JP3428325B2 - Photocurable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable cyanoacrylate composition, and its fields of use include lithography, potting, molding, coating, adhesives, sealants, and various resist materials. Etc. can be applied.

[0002]

2. Description of the Related Art α-Cyanoacrylate-based adhesives rapidly anionically polymerize and cure due to a small amount of water adsorbed on the surface of the adherend, and adhere the adherends to each other extremely firmly in a short time. Therefore, it is widely used as a room temperature one-liquid type instant adhesive for bonding metals, plastics, rubbers, woods and the like.

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

A cyanoacrylate adhesive filling a large gap or protruding from an adhesive portion is generally cured by using a primer or a curing accelerator. However, such a method requires a lot of steps and a primer. The odor of the basic compound and the solvent, which are the main components of the curing accelerator, is not preferable in the working environment.

Therefore, there is a demand for a cyanoacrylate-based adhesive which can be easily cured without impairing the excellent characteristics of the room-temperature one-component instant adhesive.

As a technique for solving such a problem, there has been proposed a cyanoacrylate adhesive composition having photocurability. For example, JP-A-62-57475
The publication discloses a cyanoacrylate-based adhesive composition containing a photopolymerization initiator that generates radicals.

JP-A-6-299122 discloses an adhesive composition containing an aromatic azide compound as a photoanionic polymerization initiator.

International Patent WO93 / 10483 discloses a technique utilizing a chromium-based inorganic complex as a photoanionic polymerization initiator.

Furthermore, Macromolecules (28 (4) 1328 (1995))
Describes a technique using Pt (acac) ₂ as a photoanionic polymerization initiator.

However, in these proposed compositions, light irradiation for a relatively long time of 1 to 2 minutes is required for curing, and in the case of radical polymerization, the reaction is blocked by oxygen, so that the surface is Have problems such as poor curing, stickiness remaining, or foaming upon irradiation with light, and poor storage stability of the composition.

On the other hand, many proposals have been made regarding a photocurable composition using a metallocene compound as a photoinitiator. The metallocene compound is usually used as an initiator for radical polymerization or cationic polymerization. For example, JP-A-6-35
Japanese Patent No. 189 discloses a photopolymerizable mixture and a recording material prepared from the same, which uses a photoinitiator composed of (A) a photoreducible dye, (B) a radiation-decomposable trihalomethyl compound, and (C) a metallocene compound. It is disclosed.

In Japanese Patent Application Laid-Open No. 5-117311, (A) a charge transfer complex consisting of a biscyclopentadienyl iron derivative and quinoids, and (B) a tetrafluoroborate salt, a hexafluorophosphate salt and a hexafluoroantimony salt. Disclosed is a photopolymerization initiator characterized by comprising a complex obtained by interacting with at least one salt selected from the group consisting of acid salts.

JP-A-4-221958 discloses a photopolymerizable mixture using a metallocene compound as a photoreaction initiator and a recording material produced therefrom.

JP-A-2-127404 contains a photoinitiator comprising (A) a photoreducible dye, (B) a radiation-decomposable trihalomethyl compound, and (C) a metallocene compound.
Photopolymerizable mixtures and recording materials made therefrom are disclosed.

JP-A-4-73763 discloses a photocurable electrodeposition coating composition using a titanocene compound as an initiator.

Furthermore, J.MACRMOL.-CHEM (A28 (5 & 6), 557 (199
In 1)), there is a report on a technique of photocuring a vinyl monomer by using ferrocene alone or in combination with carbon tetrachloride.

However, these techniques are those in which the reaction proceeds by radical polymerization or cationic polymerization as a polymerization mechanism, and are not particularly related to the technique of photopolymerizing α-cyanoacrylate which is cured mainly by anionic polymerization of the present application. ..

The inventors of the present invention have made earnest studies for the purpose of providing a photocurable composition having excellent photocurability in order to solve the above problems in the prior art. It has been found to be achieved with a curable composition.

[0019]

[Means for Solving the Problems]

(1) A photocurable composition comprising a transition metal metallocene compound of Group VIII of the Periodic Table containing (A) α-cyanoacrylate and (B) aromatic electronic ligand.

(2) In the above (1), the photocurable composition further comprises (C) a cleavage type photoinitiator,

(3) In the above (1) or (2), the aromatic electron ligand of the transition metal metallocene compound (B) of Group VIII of the periodic table containing the aromatic electron ligand is π
-Arene, indenyl or η-cyclopentadienyl, a photocurable composition,

(4) In any one of the above items (1) to (3), the periodic table containing the aromatic electron type ligand VIII
Group C transition metal metallocene compound (B) is a compound represented by the following formula (1), a photocurable composition,

[0023]

[Chemical 1]

In the formula, M is a transition metal of Group VIII of the periodic table,
R represents 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, an oxygen-containing group, a sulfur-containing group or a phosphorus-containing group,
Each R may be the same or different, and Rs may be crosslinked. Further, a represents an integer of 0 to 5. Each [R _a -C _p ]
The groups (C _p represents η-cyclopentadienyl) may be the same or different.

(5) In any one of the above items (1) to (4), the periodic table VIII containing an aromatic electron-based ligand
Group transition metal metallocene compound (B), wherein the transition metal of Group VIII of the Periodic Table is iron, osmium, ruthenium, cobalt or nickel, and a photocurable composition, and

(6) In (5) above, in the transition metal metallocene compound of Group VIII of the Periodic Table containing an aromatic electron ligand, the transition metal of Group VIII of the Periodic Table is iron. A photocurable composition comprising osmium or ruthenium.

The photocurable composition of the present invention is irradiated with light even when the distance between the adherends is widened, or when the adherends are protruded from the adhered portion or are not sandwiched between a pair of adherends such as a coating. As a result, it can be cured quickly.

Further, since the curing reaction of the photocurable composition of the present invention proceeds by anionic polymerization, the light reaches the shape of the substrate during light irradiation without being hindered 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 50.
Since it is also on the long wavelength side of 0 nm or more, the photocurable compound of the present invention can be photocured even in a wider wavelength range, that is, in the ultraviolet light and / or the visible light range. Hereinafter, the present invention will be specifically described.

1. α-Cyanoacrylate (A) The α-cyanoacrylate (A) which is an essential component of the composition of the present invention is not particularly limited, but is represented by the general formula (II). _{H 2 C = C (CN)} -COOR ...... (II)

(In the formula, R 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 Those having ~ 8 carbons are used, and ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used.)

Specific examples of cyanoacrylates include methyl α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, and butyl α-cyanoacrylate.
Alkyl and cycloalkyl α-cyanoacrylates such as cyanoacrylate and cyclohexyl α-cyanoacrylate, allyl α-cyanoacrylate, methallyl α
-Alkenyl such as cyanoacrylate and cyclohexenyl α-cyanoacrylate, and cycloalkenyl α-cyanoacrylate, alkynyl α-cyanoacrylate such as propanegyl α-cyanoacrylate, phenyl α
-Aryl α-cyanoacrylate such as cyanoacrylate and toluyl α-cyanoacrylate, methoxyethyl α-cyanoacrylate containing a hetero atom, ethoxyethyl α-cyanoacrylate, furfuryl α-cyanoacrylate, trimethylsilylmethyl α-containing silicon Examples thereof include cyanoacrylate, trimethylsilylethyl α-cyanoacrylate, trimethylsilylpropyl α-cyanoacrylate, dimethylvinylsilylmethyl α-cyanoacrylate and the like.

2. Periodic Table Group VIII Transition Metal Metallocene Compound Containing Aromatic Electron Ligands (B) Periodic Table Group VIII Transitions Containing Aromatic Electronic Ligands That Are Essential Components of the Composition of the Invention The aromatic electron-based ligand of the metal metallocene compound (B) is not particularly limited, but preferably includes π-arene, indenyl, η-cyclopentadienyl and the like, and η-cyclopentadiene Enenyl is more preferably used.

Further, as a substituent bonded to each ligand, 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, an oxygen-containing group , Sulfur-containing groups or phosphorus-containing groups. Each substituent may be the same or different, and the substituents may be crosslinked.

Specific structural examples of the group VIII transition metal metallocene compound of the periodic table containing a suitable aromatic electron type ligand include those represented by the following structural formula (1).

