JP2003277422A - Photocurable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable cyanoacrylate composition having moisture- curability, photocurability and good storage stability and causing no deterioration of curability after storage. <P>SOLUTION: This photocurable composition is characterized by comprising (A) α-cyanoacrylate, (B) a group VIII transition metal metallocene compound having an aromatic electron ligand and (C) a photocuring promoter having a structure represented by the general formula (I) (wherein, R is H, a 1-8C alkyl, a halogen or a 1-8C alkylthio; and Rs may be the same or different each other.). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-curable cyanoacrylate composition, which can be applied to lithography, potting, molding, coating, adhesives, sealing agents, and various resist materials. It relates to a photocurable composition.

[0002]

2. Description of the Related Art An .alpha.-cyanoacrylate adhesive is rapidly anionically polymerized and cured by a small amount of water adsorbed on the surface of an adherend to adhere the adherends to each other in a very short time. It is widely used as a one-liquid room temperature curing type instant adhesive for bonding metals, plastics, rubbers, woods, and the like.

However, the .alpha.-cyanoacrylate adhesive is extremely hardened when the adherends are widely spaced apart from each other, or when the adherends are protruded from the adhesion part or are not sandwiched between a pair of adherends such as a coating. It has the drawback of being slow.

Therefore, in order to bond the adherends having a large gap or to quickly cure the α-cyanoacrylate adhesive protruding from the adhered portion, it is necessary to cure it using a primer or a curing accelerator. General (JP-A-59-215376, JP-A-60-203684)
JP-A-61-176634). However, such a method is complicated and laborious in process, and a basic compound which is a main component of a primer or a curing accelerator or a solvent is used. The odor is not preferable in the working environment.

Therefore, without impairing the excellent feature of the one-component type quick curing agent at room temperature and without using a primer or a curing accelerator even when it is filled in a protruding portion or a large gap, An α-cyanoacrylate adhesive that can be easily cured was expected.

As a method for solving the above-mentioned problems, a metallocene compound alone, or a metallocene compound and a cleavage type photoinitiator are added to an α-cyanoacrylate adhesive to contain it, and α-cyanoacrylate having photocurability is added. A system adhesive composition has been previously proposed (JP-A-9-2
49708).

According to the above invention, this α-cyanoacrylate adhesive can cure the adherends in a unit of seconds, and the part protruding from the adhered part is exposed to light for a second. Since it can be cured in units, it does not impair the excellent feature of instant adhesives, which is one-component normal temperature rapid curing, and even in environments where curing is extremely slow with conventional α-cyanoacrylate adhesives. It has the feature that it can be cured quickly by irradiation with light.

However, it has been discovered that when the α-cyanoacrylate adhesive composition according to the above invention is stored for a long period of time, the photocurability may be lowered. As a method to solve this problem, it is reported that if the composition is a mixture of α-cyanoacrylate and a specific ferrocene compound further added with a photocuring accelerator, a compound having extremely excellent photocurability can be obtained even after long-term storage. (JP-A-1
No. 1-166006).

[0009]

However, in JP-A No. 11-166066, there is no study on the deep-part curability. Further, the invention of the publication does not have a detailed description on the storage stability of the photocurable composition itself, and has a drawback that it causes thickening or gelation when stored at a relatively high temperature.

[0010]

Therefore, as a result of intensive studies to solve this problem, the present inventors have found that a photocuring accelerator having a structure represented by the above general formula (1) is used as the photocuring accelerator. It was found that the α-cyanoacrylate composition containing the composition has very excellent stability even after long-term storage, and has excellent photocurability in surface curability and deep-curability. Invented.

That is, the present invention comprises (A) α-
Cyanoacrylate, (B) transition metal metallocene compound of Group VIII of the periodic table having an aromatic electron ligand,
(C) The above problems were solved by a photocurable composition containing a photocuring accelerator represented by the following general formula 1.

[0012]

[Chemical 3] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms, a halogen group, or an alkylthio group having 1 to 8 carbon atoms, and each R may be the same or different.)

The photocurable composition of the present invention should be irradiated with light even when the distance between the adherends is large, or when the adherends stick out or are not sandwiched between a pair of adherends such as a coating. Can be cured quickly.

Further, since the curing reaction of the photocurable composition of the present invention proceeds by anionic polymerization, the light arrives at the shape of the base material during light irradiation without being affected by the surface curing inhibition by oxygen as seen in radical polymerization. The part which is not cured is also cured by anionic polymerization initiated by light irradiation.

Further, the light absorption wavelength of the metallocene compound is 5
Since it is also on the long wavelength side of 00 nm or more, the photocurable compound of the present invention can be photocured even in a wider wavelength region, that is, in the ultraviolet light or the visible light region. This is also effective for adhesion of adherends containing ultraviolet absorbers such as optical disks. The present invention will be specifically described below.

The component (A) which is an α-cyanoacrylate usable in the present invention is not particularly limited as long as it is represented by the following formula (3).

[0017]

[Chemical 4] (In the formula, R ² is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group and an aryl group. The carbon number of the ester residue is not particularly limited, but is usually 1 to 8 The ester residue consisting of a substituted hydrocarbon group such as an alkoxyalkyl group or a trialkylsilylalkyl group may be used.)

Specific examples of α-cyanoacrylate include alkyl such as methyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, propyl-α-cyanoacrylate, butyl-α-cyanoacrylate and cyclohexyl-α-cyanoacrylate. And alkenyl such as cycloalkyl-α-cyanoacrylate, allyl-α-cyanoacrylate, methallyl-α-cyanoacrylate, cyclohexenyl-α-cyanoacrylate, etc. and cycloalkenyl-α-cyanoacrylate, propanegyl-α-cyanoacrylate, etc. Alkynyl-α
-Aryl-α-cyanoacrylate such as cyanoacrylate, phenyl-α-cyanoacrylate, toluyl-α-cyanoacrylate, methoxyethyl-α-cyanoacrylate containing a hetero atom, ethoxyethyl-α-cyanoacrylate, furfuryl-α -Cyanoacrylate, silicon-containing trimethylsilylmethyl-α-cyanoacrylate, trimethylsilylethyl-
α-cyanoacrylate, trimethylsilylpropyl-
α-cyanoacrylate, dimethylvinylsilylmethyl-α-cyanoacrylate and the like can be mentioned.
The cyanoacrylate may be used alone or in combination of several kinds.

The component (B), which is a transition metal metallocene compound of Group VIII of the Periodic Table having an aromatic electron type ligand, which can be used in the present invention, is an aromatic electron described in JP-A-9-249708. A transition metal metallocene compound of Group VIII of the periodic table having a system ligand can be used.

Specific examples of the group VIII transition metal metallocene compound of the periodic table containing a preferable aromatic electron type ligand include those represented by the following general formula (2).

[0021]

[Chemical 5] (In the formula, M is a transition metal of Group VIII of the periodic table, R ¹ is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, It represents an oxygen-containing group, a sulfur-containing group, or a phosphorus-containing group, each R ¹ may be the same or different, and R ^{1 s} may be crosslinked with each other, and a represents an integer of 0 to 5.
Each [Ra-Cp] group (Cp represents η-cyclopentadienyl) may be the same or different. )

Specific examples of the transition metal metallocene compound of Group VIII of the Periodic Table containing an aromatic electronic ligand are ferrocene, which is iron, osmocene, which is osmium, and ruthenocene and cobalt, which are ruthenium. Mention may be made of metallocene compounds composed of transition metals of Group VIII of the periodic table, such as cobalcene and nickelcene which is nickel. Among these, ferrocene or its derivative is preferable.

Further, the ferrocene compounds effective in the present invention are shown below as specific examples. In the present invention, iron, which is a transition metal of these compounds, is a transition metal of Group VIII of the periodic table such as osmium, ruthenium, cobalt and nickel. A metallocene compound substituted with can also be used.

Specific examples of the ferrocene compound include ferrocene, 4-acetyl-1'-bromo-1,2-diethylferrocene as a compound having a halogen atom as a substituent,
1'-bromo-1,2,3-triethylferrocene, 1
-Acetyl-1'-bromo-2,3-diethylferrocene, 1,1'-dibromo-3- (dibromoboryl) ferrocene, 1,1'-dibromo-3,3'-bis (dibromoboryl) ferrocene, 1,1 '-Dibromo-3,
3'-bis (dibromoboryl) ferrocene, 1-bromo-1'-methylferrocene, 1-bromo-1 '-(methoxymethyl) ferrocene, 1-bromo-1'-(4-methylbenzoyl) ferrocene, 1-iodo -1 '-(phenylethyl) ferrocene, 1-iodo-1'-(4-
Methoxyphenyl) ferrocene, 1- (4-chlorophenyl) -1'-iodoferrocene, 1-iodo-1'-
Phenylferrocene, 1,3-dichloro-2,4,5-
Tris (methylthio) ferrocene, 1,2,4-trichloro-3,5-bis (methylthio) ferrocene, 1,
2,3,4-Tetrachloro-5- (methylthio) ferrocene, 1-iodo-1 '-(3-methoxy-3-oxo-1-propynyl) ferrocene, 1,1'-dibromoferrocenium, 2- Acetyl-1'-bromo-1,3-
Diethylferrocene, 1'-bromo-1,2,4-triethylferrocene, 1-acetyl-1'-bromo-2,
4-diethylferrocene, 1'-bromo-1,3-diethylferrocene, 1'-bromo-1,2-diethylferrocene, 1-acetyl-1'-bromo-3-ethylferrocene, 1-acetyl-1'- Bromo-2-ethylferrocene, 1,1'-dichloroferrocenium, decachloroferrocenium, 1- (3-hydroxy-3-methyl-1-butynyl) -1'-iodoferrocene, 1-chloro-1 '-Ethynylferrocene, 1-bromo-1'-ethynylferrocene, (acetylcyclopentadienyl)
(Bromocyclopentadienyl) iron, (Bromocyclopentadienyl) (iodocyclopentadienyl)
Iron, 1-bromo-1'-phenylferrocene, 1
-Bromo-1 '-(triphenylmethyl) ferrocene,
1-bromo-1 '-((1-oxooctadecyl) oxy) ferrocene, 1-iodo-1'-((1-oxooctadecyl) oxy) ferrocene, 1-bromo-1'-
Caprioferrocene, 1-bromo-1'-pentylferrocene, 1-bromo-1 '-(2-methylpropyl) ferrocene, 1-chloro-1'-(3-oxo-3-phenyl-1-propenyl) ferrocene, 1-bromo-1 '
-Formylferrocene, 1-chloro-1'-formylferrocene, 1-bromo-1 '-(3-oxo-3-phenyl-1-propenyl) ferrocene, 1-bromo-1'
-(2-Methyl-1,3-dioxolan-2-yl) ferrocene, 1-bromo-1 '-((4-methylphenyl) methyl) ferrocene, 1-bromo-1'-((3-
Methylphenyl) methyl) ferrocene, 1-bromo-
1 '-((2-methylphenyl) methyl) ferrocene,
1- (diphenylphosphino) -1'-iodoferrocene, 1-((3-formylphenyl) ethynyl) -1 '
-Iodoferrocene, 1-((2-formylphenyl))
Ethynyl) -1'-iodoferrocene, 1,1'-dichloro-2- (trichlorosilyl) ferrocene, (1 ',
2-dichloroferrocenyl) lithium, 1-chloro-
1'-phenyl-ferrocene, 1-((4-formylphenyl) ethynyl) -1'-iodoferrocene, 1-
(Caprioethynyl) -1'-iodoferrocene, decabromoferrocene, formylnonaiodoferrocene, ethylnonaiodoferrocene, nonaiodomethylferrocene, nonabromoformylferrocene, acetylnonaiodoferrocene, 1- (ethoxycarbonyl) -1'- Iodoferrocene, 1-bromo-1 '-(ethoxycarbonyl) ferrocene, 1-chloro-1'-(ethoxycarbonyl) ferrocene, decaiodoferrocene, 1-benzoyl-1'-bromoferrocene, 1-benzoyl-
1'-chloroferrocene, 1,1 ', 2,2', 3
3 ', 4,4'-octachloro-5,5'-diiodoferrocene, 1-iodo-1'-methylferrocene, decachloroferrocene and the like can be mentioned.

