WO2008016057A1 - Curable resin composition - Google Patents

Abstract

Disclosed is a curable resin composition which can be rapidly cured by irradiation of an active energy ray such as ultraviolet light, while maintaining moisture curability and other various properties required for α-cyanoacrylate compositions. This curable resin composition can be rapidly cured by both moisture and irradiation of an active energy ray. Specifically disclosed is a curable resin composition containing (A) an α-cyanoacrylate and (B) an amine imide compound having one or more structures represented by the general formula (I) below in a molecule and/or an α-aminoacetophenone compound. (In the formula, R1 represents an aryl group which may have a functional group; and R2, R3 and R4 independently represent an aryl group and/or alkyl group which may have a functional group.)

Description

 Specification

 Curable resin composition

 Technical field

 The present invention relates to a curable resin containing α-cyanacrylate as a main component, which is rapidly polymerized and cured by the humidity of the surface of an adherend and / or by irradiation with an energy line such as ultraviolet rays. The present invention relates to a composition, and in particular, can be widely applied to lithography, potting, molding, coating, adhesive, sealant, and various resist materials.

 Background art

 [0002] The a-cyanoacrylate adhesive rapidly cures anion by a small amount of moisture adsorbed on the adherend surface, and adheres adherends very firmly in a short time. Therefore, it is widely used for bonding metals, plastics, rubber, wood, etc. as a one-component room temperature curing type instant adhesive. The α-cyanacrylate adhesive is hardened when the distance between adherends is wide, or when it sticks out from the bonded part or is not sandwiched between a pair of adherends like a coating. Has the disadvantage of becoming extremely slow.

 [0003] Therefore, in order to quickly cure the α-cyanate acrylate adhesive filled in a large gap or protruding from the bonded portion, it is generally cured using a primer or a curing accelerator. (Patent Literature 1, Patent Literature 2, and Patent Literature 3). However, such a method is complicated and time-consuming in the process, and the basic compound or solvent that is the main component of the primer or curing accelerator is used. Odor is undesirable in the working environment. Therefore, it does not impair the excellent features of instant adhesives, which are one-pack type, room temperature rapid curing, and it can be cured easily without using a primer or curing accelerator even if it fills the protruding part or large gap. An α-cyanacrylate adhesive that can be used is desired.

[0004] As a method for solving the above-mentioned problem, Patent Document 4 and Patent Document 5 describe that a meta-cathecene compound alone, or a meta-cathecene compound and a cleavage type photoradical generator as an α-cyanacrylate adhesive. There is disclosed a photocurable α-cyanacrylate composition which is added and contained. This composition can be applied to light in addition to normal moisture curing by moisture on the surface of an adherend. Curing by shooting is possible. Further, Patent Document 6 describes the addition of an aromatic azide compound to a-cyanoacrylate, and Non-Patent Document 1 describes a technique using Pt (acac) as a photoion polymerization initiator! / The report has been made.

 2

 Besides these, as photoanion generators, carboxylic acid ammonium salts (Patent Document 7), a aminoacetophenone derivatives (Patent Document 8), aromatic aminimide compounds (Patent Document 9), aminimide compounds and singlets A combination with a triplet sensitizer, that is, a combination with a hydrogen abstraction type radical generator (Patent Document 10) has been reported.

 Patent Document 1: Japanese Patent Application Laid-Open No. 59-215376

 Patent Document 2: JP-A-60-203684

 Patent Document 3: Japanese Patent Application Laid-Open No. 61-176634

 Patent Document 4: JP-A-9 249708

 Patent Document 5: Japanese Patent Laid-Open No. 11 166006

 Patent Document 6: JP-A-6-299122

 Patent Document 7: Japanese Patent Laid-Open No. 55-22669

 Patent Document 8: Japanese Patent Laid-Open No. 11 71450

 Patent Document 9: International Patent Publication WO2002 / 051905

 Patent Document 10: Japanese Unexamined Patent Publication No. 2003-26772

 Non-Patent Document 1: Macromolecules (28 (4) 1328 (1995))

 [0005] However, the photo-curable α-cyanacrylate-based composition to which a metaguchicene compound, an aromatic azide compound, and a platinum complex disclosed in Patent Documents 4 to 6 and Non-Patent Document 1 are added, respectively, There are problems that the composition tends to be colored, poor stability during storage, poor photocurability, and in some cases, rapid curing due to moisture, which is an inherent feature of α-cyanacrylate compositions There is a possibility of causing problems such as adversely affecting sex.

 [0006] On the other hand, Patent Documents 7 to 10 describe compounds that generate bases upon irradiation of light! /, But these compounds are subject to curing reactions! / The polymerizable compound is mainly an epoxy resin and is not intended for an α-cyanacrylate composition.

Disclosure of the invention Problems to be solved by the invention

[0007] The object of the present invention is to solve the above-mentioned problems, that is, while maintaining the moisture curability and other physical properties required for an α-cyanacrylate composition, active energy rays such as ultraviolet rays. An object of the present invention is to provide a curable resin composition that can be cured rapidly by irradiation of the resin and that can be rapidly polymerized and cured by irradiation of moisture or active energy rays.