[0036]

[Chemical 1]

(In the formula, M is a transition metal of Group VIII of the periodic table, R is a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group. , An oxygen-containing group, a sulfur-containing group or a phosphorus-containing group, each R may be the same or different, and R may be cross-linked with each other, and a represents an integer of 0 to 5.).

In the above formula (1), each [R _a -C _p ] group (C _p represents η-cyclopentadienyl) may be the same or different.

Periodic Table Containing Aromatic Electronic Ligands
Specific examples of the Group VIII transition metal metallocene compound include ferrocene where the transition metal is iron, osmocene that is osmium, ruthenocene that is ruthenium, cobarcene that is cobalt, and nickelcene that is nickel. Mention may be made of metallocene compounds composed of transition metals.

Of these, ferrocene, osmosene and ruthenocene or their derivatives are preferred.

Further, specific examples of ferrocene compounds in which at least one or more substituents are substituted with an aromatic electron type ligand are shown in the following and Examples. In the present invention, iron of these ferrocene compounds is osmium, A metallocene compound substituted with a transition metal of Group VIII of the periodic table such as ruthenium, cobalt and nickel can be used.

The metallocene compound used in the present invention tends to have better photocurability as the number of substituents increases.

4- as a compound having a halogen atom as a substituent
Acetyl-1'-bromo-1,2-diethylferrocene, 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.

1,1'-dimethylferrocene, 1,1'-di-n-as a compound having a hydrocarbon group having 1 to 20 carbon atoms as a substituent
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-pentyl Ferrocene, 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-penta Ethylferrocene, 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-oct-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-octethylferrocene, 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
-Octo-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, bis (penta-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 can be mentioned.

1-Methyl-1 '-(chloromethyl) as a compound having a halogenated hydrocarbon group having 1 to 20 carbon atoms as a substituent
Ferrocene, 1-chloro-1 '-(chloromethyl) 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 '-(tribromomethyl) 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,
Etc.

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- (trimethylsilyl) Ethyl) 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.

