JP2000273402A - Alpha-cyanoacrylate adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an α-cyanoacrylate adhesive composition that has excellent resistance to heat, the flexibility for relieving external stress and excellent feeling and is useful as a rapid bonding adhesive by admixing αcyanoacrylate, a plasticizer, and the like, thereto. SOLUTION: The objective adhesive composition comprises (A) αcyanoacrylate, (B) a plasticizer, (C) at least one selected from metallocene compounds of transition metals of the group VIII in the periodic table each bearing an aromatic electronic ligand or Pt(acac)2. The amount of the component (B) is 10-70 wt.% and that of the component (C) is 1-100,000 ppm based on the component A. In a preferred embodiment, the component C has an aromatic electronic ligand selected from π-allene, indenyl or ηcyclopentadienyl and is one or more compounds represented by the formula (M is a transition metal of the group VIII in the periodic table; R is a halogen, a 1-20C hydrocarbon, or the like; (a) is 0-5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the modification of an .alpha.-cyanoacrylate adhesive known as an instant adhesive.
In particular, the present invention relates to an α-cyanoacrylate-based adhesive composition having both heat resistance and flexibility, and which is cured by light irradiation.

[0002]

2. Description of the Related Art An .alpha.-cyanoacrylate adhesive is rapidly anionically polymerized and cured by a very small amount of moisture adsorbed on the surface of an adherend, and adheres adherends extremely strongly in a short time. As a one-part, room-temperature curing type instant adhesive, it is widely used for bonding metals, plastics, rubber, wood, and the like.

[0003] A well-known problem of α-cyanoacrylate adhesives is that cured products are susceptible to thermal degradation and have poor heat resistance. Therefore, there is a case where a sudden decrease in adhesive strength occurs only by being exposed to a temperature of about 100 ° C.

In addition, when an external stress or an internal stress is applied to the bonding member after bonding, the bonding strength of the α-cyanoacrylate-based adhesive decreases. The reason for this is that a cured product of an α-cyanoacrylate adhesive is usually hard and low in flexibility, and thus has little effect of relaxing external stress and internal stress,
Therefore, it is considered that the stress exerts a great influence on the bonding layer and the bonding interface, and as a result, the bonding layer is broken or peels off from the bonding surface, and the bonding strength is reduced.

For the purpose of imparting plasticity to the α-cyanoacrylate adhesive, phthalic acid esters, sebacic acid esters, saturated copolymerized polyesters (Japanese Patent Application Laid-Open No.
284279), an alkyl (meth) acrylate having 1 to 4 carbon atoms (Japanese Patent Laid-Open No. 58-185666), or an alkoxyalkyl (meth) acrylate having 1 to C carbon atoms, a phthalate compound having a melting point of 0 ° C. or more. Or polycarbonate diol or the like (JP-A-2-34)
678) is known.

However, although these prior arts are useful in terms of flexibility, they are only dispersed in a cured α-cyanoacrylate and act as a negative effect on heat resistance. I can't let that happen.

On the other hand, for the purpose of imparting photocurability to α-cyanoacrylate, JP-A-9-249708 discloses the addition of a metallocene compound or a metallocene compound and a cleavage type photoinitiator. 5652
No. 280 discloses that Pt (acac) ₂ or a metallocene compound is blended, but there is no disclosure about heat resistance or flexibility.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, that is, to provide excellent heat resistance and to relieve external stress and internal stress. An object of the present invention is to provide an α-cyanoacrylate-based instant adhesive having flexibility and excellent feeling.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by an α-cyanoacrylate-based adhesive composition having the following composition.

That is, the following (A) to (C) or (A)
The above-mentioned problem was solved by an α-cyanoacrylate adhesive composition containing (D) to (D). (A) α-cyanoacrylate (B) plasticizer (C) Group VIII transition metal metallocene compound having an aromatic electron ligand or Pt (acac) ₂
At least one compound selected from the group consisting of: (D) a radical generator

The α-cyanoacrylate (A) which can be used in the present invention is not particularly limited, but those represented by the following formula (2) are useful. H ₂ C ＝ C (CN) —COOR (2) (wherein, 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 residue is not particularly limited, but one having 1 to 8 carbon atoms is generally used, and an ester residue consisting of a substituted hydrocarbon group such as an alkoxyalkyl group or a trialkylsilylalkyl group can also be used. .)

