WO2003080685A1

WO2003080685A1 - Photocurable composition

Info

Publication number: WO2003080685A1
Application number: PCT/JP2003/003268
Authority: WO
Inventors: Shigekazu Motoki; Kazuhiro Kojima
Original assignee: Three Bond Co., Ltd.
Priority date: 2002-03-22
Filing date: 2003-03-18
Publication date: 2003-10-02
Also published as: JP2003277422A; AU2003221085A1

Abstract

A cyanoacrylate-base photocurable composition which can be cured by means of moisture or light and is so excellent in storage stability to be little deteriorated in curing characteristics even after storage. The composition comprises (A) an α-cyanoacrylate, (B) a Group VIII transition metal metallocene compound bearing aromatic electron system ligands, and (C) a photocuring accelerator represented by the general formula (1): (1) wherein Rs are each independently hydrogen, alkyl having 1 to 12 carbon atoms, halogeno, or alkylthio having 1 to 8 carbon atoms.

Description

Description Photocurable composition <Technical field>

The present invention relates to a cyanoacrylate-based composition provided with photocurability, and relates to a photocurable composition applicable to lithography, potting, molding, coating, adhesives, sealing agents, and various resist materials. Background technology>

Since the cyanoacrylate adhesive rapidly polymerizes and cures due to a small amount of water adsorbed on the surface of the adherend, and adheres the adherends extremely strongly in a short time. It is widely used as a liquid / room temperature curing type instant adhesive for bonding metals, plastics, rubber, wood, etc.

However, the α-cyanoacrylate adhesive hardens extremely when the distance between the adherends is wide, when the adhesive sticks out of the bonded part, or when it is not sandwiched between a pair of adherends such as a coating. It has the disadvantage of being slow.

Therefore, in order to bond between adherends with a large gap or to quickly cure the α-cyanoacrylate adhesive that has protruded from the bonded part, it is common to cure with a primer or a curing accelerator. (Described in JP-A-59-215736, JP-A-60-206364, JP-A-61-17634) However, such a method is complicated and time-consuming in the process, and the odor of the basic compound and the solvent, which are the main components of the primer and the curing accelerator, is not preferable in the working environment. Therefore, it is easy to use the one-pack type, instant curing at room temperature without impairing the excellent characteristics of the instant adhesive, and even if it is filled in the protruding part or large gap, without using a primer or a curing accelerator. One-thiocyanate acrylate adhesive that can be cured was expected.

To solve the above-mentioned problems, there are two methods: A c-cyanoacrylate-based adhesive composition imparted with photocurability by adding a compound and a cleavage-type photoinitiator to a hisocyanoacrylate-based adhesive was previously proposed (Japanese Patent Application Laid-Open No. — 2 497 0 8 publication).

According to the above invention, the adhesion between the adherends of the α-cyanoacrylate adhesive can be cured in units of seconds, and the portion protruding from the bonded portion can be cured by irradiating light in units of seconds. Curing without deteriorating the excellent characteristics of instantaneous adhesives such as one-component, room temperature, rapid curing, even in an environment in which curing is extremely slow with conventional c-cyanoacrylate adhesives. It has the feature that it can be cured quickly by light irradiation.

However, it has been discovered that the photocurability may be reduced when the mono-cyanoacrylate-based adhesive composition according to the above invention is stored for a long period of time. As a method for solving this problem, a compound comprising a cyanoacrylate and a specific fluorene compound further added with a photocuring accelerator can obtain a compound having extremely excellent photocuring properties even after long-term storage. (Japanese Patent Application Laid-Open No. 11-166006).

However, Japanese Unexamined Patent Application Publication No. 11-166066 does not discuss deep curability. In addition, the invention of the publication has no detailed description of the storage stability of the photocurable composition itself, and has a drawback that thickening and gelation occur during storage at a relatively high temperature. Invention disclosure>

The present inventors have conducted intensive studies to solve this problem, and as a result, have found that an α-cyanoacrylate composition containing a photocuring accelerator having a structure represented by the general formula (1) as a photocuring accelerator. Has excellent stability even after long-term storage, and has excellent light-curing properties as well as moisture-curing properties on the adherend surface as well as excellent surface curability and deep-part curability. Found, and led to the present invention.

That is, the present invention provides (A) α-cyanoacrylate, (Β) a transition metal meta-acene compound of Group VIII of the periodic table having an aromatic electron-based ligand, and (C) a compound represented by the following general formula: Solved the above problems by a photocurable composition containing a photocuring accelerator represented by

(In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkylthio group having 1 to 8 carbon atoms, and each R may be the same or different.) The curable composition should not only be cured by moisture, but also be irradiated with light when the adherends have a large distance between the adherends, when they stick out of the bonding area, or when they are not sandwiched between a pair of adherends like a coating. Can be cured more quickly.

In addition, since the curing reaction of the photocurable composition of the present invention proceeds by anion polymerization, the portion where light does not reach due to the shape of the base material at the time of light irradiation is not affected by surface curing inhibition due to oxygen seen in radical polymerization. Cured by anion polymerization initiated by light irradiation.

Furthermore, since the light absorption wavelength of the meta-mouth compound is on the long wavelength side of 500 nm or more, the photocurable compound of the present invention can be used in a wider wavelength range, that is, even in the ultraviolet or visible light range. Light curing is possible. This is also effective for bonding an adherend containing an ultraviolet absorbent such as an optical disk, for example.

Hereinafter, the present invention will be specifically described. There is no particular limitation on the component (Α), which is α-cyanoacrylate that can be used in the present invention, as long as it is represented by the following formula (3).

(In the formula, R ² is an ester residue such as an alkyl group, a cycloalkyl group, an alkyl group, a cycloalkyl group, an alkyl group, an aryl group. The number of carbon atoms of the ester residue is not particularly limited, but is usually 1 to Those having 8 carbons are also used, and ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used.)

Specific examples of α-cyanoacrylate include methyl monocyanoacrylate, ethyl_α-cyanoacrylate, propyl-1- <cyanoacrylate, butyl-α-cyanoacrylate, and xyloxy α-cyanoacrylate. Alkenyl and cycloalkyls such as alkylalkyl α-cyanoacrylates, arylyl α-cyanoacrylates, methallyl α-cyanoacrylates, cyclohexenyl-α-cyanoacrylates and alkenyl monoalkyls _alpha - Shianoakuri rate flop port Pangiru one _alpha - Shianoakuri rate etc. Arukininore one α- Shianoakuri rate, phenylene Lou α- Shianoaku Li rate, Toruiru α- Shianoaku Li rate etc. § reel one ct Shianoakuri rate, contain heteroatoms Skill Triethylsilylmethyl-α-cyanoacrylate, trimethylsilylmethyl-α-cyanoacrylate, trimethylsilylethyl α-cyanoacrylate, trimethylsilyl, trimethylsilylethyl α-cyanoacrylate, ethoxylate — Α-cyanoacrylate, dimethylvinylsilylmethyl-1-α-cyanoacrylate and the like. These α-cyanoacrylates may be used alone or in combination of several types.

Preferred examples of α-cyanoacrylate used in the present invention include ethyl-12-cyanoacrylate and methyl-2-cyanoacrylate. The (B) component which is a transition metal meta-acene compound of Group VIII having an aromatic electron ligand which can be used in the present invention is described in JP-A-9-249708. A transition metal methacrylate compound of Group VIII of the periodic table having an aromatic electron-based ligand can be used.

Specific preferred examples of the transition metal group VI II transition metal meta-acene compounds containing an aromatic electron-based ligand include those having the following general formula (2).

(Wherein, 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, silicon) Represents a containing group, an oxygen-containing group, a sulfur-containing group, or a phosphorus-containing group, and each R ¹ may be the same or different, and R ¹ may be bridged. Each of the [Ra-Cp] groups (Cp represents cyclopentagenenyl) may be the same or different.

Specific examples of meta-metallic compounds of the transition metal belonging to Group VIII of the Periodic Table containing an aromatic electron-based ligand include phenethylene, the transition metal being iron, osmosene, osmium, and ruthenocene, ruthenium. Examples thereof include metamouth compounds comprising transition metals of Group VIII such as kovalcene, which is a cobanolate, and nickelcene, which is an echnole. Of these, Hue Seng Sen or its derivatives are preferred.

Further, specific examples of the fluorene compounds useful in the present invention are shown below.In the present invention, iron, which is a transition metal of these compounds, is substituted with a group VIII transition such as osmium, ruthenium, cobalt, nickel, or the like. Meta-mouthed compounds substituted by metals Can also be used.

Specific examples of the phenoctene compound include, in addition to phenoctene, 4-acetyl-1′-bromo-1, 2-dimethylthiophene-sen, 1′-bromo-1,1,2, as a compound having a halogen atom as a substituent. 3—Triethynolehuerosen, 1—acetinole 1 ′ 1-bromo-1,2,3-Jetylhue mouth, 1, 1, 1-jib mouth 3 _ (dibromoboryl) Hue-sen, 1, 1 ′ 1 jib mouth 3,3'-Bis (dibromoborinole) huecocene, 1,1'-Dipromo 3,3'-Bis (dibromoborinole) fuerosene, 1-bromo-1 1'-Methinolehuerosen, 1-bromo-1 1, 1 (Methoxy methoxy) 1-Bromo_1, 1 (4-Methynolebenzoinole) Hue sen, 1 1 -1 1 ― ― (Feninole chinore) Hue 1, 1- 1 '― (4-Methoxypheno ) Hue mouth sen, 1 _ (4—black mouth feninole) 1 1, 1 フフ (口 1, 1 一 1 一 1 — — Hueninolehuerosen, 1, 3 — dichloro _ 2, 4, 5 — Tris (methylthio) Hue Seng, 1, 2, 4

1,2-, 3-, 4-tetramethyl-5- (methylthio) -phen, 1,1--1,1- (3-methoxy-1-3-oxo-1-1-propynyl) phen Mouth sen, 1, 1'-Dibromoferrocene, 2_acetinole 1'-Bromo-1,3, -Jetinolefuerosen, 1 'One bromo-1,2,4—Trietinolefuerosen , 1-Acetinole 1'-Bromo _ 2, 4-—Jetinolehuerosen, 1, -Bromo 1,3—Jeti / Lefelosen, 1'-Bromo _1,2-Jetinolefferocene, 1-Acetinole 1 '—Bromo 3-—Echinorefelosen, 1—Acetinole 1 ′ —Bu Mouth 2-Echinorefelosen, 1, 1' —Dichlorofuerosenium, Decachlorofuerosenium, 1 _ (3—H 1-Droxy-1-methyl-1-butynyl) 1'- Black mouth 1, 1, ethininolefferosen, 1-bromo-1'-etininolefferosen, (acetinolecyclopentageninole) (bromocyclopentageninole) iron, (promocyclopentagenine) Nore) (Edocyclopentaje-Nore) Iron, 1-Bromo 1'-Feninolehuerosen, 1-Bromo 1'-