1,1'-dimethylferrocene, 1,1'-as a compound having a hydrocarbon group having 1 to 20 carbon atoms as a substituent
Di-n-butylferrocene, bis (pentamethylcyclopentadienyl) iron, 1,1'-diethylferrocene, 1,1'-di-propylferrocene, 1,1'-
Di-n-pentylferrocene, 1,1'-di-n-hexylferrocene, 1,1 ', 2-trimethylferrocene, 1,1', 2-triethylferrocene, 1,1 ',
2-tri-propylferrocene, 1,1 ', 2-tri-
n-butylferrocene, 1,1 ', 2-tri-n-pentylferrocene, 1,1', 2-tri-n-hexylferrocene, 1,1 ', 3-trimethylferrocene, 1,
1 ', 3-triethylferrocene, 1,1', 3-tri-propylferrocene, 1,1 ', 3-tri-n-butylferrocene, 1,1', 3-tri-n-pentylferrocene, 1, 1 ', 3-tri-n-hexylferrocene, 1,1', 2,2'-tetramethylferrocene,
1,1 ', 2,2'-tetraethylferrocene, 1,
1 ', 2,2'-tetra-propylferrocene, 1,
1 ', 2,2'-# tetra-n-butylferrocene,
1,1 ′, 2,2′-tetra-n-pentylferrocene, 1,1 ′, 2,2′-tetra-n-hexylferrocene, 1,1 ′, 2,3′-tetramethylferrocene,
1,1 ', 2,3'-tetraethylferrocene, 1,
1 ', 2,3'-tetra-propylferrocene, 1,
1 ', 2,3'-tetra-n-butylferrocene, 1,
1 ', 2,3'-tetra-n-pentylferrocene,
1,1 ′, 2,3′-tetra-n-hexylferrocene, 1,1 ′, 3,3′-tetramethylferrocene,
1,1 ', 3,3'-tetraethylferrocene, 1,
1 ', 3,3'-tetra-propylferrocene, 1,
1 ', 3,3'-tetra-n-butylferrocene, 1,
1 ', 3,3'-tetra-n-pentylferrocene,
1,1 ′, 3,3′-tetra-n-hexylferrocene, 1,1 ′, 2,3-tetramethylferrocene, 1,
1 ', 2,3-tetraethylferrocene, 1,1',
2,3-tetra-propylferrocene, 1,1 ', 2
3-tetra-n-butylferrocene, 1,1 ', 2,3
-Tetra-n-pentylferrocene, 1,1 ', 2,3
-Tetra-n-hexylferrocene, 1,1 ', 2,4
-Tetramethylferrocene, 1,1 ', 2,4-tetraethylferrocene, 1,1', 2,4-tetra-propylferrocene, 1,1 ', 2,4-tetra-n-butylferrocene, 1,1 ', 2,4-Tetra-n-pentylferrocene, 1,1', 2,4-tetra-n-hexylferrocene, 1,1 ', 2,2', 3-pentamethylferrocene, 1,1 ', 2,2 ', 3-pentaethylferrocene, 1,1', 2,2 ', 3-penta-propylferrocene, 1,1', 2,2 ', 3-penta-n-butylferrocene, 1,1 ', 2,2', 3-penta-n-
Pentylferrocene, 1,1 ', 2,2', 3-penta-n-hexylferrocene, 1,1 ', 2,2', 4-
Pentamethylferrocene, 1,1 ', 2,2', 4-pentaethylferrocene, 1,1 ', 2,2', 4-penta-propylferrocene, 1,1 ', 2,2', 4-penta -N-butylferrocene, 1,1 ', 2,2', 4
-Penta-n-pentylferrocene, 1,1 ', 2
2 ', 4-penta-n-hexylferrocene, 1,
1 ', 2,3,3'-pentamethylferrocene, 1,
1 ', 2,3,3'-pentaethylferrocene, 1,
1 ', 2,3,3'-penta-propylferrocene,
1,1 ', 2,3,3'-penta-n-butylferrocene, 1,1', 2,3,3'-penta-n-pentylferrocene, 1,1 ', 2,3,3'- Penta-n-hexylferrocene, 1,1 ′, 2,3 ′, 4-pentamethylferrocene, 1,1 ′, 2,3 ′, 4-pentaethylferrocene, 1,1 ′, 2,3 ′, 4 -Penta-propylferrocene, 1,1 ', 2,3', 4-penta-n-
Butylferrocene, 1,1 ', 2,3', 4-penta-
n-pentylferrocene, 1,1 ', 2,3', 4-penta-n-hexylferrocene, 1,1 ', 2,3,4
-Pentamethylferrocene, 1,1 ', 2,3,4-pentaethylferrocene, 1,1', 2,3,4-penta-propylferrocene, 1,1 ', 2,3,4-penta-n -Butylferrocene, 1,1 ', 2,3,4-penta-n-pentylferrocene, 1,1', 2,3,4-
Penta-n-hexylferrocene, 1,1 ′, 2,3,
4,5-hexamethylferrocene, 1,1 ', 2,3
4,5-hexaethylferrocene, 1,1 ', 2,3
4,5-hexa-propylferrocene, 1,1 ', 2
3,4,5-hexa-n-butylferrocene, 1,
1 ', 2,3,4,5-hexa-n-pentylferrocene, 1,1', 2,3,4,5-hexa-n-hexylferrocene, 1,1 ', 2,2', 3 4-hexamethylferrocene, 1,1 ', 2,2', 3,4-hexaethylferrocene, 1,1 ', 2,2', 4-hexa-propylferrocene, 1,1 ', 2,2' , 3,4-Hexa-n-butylferrocene, 1,1 ', 2,2', 3,
4-hexa-n-pentylferrocene, 1,1 ', 2
2 ', 3,4-hexa-n-hexylferrocene, 1,
1 ', 2,3,3', 4-hexamethylferrocene,
1,1 ', 2,3,3', 4-hexaethylferrocene, 1,1 ', 2,3,3', 4-hexa-propylferrocene, 1,1 ', 2,3,3', 4 -Hexa-n-
Butylferrocene, 1,1 ', 2,3,3', 4-hexa-n-pentylferrocene, 1,1 ', 2,3
3 ', 4-hexa-n-hexylferrocene, 1,
1 ', 2,2', 3,3'-hexamethylferrocene,
1,1 ', 2,2', 3,3'-hexaethylferrocene, 1,1 ', 2,2', 3,3'-hexa-propylferrocene, 1,1 ', 2,2', 3 , 3'-hexa-
n-butylferrocene, 1,1 ', 2,2', 3,3 '
-Hexa-n-pentylferrocene, 1,1 ', 2
2 ', 3,3'-hexa-n-hexylferrocene,
1,1 ', 2,2', 3 ', 4-hexamethylferrocene, 1,1', 2,2 ', 3', 4-hexaethylferrocene, 1,1 ', 2,2', 3 ' , 4-hexa-propylferrocene, 1,1 ', 2,2', 3 ', 4-hexa-n-butylferrocene, 1,1', 2,2 ',
3 ', 4-hexa-n-pentylferrocene, 1,
1 ', 2,2', 3 ', 4-hexa-n-hexylferrocene, 1,1', 2,2 ', 4,4'-hexamethylferrocene, 1,1', 2,2 ', 4 , 4'-hexaethylferrocene, 1,1 ', 2,2', 4,4'-hexa-propylferrocene, 1,1 ', 2,2', 4
4'-hexa-n-butylferrocene, 1,1 ', 2
2 ', 4,4'-hexa-n-pentylferrocene,
1,1 ', 2,2', 4,4'-hexa-n-hexylferrocene, 1,1 ', 2,2', 3,4,5-heptamethylferrocene, 1,1 ', 2,2 ', 3,4,5-
Heptaethylferrocene, 1,1 ', 2,2', 3
4,5-hepta-propylferrocene, 1,1 ', 2
2 ', 3,4,5-hepta-n-butylferrocene,
1,1 ', 2,2', 3,4,5-hepta-n-pentylferrocene, 1,1 ', 2,2', 3,4,5-hepta-n-hexylferrocene, 1,1 ' , 2, 3,
3 ', 4,5-heptamethylferrocene, 1,1',
2,3,3 ', 4,5-heptaethylferrocene, 1,
1 ', 2,3,3', 4,5-hepta-propylferrocene, 1,1 ', 2,3,3', 4,5-hepta-n-
Butylferrocene, 1,1 ', 2,3,3', 4,5-
Hepta-n-pentylferrocene, 1,1 ', 2,3
3 ', 4,5-hepta-n-hexylferrocene, 1,
1 ', 2,2', 3,3 ', 4-heptamethylferrocene, 1,1', 2,2 ', 3,3', 4-heptaethylferrocene, 1,1 ', 2,2', 3,3 ', 4-hepta-propylferrocene, 1,1', 2,2 ', 3
3 ', 4-hepta-n-butylferrocene, 1,1',
2,2 ', 3,3', 4-hepta-n-pentylferrocene, 1,1 ', 2,2', 3,3 ', 4-hepta-n
-Hexylferrocene, 1,1 ', 2,3,3', 4
4'-heptamethylferrocene, 1,1 ', 2,3,
3 ', 4,4'-heptaethylferrocene, 1,1',
2,3,3 ', 4,4'-hepta-propylferrocene, 1,1', 2,3,3 ', 4,4'-hepta-n-
Butylferrocene, 1,1 ', 2,3,3', 4,4 '
-Hepta-n-pentylferrocene, 1,1 ', 2
3,3 ′, 4,4′-hepta-n-hexylferrocene, 1,1 ′, 2,2 ′, 3,3 ′, 4,5-octmethylferrocene, 1,1 ′, 2,2 ′, 3, 3 ', 4,
5-octethylferrocene, 1,1 ', 2,2',
3,3 ', 4,5-oct-propylferrocene, 1,
1 ', 2,2', 3,3 ', 4,5-oct-n-butylferrocene, 1,1', 2,2 ', 3,3', 4,5
-Octo-n-pentylferrocene, 1,1 ', 2
2 ', 3,3', 4,5-oct-n-hexylferrocene, 1,1 ', 2,2', 3,4,4 ', 5-octmethylferrocene, 1,1', 2,2 ', 3, 4,
4 ', 5-octoethylferrocene, 1,1', 2
2 ', 3,4,4', 5-oct-propylferrocene, 1,1 ', 2,2', 3,4,4 ', 5-oct-
n-butylferrocene, 1,1 ', 2,2', 3,4
4 ', 5-oct-n-pentylferrocene, 1,
1 ', 2,2', 3,4,4 ', 5-oct-n-hexylferrocene, 1,1', 2,2 ', 3,3', 4
4 ', 5-nonamethylferrocene, 1,1', 2
2 ', 3,3', 4,4 ', 5-nonaethylferrocene, 1,1', 2,2 ', 3,3', 4,4 ', 5-oct-propylferrocene, 1,1' , 2, 2 ', 3,
3 ', 4,4', 5-oct-n-butylferrocene,
1,1 ', 2,2', 3,3 ', 4,4', 5-oct-n-pentylferrocene, 1,1 ', 2,2', 3
3 ', 4,4', 5-oct-n-hexylferrocene, bis (pentaethylcyclopentadienyl) iron, bis (penta-propylcyclopentadienyl) iron, bis (penta-n-butylcyclopentadiene (Enyl) iron, bis (penta-n-pentylcyclopentadienyl) iron, Vista-n-hexylcyclopentadienyl) iron, 1,1'-dimethyl-2-ethylferrocene, 1,1'-dimethyl-3 -Ethylferrocene, 1,1'-di-n-butyl-3-methylferrocene, 1,1'-di-n-butyl-3-ethylferrocene, 1,1'-dimethyl-3,3'-diethylferrocene , 1,1 ′, 2, -trimethyl-3-ethylferrocene, 1,1′-ditriphenylmethylferrocene, 1-
Methyl-1'-triphenylmethylferrocene, 1-n
-Butyl-1'-triphenylmethylferrocene, and the like.