Specific examples of α-cyanoacrylate include alkyl and cycloalkyl α-cyanoacrylates such as methyl α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, and cyclohexyl α-cyanoacrylate. Cyanoacrylate, allyl α-cyanoacrylate, methallyl α-cyanoacrylate, cyclohexenyl α-
Alkenyl and cycloalkenyl α-cyanoacrylates such as cyanoacrylate, alkynyl α-cyanoacrylates such as propanegyl α-cyanoacrylate,
Aryl α-cyanoacrylates such as phenyl α-cyanoacrylate and toluyl α-cyanoacrylate, methoxyethyl α-cyanoacrylate containing a hetero atom, ethoxyethyl α-cyanoacrylate, furfuryl α-cyanoacrylate, and trimethylsilylmethyl containing silicon α-cyanoacrylate, trimethylsilylethyl α-cyanoacrylate, trimethylsilylpropyl α-cyanoacrylate, dimethylvinylsilylmethyl α-cyanoacrylate and the like,
These α-cyanoacrylates may be one kind,
Further, a mixture of several types may be used.

As the plasticizer (B) which can be used in the present invention, conventionally known plasticizers can be used. By calculating the solubility factor (SP value) by the Fedors method, the solubility factor with the α-cyanoacrylate polymer (SP value) is calculated. ) Is ±
It is desirable to be within 1.1. Specific examples of the plasticizer include the following various plasticizers, but are not limited thereto. (1) Aryl and diaryl ethers, such as diphenyl ether and its halogen-substituted derivatives, each substituted aryl ring contains up to about 20 carbon atoms. (2) Aryl, alkyl and alkenyl esters of fumaric acid based acids such as dialkyl fumarate and diallyl maleate. (3) Aryl, alkyl and alkenyl esters of oxalic acids such as dialkyl oxalate, dialkyl malonate, dialkyl succinate. (4) Aryl, alkyl and alkenyl esters of phthalic acid, whether ortho, meta or para, such as dimethyl phthalate, dibutyl phthalate and diisobutyl phthalate. (5) Aryl, alkyl and alkenyl esters of various polyunsaturated dicarboxylic acids such as alkyl itaconates. (6) Benzoic acid esters and their substituted benzoic acid esters such as halogen, alkyl, alkoxy and aryl. (7) Urethane (meth) acrylate having three or more (meth) acryloyl groups, such as trimethylolpropane tri (meth) acrylate (TMT) and pentaerythritol tri (meth) acrylate, epoxy (meth) acrylate, and pentane Erythritol-modified poly (meth) acrylate (8) Aryl phosphates and alkyl esters such as triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate Among the above plasticizers, group (3), (4), (6), (7)
And the plasticizer (8) are preferred, and the phthalate of (4) is particularly preferred.

The amount of the plasticizer (B) is suitably from 10% by weight to 70% by weight, more preferably from 40% by weight to 60% by weight, based on the weight of the α-cyanoacrylate (A). % By weight. The plasticizer that can be used in the present invention can be selected from one or a combination of a plurality of synthetic resins generally used as a plasticizer.

The one or more compounds (C) selected from the group VIII transition metal metallocene compounds or Pt (acac) ₂ having an aromatic electron ligand which can be used in the present invention include, in particular, Periodic Table VI having an aromatic electron-based ligand described in JP-A-9-249708
Group II transition metal metallocene compounds and US Pat.
Organic transition metal compounds such as Pt (acac) ₂ described in No. 280 can be used.

Specific preferred examples of the transition metal metallocene compounds of Group VIII of the periodic table containing an aromatic electron-based ligand include those having the following structural formula (1).

[0017]

Embedded image

Wherein M is a transition metal of Group VIII of the periodic table, R is a halogen atom, 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, and a represents an integer of 0 to 5.)

In the above formula (1), each [Ra-Cp] group (Cp represents η-cyclopentadienyl) may be the same or different.