(Triphenylmethyl) 1-Bromo 1 '_ ((1-oxotactadecyl) oxy) Phuet, 1'-1 ((1-oxotactadecyl)) Xy) Hue mouth, 1-Bromo 1'-Capryoferocene, 1_Bromo-1'-Pentyl Hue mouth, 1-Bromo-1,1- (2-methylpropyl) Hue mouth, 1_Broc 1 1, 1 (3-oxo _ 3-feninole 1-propeninole) ue mouth sen, 1-bromo- 1 '-honoleminolef erocene, 1-clo mouth one 1'-honoleminolene herosen, 1-Bromo-1,1- (3-oxo-1_3-pheninole_-11-propininole) Hue mouth, 1-Bromo-1 '-(2-methyl-1,1,3-dioxolan-1-yl) Ferrocene, 1 _Bromo-l, l-((4-methinolephenyl) methyl) phenyl, 1 -Bromo 1 '_ ((3-Methynolepheninole) methinole) Phuecene, 1-Bromo 1'-( (2-Methylphenyl) methyl) phenyl, 1— (diphenylphosphino)-1'- 1-((3-Honoremilfeil) ethinyl) 1 1 '-Edohue mouth, 1-((2-formylfurenyl) ethel)-1'-Hodofu aerosen, 1, 1'-Dichloro-2-(trichlorosilyl) Nore) Hue sen, (1,, 2-dichlorofuerose-nore) Lithium, 1-Chloro-one 1'-Feninole-fuerosen, 1-((4-Honoremilphenyl) ethininore)-1 '— Edohuerosen, 1-one (Capryochinoren)-1 'Ehodohue mouth, Decabromohuerosen, Honore Minorenononadohue mouth, Ethilnonahodohu mouth, Nonaho Domechinolehu Erosen, Nonabromohonolemino Referosen, acetinolenanodofuesen, 1-1-1 (Ethoxydazole) 1-1, 1-dofufen-form, 1 _Bromo-1-1,1- (ethoxy) Norepo-Nore) Hue mouth sen, 1-Black mouth 1 '-(Ethoxycanoleboninole) Huelosen, Decayodofuerosen, 1 _benzoinole 1'-Bromohue mouth, 1-benzoyl 1'-Black Mouth mouth mouth, 1, 1 ', 2, 2,, 3, 3', 4, 4 '-Octachloro-5, 5, One-Jodohue mouth, 1-Eod one 1'-Methylulferosen, Decachlorohuerosen, etc. Is mentioned.

Compounds having a hydrocarbon group having 1 to 20 carbon atoms as a substituent include 1,1'-dimethinolefferosene, 1,1,1-di-n-ptynoleffe mouth, bis (pentamethynole cyclopentade-nore) iron , 1, 1 '—Jetinolehuerosen, 1,1,1 Jeep mouth Pinorehuerosen, 1,1' —Di-n-pentinorefue mouth, 1, 1 '— Di-n-hexynolehue, 1, 1,, 2— Trimethinoleverosen, 1, 1,,, 2—Triethylhue sen, 1, 1 ', 2—Tripropylhue sen, 1, 1', 2—Tri_n—Buchinolefuerosene, 1, 1,, 2—Tri-n—Pentinoref Elocene, 1, 1 ', 2—Tri-n-hexylfuelocene, 1, 1', 3—Trimethinole Hue, 1, 1 ', 3—Triethylhue, 1, 1', 3—Tripropinorefuerosen, 1, 1 ', 3—tri-n-butynolephe mouth, 1, 1, ,, 3_ tree n—pentinoleffe mouth, 1, 1', 3-tri-n-hexynoleffe mouth, 1, 1 ', 2,2'-Tetramethylhue mouth, 1,1 ', 2,2' -Tetraethinolehuerosen, 1,1 ', 2,2'-Tetrapropinolehuerosen, 1,1', 2,2 '— Tetra n — Butinolehu mouth, 1, 1', 2, 2 'Tetra n _ Pentinolehu mouth, 1, 1', 2, 2 'Tetra n-hexynolephine, 1, 1,, 2, 3' -Tetramethylphene, 1, 1,, 2, 3 '—Tetrachinoleferosen, 1, 1', 2, 3 1, 1 ', 2, 3' — 1, 1 ', 2, 3' — 1, 1 ', 2, 3' — 1, 1 ', 2, 3' — Tetra 1_ n_ pentynolehu, 1, 1 ', 2,3,1-tetra-n-hexynolephen, 1,1,, 3,3'-tetramethyl-phen, 1, 1', 3,3'-tetra-ethyl-phen, 1,1 ', 3,3,1-tetra-propylphene, 1,1', 3,3'-tetra-n-butyl-phen, 1,1 ', 3,3,1-tetran-pentinolefe Mouth sen, 1, 1 ', 3,3'Te-n-hexinolefe mouth, 1,1', 2,3-Tetramethyl phen, 1,1,, 2,3-Tetrachinolefe Lips , 1, 1,, 2, 3-tetrapropinolefuerosen, 1, 1 ', 2,

3—Tetra_n—Butinolehuerosen, 1,1,, 2,3-Tetra-n-pentinolephen, 1,1,1,2,3-Tetran—hexinolephen, 1,1 ', 2,4-tetramethinolefuerocene, 1,1', 2,4-tetraethylefuecene, 1,1,, 2,4-tetra-propyluefecene, 1,1 ', 2, 4-tetra-n-butynolefferocene, 1,1 ', 2,4-tetra-n-pentinolephate, 1,1', 2,4'-tetran-hexyleffeine, 1, 1 ', 2, 2', 3 1-pentamethinolephrocene, 1, 1, 2, 3, 2, 3-pentaethynolefrocene, 1, 1, 2, 3, 2, 3-pen Terpropinolehuerosen, 1, 1,,, 2, 2,,, 3-penter n-butynoleferosen, 1,1 ', 2,2', 3-penta-n- ぺ pentinolefferocene, 1,1,, 2,2,, 3-pentan- Hexinoleffe mouth sen, 1, 1,,, 2, 2 ', 4-pentamethinolefuerocene, 1, 1', 2, 2,, 4-1 Pentaethinolefuerocene, 1, 1 ', 2, 2 ', 4_Pentapropynoleurosene, 1,1', 2,2 ', 4-Penta-n-butynolefelocene, 1,1', 2,2 ', 4_Penta-n- Pentinoleffe mouth, 1, 1,,, 2, 2 ', 4-penta-n-hexinoleffe mouth, 1, 1', 2, 3, 3, 1-pentamethinoleffesen, 1, 1 ', 2 , 3,3,1 pentaethynolehuerosen, 1,1 ', 2,3,3,1 penta-1propynolefuerosen, 1,1', 2,3,3,1 penter n-butinolev erosen, 1, 1 ', 2, 3, 3' —Penter n—Pentinolehu mouth , 1, 1 ', 2, 3, 3' —penta-n-hexylfuerocene, 1, 1,,, 2, 3,, 4-pentametinolefuerocene, 1, 1 ', 2, 3' , 4-Pentaethynolehuerosen, 1, 1 ', 2, 3', 4_Pentapropinolehuerosen, 1, 1 ', 2, 3', 4-Penta_n-Buchinolehuerosen, 1,1 ', 2,3,, 4_penta-n-pentynolephen mouth, 1,1', 2,3 ', 4, penter n_hexynoleffe mouth, 1,1', 2,3 4-pentamethinolefuerocene, 1,1 ,,, 2,3,4-pentaethinolefuelocene, 1,1,, 2,3,4-penta-propinolefuerocene, 1,1 ', 2,3 , 4-penter n-butynolefferocene, 1,1 ', 2,3,4-penta-n-pentinorefue mouth, 1,1', 2,3,4_penta-n-hexynolefe mouth , 1,1 ', 2,3,4,5_Hexamethylphenic acid, 1 1 ', 2,3,4,5_hexaechinolefferosene, 1,1', 2,3,4,5—hexapropynolephate, 1,1,2,3,4 , 5-hexene n-butynoleffe mouth, 1, 1 ', 2, 3, 4, 5-hexene n-pentinoleffe mouth, 1, 1', 2, 3, 4, 5 n-hexylfuelosene, 1, 1 ', 2, 2', 3, 4-hexametinolefuerosen, 1, 1 ', 2, 2,, 3, 4_hexaethylfuesen, 1, 1, , 2,2 ', 3,4-hexapropynolefuerosen, 1,1', 2,2,, 3,4hexa-n-butynolefuerosen, 1,1,, 2 , 2 ', 3, 4—hexa — n—pentinorefue, 1, 1', 2, 2,, 3, 4 _hexa n—hex Norefue mouth sen, 1, 1 ', 2, 3, 3', 4, 1 hexametinolehuerosen, 1, 1,, 2, 3, 3 ', 4 , 3,3 ', 4—Hexapropynelephrocene, 1,1', 2,3,3 ', 4Hexa n-butyl phenethylene, 1,1', 2,3 3 ', 4_hexa n-pentinorefue mouth, 1,1', 2,3,3 ', 4-hexa-n-hexinolefe mouth, 1,1,, 2,2,2,3,3 '1-hexamethinolephrocene, 1, 1', 2, 2 ', 3, 3' 1-hexamethylefuerose, 1, 1 ', 2, 2,, 3, 3' —hexapropizolefe , 1, 1 ', 2, 2,, 3, 3' —hexar n—butinolehuerosen, 1, 1 ′, 2,2 ′, 3,3 ′ —hexa_n—pentinorefuesen, 1, 1 ', 2,

2 ', 3,3,1-hexyl-n-hexylfurocene, 1,1,, 2,2', 3 ,,,

4_Hexamethinolefrocene, 1,1 ', 2,2', 3,, 4—Hexamethinolefrocene, 1,1 ', 2,2,, 3 ,,, 4 1,1,2,2,2 ', 3', 4-hexa-n-butylphenol, 1,1 ', 2,2 ,,,

3 ', 4—hexa-n-pentynoleffe mouth, 1, 1', 2, 2 ', 3', 4—hexa-n-hexinoleffe mouth, 1, 1,, 2, 2, 2,, 4 , 4,1-hexamethynolehuerosen, 1,1 ', 2,2', 4,4 '-hexaechinolefuerosen, 1,,

1 ', 2,2', 4,4'—Hexa-propynolefuerosen, 1,1 ', 2,2,2,4,4,1-hexa_n—butynolefuerosen, 1, 1 ', 2,2', 4,4,1-hexa-n-pentinorefue mouth, 1,1 ', 2,2', 4,4,1-hexa-n-hexinoleffe mouth, 1,1 ,, 2, 2,, 3, 4, 5—Heptamethinolephrocene, 1,1 ', 2,2,3,4,5_Heptaethinolephrocene, 1,1', 2,