1-Methyl-1 '-(chloromethyl) ferrocene, 1-chloro-1'-(chloromethyl) as a compound of which the substituent is a halogenated hydrocarbon group having 1 to 20 carbon atoms
Ferrocene, 1-methyl-1 '-(bromomethyl) ferrocene, 1-methyl-1'-(iodomethyl) ferrocene, 1,1'-di- (chloromethyl) ferrocene, 1,
1'2-tri- (chloromethyl) ferrocene, 1,
1 ', 2,2'-tetra- (chloromethyl) ferrocene, bis (pentachloromethylcyclopentadienyl)
Iron, bis (pentabromomethylcyclopentadienyl) iron, 1-methyl-1 '-(trichloromethyl) ferrocene, 1-ethyl-1'-(trichloromethyl) ferrocene, 1-methyl-1 '-(tribromo Methyl) ferrocene, 1-methyl-1 ′-(triiodomethyl) ferrocene, 1-chloro-1 ′-(trichloromethyl) ferrocene, 1-bromo-1 ′-(trichloromethyl) ferrocene, 1-bromo-1 ′ -(Tribromomethyl) ferrocene, 1,1'-di- (trichloromethyl)
Ferrocene, 1,1′-di- (tribromomethyl) ferrocene, 1,1′-di- (trichloromethyl) -2-chloroferrocene, 1-acetyl-1 ′-(trichloromethyl) ferrocene, 1,1 ′ -Diacetyl-2- (trichloromethyl) ferrocene, 1,1'-diacetyl-3
-(Trichloromethyl) ferrocene, 1-formyl-
1 '-(((chloromethyl) oxy) methyl) ferrocene, 1-acetyl-1'-(((chloromethyl) oxy) methyl) ferrocene, 1-formyl-1'-
(((Trichloromethyl) oxy) methyl) ferrocene, 1-acetyl-1 ′-(((trichloromethyl) oxy) methyl) ferrocene, and the like.

1-formyl-1 ′-(((trimethylsilyl) oxy) methyl) ferrocene, 1-(((6-
(((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -1'-formylferrocene, 1-acetyl-1 '-(((trimethylsilyl) oxy) methyl) ferrocene, 1-(( (6-
(((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -1′-acetylferrocene, 1,1′-di-(((trimethylsilyl) oxy) methyl) ferrocene, 1,1 ′ -Di-(((6-
(((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) ferrocene, 1,1 ′
-Di-(((trimethylsilyl) oxy) methyl) -2
-Acetylferrocene, 1,1'-di-(((6-
(((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -2-acetylferrocene, 1,1′-di-(((trimethylsilyl) oxy) methyl) -2-formylferrocene, 1 , 1'-di-(((6-(((1,1-dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -2-formylferrocene, 1-methyl-1 '-(((trimethylsilyl)) (Oxy) methyl) ferrocene, 1-(((6
-(((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -1'-methylferrocene, 1-ethyl-1 '-(((trimethylsilyl))
(Oxy) methyl) ferrocene, 1-(((6-
(((1,1-dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -1′-ethylferrocene, 1,1′-di-(((trimethylsilyl) oxy) methyl) -2-methylferrocene, 1,1'-di-
(((6-(((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -2-methylferrocene, 1-methyl-1 ′-(trimethylsilylmethyl) ferrocene, 1-methyl-1 '-(Trimethylsilylethyl) ferrocene, 1-methyl-1'-(trimethylsilylpropyl) ferrocene, 1,1'-di-
(Trimethylsilylmethyl) ferrocene, 1,1'-di- (trimethylsilylethyl) ferrocene, 1,1'-
Di- (dimethylsilylmethyl) ferrocene, 1-acetyl-1 ′-(trimethylsilylmethyl) ferrocene,
1,1'-diacetyl-2- (trimethylsilylmethyl) ferrocene, 1,1'-diacetyl-3- (trimethylsilylmethyl) ferrocene and the like can be mentioned.

