JP3470579B2 - Photocurable composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a photocurable cyanoacrylate-based composition, and relates to lithography, potting, molding, coating, adhesive, sealant, and the like. Further, application to various resist materials and the like can be widely considered. 2. Description of the Related Art An α-cyanoacrylate adhesive is rapidly anionically polymerized and cured by a very small amount of moisture adsorbed on the surface of an adherend, and adheres the adherends extremely strongly in a short time. Therefore, it is widely used as a one-part, room-temperature curing type instant adhesive for bonding metals, plastics, rubber, wood, and the like. However, the α-cyanoacrylate adhesive hardens when the distance between the adherends is wide, when the adhesive sticks out of the bonding portion, or when the adhesive is not sandwiched between a pair of adherends such as a coating. It has the disadvantage of being extremely slow. Therefore, in order to quickly cure an α-cyanoacrylate adhesive which is filled in a large gap or protrudes from an adhesive portion, it is generally practiced to use a primer or a curing accelerator to cure the adhesive. JP-A-59-215376, JP-A-60-203684,
JP-A-61-176634), but 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
It is not preferable in working environment. [0005] Therefore, without impairing the excellent features of the one-part type instantaneous adhesive of rapid curing at room temperature, and without using a primer or a curing accelerator, even when the adhesive is filled in a protruding portion or a large gap. There is a need for an α-cyanoacrylate adhesive that can be easily cured. [0006] As a method for solving the above-mentioned problem, the applicant has imparted photocurability by adding a metallocene compound alone or adding a metallocene compound and a cleavage type photoinitiator to an α-cyanoacrylate adhesive. An α-cyanoacrylate adhesive composition has been previously proposed. According to the above-mentioned invention, the α-cyanoacrylate-based adhesive is used in seconds in the same manner as the conventional α-cyanoacrylate-based adhesive. The parts can be adhered to each other after curing, and
Because it can be cured in seconds by irradiating light, the conventional α-cyanoacrylate-based adhesive cures extremely slowly without deteriorating the excellent characteristics of the instant adhesive that is one-part, room temperature, rapid curing. It has the feature that it can be cured quickly by light irradiation even in such an environment. On the other hand, the present inventors have further studied the above invention, and found that the photocurability may be reduced when the α-cyanoacrylate adhesive composition according to the invention is stored for a long period of time. . The inventors of the present invention have conducted intensive studies to solve this problem, and as a result, have found that an α-cyanoacrylate adhesive containing a specific ferrocene compound and a photo-curing accelerator. The present inventors have found that the composition has extremely excellent photocurability even after long-term storage, leading to the present invention. That is, (A) α-cyanoacrylate (B) is substituted with a lower alkyl group represented by the following structural formula (1).