2 ', 3,4,5_Hepterpropylphene, 1,1', 2,2 ', 3,4

5—Hepter n—Butylphenic acid, 1, 1 ′, 2,2,2,3,4,5—Hepta 1-n-pentylphenol, 1,1 ′, 2,2,3,4,5— Hepta-n-toxyl fuerosen, 1,1 ', 2,3,3', 4,5-heptamethylphen, 1,1 ', 2,3,3,, 4,5_heptaethylphen, 1 , one two Three,

3 ', 4,5—Hepta-propyl-phenecene, 1,1 ,,, 2,3,3', 4,5 Hepter n-butinolefferosene, 1,1 ', 2,3,3 ,,, 4, 5—Hepter n-pentinorefuesen, 1,1 ,,, 2,3,3 ', 4,5-hepta-n-hexinolehuerosen, 1,1 ,,, 2,2', 3,3 ', 4-heptamethino Referocene, 1,1,, 2,2 ', 3,3', 4 heptaethylphene mouth, 1,1 ', 2,2', 3,3 ', 4—heptapropinolefferocene, 1,1,, 2,2 ', 3,3,, 4—Hepter n_butylphen mouth, 1,1,, 2,2,2,3,3,, 4,1 n-pentinorefue mouth, 1, 1 ', 2, 2', 3, 3,, 4 hepta-n-hexylfuerocene, 1, 1 ', 2, 3, 3', 4, 4 '-heptamethine ,, 2,3,3 ', 4,4,1 heptaethynolehuerosen, 1,1,, 2,3,3', 4,4,1 heptapropynolehuerosen, 1,1 ,,,

2,3 ', 4,4'-Hepta-n-butylphen, 1,1', 2,3,3,4,4'-Hepter-n-Pentinolehu, 1,1,1 ', 2,3 , 3 ', 4 4' —Hepta n _ hexinoleffe mouth, 1, 1 ', 2, 2', 3, 3 ', 4 5-Oktomethinoreferosen, 2, 2', 3, 3,, 4, 5—Ok Toechinoleverosen, 1, 1 ', 2, 23, 3', 4, 5—Oktopro Pinorefuerosen, 1, 1 ', 2, 2', 3 3 ' 4,5 octets—n-butyl phenoctene, 1, 1 ', 2, 2', 3, 3 4 5—oct-n-pentinolev erocene, 1, 1 ', 2, 2', 3,3'4,5-octet n-hexinoleffe mouth, 1, 1 ', 2,2', 3,4,4 '5-octemethinolefe mouth, 1,1,2,2' , 3,4,4,, 5—Oct Toechiruhue Sen, 1 1 ', 2 2', 3,4,4 ', 5_Oct-propynolehuerosen, 1,1'2,2 '

3, 4, 4 ', 5-oct-n-butynolehuerosen, 1, 1,, 22,2', 34,4 ', 5-oct-n-pentinorefuesen, 1, 1 ', 2,2,3,4 4', 5-octet n-hexynolefe mouth, 1,1,, 2,2'3,3 '

4, 4 ', 5—Nonamethylphenic acid, 1, 1,, 2, 2', 3, 3 '4, 4'

5-Nonechilhue mouth, 1, 1 ', 2, 2'3, 3'4, 4' 5-oct-propyl uefe, 1, 1 ', 2, 2'3, 3'4, 4' 5-oct-n-butynolehuerosen, 1, 1 ', 2, 2, 3, 3, 4, 4, 5-ot-n-pentinorefuesen, 1, 1', 2 2 ' , 3 3 ', 4 4', 5-octane n-hexynoleffe mouth iron, bis (pentaethynolecyclopentadiene;) iron, bis (penterpropinolecyclopentadieni ^^) iron, bis (penta-n-butynolecyclopentane) J-Nore) Iron, Bis (penta-n-pentylcyclopentagenenyl) Iron, Vista_n-Hexinolecyclopentadienyl) Iron, 1, 1'-Dimethinole 2_ethylthiophene, 1,, 1'—Dimethinole 3—Echinoleferosen, 1, 1 'Di_n—Butinole 3—Methinoleverosen, 1, 1' Zee n—butyl-1 3—Echinoleferosen, 1, 1 '—Dimethinole 1 3, 3' —Jetylhue Mouth Sent, 1, 1,, 2, — Trimethinole 1 3—Echilff Erosen, 1, 1 ' bird Hue-Noremetinolefuerosen, 1-n-butynole 1'-tripheninolemethinolefe mouth, and the like.

As a compound having a halogenated hydrocarbon group having 1 to 20 carbon atoms as a substituent, 1-methynole_1,1- (chloromethinole) phlegmene, 1-chloro-1 '-(chloromethynole) phlegmene, 1-methynole 1 1 1 (promomethinole) phlegm, 1-methyl 1 1 '1 (iodomethyl) phlegm, 1, 1, 1- (chloromethyl) phlegm, 1, 1, 2—tri-l Chloromethinole) Phueccene, 1,1 ', 2,2, -tetra- (Chloromethinole) Phueccene, Bis (Pentacromelomethinolecyclopentadenyl) Iron, Bis (Pentabromomethinolecyclopentadenyl) Iron , 1-Methinole-1 '-(trichloromethinole) phlegmene, 1-ethynole _1'-(trichloromethyl) phlegmene, 1-methyl-1,-(tribromomethyl) Hue mouth sen, 1-methinole _ 1, 1 (triiodomethinole) Hue mouth sen, 1-black mouth-1 '-(trichloromethinole) Hue mouth sen, 1-bromo-1'-(trichloromethinole) Hue mouth sen , 1-Bromo 1 '-(Trib-mouth Mometinole) Hue-mouth, 1, 1, J- (trichloromethyl) Hue-mouth, 1, 1'-Di- (Trib-mouth Mometinole) Hue-mouth, 1 , 1'-Gee (trichloromethinole) 1 2-chlorochlorobenzene, 1 _acetyl-1 '-(Trichloromethyl) phage, 1, 1' Diacetinol — 2— (Trichloromethyl) phage, 1,, 1'-Diacetyl-1 3- (Trimethyl-methyl) 1-Honoleminole 1 '-(((Chloromethyl) oxy) Chinole) n: 1 mouth, 1-acetyl-1 '-(((chloromethyl) oxy) methyl) fue mouth, 1—honoleminole 1 1'-(((trichloromethyl) oxy) methyl) fuerocene, 1— Acetyl_1,1-(((trichloromethyl) oxy) methyl)

As a compound having a silicon-containing group having 1 to 20 carbon atoms as a substituent, 1-formyl 1 ′-((((trimethylsilyl) oxy) methyl) fueccene, 1 _ ((((6-((((1,1 —Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) -1,1 formyl phenyl, 1 _acetyl-1 ′-((((trimethylsilyl) oxy) methyl) phenyl, 1 _ (((( 6 — (((1,1, Dimethylethyl) dimethinoresilyl) oxy) hexinole) oxy) methyl) 1 1'—aceti / lefrocene, 1,1'—di ((((trimethylsilyl) oxy) methyl) , 1, 1'-di-(((6-(((1,1-dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) fuecsen, 1,1, —di ((((trimethylsilyl) oxy) ) 1,2′-acetylthiophene, 1, 1 ′ di-(((6-(((1,1-dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) 12-acetylthiophene, 1,, 1,2-(((trimethylsilyl) oxy) methyl) 1-formylphene 1,1,1'-di (((6-((((1,1,1-dimethylethyl) dimethylsilyl) methoxy) hexyl) ) Oxy) Methyl) 1-formyl phenyl, 1-methyl_1, 1-(((trimethylsilyl) oxy) methyl) phenyl, 1 — ((((6-(((1,1-dimethylethyl) dimethylsilyl) ) Oxy) Hexinole) Oxy) Methyl) _ 1 '-Methinolephrocene, 1-ethynole-1'-((((trimethylsilyl) oxy) methyl) Huecene, 1 — ((((6— (( (1, 1—dimme) Tylsilyl) oxy) hexyl) oxy) methyl) _ 1 'チルフフ口 1 1 1 1 ジジ— (((1,1-Dimethylethyl) dimethylsilyl) oxy) hexyl) oxy) methyl) _ 2 _ methylphenicene, 1 — Methyl 1 1 '― (trimethinoresilinolemethinole) phenicene, 1 — Methinole 1 '― (trimethylsilyl ethyl) Linolepropinole) Phenyl, 1, 1 'di- (trimethylsilinolemethinole) Phue, 1, 1'-di- (trimethylsilylethyl) Phuelate, 1, 1'-di-methyl Mouth sen, 1-acetinol 1, 1, (trimethylsilicene 1,1, 1'-diacetyl 1-2— (trimethinolesilino remethinole) Hue sen, 1, 1, 1, diacetyl 1-3 (trimethylsilyl) Noremethyl) ferrocene, and the like.

As a compound having an oxygen-containing group having 1 to 20 carbon atoms as a substituent, 1,1′-di- (acetinolecyclopentageninole) iron, 1,1,1-dibenzoinolerefrocene, 1,1 ′ 1-bis (1-oxotetradecyl) phenyl, 1- (3-ethoxy-1-methyl-3-oxo-1-propionyl) 1 1'-1 (1-oxo-1-3-phenylenone) 2-Peninole) Phuecin, 1-Benzoinole 1,1- (3-Ethoxy _1-Methinole-1 3-oxo_1 _Propeninole) Fue mouth, 1— (3-Ethoxy-1-1-Methinole) 3 _Oxo _ 1—Probe-no-le) 1,1,1 (Phenyl acetinol) fuerocene, 1,1'-Bis (2-furanylcarbinole) Hue mouth, 1, 1'-Bis (2) —Methylbenzoinole) Hue mouth, 1,1,1-bis (3-Methylbenzoinole) Hue mouth 1, 1 '— bis (2, 4, 6 _ trimethinobenzoyl) Hue mouth, 1, 1, 1 bis (2—black mouth benzoinole) Hue mouth, 1, 1, 1 bis (2—fluor (Lenbenzoinole) Hue mouth, 1- (1,3-dioxopentinole) 1-1, 1-methylphen mouth, (neopentyl cyclopentagel) (propiol cyclopentagel) Iron , (Pivaloylcyclopentageninole) (propinolecyclopentagenine iron, 1— (9—force noreboxy-1-1-oxononinole)-1 ′, 3—dimethinolefferocene, 1— (9— 1-, 2-dimethinolephrocene, 1- (10-ethoxy-1,10-dioxodecinole)-1 ', 3-dimethinolephrocene, 1 _ (1 0_ ethoxy-1,1,0-dioxodecyl) 1 ', 2-dimethylphene , 1- (6-Methoxy-1,6-dioxohexyl) 1 1 '— (1-oxo-octadecyl) Hue mouth, 1, 1'-bis (1-oxo quinone) Hue mouth , 1— (1-methinole 1 _ oxo 1 1 —butenyl)-1 ′-(Fenryl acetyl) 1 1-oxopropyl) _ 1 '1- (1-oxopentadecyl) phenyl, 1- (3-carboxy-1-l-oxopropyl) 1-1, 1- (1-oxononyl) phenyl, 1- (4 —Ethoxy-1,4-dioxobutyl) 1 1 ′ — (1-oxodecyl) phenyl, 1 (4—ethoxy-1,1,4-dioxobutyl) 1 1 ′ — (1 oxono-l) phenyl, 1 , 1'-bis (6-carboxy-1_oxohexyl) fuecopene, 1_ (5-carboxyl-1-oxopentenyl)-1'-