1,1′-di (acetylcyclopentadienyl) as a compound whose substituent is an oxygen-containing group having 1 to 20 carbon atoms
Iron, 1,1'-dibenzoylferrocene, 1,1'-bis (1-oxotetradecyl) ferrocene, 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-propenyl) ferrocene, 1- (3-ethoxy-1-methyl -3-oxo-1-propenyl) -1 '-(phenylacetyl) ferrocene, 1,1'-bis (2-furanylcarbonyl) ferrocene,
1,1'-bis (3-methylbenzoyl) ferrocene, 1- (1,3
-Dioxopentyl) -1'-methylferrocene, (neopentylcyclopentadienyl) (propionylcyclopentadienyl) iron, (pivaloylcyclopentadienyl) (propylcyclopentadienyl) iron, 1- ( 9-carboxy-1-oxononyl) -1 ', 3-dimethylferrocene, 1- (9-carboxy-1-oxononyl)
-1 ', 2-Dimethylferrocene, 1- (10-ethoxy-1,10-
Dioxodecyl) -1 ', 3-dimethylferrocene, 1- (10-ethoxy-1,10-dioxodecyl) -1-', 2-dimethylferrocene, 1- (6-methoxy-1,6-dioxohexyl)- 1'-
(1-oxooctadecyl) ferrocene, 1,1'-bis (1-
Oxonyl) ferrocene, 1,-(1-methyl-3-oxo-1-
Butenyl) -1 '-(phenylacetyl) ferrocene, 1-
(3-carboxy-1-oxopropyl) -1 '-(1-oxoundecyl) ferrocene, 1- (3-carboxy-1-oxopropyl) -1'-(1-oxononyl) ferrocene, 1- (4-ethoxy -1,1,4-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-dioxoheptyl) ferrocene, 1- (4-methoxy -1,4-dioxobutyl) -1 '-(6-methoxy-1,6-dioxohexyl) ferrocene, bis (o-carboxybenzoylcyclopentadienyl) iron, (cinnamoylcyclopentadienyl) (neopentyl Cyclopentadienyl) iron, 1,1'-bis (3,5,5-trimethyl-
1-oxohexyl) ferrocene, 1,1'-bis (1-oxohexadecyl) ferrocene, (neopentylcyclopentadienyl) (3,5,5-trimethylhexanoylcyclopentadienyl) iron, (neopentyl Cyclopentadienyl) (pivaloyl cyclopentadienyl) iron, ((4-carboxybutyryl) cyclopentadienyl)
((3-carboxypropinoyl) cyclopentadienyl) iron, 1,1'-bis (4-carboxy-1-oxobutyl) ferrocene, (isobutylcyclopentadienyl) (pivaloylcyclopentadienyl) iron,
(Isobutyrylcyclopentadienyl) (neopentylcyclopentadienyl) iron, 1- (5-carboxypentyl) -1 '-(1-oxooctadecyl) ferrocene, 1-
(5-carboxy-1-oxopentyl) -1'-octadecylferrocene, 1- (5-carboxy-1-oxopentyl)
-1 '-(1-oxooctadecyl) ferrocene, ((3-carboxypropionyl) cyclopentadienyl) ((3-carboxypropyl) cyclopentadienyl) iron,
(Benzylcyclopentadienyl) (pivaloylcyclopentadienyl) iron, 1- (9-carboxy-1-oxononyl) -1 ', 2,2', 3,3 ', 4,4', 5- Octamethylferrocene, 1- (10-ethoxy-1,10-dioxodecyl) -1 ',
2,2 ', 3,3', 4,4 ', 5-octamethylferrocene, (neopentylcyclopentadienyl) (phenylacetylcyclopentadienyl) iron, (phenethylcyclopentadienyl) (pivaloyl Cyclopentadienyl) iron, 1,1'-2 bis (5-methoxy-1,5-dioxopentyl) ferrocene, 1-benzoyl-1 '-(1-oxohexadecyl) ferrocene, 1-acetyl-1 '-(1-Oxohexadecyl) ferrocene, 1,1'-bis (1-oxooctadecyl) ferrocene, 1-acetyl-1'-(1-cyclohexene-
1-ylacetyl) ferrocene, 1-acetyl-1 '-(1-cycloocten-1-ylacetyl) ferrocene, 1-formyl-1', 2,2 ', 3,3', 4,4 ', 5-octamethyl -5 '-(2,4,6-trimethylbenzoyl) ferrocene, 1-benzoyl-1'-formyl-2,2', 3,3 ', 4,4', 5,5'-octamethylferrocene, benzoyl Nonamethylferrocene, 1- (3,3-dimethyl-1-oxobutyl) -1-oxobutyl) -1 '-(1-oxo-4-phenylbutyl) ferrocene, 1- (1-oxo-5-
(4- (1-oxo-3-phenyl-2-propynyl) phenyl)
Pentyl) -1 '-(1-oxo-3-phenyl-2-propynyl) ferrocene, 1- (1-oxo-4- (4- (1-oxo-3-phenyl-2-propynyl) phenyl) butyl) -1 '-(1-oxo-3-phenyl-2-propynyl) ferrocene, 1- (1-
Oxo-3-phenyl-2-propynyl) phenyl) propyl) -1 '-(1-oxo-3-phenyl-2-propynyl) ferrocene, 1- (1-oxo-3- (4- (1-oxo- 3-phenyl-
2-propenyl) phenyl) propyl) -1 '-(1-oxo-
3-phenyl-2-propynyl) ferrocene, 1- (1-oxo-3-phenylpropyl) -1 '-(1-oxo-3-phenyl-2
-Propynyl) ferrocene, 1- (phenylacetyl)-
1 '-(1-oxo-3-phenyl-2-propynyl) ferrocene, 1- (1-oxo-5-phenylpentyl) -1'-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1 -(1-oxo-4-phenylbutyl) -1 '-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (1-oxo-3-phenyl-2-propenyl) -2-propenyl) -1 '-(1-oxo-3-phenylpropyl) ferrocene, 1-benzoyl-1'
-Formylferrocene, 1-benzoyl-1 '-(3-oxo-
3-phenyl-1-propenyl) ferrocene, 1,1'-bis (1-oxo-2-pentenyl) ferrocene, 1-benzoyl-1 '-(1-hydroxy-3- (1-hydroxycyclohexyl) -1- Phenyl-2-propynyl) ferrocene, 1,1'-
Bis (3-carboxy-1-oxopropyl) ferrocene,
1,1'-bis (4-methoxy-1,4-dioxobutyl) ferrocene, 1-acetyl-1 '-(1,3-dioxobutyl) -3,3'-
Dimethylferrocene, 1,1'-bis (1-oxopentyl)
Ferrocene, ((3-carboxypropionyl) ethylcyclopentadienyl (ethylcyclopentadienyl) iron, 1,1'-bis (4- (2-methylbutyl) benzoyl)
Ferrocene, 1,1'-bis (1-oxoundecyl) ferrocene, 1- (4-hydroxyphenyl) -1 '-(1-oxo-3-
Phenyl-2-propenyl) ferrocene, 1-acetyl-1 '
-(3- (3-Methoxyphenyl) -1-oxo-2-propenyl) ferrocene, 1-acetyl-1 '-(3- (4-methylphenyl) -1-oxo-2-propenyl) ferrocene, 1- Acetyl-1 '-(3- (4-methoxyphenyl) -1-oxo-2-propenyl) ferrocene, 1- (3-methyl-1-oxo-2-butenyl) -1'-(phenylacetyl) ferrocene, 1- (4,4-
Dimethyl-1-oxo-2-pentenyl) -1 ′-(phenylacetyl) ferrocene, 1-acetyl-1 ′-(4,4-dimethyl-1-oxo-2-pentenyl) ferrocene, 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) ferrocene, 1- (3,3-dimethyl-1-oxobutyl) -1'-
(1-oxo-3-phenyl-2-propenyl) ferrocene, 1
-(3-Methyl-1-oxobutyl) -1 '-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (1-oxobutyl) -1'-(1-oxo-3-phenyl-2 -Propenyl) ferrocene, 1,1'-bis ((4-methylphenyl) acetyl)
Ferrocene, 1,1'-bis (3- (4-methylphenyl) -1-oxo-2-propenyl) ferrocene, 1,1'-bis (3- (2-furanyl) -1-oxo-2-propenyl Ferrocene, 1,1'-
Bis (hydroxyacetyl) ferrocene, 1- (6- (4-methoxyphenyl) -6-oxohexyl) -1 ', 3-bis (1-
Oxo-3-phenyl-2-propenyl) ferrocene, 1- (1
0- (4-methoxyphenyl) -10-oxodecyl) -1 ', 2-
Bis (1-oxo-3-phenyl-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-1,10-dioxodecyl) ferrocene, 1,1'-bis (9-ethoxy-1,
9-dioxononyl) ferrocene, 1,1'-bis (8-ethoxy-1,8-dioxooctyl) ferrocene, 1,1'-bis (7
-Ethoxy-1,7-dioxoheptyl) ferrocene, 1,1 '
-Bis (5-ethoxy-1,5-dioxopentyl) ferrocene, 1- (1,10-dioxo-10-phenyldecyl) -1 '-(1-
Oxo-3-phenyl-2-propenyl) ferrocene, 1-
(1,9-Dioxo-9-phenylnonyl) -1 '-(1-oxo-
3-phenyl-2-propenyl) ferrocene, 1- (1,8-dioxo-8-phenyloctyl) -1 '-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (1,7- Dioxo-7-
Phenylheptyl) -1 '-(1-oxo-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-benzoyl-1 ', 2-bis (phenylmethyl) ferrocene, 1-benzoyl-1' -(1-Hydroxy-1-phenylethyl) ferrocene, 1,1'-bis (1,1'-biphenyl) -4-ylcarbonyl) ferrocene, 1-benzoyl-1 '-(1-methylcyclopropyl) ferrocene , 1,1'-bis (3-carboxy-
1-oxo-2-propenyl) -2-methylferrocene, 1-methyl-1 ′, 2-bis (1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (6-methoxy-1,6- Dioxohexyl) -1 '-((2-oxocyclopentyl) carbonyl) ferrocene, 1,1'-bis (6-ethoxy-1,6-dioxohexyl) ferrocene, 1- (6-ethoxy-1,6 -Dioxohexyl) -2-((2-oxocyclopentyl) carbonyl) ferrocene 1,1'-bis (4-methoxybenzoyl) ferrocene, 1,1'-bis (1-oxooctyl) ferrocene, 1-carboxy- 1 '-(1,2-dioxopropyl) ferrocene, 1-
(Methoxycarbonyl) -1 '-(phenylacetyl) ferrocene, 1-carboxy-1'-(1-oxo-3-phenyl-2-
Propenyl) ferrocene, 1-carboxy-1 '-(oxophenylacetyl) ferrocene, 1- (methoxycarbonyl) -1'-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (3-methylphenyl ) -1 '-(1-Oxo-3-phenyl-2-propenyl) ferrocene, 1- (4-methylphenyl) -1'-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- ( 1-oxo-3-phenyl-2-propenyl)
-1'-phenylferrocene, 1- (3,5-dimethylphenyl) -1 '-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (3,4-dimethylphenyl) -1'- (1-oxo-
3-phenyl-2-propenyl) ferrocene, 1- (4-methoxyphenyl) -1 '-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1- (4- (ethoxycarbonyl) phenyl) -1 '-(1-Oxo-3-phenyl-2-propenyl) ferrocene, 1- (3-ethylphenyl) -1'-(1-oxo-3-
Phenyl-2-propenyl) ferrocene, 1- (4-ethylphenyl) -1 '-(1-oxo-3-phenyl-2-propenyl)
Ferrocene, 1-benzoyl-1 '-(methoxymethyl) ferrocene, 1,1'-bis (3-ethoxy-1,3-dioxopropyl) ferrocene, 1- (3,3-dimethyl-1-oxobutyl)