The periodic table containing an aromatic electron ligand
As the transition metal of the Group VIII transition metal metallocene compound, iron, osmium, ruthenium, cobalt and nickel are suitable, and iron, osmium and ruthenium are particularly preferred.

Further, specific examples of the ferrocene compound in which at least one substituent is substituted with an aromatic electron-based ligand are shown below. As a compound in which the substituent is a halogen atom, 4-acetyl-1′-bromo-1,2-diethylferrocene, 1′-
Bromo-1,2,3-triethylferrocene, 1-acetyl-1′-bromo-2,3-diethylferrocene, 1
-Iodo-1 '-(4-methoxyphenyl) ferrocene, 1-bromo-1'-(ethoxycarbonyl) ferrocene, and the like. As a compound having a hydrocarbon group having 1 to 20 carbon atoms as a substituent, 1,1′-dimethylferrocene, 1,1′-di-n
-Butylferrocene, bis (pentamethylcyclopentadienyl) iron, 1,1′-diethylferrocene,
1,1′-di-propylferrocene, 1,1′-di-n
-Pentylferrocene, 1,1′-di-n-hexylferrocene, 1,1 ′, 2-trimethylferrocene, 1,
1 ', 2-triethylferrocene, 1,1', 2-tri-propylferrocene, 1,1 ', 2-tri-n-butylferrocene, 1,1', 2-tri-n-pentylferrocene, 1, 1 ′, 2-tri-n-hexylferrocene, 1,1 ′, 3-trimethylferrocene, 1,1 ′,
3-triethylferrocene, 1,1 ′, 3-tri-propylferrocene, 1,1 ′, 3-tri-n-butylferrocene, 1,1 ′, 3-tri-n-pentylferrocene, 1,1 ′, 3-tri-n-hexylferrocene,
1,1 ′, 2,3′-tetramethylferrocene, 1,
1 ′, 2,3′-tetraethylferrocene, 1,1 ′,
2,3′-tetra-propylferrocene, 1,1 ′,
2,3′-tetra-n-butylferrocene, and the like. Examples of the compound in which the substituent is a halogenated hydrocarbon group having 1 to 20 carbon atoms include 1-methyl-1 ′-(chloromethyl) ferrocene, 1-chloro-1 ′-(chloromethyl) ferrocene, and 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, and the like. Examples of the compound in which the substituent is a silicon-containing group having 1 to 20 carbon atoms include 1-methyl-1 ′-(trimethylsilylmethyl) ferrocene, 1-methyl-1 ′-(trimethylsilylethyl) ferrocene, and 1-methyl-1 ′-( Trimethylsilylpropyl) ferrocene, 1,1′-di- (trimethylsilylmethyl) ferrocene, 1,1′-di- (trimethylsilylethyl) ferrocene, 1,1′-di- (dimethylsilylmethyl) ferrocene, 1-acetyl-1 '-
(Trimethylsilylmethyl) ferrocene, 1,1′-diacetyl-2- (trimethylsilylmethyl) ferrocene, 1,1′-diacetyl-3- (trimethylsilylmethyl) ferrocene, and the like. Examples of the compound having an oxygen-containing group having 1 to 20 carbon atoms as a substituent include 1,1′-di (acetylcyclopentadienyl) iron, 1,1′-dibenzoylferrocene, and 1,1 ′.
-Bis (1-oxonyl) ferrocene, 1,1′-bis (1-oxooctadecyl) ferrocene, 1,1′-bis (1-oxohexyl) ferrocene, 1-acetyl-
1'-ethynyl ferrocene, ferrocenyl vinyl ketone, ferrocenyl methyl methacrylate, ferrocenyl vinyl ether, and the like. As the compound having a sulfur-containing group having 1 to 20 carbon atoms, 1,1′-bis (4-mercapto-1-oxobutyl) ferrocene and 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-acetyl-1 ′-(methoxysulfonyl) ferrocene, 1-acetyl-1′-sulfo Ferrocene,
And the like. As compounds having a phosphorus-containing group having 1 to 20 carbon atoms, 1,1′-bis (diphenylphosphino) ferrocene, 1-acetyl-1 ′-((diphenylphosphino) acetyl) ferrocene, 1,1 ′ -Bis ((diphenylphosphino) acetyl) ferrocene, 1- (diphenylphosphino) -1′-formylferrocene, 1-
Acetyl-1 '-(diphenylphosphino) ferrocene, 1-acetyl-1'-(diphenylphosphinyl)
Ferrocene, and the like. As a compound in which substituents are cross-linked, 1,1′-
Diacetyl-2,3 '-(1,3-propanediyl) ferrocene, 1,2-diacetyl-1,4'-(1,4-
(Butanesyl) ferrocene, 1,1'-bis (methoxycarbonyl) -2,2 '-(oxybis (methylene))
Ferrocene, 1,1'-bis (ethoxycarbonyl)-
2,2 ′-(oxybis (methylene)) ferrocene, and the like.