(3-carboxy-l-l-oxo-propyl) phenoctene, 1,1,1-bis (7-methoxy-l, 7-dioxoheptyl) phen-l-octene, 1-1 (4-methoxyl-l, 4-dioxobutyl) 1,1- (6-methoxy-1,6-dioxohexyl) phenol, bis (o-carboxybenzoinolecyclopentagenenole) iron, (cinnamoyl pentagenenyl) (neopentinoresic pentage) 1,2,1,1-bis (3,5,5-trimethyl-1-oxohexyl) fuerosene, 1,1'-bis (1-oxohexadecyl) Pentylsic pentagenenyl) (3,5,5-trimethylhexanoinolesic pentagenenyl) Iron, (neopentinolecyclopentadene-nore) (Pivaloynolecyclopentadenyl) Iron, ((4-carboxybutyryl) cyclopentagenenyl) ((3-force benzoylpropionyl ^ /) cyclopentageninole) Iron, 1, 1'-bis (4-carboxy-1-oxoxobutyl) ) Hue mouth Sen, (Isobutinoresinku Pentajirenore) Pivaloynoresincyclopentadienyl) Iron, (Isobutyrinoresiclopentapentaenyl) (Neopentylcyclopentageninole) Iron, 11 (5-force phenolic pentyl) 1 1 ' 1 (1-oxo-octadecyl) Hue-sen, 1-(5-carboxy 1-1-oxopentinole)-1 ' ) One 1 '_ (1-oxotactadecyl) Hue mouth Sen,

((3_carboxypropionyl) cyclopentagenenyl) ((3-carboxypropynole) cyclopentagenenyl) iron, (benzylcyclopentagenenyl) (pivaloynocyclopentageninole) iron, 1_ ( 9—force norboxy _ 1 _oxo noel) 1 1 ', 2, 2', 3, 3 ', 4, 4', 5—octamethylhue mouth, 1- (10-ethoxy 1, 10, 0-dioxodecyl) 1 1 ,, 2, 2,, 3, 3 ', 4, 4 ', 5-octamethinolephrocene, (neopentylcyclopentagenenyl) (phen-norethetinoresic pentageninole) eye, (phenetinoresic pentageninole) (pivaloynole Cyclopentageninole) Iron, 1, 1'-bis (5-methoxy-1,5, -dioxopentyl) hues, 1 benzoyl- 1 '-(1-oxohexadecyl) hues, 1-acetyl 1 '― (1-oxohexadecyl) Hue mouth, 1, 1, 1 bis (1-oxo octadecinole) Hue mouth, 1-acetinol 1 1'-(1-cyclohexene 1 11 Inoureacetinole) Hue mouth, 1-Acetinole 1 '― (1-cyclooctene _ 1-inoreacetinole) Hue mouth, 1-Honoleminore 1', 2, 2 ', 3, 3', 4, 4, 5, 5-octamethyl One 5 'one ( 2, 4, 6—trimethylinobenzoyl) Hue-Sen, 1-Benzinole 1'-Hozremyl-2, 2 ', 3, 3', 4, 4 ', 5, 5'-Octamethylhue-Sen, Benzoyl Nonametinolefuerosen, 1— (3,3-dimethinole — 1-oxobutyl)-1-oxobutynole)-1 '— (1—oxo-1_4_fernbutinole)

1-(1-oxo 1 5-(4-(1-oxo 1 3-phenyl 1 2-propyl) fuinore) pentinole) 1 1 '1 (1 _ oxo 1 3 _ fuinore 1 2- Propininole) Hue mouth, 1-1 (1-oxo 4- (4- (1-oxo-3-3-phenyl-1-phenyl) phenyl) butyl) 1 1 '— (1-oxo_3— 1- (1 oxo) _ 3-phenyl 2 propyl) phenyl) propyl) 1 1 '— (1 oxo 3-phenyl 2 _propynyl) 1) (1)-(1-oxo-3-phenyl) propyl) 1 1 '-(1-1-oxo-3-fu-nore 1 2—Pu mouth Pier) Hue mouth, 1— (1—Oxo 1—3-phenylpropyl)-1 '— (1 Oxo 1—3—phenyl 1—2—Propier) Hue mouth Sen, 1— (phenylacetyl)-1 '-(1-oxo-3-3-phenyl-2—propynole)