Replaced ferrocene compound 30 to 1000 ppm (Wherein, R represents a lower alkyl group having 1 to 3 carbon atoms;
Is an integer of 0 to 5, b is an integer of 1 to 5, and a and b are
When a is 0 or more, or when a is 0 and b is 2 or more, each R
May be the same or different. ) (C) at least the following a) to c) to the compound represented
Cleavable photo-radical initiator containing at least 0.05 to 0.5 ph
r ) 2,4,6-trimethylbenzoyldiphenylphosph
Finoxide ) 2,4,6-trimethylbenzoylphenylphosph
Phonic acid ethyl ester ha) bis (2,6-dimethoxybenzoyl) -2,4
4-trimethylpentylphosphine oxide The above problem was solved by an α-cyanoacrylate-based adhesive composition containing the above (A) to (C) as essential components. The photocurable composition of the present invention irradiates light even when the distance between the adherends is wide, when the composition is protruded from an adhesive portion, or when the composition is not sandwiched between a pair of adherends such as a coating. Thereby, it can be quickly cured. BEST MODE FOR CARRYING OUT THE INVENTION (A) α- used in the present invention
Examples of the cyanoacrylate include a conventionally known α-cyanoacrylate monomer represented by the following formula (4). [0013] (In the formula, R is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms of the ester residue is not particularly limited. Those having carbon are used, and ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used.) As a specific example of α-cyanoacrylate, methyl Alkyl and cycloalkyl α-cyanoacrylates such as α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, cyclohexyl α-cyanoacrylate, allyl α-cyanoacrylate, methallyl α-cyanoacrylate , Cyclohexenyl α-
Alkenyl such as cyanoacrylate and cycloalkenyl α-cyanoacrylate Propangyl α-cyanoacrylate and other alkynyl α-cyanoacrylate, phenyl α-cyanoacrylate and aryl α-cyanoacrylate such as toluyl α-cyanoacrylate, containing a hetero atom Methoxyethyl α-cyanoacrylate, ethoxyethyl α-cyanoacrylate, furfuryl α-cyanoacrylate, trimethylsilylmethyl α-cyanoacrylate containing silicon, trimethylsilylethyl α-cyanoacrylate, trimethylsilylpropyl α-cyanoacrylate, dimethylvinylsilylmethyl α -Cyanoacrylate, etc., and these α-cyanoacrylates may be used alone or in combination of several kinds. It doesn't matter. Next, as the (B) lower alkyl-substituted ferrocene compound used in the present invention, a compound represented by the following formula (1) can be used. Embedded image (Wherein, R represents a lower alkyl group having 1 to 3 carbon atoms ;
Is an integer of 0 to 5, b is an integer of 1 to 5, and when a and b are 1 or more, or when a is 0 and b is 2 or more, each R
May be the same or different. Specific examples of the lower alkyl-substituted ferrocene compound (B) include methyl ferrocene, ethyl ferrocene, propyl ferrocene, 1,1'-dimethyl ferrocene, 1,1'-diethyl ferrocene, and 1,1'-di- Propylferrocene, 1,1 ′, 2-trimethylferrocene, 1,1′2-triethylferrocene, 1,1′2
-Tripropylferrocene, 1,1 ', 3-trimethylferrocene, 1,1', 3-triethylferrocene,
1,1 ′, 3-tripropylferrocene, 1,1 ′,
2,2′-tetramethylferrocene, 1,1 ′, 2
2'-tetraethylferrocene, 1,1 ', 2,2'-
Tetrapropyl ferrocene, 1,1 ′, 2,3′-tetramethyl ferrocene, 1,1 ′, 2,3′-tetraethyl ferrocene, 1,1 ′, 2,3′-tetrapropyl ferrocene, 1,1 ′, 3,3′-tetramethylferrocene, 1,1 ′, 3,3′-tetraethylferrocene,