The transition metal metallocene compound of Group VIII of the periodic table having an aromatic electron ligand, which is an essential component of the composition according to the present invention, or one or more compounds selected from Pt (acac) ₂ (C ) Is 1 to 100,000 based on the weight of α-cyanoacrylate (A).
Used in ppm. Preferably from about 20 to about 50,000
pm, more preferably about 100 to about 10,000p
pm. In addition, these components (C) may be added as needed.
Use a mixture of species or several species.

The preparation of the α-cyanoacrylate-based adhesive composition of the present invention is carried out by preparing the α-cyanoacrylate (A) having a plasticizer (B) and an aromatic electron-based ligand in the periodic table VIII. A group transition metal metallocene compound or Pt (acac) ₂ (C) is mixed and stirred to ensure that the components (B) and (C) are dissolved and compatible with the component (A). You. Also,
When heating and stirring are required to dissolve the component (B),
The component (A) is heated at a temperature (generally about 60 ° C.) at which the component does not deteriorate or undergo thermal polymerization, and is heated and stirred. The same applies to the component (C). However, since the components are generally dissolved and compatible at room temperature, it is not necessary to perform heating and stirring.

Further, the α-cyanoacrylate composition provided with flexibility and heat resistance comprising (A) to (C) of the present invention has a property of being cured by light such as ultraviolet light or visible light. Therefore, when or after the addition of the component (C) to the component (A), the α-cyanoacrylate adhesive composition is polymerized by visible light or ultraviolet light such as sunlight or illumination.
It is preferable to keep the light-shielded state because it may be cured.

According to another aspect of the present invention, a transition metal metallocene compound (C) of Group VIII of the periodic table having a plasticizer (B) and an aromatic electron-based ligand is added to the α-cyanoacrylate (A). ), A radical generator (D) is further added. This corresponds to (A) to
It is added in order to further improve the photocurability of the α-cyanoacrylate composition provided with flexibility and heat resistance made of (C). Specific examples of the radical generator (D) include acetophenone-based radical generators such as 4
-Phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, benzoin-based radical generators such as benzoin, benzoin methyl ether, benzoin ethyl ether, and acylphosphine oxide-based radical generators Examples thereof include acylphosphine oxide, methylisobutyroyl-methylphosphinate, methylisobutyroyl-phenylphosphinate, and other radical generators such as α-acyloxime ester, methylphenylglyoxylate, 3,3 ′, 4 , 4'-
Examples include, but are not limited to, tetra (t-butylperoxycarbonyl) benzophenone.

These radical generators (D) can be used alone or as a mixture of two or more kinds. However, acyl phosphine oxide radicals can be used because of their storage stability and little change with time in photocurability. It is preferable to use it as a generator. The amount of the radical generator (D) varies depending on the types and amounts of the components (A) to (C), but is generally 100 to 20,000 ppm relative to the weight of the α-cyanoacrylate (A). More preferably, it is 500 to 100000 ppm. Further, by adding the component (D), the amount of the component (C) can be reduced.

As described above, the α-cyanoacrylate composition containing the components (A) to (C) can impart flexibility by adding the plasticizer (B), and Heat resistance can be imparted by adding components. The α-cyanoacrylate-based composition containing the components (A) to (C) can be cured by ultraviolet light or visible light in addition to the inherent moisture curability, but can be further cured by adding the component (D). Curing characteristics by light energy irradiation can be improved while maintaining flexibility and heat resistance.