(1-oxo-1 5-phenyl-2-pentyl)-1 'one (1-oxo _ 3 -phenyl-1

2-Propenyl) Hue-Sen, 1-1 (1-oxo-41-pheninolebutynole) 1-1,-(1-oxo-1-3-phenyl-1-2-propenyl) Hue-Sen, 1— ( 1-oxo-1-3-phenyl-2-propenyl-1-2-propenyl-1 '-(1-oxo 1 3-Feninolepropynole) Hue mouth, 1-Benzoinole-1, -Honoleminolefuerosen, 1_Benzoyl-1-1,1- (3-oxo-1-3-Fe-nore-1-Propenyl) Hue Mouth sen, 1, 1'-bis (1-oxo-2-2-pentenyl) Hue sen, 1-1 benzoyl-1,1- (1-hydroxy _3-(1-hydroxycyclohexynole) 1-1-hue -Nore-I 2—Propiel) Hue mouth, 1, 1'-Bis (3-carboxy 1-oxopropyl) Hue mouth, 1, 1'-Bis (4-Methoxy-1,4 dioxobutyl) Hue mouth, 1-acetyl-1 '-(1,3-dioxobutyl) -1,3,1-dimethylphenic acid, 1,1,1-bis (1-oxopentyl) phenic acid, ((3-nitrophenoloxy) Nore) pentagel (ethylcyclo) Ntagenil) Iron, 1,1,1-bis (4-1- (2-methylbutyl) benzoyl) fluorocene, 1,1,1-bis (1-oxo-desinole) Hue-sen, 1— (4-hydroxyphene) -Le) 1 1'-1 (1-oxo-3-3-phenyl-2-propenyl) phenyl, 1-acetyl-1 '-(3- (3-methoxyphenyl) _1-oxo- 2-Prober) Hue-Sen, 1-Acetyl-1-1,1- (3- (4-Methylphen-Nole) -1-1-oxo-1 2-Pro-Pininole) Hue-Sen, 1-Acetyl-1 ' 1- (3- (4-Methoxyphenyl) 1-1-oxo-1-2-propenyl) phenyl, 1- (3-methyl-1-1-oxo-2-buteninole) 1 1 '-(phenyl-2-acetyl) Phue 1- (4,4-dimethyl_1-oxo-1-2-pentenyl) 1 1 '― (Fenrylacetyl) 1-Acetyl_1,1- (4,4-Dimethyl-1-oxo-1-2-pentenyl) phenoctene, 1 _acetinole_1 '-(3-Methyl-1-oxoxo_2-butenyl) phenoctene, 1 _____________________________________ 1- (1-oxo-2-butenyl) 3-Dimethyl-1-oxobutyl) 1 '1- (1-oxo-3-phenyl-2-propenyl) pherothene, 1-1 (3-methyl_1-oxobutyl) _1,1- (1-oxo) 1,3-phenyl-2-propenyl) phenyl, 1 _ (1-oxobutyl)-1 '-(1-oxo-3-phenyl-2-propyl) phenyl, 1, 1 , One bis ((4-methyl phenol) acetyl) Hue sen, 1, 1 'one bis (3— (4-methyl phenol) Nore) _ 1-oxo-1 2-propidinyl Hue mouth 1,1,1-bis (3- (2-furaninole) 1-1-oxo-1 2-propininolehuerosen, 1,1,1-bis (h 1- (6- (4-methoxyphenol) -1-6-oxohexyl) 1,1,, 3-bis (1-10-oxo-3-3-phenyl-2-propenyl) , 1-(10-(4-methoxyphenyl)-1-10-oxodecyl)-1 ', 2-bis (1-oxo-3--feninole-2--propininole) (4-Methoxyphenyl) 1 -5-oxopentyl) 1,1,, 3-bis (1-oxo-1-3-phenyl-12-propyl) phenyl, 11- (9- (4-methoxyphenyl) 1) 9-oxonoel) 1 1 ', 2-bis (1-oxo-3-fueninore_2-propionyl) Hue Sen, 1 _ (8— (4-methoxyphenyl) 18-oxo-octyl) 1,1,1 (1-oxo-1 3 _phenyl-1 2 _propenyl) 0—ethoxy-1,1,10—dioxodecyl) fuerosen, 1,1′-bis (9-ethoxy-1,9, dioxononyl) fuecsen, 1,1′bis (8—ethoxy-1,8, di) 1,2 -'- bis (7-ethoxy-1,7-dioxoheptyl) -1,2 -'- bis (5-ethoxy-1,5-dioxopentyl) fu Mouth sen, 1 _ (1, 1 0—dioxo 1 10—phenyl decyl) 1 1 ′ 1 (1—oxo 1 3-phenyl-1 2 _propenyl) Hue sen, 1— (1, 9—dioxo 1 9-1-2-1--1-Oxo 3-Fuenore 1-2-Pheninore 1-(1, 8-Zio) 1-8-phenyl-octyl)-1 '-(1-oxo-3-phenyl-2_propininole) 1- (1,7-dioxo-7-phenylheptinole) 1 1'-(1- 1- (2-methylbenzoyl) 1- (2-methylbenzoyl) 1- (2-methylbenzoyl) 1- (2-methylbenzoyl) (4-Methinolebenzoinole) Hue mouth, 1-benzoinole 1 ', 3-bis (hue-noremethinole) Hue mouth, 1-benzoinole 1', 2-bis (pheninolemethinole) Hue mouth, 1-benzoinole 1 1 ― ― (1-hydroxy-1 1-phenylenole) 1, 1 '-bis (1, 1, 1-biphenyl) 1 4- 4- lucanorebonyl 1-benzene , One (1-methylcyclopropyl) Le) Hue mouth, 1, 1'-bis (3-carboxy-l-oxo-l- 2-propenyl) 1,2-methyl-l-phen-l-l, 1-methyl-l, l ,, 2-bis (l-oxol) 3-Fe-Lu 2-Propenyl) Fue mouth, 1— (6-Methoxy-1,6-dihexoxy) 1 1 _ ((2-oxocyclopentyl) carbonyl) Fue mouth, 1,1'-bis (6-ethoxy-1,6-dioxohexyl) phenoctene, 1- (6-ethoxy-1,6-dioxohexyl) 1-2 ((2-oxocyclopentyl) ) Canoleboninole) Hue mouth 1, 1 'Bis (4-methoxybenzoinole) Hue mouth, 1, 1'-Bis (1-oxoxotyl) Hue mouth, 1-Power noreboxi 1 '— (1 , 2-dioxopropyl) phenyl, 1-(methoxycarbonyl) 1 1,-(phenylacetyl) 1-Carboxy-1,1- (1-oxo-3-3-phenyl-2-propenyl) 1-Carboxy 1,1-Carboxy-1,3- (2-propenyl) 1 1 (Methoxycarbonyl)-1 '1 (1-oxo 3-phenyl 2- 2-propenyl) Hue mouth, 1-(3-methylphenyl)-1'-(1 -oxo 1-3-fu 1- (4-Methylphenyl) 1-1,-(1-oxo-3-3-phenyl-1-2-propeninole) Frocene, 1- (1-oxo-1) 3—Feninole 2—Propaninole)-1'—Fuer-leuerosen, 1- (3,5-dimethylphenyl)-1 '-(1—Oxo-1 3—Feninole 1—Probenole Hue mouth sen, 1 _ (3,4—dimethinole fuñinore) 1 1,1 (1 oxo 1 3 _phenyl_2 —propininole) Mouth sen, 1- (4-Methoxy phenyl) 1-1,-(1-oxo-3-3-phenyl 2- 2-propeninole) erocene, 1- (4- (ethoxycarbonyl) phenyl) 1 1 ' — (1—oxo 1 3—Feninole 2—Proninole) Hue mouth, 1 _ (3—Echinore 1 2—Proninole) 1 1--(1 _oxo 1 3—Feninole 2—Pro) (Ninole) Hue mouth, 1- (4-Echinolene 2)-1 '-(1 oxo-1 3 _Feninole 2- 2-propininole) Hue mouth, 1-benzoyl-1, 1, 1 (Methoxymethyl) ) Hue mouth, 1,1'-bis (3_ethoxy-1,3-dioxopropyl) Hue mouth, 1- (3,3-Dimethyl-1-1-oxobutyl) 1-1 ', 3-Dimethylphene , 1— (3,3-Dimethinole-1-oxobutyl) 1,1,, 2-dimethylphenic acid, 1-acetyl — 1,-(2-Methynole 1-l-oxo _ 3—Fenr 2-l-propenyl) Fuerosene, 1-acetyl 1 1 '-(1-loxo-1 5-phenyl-1,2,4-pentadenyl) Hue mouth sen, 1, 1, 1-bis (oxofeneryl acetyl) Hue mouth, 1, 1'-bis (fueninorea cetinole) Hue sen, 1— (3-acetinole feninole)-1, 1 ( 1-oxo 3 _ feninole 2- 2-propeninole, 1, 1'-bis (cyclohex canoleboninole) fen mouth, 1, 1'-bis (1-oxo-hexinole) Hue Mouth, 1,1,1-bis (3-methyl_1-oxobutyl) ph mouth sen, 1- (1,1-dimethylethyl) 1-1,-(2,2-dimethyl-1-oxopropyl) ph mouth Sen, 1_ (1,1-dimethylethyl) 1-1,1- (2-methyl-1-1-oxopropyl) 1-Acetyl-1- 1'-1 (1-oxo-3-1-phenyl-1-2-propyl) Phuecene, 1, 1'-Bis (2,2-dimethyl-1-oxopropyl) Phuecene, 1 —Acetyl 1, 1, (1-oxobutyl) fuecone, 1—acetinol 1 1 ― ― (fueninorea cetinole)-2-(hue-noremetinole) Hue sen, 1 _benzoinole 1, 1,-(hue Ninorea cetinole) Hue mouth, 1-(1-oxobutyl) 1 1 '— (Fu-l-acetinol) Hue mouth, 1 _ benzoyl 1 1'-(1-oxobutyl) Hue mouth, 1 _ (1 -1 -'- (Feninoreacetinolle) 1'- (Feninoreacetinole) 1 '-(Feninoreacetinole) 1 -'- (Feninoreacetinole) Hueguchi-sen, 1-benzoinole 1-1, 1 (1-oxopropinole) Huechisen, 11 Acechinore 1 3—etchinore _ 1 '-( (Feni / Rarecetinole) Hue mouth, 1—acetinole 1 '1 (Feninoleacetinole) 1 3— (Feninolemethyl) Hue mouth, 1 _ (3—Ethoxy 1 1_Methyl_3—Oxo 1 1 1-Propenyl) 1 1 '1- (1-oxo-1 2-butel) Hue sen, 1- (3-ethoxy-1 1-methyl-1-3-oxo-1 1-propenyl) _ 1' 1 (1-oxo octadecyl) fue mouth, 1-1 (3-ethoxy-1-methyl-3-oxo-1-propenyl) 1, 1-(1-oxo-propyl) fue mouth, 1-acetyl- 1 '-(3_ethoxy_1-methyl-1-3-oxo-1-probe) phenoctene, 1, 1'-bis (((5-((4-methoxyphenoxy) canolebonyl) phenoxy) Pentyl) oxy) carbonyl) fu octene, 1, 1 'monobis ((3— (4— ((4—methoxyphenoxy) B) carbonyl) 1,1'-bis ((2- (4-((4-methoxyphenoxy) carbonyl) phenoxy) ethoxy) carbonyl) phenoxy-1,1,1'-bis (( Heptadecyloxy) carboyl) huecopene, 1,1'-bis ((((2,3,5,6,8,9,11,12) —Kutahi draw 1,4,7,1 0,1 3-benzopentaoxacyclopentadecine 1 15-isolexy) canoleboninole) fuecopene, 1 力ノレ一 '（（（（（（（（（（（（ 1-bis ((4-((4_ (hexyloxy) phenoxy) carbonyl) phenoxy) carbonyl) fluorocene, 1, 1'-bis ((4-((4- (pentic xy) phenoxy) carbinole) phenoxy ) Carbonyl) , 1, 1'-bis ((4-((4-butoxyphenoxy) carbonyl) phenoxy) carbonyl) phenyl, 1,1, _bis ((4_ ((4-ethoxyphenoxy) carbonyl) phenoxy) (Carboninole) Hue mouth, 1, 1, -bis ((4-((4_ (pentic acid) benzoyl) benzoyl) oxy) phenoxy) Carbon) Hue mouth, 1, 1, 1-bis ((4_ ((4-((butoxy) benzoyl) oxy) phenoxy) carbonyl) phenol, 1,1,1-bis ((4-((4_propoxybenzoinole) oxy) phenoxy) canoleboninole) phenol , 1, 1 '_ bis ((4-((4_ethoxybenzoyl) oxy) phenoxy) canolepul) fuerocene, 1, 1, 1 bis ((4— ((4-methoxybenzoyl) oxy) phenoxy ) Carbonyl) Hue mouth, 1-(((1,1,1-biphenyl) -14-yloxy) carbonyl) _ 1 'Hexinolefe, 1-butynole-1, _ (((4-((4- (Pencchi benzoyl) benzoyl) oxy) phenoxy) carbonyl) phenyl, 1-butyl-1 '_ ((4- (hexyloxy) phenoxy) force / reponinole) furosene, 1-butyl-1,-(( 4 1-Heptylphenoxy) Carboyl) Hue-Sen, 1,1'-bis ((4-formylphenoxy) arbonyl) Hue-Sen, 1,1, -bis (((3-formylphenyl) methoxy) ) Carbonyl) phenoctene, 1, 1'-bis ((4 _ (((4- (hexyloxy) benzoyl) oxy) phenoxy) carbonyl) fenoctene, 1,1'-bis ((4- (phenylmethoxy) ) Phenoxy) force rubonil) furocene, 1 ((4_ (Desi port carboxymethyl) Fuwenokishi) carbonyl) Single 1 '-((4-hydroxyphenoxy) carbonyl) phenacene, 1, 1'-bis ((4- (derosoxy) phenoxy) carbonyl) phenacene, 1, 1'-bis ((4- (Heptic mouth xy) Phenoxy) Noreboni ^ /) Hue sen, 1, 1'-bis ((4 — (1, 1-Dimethinoleethynole) phenoxy) carbonyl) Hue sen, 1, 1, — Bis (methoxycarbonyl) -1,2'-bis (methoxymethyl) phenecene, 1,1'bis (ethoxycarbonyl) -1,2,3'bis (methoxymethyl) fluorocene, 1,1'one Bis (ethoxycarbonyl) -1,2,3'-bis (methoxymethyl ^) phenyl, 1,1'bis (ethoxycarbonyl) 1,2,2'-bis (methoxymethyl) phenyl, 1_ (ethoxy Carbonyl) 1 1 ', 2-bis (methoxymethyl) Hue sen, 1, 1'-bis (((1,4-dihydro-1,4-dioxy _2-naphthale-norre) oxy) power / reponi ^ /) Hue sen, 1, 1, 1 Bis ((((4 '-(Heptic mouth) (1,1'-biphenyl) 1-4-yl) oxy) Carbonyl) Hue sen, 1, 1'-bis ((((4,1 (Hexyloxy ) (1, 1'-bi-pheninole) 1-4-inole) oxy) canoleboninole) Hue-mouth, 1, 1'-bis ((((4'-one) (1,1'-biphenyl)- 4- (yl) oxy) carboyl) fuecium sen, 1, 1'-bis (((4'-butoxy (1,1,1, biphenyl) 1 4-yl) oxy) canolebonil) huecchi Sen, (Methoxy power / Reponyl) Nonamethylfurocene, 1,1,1 (Methoxycarbol) 1,2,2 ', 3,3', 4,4 ', 5,5' 1, 1- (methoxycarbonyl) -1- (methoxycarbonyl)-1 '-(methoxycarbonyl)-1'-(phenoxymethinole) 1 '1-bis ((1,1-dimethylethoxy) carbonyl) phenyl, 1,1'-bis (((3-hydroxymethyl) phenyl) methoxy) carbonyl) 1,1' —Bis (((5- (Hydroxymethyl) 1-2-furaninole) methoxy) Carboninole) Fue mouth, 1, 1 '—Bis ((4-Hydroxy phenoxy) phenol) ^^ Hue Mouth sen, 1-acetinol 1 '-(propoxycarbinole) ph mouth sen, 1-acetyl-1'-(ethoxycarbonyl) fen mouth, Decakis (methoxycarbinole) fen mouth, 1, 1, 1 Bis ((2-propidnylo) Xy) carbonyl) fuecsen, 1, 1, 1 bis (( Heninolemethoxy) Noreboni ^ /) Hue sen, 1 _ (ethoxycanolepo-nore)-1 '-ethylhue sen, 1-(ethoxycarbonyl) one 1'-methoxy fuerosen, 1-(ethoxycanoleboninole )-1 '— pheninolefuerosen, 1—acetinole _1, — (4— (ethoxycarbinole) phenyl) ueguchisen, 1, 1, monobis ((oxosilanylmethoxy) carbo-nore) 1- (Hydroxymethyl)-1'- (Methoxycarbonyl) Hue-Sen, 1-(Methoxycarbonyl) 1 1 ', 2-Dipheninolefferocene, 1- (Methoxycanoleponinole) ) 1 1, 3-dipheninole 1, 1 'bis (methoxycanolepo-nore) 1-3-methinolephrocene, 1, 2-diformyl-1', 2 ', 3, 3' , 4, 4 ', 5, 5' — Oktamethi Rufuero 1 '—Forminore 1, 2,3,4—Tetramethinole 5— (4,7,1 0,1 3—Tetraoxate Torade 1 1-yl) Hue mouth, 1—Acetyl 1 1- (2-Ethoxy-1-2-oxechinole) Fue mouth, 1-honoleminole-1, 1,-(((6-hydroxyhexyl) oxy) methyl) Fue mouth, 1, 1 ' 1-bis (1,1-dimethinoleethinole) Hue sen, 1,1-honoleminole — 1,2,3,4,5-pentamethinoleferocene, 1— (1-methinole-1-3-oxo 1 1-butenyl) 1 1,1 (1-oxopropyl) Hue mouth, 1-acetyl-1 '1 (1-methinole 3 _oxo_1_buteninole) Hue mouth, 1'-Honolemil 1,2 —Dimethylphenic acid, 1—Forminole 1 ′, 2,2 ′, 3,3 ′, 4,4,, 5—Octamethinolefuerosen, ( Acetinolecyclopentadene-iron) (neopentylcyclopantagenole) iron, 1-acetinole 1'-ethyninolef erocene, (benzoylcyclopentagenenyl) (neopentylcyclopentadene) iron, acetyl ^^ Nonamethinolefrocene, 1—Honoleminoleate 1,1- (hydroxyphenylmethyl) -1,2,2 ', 3,3', 4,4,5,5'-Octamethyrulferosen, 1-Honoremil-1 '— (1—Hydroxyshetinole) _ 2, 2 ′, 3, 3,, 4, 4 ′, 5, 5 ′ — Octamethinolephrocene, 1—Forminole 1 3 — (Hydroxymethyl) 2, 2 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, And 2, 3, 4, 5-pentafe Norefuerose 1,1,1'-diacetyl_3,3,1-dimethinolephrocene, (acetylcyclopentenyl) ((2_carboxybutyl) cyclopentagenenyl) iron, (acetylcyclopentapentaenyl) ((2-cano Reboxyshetil) Pen mouth pentageninole) Iron, Honoleminolenorenamethinolefferosene, 1, 1, 1-diforminole 1, 2, 2 ', 3, 3,, 4, 4', 5, 5'-Octame Chinolefrocene, 1—Honoleminole 1 1'-1 (Hydroxymethinole) Hue mouth, 1-Acetinole 1, _ (1— (Acetyloxy) ethinyl) Hue mouth, 1-Acetinole 1 '1 (8— (4— (Methoxy phenyl) 18-oxo-octinole) Fe-mouth, 1-acetyl-1 ', 3-bis (pheninolemethyl) Fe-mouth, 1-acetinole 1,, 2-bis (phenylme) Le) Ferosen, 1-acetinolate 1 '-(1-hydroxy-1- 1-pheninolethine) Hue mouth, 1, 1'-diacetinolene 2-methylhuecene, 1, 1 '-diacetyl — 3-methylphene Sen, 1—Honoremil 1 2— (4-Methoxyphenynole) Hue Seng, 1— (3—Echinolefenyl)-1 '—Honoleminoleferosen, 1 _ (4—Ethylphenyl) 1 1 '-Honolemilfe sen, 1 _ (3,5-dimethylphenyole)-1' -Formylphen sen, 1— (4- (ethoxycanoleboninole) phenyl) 1,1, forminoreferocene, 1— (3,4-Dimethinolepheninole)-1 '-Honolemi-norrephenone, 1-Honoleminole-1, 1, (4-methoxypheninole) Hueinsen, 1 -Honoremil-1'-(4-Methylpheninole) Hue Mouth Sen, 1—Hono Remil 1, 1-(3-methylphenyl) Hue mouth, 1 _ acetinole 1 '1 (4-(acetyroxy) Fehenore) Hue mouth sen, 1-Honoleminole 1, 1-feninoleferosen, 1-A 1 '-(4-Methoxyphenyl) phenyl, 1-acetyl-1'-(3,4-dimethylphenyl) phenyl, 1 _acetinole_1 '_ (3,5-dimethinole (Feninore) Hueguchi Sen, 1 _Acetinole_ 1 '-(4-Methinole feninole) Huelosen, 1—Acetinole 1 1, 1 Feninolefferosen, 1 1Acetinole 1 1'-(3-Metinolefeninole) 1) Hue mouth, 1—Acetinole 1 '1 (2—Benzyru 3—Oxonone 1 butyl) Hue mouth, 1—Acetinole 1 1' ― (3—Oxor 5—Fue 2Norre 1, 4— Pentagenil) Hue mouth, 1-acetyl-1 '-(2- Ace chinore 1 5-oxo 1 5-feninole _1,3-pentageninole Hue sen, 1 _ Acetyl 1, 1-(5-oxo 1 5-phenyl 1, 3 ^ ntagenil) Hue, 1-acetyl 1 '-(1-hydroxitytyl) Hue, 1-acetinole 1' 1 ( 1-Methoxy-1 3-Fenii / le 2-Propaninole 1-Acetyl 1 1 '., 3_Bis (1-methylethynole) 1-Methoxy- 1'-Acetinole-1, 2— Dimethinolephrocene, 1'-acetinole 1, 3-Dimethinolefrocene, 1-acetyl-1 ', 3-bis (1,1-dimethylethyl) (3-Methoxy-1-3-phenyl_1-propeninole)