The substituent is an oxygen-containing group having 1 to 20 carbon atoms.
1,1'-di (acetylcyclopentadiene)
Le) Iron, 1,1'-dibenzoylferrocene,
1,1'-bis (1-oxotetradecyl) ferrose
1- (3-ethoxy-1-methyl-3-oxo-1
-Propenyl) -1 '-(1-oxo-3-phenyl-
2-propenyl) ferrocene, 1-benzoyl-1′-
(3-Ethoxy-1-methyl-3-oxo-1-propene
Nyl) ferrocene, 1- (3-ethoxy-1-methyl-
3-oxo-1-propenyl) -1 '-(phenylacetate
Cyl) ferrocene, 1,1′-bis (2-furanylcar
Bonyl) ferrocene, 1,1′-bis (2-methylben)
Zoyl) ferrocene, 1,1'-bis (3-methylben
Zoyl) ferrocene, 1,1'-bis (2,4,6-to
Limethylbenzoyl) ferrocene, 1,1′-bis (2
-Chlorobenzoyl) ferrocene, 1,1'-bis (2
-Fluorobenzoyl) ferrocene, 1- (1,3-di
Oxopentyl) -1'-methylferrocene, (neope
Cyclopentadienyl) (propionylcyclope
Iron, (pivaloyl cyclopentadi)
(Enyl) (propylcyclopentadienyl) iron,
1- (9-carboxy-1-oxononyl) -1 ′, 3
-Dimethylferrocene, 1- (9-carboxy-1-o
Xisononyl) -1 ', 2-dimethylferrocene, 1-
(10-Ethoxy-1,10-dioxodecyl)-
1 ', 3-dimethylferrocene, 1- (10-ethoxy
-1,10-Dioxodecyl) -1-', 2-dimethyl
Ferrocene, 1- (6-methoxy-1,6-dioxoh
Xyl) -1 '-(1-oxooctadecyl) ferrose
1,1,1′-bis (1-oxonyl) ferrocene,
1,-(1-methyl-3-oxo-1-butenyl)-
1 '-(phenylacetyl) ferrocene, 1- (3-ca
Rubox-1-oxopropyl) -1 '-(1-oxo
Undecyl) ferrocene, 1- (3-carboxy-1-
Oxopropyl) -1 '-(1-oxononyl) ferro
Sene, 1- (4-ethoxy-1,4-dioxobutyl)
-1 '-(1-oxoundecyl) ferrocene, 1-
(4-Ethoxy-1,4-dioxobutyl) -1'-
(1-Oxononyl) ferrocene, 1,1'-bis (6
-Carboxy-1-oxohexyl) ferrocene, 1-
(5-Carboxy-1-oxopentenyl) -1′-
(3-carboxy-1-oxopropyl) ferrocene,
1,1'-bis (7-methoxy-1,7-dioxohep
Cyl) ferrocene, 1- (4-methoxy-1,4-dio)
Xobutyl) -1 '-(6-methoxy-1,6-dioki
Sohexyl) ferrocene, bis (o-carboxybenzo
Iron cyclopentadienyl) iron, (cinnamoyl
Cyclopentadienyl) (neopentylcyclopentadiene)
Enil iron, 1,1'-bis (3,5,5-tri
Methyl-1-oxohexyl) ferrocene, 1,1′-
Bis (1-oxohexadecyl) ferrocene, (neope
Cyclopentadienyl) (3,5,5-trimethyl)
Ruhexanoyl cyclopentadienyl) iron, (ne
Opentylcyclopentadienyl) (pivaloyl cyclo)
Pentadienyl) iron, ((4-carboxybutyryl
) Cyclopentadienyl) ((3-carboxypropy
Noyl) cyclopentadienyl) iron, 1,1'-
Bis (4-carboxy-1-oxobutyl) ferrose
And (isobutylcyclopentadienyl) pivaloyl
Clopentadienyl) iron, (isobutyryl cyclo)
Pentadienyl) (neopentylcyclopentadienyl)
Le) Iron, 1- (5-Carboxypentyl) -1 '
-(1-oxooctadecyl) ferrocene, 1- (5-
Carboxy-1-oxopentyl) -1'-octadecyl
Ruferrocene, 1- (5-carboxy-1-oxopene
Chill) -1 '-(1-oxooctadecyl) ferrose
And ((3-carboxypropionyl) cyclopentadiene
(Enyl) ((3-carboxypropyl) cyclopentadi
(Enyl) iron, (benzylcyclopentadienyl)
(Pivaloyl cyclopentadienyl) iron, 1-
(9-carboxy-1-oxononyl) -1 ′, 2,
2 ', 3,3', 4,4 ', 5-octamethylferrose
1- (10-ethoxy-1,10-dioxodecyl
Le) -1 ', 2,2', 3,3 ', 4,4', 5-oct
Tamethylferrocene, (neopentylcyclopentadiene
Nyl) (phenylacetylcyclopentadienyl) eye
Ron, (phenethylcyclopentadienyl) (pivalloy
Rucyclopentadienyl) iron, 1,1'-2 bis
(5-methoxy-1,5-dioxopentyl) ferrose
1-benzoyl-1 '-(1-oxohexadecyl
) Ferrocene, 1-acetyl-1 '-(1-oxoh
Xadecyl) ferrocene, 1,1'-bis (1-oxo
Octadecyl) ferrocene, 1-acetyl-1 ′-(1
-Cyclohexen-1-ylacetyl) ferrocene, 1
-Acetyl-1 '-(1-cycloocten-1-ylua
Cetyl) ferrocene, 1-formyl-1 ′, 2,2 ′,
3,3 ', 4,4', 5-octamethyl-5 '-(2,
4,6-Trimethylbenzoyl) ferrocene, 1-ben
Zoyl-1'-formyl-2,2 ', 3,3', 4
4 ', 5,5'-octamethylferrocene, benzoyl
Nonamethylferrocene, 1- (3,3-dimethyl-1-
Oxobutyl) -1-oxobutyl) -1 ′-(1-o
Xoxo-4-phenylbutyl) ferrocene, 1- (1-o
Xo-5- (4- (1-oxo-3-phenyl-2-p-
Ropynyl) phenyl) pentyl) -1 '-(1-oxo
-3-Phenyl-2-propynyl) ferrocene, 1-
(1-oxo-4- (4- (1-oxo-3-phenyl
-2-Propinyl) phenyl) butyl) -1 '-(1-
Oxo-3-phenyl-2-propynyl) ferrocene,
1- (1-oxo-3-phenyl-2-propynyl) phenyl
Phenyl) propyl) -1 '-(1-oxo-3-phenyl
Lu-2-propynyl) ferrocene, 1- (1-oxo-
3- (4- (1-oxo-3-phenyl-2-propene
Ru) phenyl) propyl) -1 '-(1-oxo-3-
Phenyl-2-propynyl) ferrocene, 1- (1-o
Xoxo-3-phenylpropyl) -1 '-(1-oxo-
3-phenyl-2-propynyl) ferrocene, 1- (fu
Phenylacetyl) -1 '-(1-oxo-3-phenyl
-2-Propinyl) ferrocene, 1- (1-oxo-5)
-Phenylpentyl) -1 '-(1-oxo-3-phen
Nyl-2-propenyl) ferrocene, 1- (1-oxo
-4-phenylbutyl) -1 '-(1-oxo-3-fluoro)
Phenyl-2-propenyl) ferrocene, 1- (1-oxy
So-3-phenyl-2-propenyl) -2-propenyl
) -1 '-(1-oxo-3-phenylpropyl) phenyl
Jerocene, 1-benzoyl-1'-formylferrose
1-benzoyl-1 '-(3-oxo-3-phenyl
Ru-1-propenyl) ferrocene, 1,1′-bis (1
-Oxo-2-pentenyl) ferrocene, 1-benzoi
Ru-1 '-(1-hydroxy-3- (1-hydroxyoxy)
Chlohexyl) -1-phenyl-2-propynyl) fe
Rosene, 1,1'-bis (3-carboxy-1-oxo
Propyl) ferrocene, 1,1'-bis (4-methoxy
-1,4-dioxobutyl) ferrocene, 1-acetyl
-1 '-(1,3-dioxobutyl) -3,3'-dime
Tilferrocene, 1,1'-bis (1-oxopentyl
Le) ferrocene, ((3-carboxypropionyl) e
Cylcyclopentadienyl (ethylcyclopentadienyl
Le) Iron, 1,1'-bis (4- (2-methylbutyrate
Ru) benzoyl) ferrocene, 1,1′-bis (1-o
Xenoundecyl) ferrocene, 1- (4-hydroxyl)
Phenyl) -1 '-(1-oxo-3-phenyl-2-propyl
Lopenyl) ferrocene, 1-acetyl-1 '-(3-
(3-Methoxyphenyl) -1-oxo-2-propene
) Ferrocene, 1-acetyl-1 '-(3- (4-me
Cylphenyl) -1-oxo-2-propenyl) ferro
Sen, 1-acetyl-1 '-(3- (4-methoxyphen
Nyl) -1-oxo-2-propenyl) ferrocene, 1
-(3-Methyl-1-oxo-2-butenyl) -1'-
(Phenylacetyl) ferrocene, 1- (4,4-dime
Cyl-1-oxo-2-pentenyl) -1 ′-(phenyl
Luacetyl) ferrocene, 1-acetyl-1 ′-(4,
4-dimethyl-1-oxo-2-pentenyl) ferrose
1-acetyl-1 '-(3-methyl-1-oxo-
2-butenyl) ferrocene, 1-acetyl-1 ′-(1
-Oxo-2-butenyl) ferrocene, 1-acetyl-
1 '-(2-methyl-1-oxo-2-propenyl) fur
Erosene, 1- (3,3-dimethyl-1-oxobutyrate
) -1 '-(1-oxo-3-phenyl-2-propene
Nyl) ferrocene, 1- (3-methyl-1-oxobutyrate)
) -1 '-(1-oxo-3-phenyl-2-propene
Nyl) ferrocene, 1- (1-oxobutyl) -1'-
(1-oxo-3-phenyl-2-propenyl) ferro
Sen, 1,1'-bis ((4-methylphenyl) acetyl
) Ferrocene, 1,1'-bis (3- (4-methylphenyl)
Phenyl) -1-oxo-2-propenyl) ferrocene,
1,1'-bis (3- (2-furanyl) -1-oxo-
2-propenylferrocene, 1,1′-bis (hydroxy
Ciacetyl) ferrocene, 1- (6- (4-methoxyphenyl)
Phenyl) -6-oxohexyl) -1 ', 3-bis (1
-Oxo-3-phenyl-2-propenyl) ferrose
1- (10- (4-methoxyphenyl) -10-o
Xodecyl) -1 ', 2-bis (1-oxo-3-phen)
Nyl-2-propenyl) ferrocene, 1- (5- (4-
Methoxyphenyl) -5-oxopentyl) -1 ', 3
-Bis (1-oxo-3-phenyl-2-propenyl)
Ferrocene, 1- (9- (4-methoxyphenyl) -9
-Oxononyl) -1 ', 2-bis (1-oxo-3-)
Phenyl-2-propenyl) ferrocene, 1- (8-
(4-Methoxyphenyl) -8-oxooctyl)-
1 '-(1-oxo-3-phenyl-2-propenyl)
Ferrocene, 1,1'-bis (10-ethoxy-1,1
0-dioxodecyl) ferrocene, 1,1′-bis (9
-Ethoxy-1,9-dioxononyl) ferrocene,
1,1'-bis (8-ethoxy-1,8-dioxooctane
Cyl) ferrocene, 1,1′-bis (7-ethoxy-
1,7-dioxoheptyl) ferrocene, 1,1′-bi
Su (5-ethoxy-1,5-dioxopentyl) ferro
Sen, 1- (1,10-dioxo-10-phenyldecyl
) -1 '-(1-oxo-3-phenyl-2-propene
Nyl) ferrocene, 1- (1,9-dioxo-9-phen
Nylnonyl) -1 '-(1-oxo-3-phenyl-2
-Propenyl) ferrocene, 1- (1,8-dioxo-
8-phenyloctyl) -1 '-(1-oxo-3-fluoro)
Phenyl-2-propenyl) ferrocene, 1- (1,7-
Dioxo-7-phenylheptyl) -1 '-(1-oxy
So-3-phenyl-2-propenyl) ferrocene, 1-
Methyl-1 ′-(4-methylbenzoyl) ferrocene,
1- (2-methoxy-2-oxoethyl) -1 '-(4
-Methylbenzoyl) ferrocene, 1-benzoyl-
1 ', 3-bis (phenylmethyl) ferrocene, 1-be
Nzoyl-1 ', 2-bis (phenylmethyl) ferrose
1-benzoyl-1 ′-(1-hydroxy-1-phenylene
Phenylethyl) ferrocene, 1,1'-bis (1,1 '
-Biphenyl) -4-ylcarbonyl) ferrocene, 1
-Benzoyl-1 '-(1-methylcyclopropyl) phenyl
Erosene, 1,1'-bis (3-carboxy-1-oxy
So-2-propenyl) -2-methylferrocene, 1-me
Chill-1 ′, 2-bis (1-oxo-3-phenyl-2)
-Propenyl) ferrocene, 1- (6-methoxy-1 ,,
6-dioxohexyl) -1 '-((2-oxocyclo
Pentyl) carbonyl) ferrocene, 1,1'-bis
(6-Ethoxy-1,6-dioxohexyl) ferrose
1- (6-ethoxy-1,6-dioxohexyl)
-2-((2-oxocyclopentyl) carbonyl) fur
Erocene 1,1'-bis (4-methoxybenzoyl) fur
Jerocene, 1,1'-bis (1-oxooctyl) fe
Rosene, 1-carboxy-1 '-(1,2-dioxop
Ropyl) ferrocene, 1- (methoxycarbonyl)-
1 '-(phenylacetyl) ferrocene, 1-carboxy
Ci-1 '-(1-oxo-3-phenyl-2-propene
) Ferrocene, 1-carboxy-1 '-(oxophene
Nylacetyl) ferrocene, 1- (methoxycarbonyl)
) -1 '-(1-oxo-3-phenyl-2-propene
Nyl) ferrocene, 1- (3-methylphenyl) -1 '
-(1-oxo-3-phenyl-2-propenyl) phen
Rosene, 1- (4-methylphenyl) -1 '-(1-o
Xoxo-3-phenyl-2-propenyl) ferrocene, 1
-(1-oxo-3-phenyl-2-propenyl)-
1'-phenylferrocene, 1- (3,5-dimethylphenyl)
Phenyl) -1 '-(1-oxo-3-phenyl-2-propyl
Lopenyl) ferrocene, 1- (3,4-dimethylphenyi
) -1 '-(1-oxo-3-phenyl-2-propene
Nyl) ferrocene, 1- (4-methoxyphenyl)-
1 '-(1-oxo-3-phenyl-2-propenyl)
Ferrocene, 1- (4- (ethoxycarbonyl) phenyl
) -1 '-(1-oxo-3-phenyl-2-propene
Nyl) ferrocene, 1- (3-ethylphenyl) -1 '
-(1-oxo-3-phenyl-2-propenyl) phen
Rotene, 1- (4-ethylphenyl) -1 '-(1-o
Xoxo-3-phenyl-2-propenyl) ferrocene, 1
-Benzoyl-1 '-(methoxymethyl) ferrocene,
1,1'-bis (3-ethoxy-1,3-dioxopro
Pill) ferrocene, 1- (3,3-dimethyl-1-oxy)