1,1 ′, 3,3′-tetrapropylferrocene, 1,
1 ′, 2,3-tetramethylferrocene 1,1 ′, 2
3-tetraethylferrocene, 1,1 ′, 2,3-tetrapropylferrocene, 1,1 ′, 2,4-tetramethylferrocene, 1,1 ′, 2,4-tetraethylferrocene, 1,1 ′, 2 4-tetrapropylferrocene,
1,1 ′, 2,2 ′, 3-pentamethylferrocene,
1,1 ′, 2,2 ′, 3-pentaethylferrocene,
1,1 ′, 2,2 ′, 3-pentapropylferrocene,
1,1 ′, 2,2 ′, 4-pentamethylferrocene,
1,1 ′, 2,2 ′, 4-pentaethylferrocene,
1,1 ′, 2,2 ′, 4-pentapropylferrocene,
1,1 ′, 2,3,3′-pentamethylferrocene,
1,1 ′, 2,3,3′-pentaethylferrocene,
1,1 ′, 2,3,3′-pentapropylferrocene,
1,1 ′, 2,3 ′, 4-pentamethylferrocene,
1,1 ′, 2,3 ′, 4-pentaethylferrocene,
1,1 ′, 2,3 ′, 4-pentapropylferrocene,
1,1 ′, 2,3,4-pentamethylferrocene, 1,
1 ', 2,3,4-pentaethylferrocene, 1,
1 ', 2,3,4-pentapropylferrocene, 1,
1 ', 2,3,4,5-hexamethylferrocene, 1,
1 ′, 2,3,4,5-hexaethylferrocene, 1,
1 ′, 2,3,4,5-hexapropylferrocene,
1,1 ′, 2,2 ′, 3,4-hexamethylferrocene, 1,1 ′, 2,2 ′, 3,4-hexaethylferrocene, 1,1 ′, 2,2 ′, 3,4- Hexapropyl ferrocene, 1,1 ', 2,3,3', 4-hexamethylferrocene, 1,1 ', 2,3,3', 4-hexaethylferrocene, 1,1 ', 2,3,3 ', 4-hexapropylferrocene, 1,1', 2,2 ', 3,3'-hexamethylferrocene, 1,1', 2,2 ', 3,3'
-Hexaethylferrocene, 1,1 ', 2,2', 3
3′-hexapropylferrocene, 1,1 ′, 2
2 ′, 3 ′, 4-hexamethylferrocene, 1,1 ′,
2,2 ′, 3 ′, 4-hexaethylferrocene, 1,
1 ′, 2,2 ′, 3 ′, 4-hexapropylferrocene, 1,1 ′, 2,2 ′, 4,4′-hexamethylferrocene, 1,1 ′, 2,2 ′, 4,4 ′ -Hexaethylferrocene, 1,1 ', 2,2', 4,4'-hexapropylferrocene, 1,1 ', 2,2', 3,4,5-
Heptamethylferrocene, 1,1 ', 2,2', 3,
4,5-heptaethylferrocene, 1,1 ′, 2
2 ', 3,4,5-heptapropylferrocene, 1,
1 ′, 2,3,3 ′, 4,5-heptamethylferrocene, 1,1 ′, 2,3,3 ′, 4,5-heptaethylferrocene, 1,1 ′, 2,3,3 ′, 4,5-heptapropylferrocene, 1,1 ′, 2,2 ′, 3,3 ′,
4, -heptamethylferrocene, 1,1 ′, 2,2 ′,
3,3 ′, 4, -heptaethylferrocene, 1,1 ′,
2,2 ′, 3,3 ′, 4, -heptapropylferrocene, 1,1 ′, 2,3,3 ′, 4,4′-heptamethylferrocene, 1,1 ′, 2,3,3 ′, 4,4′-heptaethylferrocene, 1,1 ′, 2,3,3 ′, 4
4'-heptapropylferrocene, 1,1 ', 2
2 ', 3,3', 4,5-octamethylferrocene,
1,1 ′, 2,2 ′, 3,3 ′, 4,5-octaethylferrocene, 1,1 ′, 2,2 ′, 3,3 ′, 4,5-
Octapropyl ferrocene, 1,1 ', 2,2', 3
4,4 ', 5-octamethylferrocene, 1,1',
2,2 ′, 3,4,4 ′, 5-octaethylferrocene, 1,1 ′, 2,2 ′, 3,4,4 ′, 5-octapropylferrocene, 1,1 ′, 2,2 ′ , 3,3 ',
4,4 ′, 5-nonamethylferrocene, 1,1 ′, 2
2 ′, 3,3 ′, 4,4 ′, 5-nonaethylferrocene, 1,1 ′, 2,2 ′, 3,3 ′, 4,4 ′, 5-nonapropylferrocene, bis (pentaethylcyclo Pentadienyl) iron, bis (pentapropylcyclopentadienyl) iron, 1,1′-dimethyl-2-ethylferrocene, 1,1′-dimethyl-3-ethylferrocene, 1,1′-dimethyl-3, Examples thereof include 3′-diethylferrocene, 1,1 ′, 2-trimethyl-3-ethylferrocene, and the like, preferably 1,1′-dimethylferrocene, ethylferrocene and the like. Next, as the photo-curing accelerator (C) used in the present invention, a cleavage type photo-radical initiator conventionally used when photo-polymerizing a radical-polymerizable compound can be used.
Particularly, a compound represented by the following formula (2) is preferable. Embedded image (Wherein, R ¹ and R ² represent a lower alkyl group, a lower alkoxyl group, or a phenyl group, a phenyl group substituted with 1 to 3 lower alkyl groups or a lower alkoxyl group, and R ¹ and R ² are the same. But they may be different.