1-acetyl-1 ', 2-bis (1,1-dimethylethyl) phenyl, 1-acetyl- 1', 2-bis (1-methylethynole) phenyl, 1-acetyl 1,1,,

2—Jetilhue mouth, 1—Acetinole 1 '― (3-oxobutizole) Fuerosen, 1 _Acetinole 1 1, 1 (3—acetinole 2) Hue mouth, 1—acetinole 1--(4—acetinole) Nore) Hue mouth, 1-acetinol 1'-Methoxy fusen, 1-acetinol 1 '-(Tributinolestaninole) Hue mouth, 1-formyl 1'-1 (tributylstannyl) Hue mouth And the like.

1-butyl-1 '-(4-mercapto1-1-oxobutyl) compound as a compound having an i-containing group having 1 to 20 carbon atoms as a substituent, 1,1'-bis (4-mercapto-1-oxobutynole) Hue mouth, 1- (4-Menolecapto-1—oxobutynole) 1-1,-(1-oxobutyl) Hue mouth, 1-butinole 1 '― ((4 mercapto-1 1-oxobutynole) Hue mouth, 1- (2— Hueneruechore 1-1 '1 (2-Chenolecanoleboninole) Hueguchi Sen 1-Etchinore 1 3-(1-Hydroxyshetyl) 1-1, 1 (2-Cheneycanolebonil) Hueguchi Sen 1 — (Feninoleacetyl)-1 '-(2-Cercanolebonyl) phenic acid, 1-benzoyl 1'-(2-Cheninolecanolebonyl) Hue's acid, 1— (1-oxopropyl) 1 1 '— (2— E sulfonyl carbonyl) Hue opening sensor, 1, 1, One-bis ((2- ((1,

3—Dithiol—2—ylidene) —1,3—Dithiol-14_yl) thioethoxy) canolebonyl) phenoctene, 1— (methoxycarbonyl) -1,1, ((feninolethio) methyl) phenyl Mouth sen, 1, 1'-bis ((2- (3-Chenyl) ethoxy) Carbonyl) fuecopene, 1,1'-bis (((5- (hydroxymethyl) 1-2-cheel) methoxy) carbol) fuecopene, 1- (methoxycarbonyl) 1-1 '-(me Toxisulfonyl) Phueccene, 1-acetyl-1- 1'-1 (5-acetinol 3-phenyl-2_Chenyl) Phueccene, cyclopentageninole ((1-formyl-1-2_ ( 2—Chenyl) Bull) Cyclopentagenenyl) Iron, 1—Honoremil 1 1′—Sulfoferocene, 1—Acetyl 1 1 ′ — (Methoxysal Foninole) Hue Keng, 1 _Acetinole _ 1 '—Sanorev Off-erosen, and the like.

As a compound having a phosphorus-containing group having 1 to 20 carbon atoms as a substituent, 1,1'-bis (dipheninolephosphine) phenyl, 1-acetinole-1 '-((diphenylenophosphine) acetinole) Sen, 1, 1'-bis ((dipheninolephosphino) acetyl) fen, sen, 1— (diphenylphosphino) 1,1, formylhuen sen, 1-acetinole 1 '-(dipheninolephosphino) Hue mouth, 1-acetyl-1 '-(diphenylphosphiel) Hue mouth and the like.