Sobutyl) -1 ', 3-dimethylferrocene, 1-
(3,3-Dimethyl-1-oxobutyl) -1 ′, 2-
Dimethylferrocene, 1-acetyl-1 '-(2-methyl
L-1-oxo-3-phenyl-2-propenyl) phen
Rosene, 1-acetyl-1 '-(1-oxo-5-phen
Nyl-2,4-pentadienyl) ferrocene, 1,1 ′
-Bis (oxophenylacetyl) ferrocene, 1,
1'-bis (phenylacetyl) ferrocene, 1- (3
-Acetylphenyl) -1 '-(1-oxo-3-phen
Nyl-2-propenyl) ferrocene, 1,1'-bis
(Cyclohexylcarbonyl) ferrocene, 1,1'-
Bis (1-oxohexyl) ferrocene, 1,1'-bi
Sus (3-methyl-1-oxobutyl) ferrocene, 1-
(1,1-Dimethylethyl) -1 '-(2,2-dimethyl)
Ru-1-oxopropyl) ferrocene, 1- (1,1-
Dimethylethyl) -1 '-(2-methyl-1-oxop
Ropyl) ferrocene, 1-acetyl-1 '-(1-oxy
So-3-phenyl-2-propynyl) ferrocene, 1,
1'-bis (2,2-dimethyl-1-oxopropyl)
Ferrocene, 1-acetyl-1 '-(1-oxobutyrate
) Ferrocene, 1-acetyl-1 '-(phenylacetate
Tyl) -2- (phenylmethyl) ferrocene, 1-ben
Zoyl-1 ′-(phenylacetyl) ferrocene, 1-
(1-oxobutyl) -1 '-(phenylacetyl) phenyl
Erocene, 1-benzoyl-1 '-(1-oxobutyrate
) Ferrocene, 1- (1-oxopropyl) -1'-
(Phenylacetyl) ferrocene, 1-acetyl-1 '
-(Phenylacetyl) ferrocene, 1-benzoyl-
1 '-(1-oxopropyl) ferrocene, 1-acetyl
Lu-3-ethyl-1 '-(phenylacetyl) ferrose
1-acetyl-1 '-(phenylacetyl) -3-
(Phenylmethyl) ferrocene, 1- (3-ethoxy-
1-methyl-3-oxo-1-propenyl) -1'-
(1-oxo-2-butenyl) ferrocene, 1- (3-
Ethoxy-1-methyl-3-oxo-1-propenyl)
-1 '-(1-oxooctadecyl) ferrocene, 1-
(3-Ethoxy-1-methyl-3-oxo-1-propene
Nil) -1 '-(1-oxopropyl) ferrocene, 1
-Acetyl-1 '-(3-ethoxy-1-methyl-3-
Oxo-1-propenyl) ferrocene, 1,1′-bis
(((5-((4-methoxyphenoxy) carbonyl))
Phenoxy) Pentyl) Oxy) Carbonyl) Ferrose
1,1,1′-bis ((3- (4-((4-methoxyphenyl
Enoxy) carbonyl) phenoxy) propoxy) cal
Bonyl) ferrocene, 1,1′-bis ((2- (4-
((4-Methoxyphenoxy) carbonyl) phenoxy
Ci) ethoxy) carbonyl) ferrocene, 1,1'-bi
Su ((heptadecyloxy) carbonyl) ferrocene,
1,1'-bis (((2,3,5,6,8,9,11,
12-octahydro-1,4,7,10,13-benzo
Pentaoxacyclopentadecyn-15-yl) oxy
Si) Carbonylferrocene, 1-carboxy-1'-
((Phenylmethoxy) carbonyl) ferrocene, 1,
1'-bis ((4-((4- (hexyloxy) phenoxy
Si) Carbonyl) Phenoxy) Carbonyl) Ferrose
1,1,1′-bis ((4-((4- (pentyloxy)
Phenoxy) carbonyl) phenoxy) carbonyl) fu
Erosene, 1,1'-bis ((4-((4-butoxy
Enoxy) carbonyl) phenoxy) carbonyl) phen
Rotene, 1,1'-bis ((4-((4-ethoxyphen
Noxy) carbonyl) phenoxy) carbonyl) ferro
Sen, 1,1'-bis ((4-((4- (pentyloxy
Ci) benzoyl) oxy) phenoxy) carbonyl) fu
Erosene, 1,1'-bis ((4-((4- (butoxy
Benzoyl) oxy) phenoxy) carbonyl) ferro
Sen, 1,1'-bis ((4-((4-propoxyben
Zoyl) oxy) phenoxy) carbonyl) ferrose
1,1,1′-bis ((4-((4-ethoxybenzoyl
Le) oxy) phenoxy) carbonyl) ferrocene,
1,1'-bis ((4-((4-methoxybenzoyl)
Oxy) phenoxy) carbonyl) ferrocene, 1-
(((1,1'-biphenyl) -4-yloxy) carbo
Nyl) -1'-hexylferrocene, 1-butyl-1 '
-((4-((4- (pentyloxy) benzoyl) oxy)
Si) phenoxy) carbonyl) ferrocene, 1-butyl
-1 '-((4- (hexyloxy) phenoxy) carbo
Nyl) ferrocene, 1-butyl-1 '-((4-hepti
Rufenoki) carbonyl) ferrocene, 1,1'-bis
((4-formylphenoxy) arbonyl) ferrose
1,1, '-bis (((3-formylphenyl) meth)
Xy) carbonylferrocene, 1,1'-bis ((4-
((4- (hexyloxy) benzoyl) oxy) pheno
Xy) carbonyl) ferrocene, 1,1'-bis ((4
-(Phenylmethoxy) phenoxy) carbonylferro
Sen, 1-((4- (decyloxy) phenoxy) carbo
Nyl) -1 '-((4-hydroxyphenoxy) carbo
Nyl) ferrocene, 1,1'-bis ((4- (deroshiki
Ci) phenoxy) carbonyl) ferrocene, 1,1'-
Bis ((4- (heptyloxy) phenoxy) carboni
Le) ferrocene, 1,1′-bis ((4- (1,1-di
Methylethyl) phenoxy) carbonylferrocene,
1,1'-bis (methoxycarbonyl) -2,2'-bi
Sus (methoxymethyl) ferrocene, 1,1'-bis (d
Toxycarbonyl) -2,3'-bis (methoxymethyi)
) Ferrocene, 1,1'-bis (ethoxycarboni
) -2,3'-bis (methoxymethyl) ferrocene,
1,1'bis (ethoxycarbonyl) -2,2'-bis
(Methoxymethyl) ferrocene, 1- (ethoxycarbo
Nyl) -1 ', 2-bis (methoxymethyl) ferrose
1,1,1′-bis (((1,4-dihydro-1,4-
Dioxy-2-naphthalenyl) oxy) carbonyl) fu
Erosene, 1,1'-bis (((4 '-(Heptyloxy
) (1,1'-Biphenyl) -4-yl) oxy) carb
Rubonyl) ferrocene, 1,1'-bis (((4'-
(Hexyloxy) (1,1'-biphenyl) -4-i
Ru) oxy) carbonyl) ferrocene, 1,1′-bis
((4 '-(pentyloxy) (1,1'-biphenyl)
-4-yl) oxy) carbonyl) ferrocene, 1,
1'-bis (((4'-butoxy (1,1'-biphenyl
Ru) -4-yl) oxy) carbonyl) ferrocene,
(Methoxycarbonyl) nonamethylferrocene, 1,
1 '-(methoxycarbonyl) -2,2', 3,3 ',
4,4 ', 5,5'-octamethylferrocene, 1-
(2-Acetyl-3-oxobutyl) -1 '-(meth
Cycarbonyl) ferrocene, 1- (methoxycarbonyl)
) -1 '-(phenoxymethyl) ferrocene, 1,
1'-bis ((1,1-dimethylethoxy) carboni
) Ferrocene, 1,1'-bis (((3-hydroxy
Methyl) phenyl) methoxy) carbonyl) ferrose
1,1,1′-bis (((5- (hydroxymethyl)-
2-furanyl) methoxy) carbonyl) ferrocene,
1,1'-bis ((4-hydroxyphenoxy) carbo
Nyl) ferrocene, 1-acetyl-1 ′-(propoxy
Carbonyl) ferrocene, 1-acetyl-1 '-(eth
Xycarbonyl) ferrocene, decaquis (methoxycal)
Bonyl) ferrocene, 1,1'-bis ((2-propenyl
Ruoxy) carbonyl) ferrocene, 1,1′-bis
((Phenylmethoxy) carbonyl) ferrocene, 1-
(Ethoxycarbonyl) -1'-ethylferrocene, 1
-(Ethoxycarbonyl) -1'-methoxyferrose
1- (ethoxycarbonyl) -1'-phenylphen
Rosene, 1-acetyl-1 '-(4- (ethoxycarbo
Nyl) phenyl) ferrocene, 1,1'-bis ((Oki
Silanylmethoxy) carbonyl) ferrocene, 1- (hi
Droxymethyl) -1 '-(methoxycarbonyl) phen
Rosene, 1- (methoxycarbonyl) -1 ', 2-diph
Phenylferrocene, 1- (methoxycarbonyl)-
1 ', 3-diphenylferrocene, 1,1'-bis (me
Toxycarbonyl) -3-methylferrocene, 1,2-
Diformyl-1 ', 2', 3,3 ', 4,4', 5
5'-octamethylferrocene, 1'-formyl-1,
2,3,4-tetramethyl-5- (4,7,10,13
-Tetraoxatetradec-1-yl) ferrocene, 1
-Acetyl-1 '-(2-ethoxy-2-oxoethyl
Le) ferrocene, 1-formyl-1 ′-(((6-hydr
Roxyhexyl) oxy) methyl) ferrocene, 1,
1'-diacetyl-3,3'-bis (1,1-dimethyl
Ethyl) ferrocene, 1'-formyl-1,2,3,
4,5-pentamethylferrocene, 1- (1-methyl-
3-oxo-1-butenyl) -1 ′-(1-oxopro
Pill) ferrocene, 1-acetyl-1 '-(1-methyl
-3-Oxo-1-butenyl) ferrocene, 1'-form
Mill-1,2-dimethylferrocene, 1-formyl-
1 ', 2,2', 3,3 ', 4,4', 5-octamethy
Ruferrocene, (acetylcyclopentadienyl) (ne
Opentylcyclopantadienyl) iron, 1-ace
Tyl-1'-ethynylferrocene, (benzoylcyclo
Pentadienyl) (neopentylcyclopentadiene)
Iron, acetylnonamethylferrocene, 1-holmi
Ru-1 '-(hydroxyphenylmethyl) -2,2',
3,3 ', 4,4', 5,5'-octamethylferrose
1-formyl-1 '-(1-hydroxyethyl)-
2,2 ', 3,3', 4,4 ', 5,5'-octamethy
Ruferrocene, 1-formyl-3- (hydroxymethyi
Le) -1 ', 2,2', 3 ', 4,4', 5,5'-o
Kutamethylferrocene, (acetylcyclopentadiene
Iron) (hydroxycyclopentadienyl) iron,
1'-acetyl-1,2,3,4,5-pentaphenyl
Ferrocene, 1,1'-diacetyl-3,3'-dimethyl
Ruferrocene, (acetylcyclopentadienyl)
((2-Carboxyvinyl) cyclopentadienyl) a
Iron, (acetylcyclopentadienyl) ((2-ca
Ruboxiethyl) cyclopentadienyl) iron, e
Lumilnonamethylferrocene, 1,1'-diformyl-
2,2 ', 3,3', 4,4 ', 5,5'-octamethy
Ruferrocene, 1-formyl-1 '-(hydroxymethyi
) Ferrocene, 1-acetyl-1 '-(1- (acetyl
Roxy) ethynyl) ferrocene, 1-acetyl-1′-
(8- (4-methoxyphenyl) -8-oxooctyl
) Ferrocene, 1-acetyl-1 ′, 3-bis (phen)
Nylmethyl) ferrocene, 1-acetyl-1 ', 2-bi
Su (phenylmethyl) ferrocene, 1-acetyl-1 '
-(1-Hydroxy-1-phenylethyl) ferrose
1,1,1′-diacetyl-2-methylferrocene,
1,1′-diacetyl-3-methylferrocene, 1-ho
Rumil-2- (4-methoxyphenyl) ferrocene, 1
-(3-Ethylphenyl) -1'-formylferrose
1- (4-ethylphenyl) -1'-formylfe
Rosene, 1- (3,5-dimethylphenyl) -1'-ho
Rumilferrocene, 1- (4- (ethoxycarbonyl))
Phenyl) -1'-formylferrocene, 1- (3,4
-Dimethylphenyl) -1'-formylferrocene, 1
-Formyl-1 '-(4-methoxyphenyl) ferrose
1-formyl-1 '-(4-methylphenyl) phen
Rosene, 1-formyl-1 '-(3-methylphenyl)
Ferrocene, 1-acetyl-1 '-(4- (acetyloxy
Si) phenyl) ferrocene, 1-formyl-1'-phen
Nylferrocene, 1-acetyl-1 '-(4-methoxy
Phenyl) ferrocene, 1-acetyl-1 '-(3,4
-Dimethylphenyl) ferrocene, 1-acetyl-1 '
-(3,5-Dimethylphenyl) ferrocene, 1-ace
Cyl-1 ′-(4-methylphenyl) ferrocene, 1-
Acetyl-1'-phenylferrocene, 1-acetyl-
1 '-(3-methylphenyl) ferrocene, 1-acetyl
Ru-1 ′-(2-benzoyl-3-oxo-1-butenyl
Ru) ferrocene, 1-acetyl-1 ′-(3-oxo-
5-phenyl-1,4-pentadienyl) ferrocene,
1-acetyl-1 '-(2-acetyl-5-oxo-5
-Phenyl-1,3-pentadienyl) ferrocene, 1
-Acetyl-1 '-(5-oxo-5-phenyl-1,
3-pentadienyl) ferrocene, 1-acetyl-1 '
-(1-hydroxyethyl) ferrocene, 1-acetyl
-1 '-(1-methoxy-3-phenyl-2-propene
Ru) ferrocene, 1-acetyl-1 ′, 3-bis (1-
Methylethyl) ferrocene, 1'-acetyl-1,2-
Dimethylferrocene, 1'-acetyl-1,3-dimethyl
Ruferrocene, 1-acetyl-1 ', 3-bis (1,1
-Dimethylethyl) ferrocene, 1-acetyl-1'-
(3-Methoxy-3-phenyl-1-propenyl) phen
Rosene, 1-acetyl-1 ', 2-bis (1,1-dim
Tylethyl) ferrocene, 1-acetyl-1 ′, 2-bi
Sus (1-methylethyl) ferrocene, 1-acetyl-
1 ', 2-diethylferrocene, 1-acetyl-1'-
(3-oxobutyl) ferrocene, 1-acetyl-1 '
-(3-acetylphenyl) ferrocene, 1-acetyl
-1 '-(4-acetylphenyl) ferrocene, 1-a
Cetyl-1'-methoxyferrocene, 1-acetyl-
1 '-(tributylstannyl) ferrocene, 1-form
Mil-1 ′-(tributylstannyl) ferrocene, etc.
Can be mentioned.