Further, some of the following components may be further added as long as the effects of the present invention are not impaired. (1) Anionic polymerization inhibitor (2) Radical polymerization inhibitor (3) Photocuring accelerator (4) Thickener (5) Specific additives such as curing accelerator, toughener and heat stabilizer (6) Fragrance, Dyes, pigments, etc.

[0029] 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, p-toluenesulfonic acid, and the like. The amount of the anionic polymerization inhibitor added is 0.1 to 10,000 pp with respect to the weight of the α-cyanoacrylate (A) component.
m.

Examples of the radical polymerization inhibitor include quinone, hydroquinone, t-butylcatechol, p-methoxyphenol and the like.

[0031] 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 polymer additives are also added for toughening. Examples thereof include an acrylic elastomer, an acryloniloryl copolymer elastomer, a fluoroelastomer, and a fine silica filler. These substances also function as thickeners. Also,
In the present invention, other additives known to those skilled in the art can be used.

The composition according to the present invention can be used for a variety of conventionally used α-cyanoacrylates, for photocurable resins, for example, for sealing electronic parts and for fishing rods. Attachment of reel sheet, threading guide, etc., fixation of wire such as coil,
It can be usefully used for sealing and protecting coatings of flexible materials such as lead wires and catheters, adhesives for dental treatment, fillers, and the like.

[0034]

Examples 1 to 8 and Comparative Examples 1 to 3 The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. As shown in Table 1 below, α-cyanoacrylate-based adhesive compositions of the present invention were prepared. Table 1 shows the results of testing each composition for each of the following items. The above adjustment was performed in a dark room and stored in a light-shielded container.

[0035]

[Table 1]

The respective test methods at this time are as follows. . The set time (sec) refers to cutting a 6φNBR rubber cord at a right angle with a cutter or the like to create a fracture surface. An adhesive was applied to and adhered to the fractured surface, and after leaving for a predetermined period of time, the time at which the fracture did not occur even when tensile strength was applied was taken as the set time. . The viscosity (mPa · s) was measured using a vibrating viscometer. . The photo-curing test (mJ / cm ² ) was 30 mm in inner diameter.
Was prepared, and 1 g of each of the compositions prepared in Examples and Comparative Examples was taken in the cap, and the cap was passed through a belt conveyor type ultraviolet irradiation apparatus and irradiated with light. The amount of light irradiation until each composition was cured was calculated based on the number of times the sample passed through the ultraviolet irradiation device, and was shown as an integrated light amount. The ultraviolet irradiation apparatus (manufactured by Oak Manufacturing Co., Ltd.) used here had a 4 kW high-pressure mercury lamp, and the integrated light amount per light irradiation was about 1000 mJ / c.
a m ^2. In addition, the integrated light amount is an integrated light meter UV-35.
0 (manufactured by Oak Manufacturing Co., Ltd.). . Cured angles (degrees) of the cured products were compared by performing the above test immediately after preparing each composition (initial stage) and after storing in a thermostat at 70 ° C. for 7 days. (The inside of the thermostat is shaded)

From these results, it can be seen that, compared to Comparative Examples 2 and 3, even if the component (B) of the present invention was added, the one-part α-cyanoacrylate adhesive composition had preservability. I understand. In particular, a system to which a ruthenocene-based compound is added has sufficient storage stability even at 70 ° C. for 7 days. In addition, as compared with Comparative Example 1, it can be seen that the shear adhesive strength when heated is improved. Further, comparing Examples 2 and 3, the addition amount of the component (B) can be reduced by adding the radical generator (D).

The TB1741 in Table 1 represents an α-cyanoacrylate adhesive manufactured by Three Bond Co., which is a mixture of ethyl α-cyanoacrylate as a main component and a very small amount of a stabilizer or a polymerization inhibitor. . EPEG is ethylphthalylethyl glycolate, Cp ₂ Ru is ruthenocene, (EtCp) CpFe is ethylferrocene, TMPPAD is 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester, Irg1700 “Irgacure 1700” (manufactured by Ciba Specialty Chemicals) and “APO” represent acylphosphine oxide, respectively.