1,1'-Diacetyl-1,2,3'3-propanesyl) phenicene, 1,2_Diacetyl-1,4 '-(1,4-butanezinole) 1,1,1-bis (methoxycanoleponyl) 1,2,2 '-(oxybis (methylene)) phenoctene, 1,1,1-bis (ethoxycarbol) 1,2,2'-(oxybis (Methylene)) 1-benzoyl 1 '-(3-oxo-3-phenyl-1_propenyl) 1,3,3,-(1,3-propanyl) 1-benzoyl 1 (Fer-L-acetyl)-1 ', 3— (1,3_propanezyl) phenyl, 1— ((4-Methoxyphenyl) acetyl) 1', 3— (1, 5-pentanezinole) Sen, 1 — ((4-Methoxyethoxy-Nore) Aceti ^^-1 ', 3— (1,3-propanyl) 1, 1 '_ (1, 5—pentanyl) 1 3— (phenylacetyl) Hue-Sen, 1 _formyl-1 1,, 3_ (1,5-pentanezyl) Hue-Sen, 1, 1' — Diacetyl 1, 3, 1 (1, 5-pentanezyl) Hue, 1, 1-benzoinole 1 ', 2-(1, 3-penta-pentanezinole) Hue, 1', 2-(1, 4) —Butanesil) ー 1—E Noremil 1, 2, 3-(1,3-propanesil) Hue sen, 1, 1, 1 diacetinole 2,, 3-(1, 5 -pentanezyl) Hue sen, 1 1 (1-oxo)

2—probel)-1 ', 3— (1,3—propanyl) Hue sen, 1— (Methoxycarbinole)-1', 2-(1,3—propanine) Hue sen, 1 _ トノノ '1 ― ― (1-oxo 3 3 エ-Feru 2 —-P ぺ ininole)-2, 3-

(1, 3—propanesil) Hue mouth, 1—acetyl 1 1 ′, 3— (3—ferinole 1,5—pentanezyl) Hue mouth, 1, 1 ′ diacetinol 2, 3,-(1 , 4-butanesil) Hue mouth, 1, 1 '-diacetyl 1, 3'-(1,4-butanesil) Hue mouth, 1, 1 'diacetil _ 2, 3,-(1,4-butanesil) Hue sen, 1- (Methoxycanoleponyl)-1,, 3 _ (1,3-propanesil) Hue sen, 1-honoleminole 1 ', 3-(1,3-Propaneyl) Hue sen , 1—Honoreminore 1,, 2— (1,3—Propanezinole) Fuerosen, 1 '—Acetinole 1 _ (1 一 oxo-1 2—Propaninole) 1 2,3'-

(1,5-pentanezinole) Hue mouth, 1-acetinole 1 '1 (1-oxo-1 2_propininole) 1,3,3'-1 (1,5-pentanezinole) Hue mouth, 1-benzoylou 1 '-(3-oxo-1-3-phenyl-1-propenyl) 1,3,3'-1

(1,5-pentanedinyl) 1-benzoinole-1,3-honoleminole 1,3,3'-1 (1,5-pentanedinole) 1-benzoinole-1,1-benzoinole 1'-honolenemil 3,3'-1 (1,3—propanyl) Hue mouth, 1, 1'-Bis (methoxycarbyl) — 2, 2 ': 3, 3'—Bis (1,3-propanyl) Hue mouth, 1, 1, 1 Bis (methoxycanoleponyl) one, 2 ': 4,4'-bis (1,

3-propanyl) Hue sen, 1, 1'-bis (methoxycanoleponyl) 1,2,4: 2 ', 4-bis (1,3_propanyl) hue sen, 1_ (methoxycarbo) -1), 1 ', 2: 3,, 4-bis (1,3_propanyl) herosen, 1,4-bis (methoxycanoleponyl) 1', 2: 2 ', 3-bis ( 1, 3 —propanesil) Hue mouth, 1 _ (methoxycarbonyl)-1 ', 2: 2',

3-bis (1,3_propanyl) Hue sen, 1,, 2— (1,4-butanezyl) 1 1- (4-methoxy-1 1,4-dioxobutyl) 1 2 ', 3— (1 1,3'-propanesilyl 1,1,1'-bis (methoxycarbonyl)-2,3,1- (1,3-propanylinole) huecopene, 1,1'-bis (methoxycarbonyl) 1), 3 '-(1,3-propanyl) phuetocene, 1-, (methoxycarbonyl) 1-1,, 3- (1,3-propanyl) furosene, 1,1'-bis (methoxycarbonyl) Carbonyl) 1, 2, 2'- (1, 3-propanyl) 1-forminole, 1-forminole 1 ', 2_ (1, 5-pentanezyl) phene-form, 1-acetinol 1'- (1— Oxo-1 3-pheninole 2-propeninole) — 3,3 '-(1,5-pentanezyl) phen-octene, 1,1'-bis (1-oxo3_phenyl_2-propenyl) 3, 3 '-(1, 5-pentanedisyl) Hue-Sen, 1-Honoleminolay 1,, 2: 3', 4-bis ( 1) 1-acetyl-1, 2, 2- (1,3-cyclopentanezyl) fuerosene, 1, 1 'diacetino-le 3,3' — (1, 5, pentanezyl) huecou-sen, 1 , 2-Diacetyl- 1,, 4-(1,3_propanyl) Hue mouth, 1,1'-Diacetinol 3,3,-(1,3_propanyl) Hue mouth, 1,1,1'Diacetyl- 2, 2 '-(1,3—propanyl) Hue mouth, 1, 4-diacetyl 1, 2, 2 (1,3_propanesilinole) Hue mouth, 1— (1-oxo-one 3-ferenole) 1 2, 1, 2,-(1, 3-propanyl) Hue, 1, 1 '-bis (1 _ oxo 1 3-fuininole 2 _ propininole) 1, 3, 3 '1 (1,3-propanine) Hue mouth, 1, 1'-1 bis (1-oxo-1 3-phenyl-2-propenyl) 1 2, 3 '-(1,3-propanyl) Hue mouth, 1- (1-1-oxo-3-3-phenyl-2-propyl) 1,1,, 3-(1,3-propanyl) Hue mouth, 1-acetyl-1 '-(1-oxo-3-phenyl-2-propenyl) -3,3'-(1,3 -propanyl) Hue mouth, 1-acetinol 1—oxo 3—phenyl 2—propionyl) -2,2 '-(1,3—propanyl) Hue mouth, 1_acetyl 1'1 (1—oxo 3-3-phenyl 1 2 —Propenyl) 1,2,3′-1 (1,3—Propanyl) Hue mouth, 1, 1 '—Diacetyl 1,3,1,1 (1,3—Prononyl) Hue mouth, 1, 1 'One diacetyl—2,2' one (1,3—propane Jil) Hue mouth sen, 1, 1'-Diacetyl one, two, three 'one (1,3—propanyl) Hue mouth, one—acetinolate 1', 2_ (1,3—propanyl) Hue mouth, One —Benzyl _ 1,,, 3— (1,3—Prono ヽ⁰ Nejinore) Hue mouth, 1 1, 2— (1, 3—Propaneyl) Hue mouth, 1— (1 oxopropyl) _ 1,, 3— (1,3_propanyl) Hue mouth, 1-1 (1 oxopropyl) 1 1,, 2— (1, 3—propanyl) Hue mouth, 1 _ acetyl 1 ', 3— ( 1, 3 _ propanesil) Hue mouth, 1 acetylene 1 ', 3— (4 oxo 1, 4-butanesil) Hue mouth, 1 acetic acid 1', 2 — (4 oxo 1 , 4—butanesil) Hue mouth sen, 1 acetinor _ 1 ', 2_ (1-oxo-1,4—butanesil) Hue mouth sen, 1 —Acetino _ 1 ', 3— (5-oxo-1,5-pentanezinole) Fueguchi, 1—acetyl-1 1 ′, 2-(5-oxo-1,1,5-pentanezyl) Fueguchi, 1—a cetir-1, 1, 3— (3-oxo-1,3_propanyl) fen mouth, 1 acetyl-1 ', 3— (3-oxo-1 1,3_propanyl) fen mouth, 1— Acetyl 1 1, 2— (3-oxo 1, 3 _propanyl) Hue sen, 1-acetyl-1 ′, 2— (1 oxo 1, 3 _propanyl) Hue sen, 1-acetyl 1 1 ', 2: 3', 4 1 bis (1, 3 _ propanesil) herosen, 1-acetyl 1 ', 3-(1, 5-pentanecinole) Hue sen, 1-acetyl 1', 2-( 1,5-Pentanezinole) Fe-Sen, 1-Acetyl 1, 1, 3- (1,4-butanesyl) Hue-Sen, 1-Acet Lae 1,, 2 _ (1,4—butanesil) Hue mouth, 1—formyl 1 1 ′, 3— (1, 3, propane dinole) Hue mouth, 1—formyl 1 1, 2— (1, 3—propanyl) Hue mouth, 1— (4-Methoxy-1,4-dioxobutyl) 1-1,, 2— (1,3—propanyl) Hue mouth, 1— (4—Methoxy 1 1, 4 —Dioxobutynole)-1 ', 3-(1,3-propanyl) fen mouth, 1— (3-carboxy-1-1-oxopropyl) one 1', 2— (1,3_propanyl) fen mouth, 1— (3-Carboxy 1-oxopropyl) 1 1 ', 3— (1,3_propanedinole) Hue mouth, 1-dodo 1,, 2: 3,, 4-bis (1,3-propane) Jil) Hue mouth Sen, 1-one one 1 ', 3, one (1,5-pentanezinole) Huelosen, 1, 1'-Jib mouth 2, 2, ': 3, 3,: 5, 5'-Tris (1,3—propanenoresinole) Hue mouth, 1,1'-Dichloro-2,2'- (dipheninoleresylene) Hue mouth, 1,1,1 Mouth silen) Hue mouth, 1, 1'-Jodo 1 2, 3,-(1,3_propanyl) Hue mouth, 1, 1, 1 jib mouth mode 2, 3,-(1,3_propanyl) ) Hue mouth sen, 1, 1, one-joy 3,3 '-(1,3-propanesil) Huelosene, 1,1' one bromo one 3,3 '-(1,3-propane ninole) Hue mouth sen , 1-Yodo 1 ', 3- (1, 3-Puronoヽ⁰ Nejiinore) Hue opening Sen, 1-bromo-1', 3 (1, 3-Puropanejiiru) Hue opening Sen, 1, 1, Jo One 2,

2 '_ (1,3—propanyl) Hue mouth, 1, 1', dibromo 2,2 '— (1,3—propanyl) Hue mouth, 1—one, one, two, (1, 3- 1), 1—Bromo 1 ', 2— (1,3_propanezy) 1), 3— (1,5—Dioxo 1 3 _Feninole 1) 1,5-Pentanezyl) Hue mouth, 1-Bromo 1 ', 3— (1,5-Dioxo_3-Feninole 1,5,5-Pentanezinole) Hue mouth, 1-Bromo-1' ,

3-(3 _ 1,4-dioxo-1,5-pentanexyl) fuerocene.

Preferable examples of the transition metal metallocene compound used in the present invention include Feguchi and Ethilfe.

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

The alkyl group having 1 to 12 carbon atoms may be linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butynole, pentinole, isopentinole, Chisinole, Heptinole, Octinole, Nonyl, decyl or dodecyl group. Preferred are, for example, alkyl groups having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

The alkylthio group having 1 to 8 carbon atoms may be linear or branched, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, tert-butylthio, hexylthio or octylthio, especially methylthio. Halogen atoms are, for example, chlorine, bromine and iodine, with chlorine being particularly preferred. Among them, the most preferred is a compound of the formula (1), which is available from CirbaSpec! A1tyChemicals (Irgacure).