1-Butyl-1 '-(4-mercapto-1) is a compound having a sulfur-containing group having 1 to 20 carbon atoms as a substituent.
-Oxobutyl) ferrocenium, 1,1'-bis (4
-Mercapto-1-oxobutyl) ferrocene, 1-
(4-Mercapto-1-oxobutyl) -1 '-(1-
Oxobutyl) ferrocene, 1-butyl-1 ′-(4-
Mercapto-1-oxobutyl) ferrocene, 1- (2
-Phenylethyl) -1 '-(2-thienylcarbonyl) ferrocene, 1-ethyl-3- (1-hydroxyethyl) -1'-(2-thienylcarbonyl) ferrocene, 1- (phenylacetyl) -1'- (2-thienylcarbonyl) ferrocene, 1-benzoyl-1 ′-(2
-Thienylcarbonyl) ferrocene, 1- (1-oxopropyl) -1 '-(2-thienylcarbonyl) ferrocene, 1,1'-bis ((2-((2-((1,3-dithio-l- 2-ylidene) -1,3-dithiol-4-
Yl) thio) ethoxy) carbonyl) ferrocene, 1-
(Methoxycarbonyl) -1 '-((phenylthio) methyl) ferrocene, 1,1'-bis ((2- (3-thienyl) ethoxy) carbonyl) ferrocene, 1,1'-
Bis (((5- (hydroxymethyl) -2-thienyl))
(Methoxy) carbonyl) ferrocene, 1- (methoxycarbonyl) -1 ′-(methoxysulfonyl) ferrocene, 1-acetyl-1 ′-(5-acetyl-3-phenyl-2-thienyl) ferrocene, cyclopentadienyl ((1-formyl-2- (2-thienyl) vinyl) cyclopentadienyl) iron, 1-formyl-1'-sulfoferrocene, 1-acetyl-1 '-(methoxysulfonyl) ferrocene, 1- Acetyl-1'-sulfoferrocene and the like can be mentioned.