R ³ is an unsubstituted or substituted acetyloxy group-substituted linear or branched alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms, a lower alkyl group, a lower alkoxyl group, or an unsubstituted or substituted acetyloxy group; An aryl group substituted or substituted with a halogen atom, or an atomic group represented by the following formula (3). [Image Omitted] (In the formula, R ⁴ and R ⁵ are the same as R ¹ and R ^2, and X represents a p-phenylene group.) A specific example of the photocuring accelerator is 4
-Phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-
1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1
Examples of acetophenone-based photocuring accelerators such as-(4- (methylthio) phenyl) -2-moφholinopropan-1-one and the like, and benzoin-based photocuring accelerators include:
Examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl methyl ketal. Further, as another photo-curing accelerator, α-
Asiloxime ester, methylphenylglyoxylate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,2′-azobis (2-methylbutyronitrile) and the like can be mentioned. Specific examples of the acylphosphine oxide-based photocuring accelerator represented by the above formula (2) preferably used in the present invention include methyl isobutyroyl-
Methyl phosphinate methyl isobutyroyl-phenyl phosphinate, methyl pivaloyl phosphinate, methyl 2-ethylhexanoyl-phosphinate, isopropyl 2-ethylhexanoyl-phenyl phosphonate, methyl P-tolyl-phenyl phosphinate, methyl O- Tolyl-phenylphosphinate, methyl 2,4
-Dimethylbenzoyl-phenylphosphinate, methylacyloyl-phenylphosphonate, isobutyroyl-diphenylphosphine oxide, 2-methylhexanoyl-diphenylphosphine oxide, O-toluyl-
Examples include diphenylphosphine oxide, P-tert-butylbenzoyl-diphenylphosphine oxide, 3-polydylcarbonyl-diphenylphosphine oxide, acryloyl-diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, and aziboyl-bis (diphenylphosphine oxide). In addition, these various photocuring accelerators may be used alone or in combination of two or more, and there is no particular restriction. When the acylphosphine oxide-based photocuring accelerator represented by the above formula (2) is used, the change in viscosity of the composition over a long period of time is smaller than that of other photocuring accelerators. Shows storage stability. Next, a method for preparing the photocurable composition of the present invention will be described. The photocurable composition of the present invention is prepared by adding (B) a lower alkyl-substituted ferrocene compound and (C) a photocuring accelerator to (A) α-cyanoacrylate and dissolving them reliably. . At this time, for example, when the component (B) or the component (C) is difficult to dissolve, the component (A) is heated (generally at about 60 ° C.) so as not to deteriorate or cause heat polymerization. Is also good. Further, the component (B) and the component (C) are replaced with the component (A)
When added to the components and after the composition is adjusted, the composition must be kept in a light-shielded state so as not to be exposed to light. The amount of the lower alkyl-substituted ferrocene compound (B) varies depending on the type and combination of the components (B) and (C).
It is 50,000 ppm, preferably 10-3000 ppm, more preferably 30-1000 ppm. On the other hand, the addition amount of the photocuring accelerator (C) also varies depending on the type and combination of the component (B) and the component (C), but is preferably 0.01 to 5% by weight, and more preferably 0.01 to 5% by weight based on the component (A). It is 0.05 to 0.5% by weight. In addition, when each component is used as a mixture of two or more, the total amount of each component is 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) Anionic polymerization inhibitor (2) Radical polymerization inhibitor (3) Thickener (4) Special additives such as curing accelerator, plasticizer strengthening agent and heat stabilizer (5) Fragrance, dye, pigment and the like. For example, an anionic polymerization inhibitor is added to increase the stability of the composition during storage. Examples of known inhibitors include sulfur dioxide, sulfur trioxide, nitric oxide, hydrogen fluoride, p-toluenesulfonic acid, and the like. The addition amount of the anionic polymerization inhibitor is suitably from 0.1 to 10000 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). Further, in the present invention, a high molecular polymer such as an acrylic elastomer, an acrylonitrile copolymer elastomer, a fluoroelastomer, and a fine silica filler can be added for toughening a cured product of the photocurable composition. Next, when the photocurable composition of the present invention is cured by light irradiation, ultraviolet rays, visible rays, and near-infrared rays are irradiated using a high-pressure mercury lamp, a halogen lamp, a xenon lamp, sunlight, or the like. It can be cured by irradiation. The photocurable composition according to the present invention can be used for various applications as conventionally used α-cyanoacrylates and photocurable resins, as well as for sealing electronic parts, Installation of reel sheet and threading guide on hanging rod, fixation of wire such as coil,
It is useful for fixing magnetic heads to pedestals, fillers used for treating teeth, bonding and decorating artificial nails, especially for bonding, fixing, and coating of articles that require a combination of moisture curing and light curing. . The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Prior to the examples, measuring instruments and the like used for evaluating the photocurable composition of the present invention will be described. For evaluation of photocurability, the inner diameter was 30 mm.
Was prepared, and 1 g of the sample prepared in Examples and Comparative Examples was taken in the cap, and the cap was passed through a belt-conveyor-type ultraviolet irradiation device and irradiated with light. The amount of light irradiation until each sample was cured was calculated based on the number of times the sample passed through the ultraviolet irradiation device, and was represented by the integrated light amount. The ultraviolet irradiation device (Oak Seisakusho) used here has a 4 kW high-pressure mercury lamp and
The accumulated light amount by the light irradiation is about 1000 mJ / cm ²
It is. The integrated light amount is a value measured by an integrated light meter UV-350 (manufactured by Oak Manufacturing Co., Ltd.). Examples 1 to 4 and Comparative Examples 1 to 4 Next, the photocurable compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared at the compounding ratios shown in Table 1. Next, each of these samples was irradiated with light using the above-mentioned ultraviolet irradiation device, and its curability was measured. Table 1 shows the results. [Table 1] The numerical values shown in Table 1 are all parts by weight, and the α-cyanoacrylate used in the Examples and Comparative Examples is the same as Three Bond 1741 (ethyl α-cyanoacrylate adhesive, hereinafter TB1741). The ferrocene compounds and other abbreviations shown in Table 1 mean the following. “Cp” indicates “η-cyclopentadienyl”. “Fe” indicates “iron” that is the central metal of the ferrocene compound.