[0039]

Examples 9 to 16 and Comparative Examples 4 and 5 As shown in Table 2 below, α-cyanoacrylate adhesive compositions of the present invention were prepared. Table 2 shows the results of testing the respective compositions.

[0040]

[Table 2]

From these results, it can be seen from the comparison between Example 12 and Comparative Example 4 and Example 13 and Comparative Example 5 that the α-cyanoacrylate adhesive composition of the present invention has improved shear adhesive strength when heated. I understand. (AcCp) in the table
₂ Fe is diacetylferrocene, Pt (aca
c) ₂ represents platinum acetylacetonate, respectively.

[0042]

Examples 17 to 30 and Comparative Examples 6 to 14
The composition of the present invention was prepared by changing the transition metal metallocene compound (C) of the group VIII of the periodic table having a cyanoacrylate (A) and an aromatic electron-based ligand (C) and changing the type of the plasticizer (B). It was adjusted. Table 3 shows the results. Further, a system in which the component (C) was removed from the composition of the present invention shown in Table 3 was shown in Table 4 as a comparative example.

[0043]

[Table 3]

[0044]

[Table 4]

From the results of Tables 3 and 4, it can be seen from the Periodic Table VIII that the α-cyanoacrylate composition containing the α-cyanoacrylate (A) and the plasticizer (B) has an aromatic electron ligand. It can be seen that the heat resistance was improved by adding the group IV transition metal metallocene compound (C).

[0046]

Examples 31 to 33 and Comparative Examples 15 to 17
Ethoxyethyl α-cyanoacrylate (including ThreeBond 1721, a very slight stabilizer and a polymerization inhibitor) was used as α-cyanoacrylate, and the compositions of the present invention and comparative examples were prepared with the formulations shown in Table 5. Each of these compositions was subjected to the same test as described above, and the results are shown in Table 5.

[0047]

[Table 5]

From these results, it was found that the heat resistance was improved even when the kind of α-cyanoacrylate was changed.

[0049]

The α-cyanoacrylate-based adhesive composition of the present invention has a periodic table having an aromatic electron-based ligand.
Group VIII transition metal metallocene compound or Pt (aca
c) By adding one or more compounds (C) selected from ₂ , heat resistance can be improved and photocurability can be imparted. Further, flexibility can be imparted to the cured product by adding the plasticizer (B). Furthermore, the photocurability can be improved by using the radical generator (D) in combination.

Further, by selecting and using a type of the plasticizer (B) having a difference in solubility factor (SP value) from the α-cyanoacrylate polymer within ± 1.1, separation of the cured product at the time of photocuring can be improved. Can be suppressed. In particular, by using a ruthenocene compound as the transition metal metallocene compound (C) of Group VIII of the periodic table having an aromatic electron ligand, each of the above properties can be imparted in a well-balanced manner.

Continued on the front page F term (reference) 4J040 FA121 FA142 FA262 FA292 GA01 GA07 GA08 GA10 GA29 HB16 HB19 HB32 HB33 HB34 HD23 HD43 JA01 JB04 JB08 KA13 KA31 LA06 LA08 MA02 MA08 MA10 MA12 NA02 NA03 NA05 NA19 NA20

Claims (16)