1,1'-bis (diphenylphosphino) ferrocene, 1-acetyl-1 '-((diphenylphosphino) acetyl) ferrocene, 1,1'-bis (diphenylphosphino) ferrocene as a compound whose substituent is a phosphorus-containing group having 1 to 20 carbon atoms. 1'-bis ((diphenylphosphino) acetyl) ferrocene, 1-
(Diphenylphosphino) -1'-formylferrocene, 1-acetyl-1 '-(diphenylphosphino) ferrocene, 1-acetyl-1'-(diphenylphosphinyl) ferrocene and the like can be mentioned.

As the compound in which the substituents are cross-linked, 1,1'-diacetyl-2,3 '-(1,3-propanesyl) ferrocene, 1,2-diacetyl-1,4'-
(1,4-Butanadyyl) ferrocene, 1,1'-bis (methoxycarbonyl) -2,2 '-(oxybis (methylene)) ferrocene, 1,1'-bis (ethoxycarbonyl) -2,2'-( Oxybis (methylene)) ferrocene, 1-benzoyl-1 ′-(3-oxo-3-phenyl-1-propenyl) -3,3 ′-(1,3-propanediyl) ferrocene, 1- (phenylacetyl)-
1 ', 3- (1,3-propanesyl) ferrocene, 1
-((4-Methoxyphenyl) acetyl) -1 ', 3-
(1,5-pentadienyl) ferrocene, 1-((4-
Methoxyphenyl) acetyl) -1 ', 3- (1,3-
Propanediyl) ferrocene, 1,1 ′-(1,5-pentanesyl) -3- (phenylacetyl) ferrocene,
1-formyl-1 ', 3- (1,5-pentadienyl)
Ferrocene, 1,1'-diacetyl-3,3 '-(1,
5-pentadienyl) ferrocene, 1-benzoyl-
1 ', 2- (1,3-cyclopentadienyl) ferrocene, 1', 2- (1,4-butadiyl) -1-formyl-2 ', 3- (1,3-propanediyl) ferrocene, 1, 1'-diacetyl-2 ', 3- (1,5-pentadienyl) ferrocene, 1- (1-oxo-2-propenyl) -1', 3- (1,3-propanediyl) ferrocene, 1- (methoxycarbonyl) ) -1 ', 2-
(1,3-propanediyl) ferrocene, 1-acetol-1 '-(1-oxo-3-phenyl-2-propenyl) -2', 3- (1,3-propanediyl) ferrocene, 1-acetyl-1 '. , 3- (3-phenyl-1,5
-Pentanesyl) ferrocene, 1,1'-diacetyl-2,3 '-(1,4-butanesyl) ferrocene,
1,1'-diacetyl-3,3 '-(1,4-butanediyl) ferrocene, 1,1'-diacetyl-2,3'-
(1,4-butadienyl) ferrocene, 1- (methoxycarbonyl) -1 ′, 3- (1,3-propanediyl)
Ferrocene, 1-formyl-1 ', 3- (1,3-propanesyl) ferrocene, 1-formyl-1', 2-
(1,3-propanediyl) ferrocene, 1'-acetyl-1- (1-oxo-2-propenyl) -2,3'-
(1,5-Pentanadyyl) ferrocene, 1-acetyl-1 ′-(1-oxo-2-propenyl) -3,3′-
(1,5-Pentanadyyl) ferrocene, 1-benzoyl-1 ′-(3-oxo-3-phenyl-1-propenyl) -3,3 ′-(1,5-pentadienyl) ferrocene, 1-benzoyl-1 ′ -Formyl-3,3'-
(1,5-Pentanadyyl) ferrocene, 1-benzoyl-1′-formyl-3,3 ′-(1,3-propanediyl) ferrocene, 1,1′-bis (methoxycarbonyl) -2,2 ′: 3 3'-bis (1,3-propanediyl) ferrocene, 1,1'-bis (methoxycarbonyl) -2,2 ': 4,4'-bis (1,3-propanediyl) ferrocene, 1,1'-bis (Methoxycarbonyl) -2,4 ': 2', 4-bis (1,3-propanediyl) ferrocene, 1- (methoxycarbonyl)-
1 ', 2: 3', 4-bis (1,3-propanesyl)
Ferrocene, 1,4-bis (methoxycarbonyl)-
1 ', 2: 2', 3-bis (1,3-propanedil)
Ferrocene, 1- (methoxycarbonyl) -1 ′, 2:
2 ', 3-bis (1,3-propanediyl) ferrocene, 1', 2- (1,4-butenediyl) -1- (4-
Methoxy-1,4-dioxobutyl) -2 ', 3- (1
-Oxo-l, 3-propanediyl) ferrocene, 1,
1'-bis (methoxycarbonyl) -2,3 '-(1,
3-propanediyl) ferrocene, 1,1'-bis (methoxycarbonyl) -3,3 '-(1,3-propanediyl) ferrocene, 1- (methoxycarbonyl)-
1 ', 3- (1,3-propanethyl) ferrocene,
1,1'-bis (methoxycarbonyl) -2,2'-
(1,3-propanediyl) ferrocene, 1-formyl-1 ′, 2- (1,5-pentanediyl) ferrocene,
1-acetyl-1 '-(1-oxo-3-phenyl-2
-Propenyl) -3,3 '-(1,5-pentanediyl) ferrocene, 1,1'-bis (1-oxo-3-phenyl-2-propenyl) -3,3'-(1,5-pentanedyl) Ferrocene, 1-formyl-1 ', 2:
3 ', 4-bis (pentadienyl) ferrocene, 1-acetyl-1', 2- (1,3-cyclopentadiyl)
Ferrocene, 1,1'-diacetyl-3,3 '-(1,
5-pentadienyl) ferrocene, 1,2-diacetyl-1 ′, 4- (1,3-propanediyl) ferrocene,
1,1'-diacetyl-3,3 '-(1,3-propanesyl) ferrocene, 1,1'-diacetyl-2,2'
-(1,3-propanediyl) ferrocene, 1,4-diacetyl-1 ', 2- (1,3-propanediyl) ferrocene, 1- (1-oxo-3-phenyl-2-propenyl) -1,2' -(1,3-Propanediyl) ferrocene, 1,1'-bis (1-oxo-3-phenyl-2)
-Propenyl) -3,3 '-(1,3-propanesyl) ferrocene, 1,1'-1bis (1-oxo-3-)
Phenyl-2-propenyl) -2,3 '-(1,3-propanediyl) ferrocene, 1- (1-1oxo-3-)
Phenyl-2-propenyl) -1 ', 3- (1,3-,
Propaneyl) ferrocene, 1-acetyl-1'-
(1-oxo-3-phenyl-2-propenyl) -3,
3 '-(1,3-propanediyl) ferrocene, 1-acetyl-1'-(1-oxo-3-phenyl-2-propenyl) -2,2 '-(1,3-propanediyl) ferrocene, 1-acetyl -1 '-(1-oxo-3-phenyl-2-propenyl) -2,3'-(1,3-propanediyl) ferrocene, 1,1'-diacetyl-3,
3 '-(1,3-propanecyl) ferrocene, 1,
1'-diacetyl-2,2 '-(1,3-propanesyl) ferrocene, 1,1'-diacetyl-2,3'-
(1,3-propanediyl) ferrocene, 1-acetyl-1 ′, 2- (1,3-propanediyl) ferrocene,
1-benzoyl-1 ', 3- (1,3-propanediyl) ferrocene, 1-benzoyl-1', 2- (1,3
-Propanediyl) ferrocene, 1- (1-oxopropyl) -1 ', 3- (1,3-propanediyl) ferrocene, 1- (1-oxopropyl) -1', 2- (1,
3-propanesyl) ferrocene, 1-acetyl-
1 ', 3- (1,3-propanesyl) ferrocene, 1
-Acetyl-1 ', 3- (4-oxo-1,4-butanedyl) ferrocene, 1-acetyl-1', 2- (4-
Oxo-1,4-butanediyl) ferrocene, 1-acetyl-1 ′, 2- (1-oxo-1,4-butanediyl) ferrocene, 1-acetyl-1 ′, 3- (5-oxo-1,5- (Pentenedyl) ferrocene, 1-acetyl-1 ', 2- (5-oxo-1,5-pentanedyl) ferrocene, 1-acetyl-1', 3- (3-oxo-1,3-propanedyl) ferrocene, 1- Acetyl-1 ', 3- (3-oxo-1,3-propanediyl) ferrocene, 1-acetyl-1', 2- (3-oxo-1,3-propanediyl) ferrocene, 1-acetyl-1 ', 2 -(1-oxo-1,3-propanesyl) ferrocene, 1-acetyl-1 ', 2: 3', 4-
Bis (1,3-propanediyl) ferrocene, 1-acetyl-1 ′, 3- (1,5-pentadienyl) ferrocene, 1-acetyl-1 ′, 2- (1,5-pentadienyl) ferrocene, 1-acetyl- 1 ', 3- (1,4-
Butanesyl) ferrocene, 1-acetyl-1 ', 2-
(1,4-butanesyl) ferrocene, 1-formyl-
1 ', 3- (1,3-propanesyl) ferrocene, 1
-Formyl-1 ', 2- (1,3-propanediyl) ferrocene, 1- (4-methoxy-1,4-dioxobutyl) -1', 2- (1,3-propanediyl) ferrocene, 1- (4- Methoxy-1,4-dioxobutyl)-
1 ', 3- (1,3-propanesyl) ferrocene, 1
-(3-carboxy-1-oxopropyl) -1 ', 2
-(1,3-Propaneyl) ferrocene, 1- (3-
Carboxy-1-oxopropyl) -1 ′, 3- (1,
3-propanesyl) ferrocene, 1-iodo-1 ',
2: 3 ′, 4-bis (1,3-propanediyl) ferrocene, 1-iodo-1 ′, 3,-(1,5-pentadienyl) ferrocene, 1,1′-dibromo-2,2 ′:
3,3 ′: 5,5′-tris (1,3-propaneldiyl) ferrocene, 1,1′-dichloro-2,2 ′-(diphenylsilylene) ferrocene, 1,1′-dichloro-
2,2 '-(dichlorosilylene) ferrocene, 1,1'
-Diiodo-2,3 '-(1,3-propanediyl) ferrocene, 1,1'-dibromo-2,3'-(1,3-
Propaneyl) ferrocene, 1,1'-diiodine-
3,3 '-(1,3-propanesyl) ferrocene,
1,1'-dibromo-3,3 '-(1,3-propanesyl) ferrocene, 1-iodo-1', 3- (1,3-
Propaneyl) ferrocene, 1-bromo-1 ', 3-
(1,3-propanediyl) ferrocene, 1,1'-diiodo-2,2 '-(1,3-propanediyl) ferrocene, 1,1', dibrolomo-2,2 '-(1,3-propanediyl) ferrocene , 1-iodo-1 ', 2-
(1,3-propanediyl) ferrocene, 1-bromo-
1 ', 2- (1,3-propanesyl) ferrocene, 1
-Chloro-1 ', 3- (1,5-dioxo-3-phenyl-1,5-pentanediyl) ferrocene, 1-bromo-1', 3- (1,5-dioxo-3-phenyl-1,
5-pentadienyl) ferrocene, 1-bromo-1 ′,
Examples thereof include 3- (3-carboxy-1,5-dioxo-1,5-pentanediyl) ferrocene.

The component (C), which is the photocuring accelerator used in the present invention, is a bisacylphosphine oxide (BAPO) compound having the structure represented by the general formula (1). R ¹ in the formula is unsubstituted or has 1 to 12 carbon atoms.
And an alkyl group having 1 to 8 carbon atoms, or a halogen group having 1 to 8 carbon atoms, and each R ¹ may be the same or different.

The alkyl group having 1 to 12 carbon atoms may be linear or branched and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, It is a hexyl, heptyl, octyl, nonyl, decyl or dodecyl group. For example, the number of carbon atoms is preferably 1 to
6, more preferably an alkyl group having 1 to 4 carbon atoms.