-1 ', 3-dimethylferrocene, 1- (3,3-dimethyl-1-oxobutyl) -1', 2-dimethylferrocene, 1-acetyl-1 '-(2-methyl-1-oxo-3-phenyl -2-propenyl) ferrocene, 1-acetyl-1 '-(1-oxo-5-phenyl-2,4-pentadienyl) ferrocene, 1,1'-bis (oxophenylacetyl) ferrocene, 1,1'-bis (Phenylacetyl) ferrocene, 1- (3-acetylphenyl)
-1 '-(1-oxo-3-phenyl-2-propenyl) ferrocene, 1,1'-bis (cyclohexylcarbonyl) ferrocene, 1,1'-bis (1-oxohexyl) ferrocene, 1,1'
-Bis (3-methyl-1-oxobutyl) ferrocene, 1-
(1,1-Dimethylethyl) -1 '-(2,2-dimethyl-1-oxopropyl) ferrocene, 1- (1,1-dimethylethyl) -1'
-(2-Methyl-1-oxopropyl) ferrocene, 1-acetyl-1 '-(1-oxo-3-phenyl-2-propynyl) ferrocene, 1,1'-bis (2,2-dimethyl-1- Oxopropyl)
Ferrocene, 1-acetyl-1 '-(1-oxobutyl) ferrocene, 1-acetyl-1'-(phenylacetyl) -2- (phenylmethyl) ferrocene, 1-benzoyl-1 '-(phenylacetyl) ferrocene, 1 -(1-oxobutyl) -1 '
-(Phenylacetyl) ferrocene, 1-benzoyl-1'-
(1-oxobutyl) ferrocene, 1- (1-oxopropyl) -1 '-(phenylacetyl) ferrocene, 1-acetyl-1'-(phenylacetyl) ferrocene, 1-benzoyl-
1 '-(1-oxopropyl) ferrocene, 1-acetyl-3-ethyl-1'-(phenylacetyl) ferrocene, 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-propenyl) -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) ferrocene, 1,1 ′ -Bis ((3- (4-((4-methoxyphenoxy) carbonyl) phenoxy) propoxy) carbonyl) ferrocene, 1,1'-bis ((2- (4-((4-methoxyphenoxy) carbonyl) phenoxy) Ethoxy) carbonyl) ferrocene, 1,1'-bis ((heptadecyloxy) carbonyl) ferrocene, 1,1'-bis (((2,3,
5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecyn-15-yl) oxy) carbonylferrocene, 1-carboxy-1 '-((phenyl (Methoxy) carbonyl) ferrocene, 1,1'-bis ((4-((4-
(Hexyloxy) phenoxy) carbonyl) phenoxy) carbonyl) ferrocene, 1,1′-bis ((4-((4- (pentyloxy) phenoxy) carbonyl) phenoxy) carbonyl) ferrocene, 1,1′-bis ((4- ((4-butoxyphenoxy) carbonyl) phenoxy) carbonyl) ferrocene, 1,1'-bis ((4-((4-ethoxyphenoxy))
Carbonyl) phenoxy) carbonyl) ferrocene, 1,
1'-bis ((4-((4- (pentyloxy) benzoyl) oxy) phenoxy) carbonyl) ferrocene, 1,1'-bis ((4-((4- (butoxybenzoyl) oxy) phenoxy) carbonyl) ferrocene , 1,1'-bis ((4-((4-propoxybenzoyl) oxy) phenoxy) carbonyl) ferrocene, 1,1'-bis ((4-((4-ethoxybenzoyl) oxy) phenoxy) carbonyl) ferrocene ,
1,1'-bis ((4-((4-methoxybenzoyl) oxy) phenoxy) carbonyl) ferrocene, 1-(((1,1'-biphenyl) -4-yloxy) carbonyl) -1'-hexylferrocene , 1-butyl-1 '-((4-((4- (pentyloxy) benzoyl) oxy) phenoxy) carbonyl) ferrocene,
1-butyl-1 '-((4- (hexyloxy) phenoxy) carbonyl) ferrocene, 1-butyl-1'-((4-heptylphenoxy) carbonyl) ferrocene, 1,1'-bis ((4-formylphenoxy) ) Orbonyl) ferrocene, 1,1'-bis (((3-formylphenyl) methoxy) carbonylferrocene, 1,1'-bis ((4-((4- (hexyloxy) benzoyl) oxy) phenoxy) carbonyl) ferrocene ,
1,1'-bis ((4- (phenylmethoxy) phenoxy) carbonylferrocene, 1-((4- (decyloxy) phenoxy) carbonyl) -1 '-((4-hydroxyphenoxy) carbonyl) ferrocene, 1,1 '-Bis ((4- (deroxyxy) phenoxy) carbonyl) ferrocene, 1,1'-bis
((4- (heptyloxy) phenoxy) carbonyl) ferrocene, 1,1'-bis ((4- (1,1-dimethylethyl) phenoxy) carbonylferrocene, 1,1'-bis (methoxycarbonyl) -2,2 '-Bis (methoxymethyl) ferrocene,
1,1'-bis (ethoxycarbonyl) -2,3'-bis (methoxymethyl) ferrocene, 1,1'-bis (ethoxycarbonyl) -2,3'-bis (methoxymethyl) ferrocene, 1,
1'bis (ethoxycarbonyl) -2,2'-bis (methoxymethyl) ferrocene, 1- (ethoxycarbonyl) -1 ', 2-
Bis (methoxymethyl) ferrocene, 1,1'-bis (((1,4-dihydro-1,4-dioxy-2-naphthalenyl)
(Oxy) carbonyl) ferrocene, 1,1'-bis (((4 '
-(Heptyrosine) (1,1'-biphenyl) -4-yl) oxy) carbonyl) ferrocene, 1,1'-bis (((4 '-(hexyloxy) (1,1'-biphenyl) -4-yl) ) Oxy)
Carbonyl) ferrocene, 1,1'-bis ((4 '-(pentyloxy) (1,1'-biphenyl) -4-yl) oxy) carbonyl) ferrocene, 1,1'-bis (((4'-butoxy (1,1 '
-Biphenyl) -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 '-( Methoxycarbonyl) ferrocene, 1- (methoxycarbonyl) -1 '-(phenoxymethyl) ferrocene, 1,1'-bis ((1,1-dimethylethoxy) carbonyl) ferrocene, 1,1'-bis (((3 -Hydroxymethyl) phenyl) methoxy) carbonyl) ferrocene, 1,
1'-bis (((5- (hydroxymethyl) -2-furanyl)
Methoxy) carbonyl) ferrocene, 1,1'-bis ((4-
Hydroxyphenoxy) carbonyl) ferrocene, 1-acetyl-1 ′-(propoxycarbonyl) ferrocene, 1-acetyl-1 ′-(ethoxycarbonyl) ferrocene, decaquis (methoxycarbonyl) ferrocene, 1,1′-bis ((2-
Propenyloxy) carbonyl) ferrocene, 1,1'-
Bis ((phenylmethoxy) carbonyl) ferrocene,
1- (ethoxycarbonyl) -1'-ethylferrocene, 1-
(Ethoxycarbonyl) -1'-methoxyferrocene, 1-
(Ethoxycarbonyl) -1'-phenylferrocene, 1-
Acetyl-1 '-(4- (ethoxycarbonyl) phenyl) ferrocene, 1,1'-bis ((oxiranylmethoxy) carbonyl) ferrocene, 1- (hydroxymethyl) -1'-(methoxycarbonyl) ferrocene, 1 -(Methoxycarbonyl) -1 ', 2-diphenylferrocene, 1- (methoxycarbonyl) -1', 3-diphenylferrocene, 1,1'-bis (methoxycarbonyl) -3-methylferrocene, 1,2-diformyl -1 ', 2', 3,3 ', 4,4', 5,5'-octamethylferrocene, 1'-formyl-1,2,3,4-tetramethyl-5- (4,7,1
0,13- tetraoxatetradec-1-yl) ferrocene,
1-acetyl-1 '-(2-ethoxy-2-oxoethyl) ferrocene, 1-formyl-1'-(((6-hydroxyhexyl) oxy) methyl) ferrocene, 1,1'-diacetyl-3,3 ' -Bis (1,1-dimethylethyl) ferrocene, 1'-formyl-
1,2,3,4,5-pentamethylferrocene, 1- (1-methyl-3-
Oxo-1-butenyl) -1 ′-(1-oxopropyl) ferrocene, 1-acetyl-1 ′-(1-methyl-3-oxo-1-butenyl) ferrocene, 1′-formyl-1,2-dimethyl Ferrocene, 1-formyl-1 ', 2,2', 3,3 ', 4,4', 5-octamethylferrocene, (acetylcyclopentadienyl) (neopentylcyclopantadienyl) iron, 1-acetyl −
1'-ethynylferrocene, (benzoylcyclopentadienyl) (neopentylcyclopentadiene) iron, acetylnonamethylferrocene, 1-formyl-1'-
(Hydroxyphenylmethyl) -2,2 ', 3,3', 4,4 ', 5,5'-
Octamethylferrocene, 1-formyl-1 '-(1-hydroxyethyl) -2,2', 3,3 ', 4,4', 5,5'-octamethylferrocene, 1-formyl-3- (hydroxy Methyl) -1 ', 2,2',
3 ', 4,4', 5,5'-octamethylferrocene, (acetylcyclopentadienyl) (hydroxycyclopentadienyl) iron, 1'-acetyl-1,2,3,4,5-pentaphenyl Ferrocene, 1,1'-diacetyl-3,3'-dimethylferrocene, (acetylcyclopentadienyl) ((2-carboxyvinyl) cyclopentadienyl) iron, (acetylcyclopentadienyl) ((2-carboxy Ethyl) cyclopentadienyl) iron, formyl nonamethylferrocene, 1,1'-diformyl-2,2 ', 3,3', 4,4 ',
5,5'-octamethylferrocene, 1-formyl-1 '-(hydroxymethyl) ferrocene, 1-acetyl-1'-(1- (acetyloxy) ethynyl) ferrocene, 1-acetyl-1 '-(8-
(4-Methoxyphenyl) -8-oxooctyl) ferrocene, 1-acetyl-1 ', 3-bis (phenylmethyl) ferrocene, 1-acetyl-1', 2-bis (phenylmethyl) ferrocene, 1-acetyl- 1 '-(1-hydroxy-1-phenylethyl) ferrocene, 1,1'-diacetyl-2-methylferrocene, 1,1'-diacetyl-3-methylferrocene, 1-formyl-2- (4-methoxyphenyl) ) Ferrocene, 1- (3-ethylphenyl) -1'-formylferrocene, 1- (4-ethylphenyl) -1'-formylferrocene, 1- (3,5-dimethylphenyl) -1'-formylferrocene, 1- (4- (ethoxycarbonyl) phenyl) -1'-formylferrocene, 1- (3,4-dimethylphenyl) -1'-formylferrocene, 1-formyl-1 '-(4-methoxyphenyl) ferrocene, 1-formyl-1 '-(4-methylphenyl) ferrocene,
1-formyl-1 '-(3-methylphenyl) ferrocene, 1-acetyl-1'-(4- (acetyloxy) phenyl) ferrocene, 1-formyl-1'-phenylferrocene, 1-acetyl-1 '-( 4-methoxyphenyl) ferrocene, 1-acetyl-
1 '-(3,4-dimethylphenyl) ferrocene, 1-acetyl-
1 '-(3,5-dimethylphenyl) ferrocene, 1-acetyl-
1 '-(4-methylphenyl) ferrocene, 1-acetyl-1'-
Phenylferrocene, 1-acetyl-1 '-(3-methylphenyl) ferrocene, 1-acetyl-1'-(2-benzoyl-3-oxo-1-butenyl) 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-propenyl) ferrocene , 1-acetyl-1 ', 3-bis (1-methylethyl) ferrocene, 1'-acetyl-1,2-dimethylferrocene, 1'-acetyl-1,3-dimethylferrocene, 1-
Acetyl-1 ', 3-bis (1,1-dimethylethyl) ferrocene, 1-acetyl-1'-(3-methoxy-3-phenyl-1-propenyl) ferrocene, 1-acetyl-1 ', 2-bis (1,1-Dimethylethyl) ferrocene, 1-acetyl-1 ', 2-bis (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-acetyl-1'-methoxyferrocene, 1-acetyl-1 '-( Examples thereof include tributylstannyl) ferrocene, 1-formyl-1 ′-(tributylstannyl) ferrocene, and the like.