As a substituent of ferrocene, “Me” is “methyl group” “Et” is “ethyl group” “Pr” is “propyl group” “nPe” is “normal pentyl group” “nHx” is “norma” "Lhexyl group""tAm" refers to "tertiary amyl group". As for the photo-curing accelerator, “TMDPO” means “2,4,6-trimethylbenzoyldiphenylphosphine oxide”
Is shown. “TMPAE” indicates “2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester”. “Irg1700” means “Irgacure 1700 (manufactured by Ciba Geigy)”, and 2-hydroxy-2-methyl-1-phenyl-1-one and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl It is a 75:25 mixture of pentylphosphine oxide. “Irg1800” is the name of “Irgacure 1
800 (manufactured by Ciba Geigy), and 1-hydroxy-cyclohexyl-phenyl-ketone and bis (2,6-
Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide in a 75:25 mixture. “Irg184” indicates “Irgacure 184 (manufactured by Ciba Geigy)” and is 1-hydroxycyclohexyl phenyl ketone. Further, in the evaluation items of photocurability shown in Table 1, "blank" indicates the photocurability immediately after blending of each composition, and "70 ° C. × 1 W" indicates that each composition It shows the photocurability of the product after a one-week storage stability test in a 70 ° C constant temperature bath. As can be seen from Table 1, the α-cyanoacrylate composition provided with the photocurability by using the lower alkyl-substituted ferrocene compound has a higher photo-curability than the higher alkyl-substituted ferrocene compound even after the preservability test. It can be seen that the curability does not decrease. Examples 5 to 10 and Comparative Examples 5 to 10 Examples 5 to 10 and Comparative Examples 5 to 10 were adjusted at the mixing ratios shown in Table 2. Next, each of these samples was evaluated for photocurability and viscosity change in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 4. Table 2 shows the results. In addition, the viscosity item in the table was measured and compared with the viscosity of each composition immediately after compounding after conducting a one-week storage stability promotion test in a 70 ° C constant temperature bath. [Table 2] As a result, the photocurability of the α-cyanoacrylate composition imparted with photocurability using the lower alkyl-substituted ferrocene compound does not decrease even after the storage test regardless of the type of photocuring accelerator. The composition according to the present invention, that is, the composition provided with photocurability comprising α-cyanoacrylate, a lower alkyl-substituted ferrocene compound and a photocuring accelerator, has a large distance between adherends. Or, even if it protrudes from the adhesive part or is not sandwiched between a pair of adherends like a coating, the conventional effect that it can be quickly cured by irradiating light as it is,
Even if this composition is stored for a long period of time, photocurability hardly deteriorates and storage stability is extremely excellent. In particular, when the acylphosphine oxide-based photocuring accelerator represented by the above formula (2) is used as the photocuring accelerator, the increase in viscosity after long-term storage can be suppressed, and the stability is extremely high. A good composition can be obtained. Further, since the light absorption wavelength of the lower alkyl-substituted ferrocene compound is on the long wavelength side of 500 nm or more,
Photocuring is possible even with light in a wider wavelength range, that is, light in the ultraviolet to visible light range. Further, the composition is effective in that the composition is hardly colored since the addition amount of the lower alkyl-substituted ferrocene is small, so that the composition has no coloring property.

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Claims (1)

(57) [Claim 1] (A) α-cyanoacrylate (B) substituted with a lower alkyl group represented by the following structural formula (1)
Replaced ferrocene compound 30 to 1000 ppm (Wherein, R represents a lower alkyl group having 1 to 3 carbon atoms;
Is an integer of 0 to 5, b is an integer of 1 to 5, and a and b are
When a is 0 or more, or when a is 0 and b is 2 or more, each R
May be the same or different. ) (C) at least the following a) to c) to the compound represented
0.01 to 5 phr i) 2,4,6-trimethylbenzoyldiphenylphospho
Finoxide ) 2,4,6-trimethylbenzoylphenylphosph
Phonic acid ethyl ester ha) bis (2,6-dimethoxybenzoyl) -2,4
4-trimethylpentylphosphine oxide A photocurable composition comprising the above (A) to (C) as essential components.