The C1-8 alkylthio group may be linear or branched and is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio,
It is tert-butylthio, hexylthio or octylthio, especially methylthio.

Halogen groups are, for example, chlorine, bromine and iodine, with chlorine being particularly preferred.

The most preferable one among these is that the compound of the above formula (1) is Ciba SpecialtyChe.
Irgacure (Irgac) available from
ure) 819.

The photocurable composition of the present invention can also be used as a mixture with the photocuring accelerators described below within the range not impairing the gist of the present invention. As a specific example, 4-
Phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl ) -2-Hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-
1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1
Examples of the acetophenone-based photocuring accelerator include-(4- (methylthio) phenyl) -2-morpholinopropan-1-one, and examples of the benzoin-based photocuring accelerator include:
Examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketal.

Next, a method for preparing the photocurable composition of the present invention will be described. The photocurable composition of the present invention is a transition metal metallocene compound of Group VIII of the periodic table containing (A) α-cyanoacrylate and (B) an aromatic electron-based ligand, and (C) a general formula. It is prepared by adding and mixing a photo-curing accelerator having a structure represented by 1 and surely dissolving it. At this time, for example, the (B) component or the (C)
If the components are difficult to dissolve, heat the component (A) to such an extent that it does not deteriorate or heat-polymerize (generally 60
It may be dissolved. Further, when the component (B) and the component (C) are added to the component (A), and the prepared composition must be kept in a light-shielded state so as not to be exposed to light.

The amount of the component (B) added varies depending on the selected component and the combination with the component (C).
It is 1 to 50,000 ppm, preferably 5 to 30,000 ppm, and more preferably 10 to 1 with respect to the component (A).
It is 0000 ppm. On the other hand, the addition amount of the (C) photocuring accelerator varies depending on the type and combination of the (B) component and the (C) component, but is 0.01% with respect to the (A) component.
10 to 10% by weight, preferably 0.05 to 3.0% by weight. When each component is used as a mixture of two or more kinds, the total amount of each component is preferably the above-mentioned addition amount.

Further, as long as the curability of the present invention is not impaired, some of the following components may be further added. (1) anionic polymerization inhibitor, (2) radical polymerization inhibitor, (3)
Thickeners (4) Special additives such as curing accelerators, plasticizer tougheners and heat stabilizers, (5) fragrances, dyes, pigments and the like.

For example, an anionic polymerization inhibitor is added to increase the stability of the composition during storage. Examples of known inhibitors include sulfur dioxide, sulfur trioxide, nitric oxide, hydrogen fluoride and p-toluenesulfonic acid. The addition amount of the anionic polymerization inhibitor is appropriately 0.1 to 10,000 ppm with respect to the weight of the component (A).
Further, examples of the radical polymerization inhibitor include quinone, hydroquinone, t-butylcatechol, p-methoxylphenol and the like.

In addition, thickeners are added to increase the viscosity of the photocurable composition of this invention. Examples of the thickener include poly (methyl) methacrylate, methacrylate type copolymer, acrylic rubber, cellulose derivative, polyvinyl acetate, poly (α-cyanoacrylate) and the like. Further, in the present invention, a high molecular polymer such as an acrylic elastomer, an acrylonitrile copolymer elastomer, a fluoroelastomer, and a fine silica filler may be added for the toughening of the cured product of the photocurable composition.

Curing of the photocurable composition of the present invention is of two types: curing by anionic polymerization utilizing a small amount of water on the surface of an adherend and curing by photoanionic polymerization by light irradiation utilizing a metallocene compound.

The method of curing by light irradiation is as follows. After applying the photocurable composition to the adherend, a high pressure mercury lamp, a halogen lamp,
It is cured by mainly irradiating with an electron beam, ultraviolet rays, visible light, and near-infrared light using a xenon lamp or sunlight. The effective wavelength of the irradiation light varies depending on the kind of the metallocene compound and the photo-curing accelerator, but ultraviolet light or visible light is preferable.

The photocurable composition according to the present invention can be used for various α-cyanoacrylates conventionally used and for photocurable resins, and for example, encapsulation of electronic parts, Installation of reel seats, threading guides, etc. on fishing rods, fixing of wire materials such as coils,
It is useful for fixing magnetic head to pedestal, filling agent used for tooth treatment, adhesion and decoration of artificial nails, especially for adhesion, fixation and coating of articles that require curing with moisture and photocuring in combination. .

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Prior to the examples, measuring instruments and the like used for evaluating the photocurable composition of the present invention will be described.

The ultraviolet irradiation device used for the evaluation of photocurability was 4
The sample was irradiated with light from a distance of 15 cm using a kW high pressure mercury lamp (manufactured by Ushio Inc.). The integrated light amount of one light irradiation is 350 mJ / cm ² . Integrated light amount is integrated light meter U
It was measured by IT-150 (manufactured by USHIO INC.).

For the evaluation of photocurability (surface curability), a polyethylene container having an inner diameter of 30 mm was prepared, 1 g of the sample prepared in Examples and Comparative Examples (resin film thickness of about 1 mm) was taken, and this was carried on a belt conveyor. It was confirmed that the sample was cured or uncured by passing it through the ultraviolet irradiation device. One that was 1 mm thick and completely cured was evaluated as ◯, and one that was not completely cured was evaluated as x.

To evaluate the photo-curability (deep-curability), 6 g (resin film thickness of about 9 mm) was added to the above polyethylene container.
And was irradiated with light with an integrated light amount of 350 mJ / cm ^{2 in} the same manner as above. At this time, the film thickness meter SM-114 (TECLOCKCORPO
(Made by Ration Co., Ltd.), and those having a completely cured portion of 4 mm or more were evaluated as ○, 2 to 4 mm as Δ, and 2 mm or less as ×.

[0050]

Examples 1 to 4 and Comparative Examples 1 to 5 The photocurable compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were prepared at the respective compounding ratios shown in Table 1. Then, with respect to each of these samples, evaluation regarding photocurability and evaluation of change in viscosity were performed. The results are shown in Table 1.

[0051]

[Table 1]

All numerical values shown in the formulation table in Table 1 are parts by weight. "-" In the table indicates that the sample could not be measured due to gelation or solidification. In addition, various abbreviations mean the following. "ECA" means ethyl-2
-Cyanoacrylate, "MCA" is methyl-2-cyanoacrylate. "PMMA" means polymethylmethacrylate. “Cp ₂ Fe” means ferrocene and “(EtCp) CpFe” means ethylferrocene. “Irgacure819” is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Ciba Specialty Chem).
icals company). "Irgacure 170
0 "is 2-hydroxy-2-methyl-1-phenyl-
1-one and bis (2,6-dimethoxybenzoyl)-
It is a 75:25 mixture of 2,4,4-trimethylpentylphosphine oxide (CibaSpecial).
manufactured by tyChemicals). "LucirinTP
"O" is 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide (manufactured by BASF).
"Lucirin TPO-L" is 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BA
Manufactured by SF). Irgacure819 has the following structural formula.

[0053]

[Chemical 6]

Further, "Blank" in Table 1 is measured immediately after compounding, and "70 days after 70 ° C" is measured after a storage promotion test for 7 days in a constant temperature bath at 70 ° C.

In Examples 1 to 3 and Comparative Examples 1 to 4, polymethylmethacrylate (PMMA) was added to the formulations because the effect of the present invention that the storage stability is good appears remarkably. ing.

It can be seen from Table 1 that the formulations shown in Examples 1 to 5 show very excellent photocurability in both surface curability and deep part curability even after storage, and in particular, deep part curability is remarkably improved. I know that Further, it can be seen that the change in viscosity is extremely small even after a long period of time, and the storage stability is further excellent even when compared with Comparative Examples.

Comparing Example 1 and Example 2, it can be seen that the storage stability is better when ferrocene is used as the component (B) than when ethylferrocene is used.

Comparing Example 1 and Comparative Examples 1 to 4,
It can be seen that there is a big difference in storage stability. "Irgacure 1700" used in Comparative Example 1 has a structure similar to that of the component (C) of the present invention, but is considered to have poor storage stability because R is a methoxy group. next,
"Lucirin TPO" and "Lucirin TPO"
-L ", considering its structure," Irgacure819 "represented by the following formula (4) has excellent symmetry and is more stable, while" Lucirin "is
It can be seen that "TPO" and "Lucirin TPO-L" lack electronic balance. In addition, "Irga
cure819 "and" LucirinTPO "
Since “Irgacure819” has a larger number of substitutions with a methyl group, it is considered that the compatibility with cyanoacrylate is excellent and the storage stability is favorably influenced.

[0059]

The photocurable composition according to the present invention, that is,
A photocurable composition containing a transition metal metallocene compound of Group VIII of the periodic table having an α-cyanoacrylate and an aromatic electron-based ligand, and a photocuring accelerator having a structure represented by the general formula (1) is , The distance between adherends is wide,
Even if it sticks out from the adhesive part or is not sandwiched by a pair of adherends such as coating, it can be cured quickly by irradiating light, while maintaining the same effect as before, but further surface curing Of the composition and the curability of the film thickness, and further, even when the composition is stored for a long period of time, the photocurability does not deteriorate, and the storage stability is extremely excellent.
Further, since the light absorption wavelength of the photo-curing accelerator having the structure represented by the formula (1) is also on the long wavelength side, the photo-curing can be performed not only in a wider wavelength region, that is, in the visible light region, but also in the visible light region. It is possible.

Claims (3)

[Claims] 1. A transition metal metallocene compound of Group VIII of the Periodic Table having (A) α-cyanoacrylate, (B) an aromatic electronic ligand, and (C) the following general formula (1) as essential components. A photocurable composition comprising a photocuring accelerator having a structure shown in FIG. [Chemical 1] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms, a halogen group, or an alkylthio group having 1 to 8 carbon atoms, and each R may be the same or different.) 2. The ratio of the component (B) to the component (A) is 1
The photocurable composition according to claim 1, which comprises ˜50000 ppm and 0.01 to 10% by weight of the component (C). 3. The photocurable composition according to claim 1, wherein the component (B) is a compound represented by the following general formula (2). [Chemical 2] (In the formula, M is a transition metal of Group VIII of the periodic table, R ¹ is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, It represents an oxygen-containing group, a sulfur-containing group, or a phosphorus-containing group, each R ¹ may be the same or different, and R ^{1 s} may be crosslinked with each other, and a represents an integer of 0 to 5.
Each [Ra-Cp] group (Cp represents η-cyclopentadienyl) may be the same or different. )