1-butyl-1 '-(4-mercapto-1-oxobutyl) ferrocenium, 1,1'-bis (4-mercapto-1--) as a compound having a sulfur-containing group having 1 to 20 carbon atoms as a substituent
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-dithiole-
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' -Sulfoferocene, etc. can be mentioned.

1,1'-bis (diphenylphosphino) ferrocene, 1-acetyl-1 '-((diphenylphosphino) acetyl) ferrocene, as a compound having a phosphorus-containing group whose substituent is 1 to 20 carbon atoms, 1, 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 a compound in which substituents are crosslinked
1,1'-Diacetyl-2,3 '-(1,3-propanediyl) ferrocene, 1,2-diacetyl-1,4'-(1,4-butanadiyl) 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-propanediyl) ferrocene, 1-((4-methoxyphenyl) acetyl )
-1 ', 3- (1,5-Pentanadyyl) ferrocene, 1-((4-methoxyphenyl) acetyl) -1', 3- (1,3-propanediyl) ferrocene, 1,1 '-(1,5 -Pentanezyl) -3- (phenylacetyl) ferrocene, 1-formyl-1 ', 3- (1,5-
(Pentenedyl) ferrocene, 1,1'-diacetyl-3,3 '
-(1,5-pentanediyl) ferrocene, 1-benzoyl-
1 ', 2- (1,3-Cyclopentanesyl) ferrocene, 1', 2-
(1,4-butadiyl) -1-formyl-2 ', 3- (1,3-propanediyl) ferrocene, 1,1'-diacetyl-2', 3- (1,5-
(Pentenedyl) ferrocene, 1- (1-oxo-2-propenyl) -1 ', 3- (1,3-propanedyl) ferrocene, 1- (
Methoxycarbonyl) -1 ', 2- (1,3-propanadiyl) ferrocene, 1-acetol-1'-(1-oxo-3-phenyl-2-
Propenyl) -2 ', 3- (1,3-propanadiyl) ferrocene, 1-acetyl-1', 3- (3-phenyl-1,5-pentadienyl) ferrocene, 1,1'-diacetyl-2,3 ' -(1,4-butadiyl) ferrocene, 1,1'-diacetyl-3,3 '-(1,4-butadiyl) ferrocene, 1,1'-diacetyl-2,3'-(1,
4-butanesyl) ferrocene, 1- (methoxycarbonyl) -1 ', 3- (1,3-propanediyl) ferrocene, 1-formyl-1', 3- (1,3-propanediyl) ferrocene, 1-formyl-1 ', 2- (1,3-propanediyl) ferrocene, 1'-acetyl-1- (1-oxo-2-propenyl) -2,3'-(1,5-pentadienyl) ferrocene, 1-acetyl-1 ' -(1-Oxo-2-propenyl) -3,3 '-(1,5-pentanediyl) ferrocene, 1-benzoyl-1'-(3-oxo-3-phenyl-1-propenyl) -3,3 ' -(1,5-pentadienyl) ferrocene,
1-benzoyl-1'-formyl-3,3 '-(1,5-pentanediyl) 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-propanesyl) ferrocene, 1,
1'-bis (methoxycarbonyl) -2,4 ': 2', 4-bis (1,
3-propanediyl) ferrocene, 1- (methoxycarbonyl) -1 ', 2: 3', 4-bis (1,3-propanediyl) ferrocene, 1,4-bis (methoxycarbonyl) -1 ', 2: 2' , 3-Bis (1,3-propanediyl) ferrocene, 1- (methoxycarbonyl) -1 ', 2: 2', 3-bis (1,3-propanediyl) ferrocene, 1 ', 2- (1,4- Butanesyl) -1- (4-methoxy-
1,4-dioxobutyl) -2 ', 3- (1-oxo-1,3-propanadiyl) ferrocene, 1,1'-bis (methoxycarbonyl) -2,3'-(1,3-propanadiyl) ferrocene, 1,1'-
Bis (methoxycarbonyl) -3,3 '-(1,3-propanediyl) ferrocene, 1- (methoxycarbonyl) -1', 3- (
1,3-propanediyl) ferrocene, 1,1'-bis (methoxycarbonyl) -2,2 '-(1,3-propanediyl) ferrocene, 1-formyl-1', 2- (1,5-pentadienyl) 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-Pentaneidyl) 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-propanediyl) 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-propanesyl) ferrocene, 1,1'-bis (1-oxo-3-phenyl-2-propenyl) -3,3 '-(1,3-propanethyl) ferrocene, 1,1'-1
Bis (1-oxo-3-phenyl-2-propenyl) -2,3'-
(1,3-propanesyl) ferrocene, 1- (1-1oxo-3-
Phenyl-2-propenyl) -1 ', 3- (1,3-, propanadiyl) 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-propanesyl) ferrocene,
1,1'-diacetyl-2,2 '-(1,3-propanediyl) 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-propanesyl) ferrocene, 1- (1-oxopropyl) -1 ', 3-
(1,3-propanediyl) ferrocene, 1- (1-oxopropyl) -1 ', 2- (1,3-propanediyl) ferrocene, 1-acetyl-1', 3- (1,3-propanediyl) ferrocene, 1-Acetyl-1 ', 3- (4-oxo-1,4-butanediyl) 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-Pentanadyyl) ferrocene, 1-acetyl-1 ', 2- (5-
Oxo-1,5-pentadienyl) ferrocene, 1-acetyl-1 ′, 3- (3-oxo-1,3-propanediyl) 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-butanediyl) ferrocene, 1-acetyl-
1 ', 2- (1,4-butadiyl) ferrocene, 1-formyl-
1 ', 3- (1,3-Propaneyl) 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-propanediyl) ferrocene, 1- (3-
Carboxy-1-oxopropyl) -1 ', 2- (1,3-propanediyl) ferrocene, 1- (3-carboxy-1-oxopropyl) -1', 3- (1,3-propanediyl) 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-propanediyl) ) Ferrocene, 1,1'-
Diiodo-3,3 '-(1,3 -propanecyl) ferrocene,
1,1'-dibromo-3,3 '-(1,3-propanediyl) ferrocene, 1-iodo-1', 3- (1,3-propanediyl) ferrocene, 1-bromo-1 ', 3- (1 , 3-Propanediyl) ferrocene, 1,1'-diiodo-2,2 '-(1,3-propanediyl) ferrocene, 1,1', dibroromomo-2,2 '-(1,3-propanediyl) ferrocene, 1 -Iodo-1 ', 2- (1,3-propanediyl) ferrocene, 1-bromo-1', 2- (1,3-propanediyl) ferrocene, 1-chloro-1 ', 3- (1,5-dioxo -3-Phenyl-1,5-pentadienyl) ferrocene, 1-bromo-
1 ', 3- (1,5-dioxo-3-phenyl-1,5-pentanediyl) ferrocene, 1-bromo-1', 3- (3-carboxy-1,5-
Examples thereof include dioxo-1,5-pentadienyl) ferrocene.

