Either of claims 1 or 2, wherein the photosensitive composition contains 100 to 5,000 parts by mass of the photoradical polymerization initiator (C) with respect to 100 parts by mass of the photoradical polymerization initiator (B). Method for manufacturing a plated model described in Crab. The method for producing a plated model according to any one of claims 1 to 3, wherein the photosensitive composition further contains an alkali-soluble resin (D). The plated 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 for producing a plated model according to any one of claims 1 to 5, wherein the plating treatment is a gold plating treatment. 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 a photoradical polymerization initiator represented by the following formula (1). Photosensitivity for manufacturing plated shaped products, which contains at least one photoradical polymerization initiator (C) selected from (C1) and a photoradical polymerization initiator (C2) represented by the following formula (2). Composition.

(In formula (1), R ¹¹ represents a hydroxyl group, a morpholino group, an amino group, or an alkoxy group;
R ¹² and R ¹³ independently represent an alkyl group, an aralkyl group, or an aryl group;
X indicates an oxygen atom or a sulfur atom;
n indicates 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 formula (2), two R ^21s represent a hydroxyl group, a morpholino group, an amino group, or an alkoxy group, and at least one of the two R ^21s is a hydroxyl group;
The two R ²² and the 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. )