[Claims] 1. An α-cyanoacrylate adhesive composition containing the following (A) to (C): (A) α-cyanoacrylate (B) plasticizer (C) Periodic law having an aromatic electron ligand Table VIII transition metal metallocene compounds or Pt (acac) ₂
At least one compound selected from 2. A transition metal metallocene compound of the group VIII of the periodic table having an aromatic electronic ligand, wherein the plasticizer (B) is 10 to 70% by weight based on the weight of the α-cyanoacrylate (A). The α-cyanoacrylate adhesive composition according to claim 1, wherein the α-cyanoacrylate adhesive composition contains 1 to 100,000 ppm of one or more compounds (C) selected from Pt (acac) ₂ . 3. The transition metal metallocene compound of Group VIII of the Periodic Table having the aromatic electron ligand, wherein the aromatic metal coordination is selected from π-arene, indenyl and η-cyclopentadienyl. 2. The α according to claim 1, wherein
-Cyanoacrylate-based adhesive composition 4. The transition metal metallocene compound of Group VIII of the periodic table having the aromatic electron-based ligand is represented by the following formula (1):
The compound according to claim 1, which is at least one compound represented by the formula:
-Cyanoacrylate-based adhesive composition (Wherein, M is a transition metal of Group VIII of the periodic table, R is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, and an oxygen-containing group. A group, a sulfur-containing group or a phosphorus-containing group, each R may be the same or different, and R may be cross-linked, and a represents an integer of 0 to 5. Each [Ra-Cp] (Cp represents η-cyclopentadienyl), which may be the same or different.) 5. The transition metal metallocene compound of Group VIII of the periodic table having an aromatic electron ligand is selected from iron, osmium, ruthenium, cobalt and nickel having an aromatic electron ligand. The α-cyanoacrylate adhesive composition according to claim 1, which is one or more compounds. 6. The transition metal metallocene compound of Group VIII of the Periodic Table having an aromatic electron ligand, wherein at least one selected from iron, osmium and ruthenium having an aromatic electron ligand. The α-cyanoacrylate adhesive composition according to claim 1, which is a compound. 7. The α-cyanoacrylate adhesive composition according to claim 1, wherein a difference in solubility factor (SP value) between the plasticizer and the α-cyanoacrylate polymer is within ± 1.1. 8. The α-cyanoacrylate adhesive composition according to claim 1, wherein the plasticizer is a phthalate compound. 9. An α-cyanoacrylate adhesive composition comprising the following (A) to (D): (A) α-cyanoacrylate (B) plasticizer (C) Periodic law having an aromatic electron-based ligand Table VIII transition metal metallocene compounds or Pt (acac) ₂
At least one compound selected from the group consisting of: (D) a radical generator 10. A transition metal metallocene compound of the group VIII of the periodic table having 10 to 70% by weight of the plasticizer (B) based on the weight of the α-cyanoacrylate (A) and having an aromatic electron ligand. Or 1 selected from Pt (acac) ₂
10. The composition of claim 9, further comprising 1 to 100,000 ppm of the compound (C) and 1 to 10,000 ppm of the radical generator (D).
Α-cyanoacrylate-based adhesive composition according to 11. The transition metal metallocene compound of Group VIII of the periodic table having the aromatic electron ligand, wherein the aromatic electron coordinate is selected from π-arene, indenyl and η-cyclopentadienyl. 10. The α according to claim 9, wherein
-Cyanoacrylate-based adhesive composition 12. The method according to claim 9, wherein the transition metal metallocene compound of Group VIII of the periodic table having the aromatic electron-based ligand is at least one compound represented by the following formula (1). α-Cyanoacrylate-based adhesive composition (Wherein, M is a transition metal of Group VIII of the periodic table, R is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, and an oxygen-containing group. A group, a sulfur-containing group or a phosphorus-containing group, each R may be the same or different, and R may be cross-linked, and a represents an integer of 0 to 5. Each [Ra-Cp] (Cp represents η-cyclopentadienyl), which may be the same or different.) 13. The transition metal metallocene compound of Group VIII of the periodic table having an aromatic electron ligand is selected from iron, osmium, ruthenium, cobalt and nickel having an aromatic electron ligand. The α-cyanoacrylate adhesive composition according to claim 9, which is one or more compounds. 14. The transition metal metallocene compound belonging to Group VIII of the periodic table having an aromatic electron-based ligand, wherein at least one selected from iron, osmium and ruthenium having an aromatic electron-based ligand is used. The α- according to claim 9, which is a compound.
Cyanoacrylate adhesive composition 15. The α-cyanoacrylate adhesive composition according to claim 9, wherein the difference in solubility factor (SP value) between the plasticizer and the α-cyanoacrylate polymer is within ± 1.1. 16. The α-cyanoacrylate adhesive composition according to claim 9, wherein the plasticizer is a phthalate compound.