3. Cleavage type photoinitiator (C) This invention further uses a cleavage type photoinitiator as an essential component in claim 2, but the cleavage type photoinitiator (accelerator) (C) used here is not particularly limited. Although not shown, specific examples of the cleavage type photoinitiator include the following compounds including the compounds listed in Examples, that is, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone and 4-t as an acetophenone photoinitiator. -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-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- (4
-(Methylthio) phenyl) -2-morpholinopropane-
1. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether benzyl methyl ketal as benzoin photoinitiator, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate as other photoinitiator , 3,3 ', 4,4'-
Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 2,2′-azobis (2-methylbutyronitrile).

When a peroxide type cleavage type photoinitiator is used, the composition of the present invention can be cured by heating. When an azo-based cleavage type photoinitiator is used, it can be foamed depending on the addition amount and the amount of irradiation light.

The photocurable composition of the present invention comprises the above-mentioned (A) α-cyanoacrylate and (B) a transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electronic ligand. Alternatively, this is further mixed with each of the (C) cleavage type photoinitiator and stirred to surely dissolve the (B) component or the (B) component and the (C) component in the (A) component.
It is adjusted by making them compatible.

When it is necessary to heat and stir to dissolve (C), it is heated and heated and stirred at a temperature (generally about 60 ° C.) at which (A) does not deteriorate or heat-polymerize. To do.

The same applies to the component (B), but since it generally dissolves and is compatible at room temperature, it is not necessary to carry out heating and stirring.

Further, when (B) and (C), especially (B) is added to (A), and after the addition, the system must be kept in a light-shielded state.

Furthermore, when the component (C) is added to the component (B), it is added little by little while stirring, and it is not added all at once.

Even if each component is used alone, 2
You may use it as a mixture of more than one kind.

The amount of the component (B) added varies depending on the type of the component (B), but is preferably 10 to 100,000 ppm relative to the component (A).
30 to 50,000 ppm, particularly preferably 50 to 10,000 ppm.

The amount of the component (C) added varies depending on the type and amount of the component (B) and the type of the component (C).
100 to 20,000 ppm, preferably 300 with respect to component (A)
˜15,000 ppm, particularly preferably 500 to 10,000 ppm.

By adding the component (C),
The addition amount of (B) can be reduced.

When each component is used as a mixture of two or more kinds, the total amount of each component is the above-mentioned addition amount. Further, some of the following components may be added as long as the curing of the present invention is not impaired.

(1) Anionic polymerization inhibitor (2) Radical polymerization inhibitor (3) Thickener (4) Specific additive such as curing accelerator, plasticizer, toughener and heat stabilizer (5) Perfume, dye , Pigment, etc.

It is also possible to use a radically polymerizable compound such as an acrylate ester in combination with the photocurable composition of the present invention. Even if the radically polymerizable compound is used in combination, the cleavage type initiator is used, so that the compound can be rapidly cured.

Anionic polymerization inhibitors are 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 amount of the anionic polymerization inhibitor added is 0.1 to 10,000 ppm by weight based on the weight of the component (A).

Examples of radical polymerization inhibitors include quinone, hydroquinone, t-butylcatechol, p-methoxyl-phenol and the like.

The amount of the radical polymerization inhibitor added is 0.1 to 10,000 ppm by weight based on the weight of the component (A).

Thickeners are added to increase the viscosity of the composition. Examples of the thickener include poly (methyl) methacrylate, methacrylate type copolymer, acrylic rubber, cellulose derivative, polyvinyl acetate and poly (α-cyanoacrylate).

Many conventional polymeric additives are also added for toughening. Examples thereof include acrylic elastomers, acrylonitrile copolymer elastomers, fluoroelastomers and fine silica fillers. These substances also function as thickeners. Also,
In the present invention, other additives known to those skilled in the art can be used.

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

The method of curing by light irradiation is as follows. After applying the photocurable composition to an 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 cleavage type photoinitiator, but ultraviolet light and visible light are preferable.

The composition according to the present invention can be used as various cyanoacrylates which have been conventionally used, and as a photocurable resin, and for example, for sealing electronic parts and reel sheets for fishing rods, Attaching threading guides, fixing wires such as coils, fixing the magnetic head to the pedestal, filling materials used for tooth treatment, connecting artificial nails, decoration, etc. It can be usefully used for connection, fixing, and coating of articles that require photocuring together.

[0074]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention is described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The ultraviolet irradiation device used for photocurability evaluation was 4K.
Using a W high-pressure mercury lamp (Oak Seisakusho), the sample was irradiated with light from a distance of 15 cm. The data of photocurability shown in Examples and Comparative Examples are cumulative light amounts until photocuring, and the cumulative light amount of one light irradiation is 1,000 mJ / cm ^2. Then, the light irradiation was repeated until the light was cured. Integrated light intensity UV-3
It is the value measured by 50 (Oak Seisakusho).

Further, the photocurability test results shown in Examples and Comparative Examples are cumulative light amounts until photocuring, and the cumulative light amount of one light irradiation was 1000 mJ / cm ² until photocuring. The light irradiation was repeated.

The α-cyanoacrylate used in Examples and Comparative Examples is ThreeBond 1741 (ethyl α-cyanoacrylate adhesive, abbreviated as TB1741 hereinafter) unless otherwise specified.

Cleavage type used in Examples and Comparative Examples (hereinafter referred to as P
Photoinitiator is acylphosphine oxide (hereinafter abbreviated as APO), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba-Geigy),
Irgacure 651 (Ciba Geigy's benzyl dimethyl tar), Vicure 55 (Stopher's methylphenylglyoxylate), BTTB (NOF Corporation 3,3 ', 4,4'-)
Tetra (t-butylperoxycarbonyl) benzophenone) and V-59 (2,2'-azobis (2-methylbutyronitrile) manufactured by Wako Pure Chemical Industries, Ltd.).

Examples 1 to 11 and Comparative Examples 1 to 13 As Examples 1 to 5, a predetermined amount of ferrocene (hereinafter abbreviated as Cp ₂ Fe) as a metallocene compound was added to TB1741 to impart photocurability. A cyanoacrylate composition was obtained.

In Examples 6 to 11, TB1741 was added with Cp ₂ Fe as a metallocene compound and various P1 type photoinitiators in predetermined amounts to obtain photocurable cyanoacrylate compositions.

As Comparative Example 1, TB1741 was irradiated with light, and it was confirmed that a cured product could not be obtained. Comparative Examples 2-7
As a result, only a predetermined amount of various P1 type photoinitiators was added to TB1741 to obtain a cyanoacrylate composition. As Comparative Examples 8 to 10, only a predetermined amount of various hydrogen abstraction type (hereinafter abbreviated as P2 type) photoinitiators were added to TB1741,
A cyanoacrylate-based composition was obtained. Comparative Examples 11 to 13
As TB1741, as Cp ₂ Fe as a metallocene compound
And various P2 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results of Examples 1 to 11 and Comparative Examples 1 to 13 are shown in Table 1 below.

[0082]

[Table 1]

Examples 12 to 20 and Comparative Examples 14 to 16 As Examples 12 to 14, only a predetermined amount of ethylferrocene (hereinafter abbreviated as (EtCp) CpFe) as a metallocene compound was added to TB1741 to obtain a photocurable composition. A cyanoacrylate-based composition provided with was obtained.

As Examples 15 to 20, for TB1741,
A predetermined amount of (EtCp) CpFe as a metallocene compound and various P1 type photoinitiators were added to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 14 to 16, TB1741 was prepared as follows.
A predetermined amount of (EtCp) CpFe and various P2 type photoinitiators were added to obtain a cyanoacrylate composition having photocurability.
The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. Example 12-
The results of 20 and Comparative Examples 14 to 16 are shown in Table 2 below.

[0086]

[Table 2]

Examples 21 to 26, Comparative Examples 17 to 19 As Examples 21 to 22, only a predetermined amount of n-butylferrocene (hereinafter, abbreviated as (BuCp) CpFe) as a metallocene compound was added to TB1741 to give a light source. A cyanoacrylate-based composition having curability was obtained.