8 1 9

In addition, the photocurable composition of the present invention can be used in combination with the following photocuring accelerators as long as the purpose of the present invention is not impaired. Specific examples thereof include 4-phenoxydichloroacetophenone, 4-t-butynoledichloroacetophenone, 4-t-butynole-trichloroacetophenone, diethoxyacetophenone, and 2-hydroxy-1-methyl-1-. Phenylpropane 1-one, 1- (4-isopropylphenyl) 1-2-hydroxy-1 2-methinolepropane 1-one, 1_ (4-dodecylphenyl) 1-2-hydroxy-1 2-methylpropane 1 1 —On, 4— (2—Hydroxyxetoxy) 1-Fe 2 Λ ^ — (2-Hydroxy-1 2-Propyl Λ ^) Ketone, 1-Hydroxycyclohexynolepheninole ketone, 2-Methyl-1 1- (4 — (Methylthio) phenyl) 12-molyphorinopropane 11-one and other acetophenone-based photocuring accelerators, and benzoin-based photocuring accelerators. Examples include benzoin, benzoin methine oleate, benzoin ethino oleate, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketanol. Next, a method for preparing the photocurable composition of the present invention will be described. The photocurable composition according to the present invention is characterized in that (ii) a transition metal metaopencene compound of Group VIII of the periodic table containing (ii) an aromatic electron-based ligand in the cyanoacrylate; ) Add and mix a photo-curing accelerator having the structure represented by the general formula (1) to ensure dissolution. And is prepared by At this time, for example, if the component (B) or the component (C) is difficult to dissolve, heat the component (A) to such an extent that the component does not deteriorate or undergo heat polymerization (generally around 60 ° C). You may. In addition, when the components (B) and (C) are added to the component (A), the composition after preparation must be kept in a light-shielded state so as not to be exposed to light.

The amount of the component (B) varies depending on the selected component and the combination with the component (C). However, the amount is 1 to 50,000 ppm, preferably 5 to 30,000 ppm, based on the weight of the component (A). More preferably, 10 to :! O O O O p pm. On the other hand, the amount of the photocuring accelerator (C) also varies depending on the type and combination of the component (B) and the component (C), but the amount is 0.01 to 1 with respect to the weight of the component (A). 0% by weight, preferably 0.05 to 3.0% by weight. In addition, when each component is used as a mixture of two or more kinds, it is preferable that the total amount of each component be the above-mentioned addition amount.

Further, some of the following components may be further added as long as the curability of the present invention is not impaired. (1) anion polymerization inhibitor, (2) radical polymerization inhibitor, (3) thickener (4) special additives, such as curing accelerators, plasticizer strengtheners and heat stabilizers, (5) fragrances, Dyes, paints, etc.

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, P-toluenesulfonic acid, and the like. The amount of the anion polymerization inhibitor to be added is suitably from 0.1 to 10,000 ppm based on the weight of the component (A). Examples of the radical polymerization inhibitor include quinone, hydroquinone, t-butylcatechol, p-methoxylphenol and the like.

Further, a thickener is added to increase the viscosity of the photocurable composition of the present invention. Examples of the thickener include poly (methyl) methacrylate, methacrylate type copolymer, acrylic rubber, cellulose derivative, polyvinyl acetate, and poly (α-cyanoacrylate). In addition, the present invention provides an acrylic elastomer, atarilonitto for the purpose of toughening a cured product of the photocurable composition. A high molecular polymer such as a ril copolymer elastomer, a fluoroelastomer, and a fine silica filler can also be added.

The curing mechanism of the photocurable composition of the present invention can be cured by two kinds of curing: anion polymerization using a small amount of moisture on the surface of the adherend and photoanneal polymerization by light irradiation using a metallocene compound. It is possible.

The method of curing by light irradiation is to apply a photocurable composition to an adherend, and then use a high-pressure mercury lamp, halogen lamp, xenon lamp, sunlight, etc. to mainly use electron beams, ultraviolet rays, visible light, near red It is cured by irradiating external light. The effective wavelength of the irradiation light varies depending on the type of the meta-mouth compound and the photo-curing accelerator, but ultraviolet light and visible light are preferred.

The photocurable composition according to the present invention can be used for a variety of conventionally used α-cyanoacrylates and photocurable resins, as well as for sealing and suspending electronic components. Moisture such as attaching reel sheet and threading guide on pole, fixing wire such as coil, fixing magnetic head to pedestal, filler used for dental treatment, bonding and decoration of artificial nail, etc. It is useful for bonding, fixing, and coating of items that require both photo-curing and photo-curing.

Hereinafter, the present invention will be described 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 viscosity was evaluated at 60 rpm using a BL adapter of a N type viscometer (manufactured by Tokyo Keiki Co., Ltd.) using a BL adapter, a BL No. 2 and a BL No. 3 rotor. The measurement temperature is 25 ° C.

The sample was irradiated with light from a distance of 15 cm using a 4 kW high-pressure mercury lamp (manufactured by Shio Electric Co., Ltd.) as the UV irradiation device used for the photocurability evaluation. The integrated light amount of one light irradiation is 350 mj / cm ² . The integrated light quantity was measured with an integrated light meter UIT-150 (manufactured by Shio Electric Co., Ltd.). To evaluate the photocurability (surface curability), prepare a polyethylene container with an inner diameter of 3 Omm, and take 1 g (resin film thickness of about lmm) of the sample prepared in Examples and Comparative Examples in this container. The sample was passed through a belt conveyor set UV irradiation device, and the cured and uncured sample was confirmed. 1 mm thick and completely cured were marked as 〇, and those that were not completely cured were marked X.

For evaluation of photocurability (deep-curing property), 6 g (resin film thickness: about 9 mm) was placed in the above-mentioned polyethylene container, and irradiated with an integrated light amount of 350 mj / cm ^{2 in} the same manner as above. At this time, how much thickness was cured from the surface was measured with a film thickness meter SM-114 (manufactured by TEC LOCK COR POR ATION). 〇, 2 mm or more, less than 4 mm, △, and less than 2 mm, X.

[Examples 1 to 4 and Comparative Example:! ~ Five ]

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

In addition, all the numerical values described in the composition table of Table 1 are parts by weight. "One" in the table indicates that the sample could not be measured due to gelation or solidification. Various abbreviations mean the following. "ECA" is ethyl-12-cyanoacrylate and "MCA" is methyl-12-cyanoacrylate. "PMMA" means polymethyl methacrylate. “C p ₂ F e” means Hue sen and “(E t C p) C p Fe” means etil Hue sen. “Irgacure 819” is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Ciba Specialty Chemicals). “Irgacure 1 700” is a 2-hydroxy-2-methyl-1-phenylenone 1-one and bis (2,6-dimethoxybenzoy —2,4,4-trimethylpentinolephosphine oxyside 75: It is a mixture of 25 (manufactured by Ciba Specialty Chemica 1s Co.) "Lucirin TPO" is 2,4,6-trimethylbenzoylphenylethoxy phosphinoxide (manufactured by BASF) “Lucirin TPO-L” is 2,4,6-trimethylbenzinoresiphenyl-phosphine phosphide (manufactured by BASF), and Irgacure 819 has the following structure: It is an expression.

Furthermore, “Blank” in Table 1 was measured immediately after blending, and “After 7 days at 70 ° C” was measured after a 7-day preservation test in a 70 ° C constant temperature bath.

In Examples 1 to 3 and Comparative Examples 1 to 4, polymethyl methacrylate (PM) was added to the formulation because the effect of the present invention that storage stability was good was remarkably exhibited. MA).

From Table 1, it can be seen that the formulations shown in Examples 1 to 5 show extremely excellent photocurability, both in surface curability and deep curability, even after storage, and in particular, the deep curability is significantly improved. You can see that. In addition, the change in viscosity is extremely small even after a long period of time, and it can be seen that the storage stability is superior to that of the comparative example.

Comparing Example 1 with Example 2, it can be seen that storage stability is more excellent when using fuecopene sensation than when using ethyl fouesen as the component (B).

Comparing Example 1 and Comparative Examples 1 to 4, it can be seen that a great difference appears in the 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, regarding “Lu cirin TPO” and “Lu cirin TPO — L”, considering the structure, “Irgacure 8 19” shown in the above structural formula has excellent symmetry and is a more stable structure. On the other hand, it can be seen that “L ucirin TP 0” and “L ucirin TPO-L” lack electronic balance. Also, "I rgacure 8 1 9" and "tooth _{11 0: 1 1: 1 11} TPO " is a, since the number of substitution by methyl groups is more of "I rgacure 8 1 9" is large, the phase of the Xia cyanoacrylate It has excellent solubility and is considered to have a positive effect on storage stability. Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a Japanese patent application filed on March 22, 2002 (Japanese Patent Application No. 2002-079998), the contents of which are incorporated herein by reference. Industrial applicability>

A photocurable composition according to the present invention, that is, a transition metal metamouth compound of Group VIII of the periodic table having α-cyanoacrylate and an aromatic electron-based ligand, and The photocurable composition containing the photocuring accelerator having the structure represented by the general formula (1) can be cured not only by moisture, but also when the adherends have a large space between the adherends, when they stick out of the bonded part, or when the coating is applied. Even when it is not sandwiched between a pair of adherends, it can be quickly cured by irradiating light. Furthermore, even if this composition is stored for a long period of time, the photocurability hardly deteriorates and the storage stability is extremely excellent. Also, the above equation

Since the light absorption wavelength of the photo-curing accelerator having the structure shown in (1) is also on the longer wavelength side, photo-curing is possible not only with a wider wavelength range, i.e., not only ultraviolet light but also visible light. .

Claims

The scope of the claims

1. (Α) _α -cyanoacrylate, (Β) a transition metal meta-acene compound of Group VIII of the Periodic Table having an aromatic electron ligand, and (C) a compound represented by the following general formula (1) A photocurable composition comprising a photocuring accelerator having a structure.

(In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkylthio group having 1 to 8 carbon atoms, and each R may be the same or different.)

2. With respect to the weight of the component (Α), add the component (Β) The photocurable composition according to claim 1, wherein the composition (C) is contained in an amount of 0.01 to 10% by weight.

3. The photocurable composition according to claim 1, wherein the component (B) is a compound represented by the following general formula (2).

(Wherein 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, or a silicon-containing group. , An oxygen-containing group, a sulfur-containing group, or a phosphorus-containing group, wherein each R ¹ may be the same or different, and R ¹ may be cross-linked, and a is an integer of 0 to 5. Each [R a _C p] group (C p is η-cyclopentagel) may be the same or different.