As Examples 23 to 26, with respect to TB1741,
(BuCp) CpFe as a metallocene compound and various P1 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 17 to 19, with respect to TB1741,
A predetermined amount of (BuCp) CpFe and various P2 type photoinitiators were added to obtain a cyanoacrylate composition having photocurability.
The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. Examples 21 to
The results of No. 26 and Comparative Examples 17 to 19 are shown in Table 3 below.

[0090]

[Table 3]

Examples 27 to 31, Comparative Examples 20 to 22 As Example 27, only a predetermined amount of tert-amylferrocene (hereinafter, abbreviated as (AmCp) CpFe) as a metallocene compound was added to TB1741 to give a photocurable composition. A cyanoacrylate-based composition provided with was obtained.

As Examples 28 to 31, for TB1741,
A predetermined amount of (AmCp) CpFe as a metallocene compound and various P1 type photoinitiators were added to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 20 to 22, for TB1741,
(AmCp) CpFe as a metallocene compound and a predetermined amount of various P2 type photoinitiators were added to obtain a cyanoacrylate composition. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results of Examples 27 to 31 and Comparative Examples 20 to 22 are shown in Table 4 below.

[0094]

[Table 4]

Examples 32 to 37, Comparative Examples 23 to 25 As Examples 32 to 33, only a predetermined amount of benzoylferrocene (hereinafter abbreviated as (BzoCp) CpFe) as a metallocene compound was added to TB1741 to obtain a photocurable composition. A cyanoacrylate-based composition provided with was obtained.

As Examples 34 to 37, with respect to TB1741,
(BzoCp) CpFe 3 as a metallocene compound and various P1 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 23 to 25, with respect to TB1741,
(BzoCp) CpFe 3 as a metallocene compound and various P2 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition. To evaluate the photocurability of each composition, 1 g of a sample was filled in a polyethylene dish having an inner diameter of 30 mm,
Light irradiation was performed, and the integrated light amount until a cured product was obtained was measured and evaluated. Examples 32-37 and Comparative Examples 23-25
The results are shown in Table 5 below.

[0098]

[Table 5]

Examples 38 to 42, Comparative Examples 26 to 28 As Example 38, TB1741 was used as a metallocene compound with cyclohexenyl ferrocene (hereinafter (CyheCp) CpFe).
Abbreviated) was added in a predetermined amount to obtain a photocurable cyanoacrylate composition.

As Examples 39 to 42, for TB1741,
(CyheCp) CpFe as a metallocene compound and various P1 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 26 to 28, with respect to TB1741,
(CyheCp) CpFe as a metallocene compound and a predetermined amount of various P2 type photoinitiators were added to obtain a photocurable cyanoacrylate composition. To evaluate the photocurability of each composition, 1 g of a sample was filled in a polyethylene dish having an inner diameter of 30 mm,
Light irradiation was performed, and the integrated light amount until a cured product was obtained was measured and evaluated. Examples 38-42 and Comparative Examples 26-28
The results are shown in Table 6 below.

[0102]

[Table 6]

Examples 43 to 47, Comparative Examples 29 to 31 As Example 43, TB174 was used as a metallocene compound with cyclopentenylferrocene (hereinafter (CypeCp) CpF).
( abbreviated as e ) only was added in a predetermined amount to obtain a photocurable cyanoacrylate composition.

As Examples 44 to 47, with respect to TB1741,
A predetermined amount of (CypeCp) CpFe as a metallocene compound and various P1 type photoinitiators were added to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 29 to 31, with respect to TB1741,
A predetermined amount of (CypeCp) CpFe as a metallocene compound and various P2 type photoinitiators were added to obtain a photocurable cyanoacrylate composition. To evaluate the photocurability of each composition, 1 g of a sample was filled in a polyethylene dish having an inner diameter of 30 mm,
Light irradiation was performed, and the integrated light amount until a cured product was obtained was measured and evaluated. Examples 43-47 and Comparative Examples 29-31
The results are shown in Table 7 below.

[0106]

[Table 7]

Examples 48 to 53 and Comparative Examples 32 to 34 As Examples 48 to 49, TB1741 was used as a metallocene compound with ferrocene carboxaldehyde (hereinafter, referred to as (C
Only aAlCp) CpFe) was added in a predetermined amount to obtain a photocurable cyanoacrylate-based composition.

As Examples 50 to 53, with respect to TB1741,
(CaAlCp) CpFe as a metallocene compound and various P1 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition.

As Comparative Examples 32-34, with respect to TB1741,
(CaAlCp) CpFe as a metallocene compound and various P2 type photoinitiators were added in a predetermined amount to obtain a photocurable cyanoacrylate composition. To evaluate the photocurability of each composition, 1 g of a sample was filled in a polyethylene dish having an inner diameter of 30 mm,
Light irradiation was performed, and the integrated light amount until a cured product was obtained was measured and evaluated. Examples 48-53 and Comparative Examples 32-34
The results are shown in Table 8 below.

[0110]

[Table 8]

Examples 54 to 71 As Examples 54 to 71, a predetermined amount of various metallocene compounds was added to TB1741 to obtain photocurable cyanoacrylate compositions. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating the sample with light, and measuring the cumulative amount of light until a cured product was obtained. The results of Examples 54-71 are shown in Table 9 below.

[0112]

[Table 9]

Examples 72 to 76 and Comparative Examples 35 to 37 As Examples 72 to 76, a predetermined amount of Cp ₂ Fe as a metallocene compound and APO as a P1 type photoinitiator was added to TB1741 to improve photocurability. The applied cyanoacrylate composition was obtained.

As Comparative Examples 35 to 37, P.
A predetermined amount of APO was added as a type 1 photoinitiator to obtain a photocurable cyanoacrylate composition. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results of Examples 72 to 76 and Comparative Examples 35 to 37 are shown in Table 10 below.

[0115]

[Table 10]

Examples 77 to 81 As Comparative Examples 77 to 81, TB1741 was used, (EtCp) CpFe as a metallocene compound, and AP as a P1 type photoinitiator.
A predetermined amount of O was added to obtain a cyanoacrylate composition having photocurability. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results are shown in Table 11 below.

[0117]

[Table 11]

Examples 82-86 As Examples 82-86, TB1741 was prepared by using (BuCp) CpFe as a metallocene compound and AP as a P1 type photoinitiator.
A predetermined amount of O was added to obtain a cyanoacrylate-based composition. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating the sample with light, and measuring the cumulative amount of light until a cured product was obtained. The results are shown in Table 12 below.

[0119]

[Table 12]

Examples 87 to 91 As Examples 87 to 91, TB1741 was prepared by using (AmCp) CpFe as a metallocene compound and AP as a P1 type photoinitiator.
A predetermined amount of O was added to obtain a cyanoacrylate composition having photocurability. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results are shown in Table 13 below.

[0121]

[Table 13]

Examples 92 to 93 In Examples 92 to 93, TB1741 was used as a metallocene compound (BzoCp) CpFe and a P1 type photoinitiator as A.
A predetermined amount of PO was added to obtain a photocurable cyanoacrylate-based composition. Evaluation of photocurability of each composition,
1 g of the sample was filled in a polyethylene dish having an inner diameter of 30 mm, light irradiation was performed, and the cumulative amount of light until a cured product was obtained was measured and evaluated. The results are shown in Table 14 below.

[0123]

[Table 14]

Examples 94 to 96 As Examples 94 to 96, TB1741 was prepared by using (CyheCp) CpFe as a metallocene compound and A as a P1 type photoinitiator.
A predetermined amount of PO was added to obtain a photocurable cyanoacrylate-based composition. Evaluation of photocurability of each composition,
1 g of the sample was filled in a polyethylene dish having an inner diameter of 30 mm, light irradiation was performed, and the cumulative amount of light until a cured product was obtained was measured and evaluated. The results are shown in Table 15 below.

[0125]

[Table 15]

Examples 97 to 98 As Examples 97 to 98, TB1741 was used as (CypeCp) CpFe as a metallocene compound and A as a P1 type photoinitiator.
A predetermined amount of PO was added to obtain a photocurable cyanoacrylate-based composition. Evaluation of photocurability of each composition,
1 g of the sample was filled in a polyethylene dish having an inner diameter of 30 mm, light irradiation was performed, and the cumulative amount of light until a cured product was obtained was measured and evaluated. The results are shown in Table 16 below.

[0127]

[Table 16]

Examples 99 to 101 As Examples 99 to 101, TB1741 was added with (CaAlCp) CpFe as a metallocene compound and a predetermined amount of APO as a P1 type photoinitiator to give a photocurable cyanoacrylate system. A composition was obtained. To evaluate the photocurability of each composition, 1 g of a sample was filled in a polyethylene dish having an inner diameter of 30 mm,
Light irradiation was performed, and the integrated light amount until a cured product was obtained was measured and evaluated. The results are shown in Table 17 below.

[0129]

[Table 17]

Examples 102 to 112 As Examples 102 to 109, TB1741 was prepared by using 1,1′-di-n-butylferrocene, bis (pentamethylcyclopentadienyl) ruthenium and bis (cyclopentadiene) as metallocene compounds. (Enyl) osmium (hereinafter, each is abbreviated as (BuCp) ₂ Fe, (Me ₅ Cp) ₂ Ru and Cp ₂ Os) is added in a predetermined amount to obtain a photocurable cyanoacrylate composition. .

As Examples 110 to 112, TB1741 was prepared by using (BuCp) ₂ Fe, (Me ₅ Cp) ₂ Ru, and (Me ₅ Cp) ₂ Ru as metallocene compounds.
A predetermined amount of Cp ₂ Os and APO as a P1 type photoinitiator were added to obtain a photocurable cyanoacrylate composition. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results are shown in Table 18 below.

[0132]

[Table 18]

Examples 113 to 117 and Comparative Example 38 As Examples 113 to 117 and Comparative Example 38, a predetermined amount of (AcCp) ₂ Fe as a metallocene compound was added to TB1741 to give a photocurable cyanoacrylate composition. I got a thing. For the storage stability test, place the sample in a polyethylene container protected from light.
After injecting 20 g, the mixture was stored at 70 ° C. for 1 week, and the viscosity and photocurability were confirmed. The viscosity was measured at room temperature by mounting an adapter on a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Further, the photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the integrated light quantity until a cured product was obtained. The results are shown in Table 19 below.

[0134]

[Table 19]

Examples 118 to 121 To TB1741, 1000 ppm of (AcCp) ₂ Fe was added, and further a radical polymerization inhibitor (hydroquinone) or an anionic polymerization inhibitor (p-toluenesulfonic acid) was added in a predetermined amount.
The photocurability of the obtained composition was evaluated, and it was confirmed that the photocuring reaction proceeded by anionic polymerization. Each composition was filled with 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiated with light, and the cumulative amount of light until a cured product was obtained was measured and evaluated. The results are shown in Table 20 below.

[0136]

[Table 20]

Examples 122 to 123 As α-cyanoacrylate, methyl-α-cyanoacrylate (hereinafter abbreviated as MCA) and ethoxyethyl-α-cyanoacrylate (hereinafter abbreviated as EECA) were used, and (AcCp) 1000 ppm of ₂ Fe was added to obtain a cyanoacrylate composition having photocurability. The photocurability of each composition was evaluated by filling 1 g of a sample in a polyethylene dish having an inner diameter of 30 mm, irradiating with light, and measuring the cumulative amount of light until a cured product was obtained. The results are shown in Table 2 below.
Shown in 1.

[0138]

[Table 21]

Examples 124 to 125 MCA and EECA were used as α-cyanoacrylates, and Cp ₂ Fe as a metallocene compound was added to 50% each.
0ppm, add 2,000ppm of APO as P1 type photoinitiator,
A cyanoacrylate composition having photocurability was obtained. 1 g of each composition was filled in a polyethylene dish having an inner diameter of 30 mm, irradiated with light, and the cumulative amount of light until a cured product was obtained was measured and evaluated. The results are shown in Table 22 below.

[0140]

[Table 22]

[0141]

In summary, the composition according to the present invention,
That is, a photocurable composition comprising α-cyanoacrylate and a metallocene compound, or a composition obtained by further adding a cleavage type photoinitiator to this composition has a large gap between adherends and an adhesive part. Even when it protrudes or is not sandwiched between a pair of adherends such as coating, it can be quickly cured by irradiation with light.

Further, since the curing reaction proceeds by anionic polymerization, the curing inhibition by oxygen, which is seen in radical polymerization, is not received, and at the time of light irradiation, the portion where light does not reach due to the shape of the substrate is also started by light irradiation. It is cured by the anionic polymerization performed.

In addition, the light absorption wavelength of the metallocene compound is 50
Since it is on the long wavelength side of 0 nm or more, photocuring is possible even with light in a wider wavelength region, that is, ultraviolet light and / or visible light region.

Further, in the system in which the cleavage type photoinitiator is added,
By selecting the type of the cleavage-type photoinitiator, it is possible to significantly improve the curing rate by photoirradiation of the composition having photocurability composed of α-cyanoacrylate and a metallocene compound. It is also possible to control the effective wavelength of light required for curing.

Since the addition amount of the relatively expensive metallocene compound can be reduced by adding the cleavage type photoinitiator, the cost of the composition can be reduced.
Further, the metallocene compound may color the solution when it is dissolved in α-cyanoacrylate, and in such a case also, the amount of the metallocene compound used can be reduced, which also means that the composition has no coloration. It is valid.

In addition to this, in the system in which the cleavage-type photoinitiator is added, the cleavage-type photoinitiator also functions as an initiator for radical polymerization. Therefore, even if a radical-polymerizable compound such as acryl is used in combination, curing does not occur. It is possible.

When a peroxide-type cleavage type photoinitiator is used, it can be cured by heating. When an azo-type cleavage type photoinitiator is used, foaming is effected depending on the amount of addition or the amount of irradiation light. Is also possible.

[Table 9]

[Table 9]

Continuation of front page (51) Int.Cl. ⁷ identification code FI C09J 4/04 C09J 4/04 (56) References JP-A-62-247356 (JP, A) JP-A-61-176634 (JP, A) JP-A-8-120227 (JP, A) JP-A-6-35189 (JP, A) JP-A-5-117311 (JP, A) JP-A-46-3146 (JP, A) JP-A-4-305591 (JP, A) International Publication 95/031486 (WO, A1) Shizuo Kubota, Takayuki Otsu, Polymerization of Vinyl Monomers with Various Metallocenes, Journal of High Molecular Sciences, Japan, 1976, Vol. 33, No. 4, 201 −208 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/00-4/82 C08F 20/00-22/40 C08F 120/00-122/40 C08F 220/00-220 / 40 C09J 1/00-201/10 CA (STN) EUROPAT (QUESTEL) REGISTRY (STN) WPI / L (QUESTEL)

Claims (6)

(57) [Claims] 1. A transition metal metallocene compound of Group VIII of the Periodic Table containing (A) α-cyanoacrylate (B) aromatic electron ligand as an essential component.
A photocurable composition for photocuring. 2. The photocurable composition according to claim 1, wherein the photocurable composition contains (C) a cleavage-type photoinitiator. 3. The aromatic electron ligand of the transition metal metallocene compound (B) of Group VIII of the periodic table containing the aromatic electron ligand is π-arene, indenyl or η-cyclopentadiene. The photocurable composition according to claim 1, which is enyl. 4. The photocurable composition according to claim 1, wherein the transition metal metallocene compound (B) of Group VIII of the Periodic Table containing an aromatic electronic ligand is represented by the following formula (1): Sex composition. [Chemical 1] (In the formula, M is a transition metal of Group VIII of the periodic table, R is a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom.
To 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups or phosphorus-containing groups, each R may be the same or different, and Rs may be crosslinked.
Further, a represents an integer of 0 to 5. Each [R _a -C _p ] group (C _p is η-
(Indicating cyclopentadienyl) may be the same or different) 5. A transition metal metallocene compound (B) of Group VIII of the periodic table containing an aromatic electronic ligand,
The photocurable composition according to claim 1, wherein the transition metal of Group VIII of the periodic table is iron, osmium, ruthenium, cobalt or nickel. 6. A transition metal metallocene compound (B) of Group VIII of the periodic table containing an aromatic electronic ligand,
The photocurable composition according to claim 5, wherein the transition metal of Group VIII of the periodic table is iron, osmium, or ruthenium.