 Means for solving the problem

[0008] The inventors

 (A) a-cyananoacrylate

 (B) —Aminimide compound having at least one structure represented by the general formula (I) in the molecule and / or α-aminoacetophenone compound

 The above-mentioned problems have been solved by a curable resin composition containing the above.

[0009] [Chemical 1]

 (In the formula, R1 represents an aryl group which may have a functional group. R2, R3

 And R4 each independently represents an alkyl group which may have a functional group or Z and aryl group. ) The invention's effect

 [0010] The curable resin composition containing the components (A) and (B) of the present invention as a main component has a conventional moisture-hardening property and can be easily overlapped by irradiation with active energy rays such as ultraviolet rays. Harden. Therefore, the weakness of the moisture-curing α-cyanacrylate-based composition, poor thick-film curability when used in large quantities and a decrease in curing speed! This can be solved.

In addition, the curable resin composition comprising the above (ii) and (ii) as a main component becomes a colorless and transparent liquid composition and can be used for applications other than adhesives, such as coating agents and paints. is there.

 [0011] Furthermore, in the curable resin composition of the present invention in which the component (C) is used in combination, the active energy linear curability is further improved. Therefore, since the amount of component (B) that affects the storage stability of component (A) can be reduced by the combined use of component (C), the storage stability is high V and the curable resin composition. Can be obtained.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 As the (A) a-cyanoacrylate used in the present invention, those having a conventional force represented by the following general formula (Π) can be used.

 H C = C (CN) — COOR (II)

 2

 (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, an aryl group, etc. The number of carbon atoms of the ester residue is not particularly limited, but usually 1 to Those having 8 carbons are also used, and ester residues consisting of alkoxyalkyl groups, trialkylsilylalkyl groups, and substituted hydrocarbon groups can also be used.

 Specific examples include methyl α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, cyclohexyl α-cyanoacrylate, and other alkyl and cyclohexane. Alkenyl and cycloalkenyl such as alkyl α-cyanoacrylate, allyl α-cyanoacrylate, methallyl α-cyanoacrylate, cyclohexenyl α-cyanoacrylate, α-cyanoacrylate, propanegyl α-cyanoacrylate, etc. Alolequininore α-cyanoacrylate, phenolic α-cyanoacrylate, tolyl α-cyanoacrylate, and other such aryl α-cyanoacrylates, heteromethoxy-containing methoxyethyl α-cyanoacrylates, ethoxyethyl α-cyanoacrylate Furfuryl α-cyanoacrylate, trimethylsilylmethyl α-cyanoacrylate, trimethylsilylethyl α-cyanoacrylate, trimethylsilylpropyl α-cyanoacrylate, dimethylvinylsilylmethyl α-cyanoacrylate, etc. It is done.

[0014] In the present invention, (ii)-an amine having at least one structure represented by the general formula (I) in the molecule And / or α-aminoacetophenone compounds rapidly become one or more basic substances or basic substances by changing the molecular structure or cleaving within the molecule by irradiation with active energy rays. It is a compound that generates a similar substance (photobase generator). Among these, examples of the amine imide compound having one or more structures represented by the general formula (I) in the molecule include compounds represented by the general formula (I).

 [0015] [Chemical 2]

General formula (I)

 (In the formula, R 1 represents an aryl group which may have a functional group. R 2, R 3 and R 4 each independently represents an alkyl group or a da and aryl group which may have a functional group. )

A known method can be used as a method for synthesizing this amine imide compound. For example, as described in Encyclopedia of Polymer Science and Engineering, John Ailey & Sons Ltd., (1985), Volume 1, p740, the corresponding carboxylate ester with hydrazine halide and sodium alkoxide. It can be obtained from reaction or reaction of carboxylic acid ester with hydrazine and epoxy compound.

 The method for synthesizing the aminimide used in the present invention is not particularly limited! /, But considering the simplicity and safety of synthesis, a synthesis method from a carboxylic acid ester, hydrazine and an epoxy compound is preferable. . In this case, the synthesis temperature and time are not particularly limited, but in general, the desired aminimide compound can be obtained by stirring at a temperature of 0 to 100 ° C for 30 minutes to 7 days.

[0017] The carboxylic acid ester as a raw material of the aminimide compound of the present invention used in the case of this synthesis method is a monofunctional or polyfunctional force having a Ri COO structure in the molecule. Any rubonate compound! R1 has a functional group! /, May be! /, And an aryl group. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, diphenyl, triphenyl, fluorene, and anthracene groups. Examples of the functional group that R1 may have include alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, carbon atoms;! -8 alkylthio groups, and carbon atoms. ;! ~ 8 alkylidene group, cycloalkyl group having 4-8 carbon atoms, cycloalkenyl group having 4-8 carbon atoms, amino group, alkylamino group having 1-6 carbon atoms, 2-2 carbon atoms 3 dialquinolamino groups, morpholino groups, mercapto groups, hydroxyl groups, carbon atoms;! ~ 6 hydroxyalkyl groups, halogen atoms, ester groups having 1 to 6 carbon atoms, carbon atoms;! ~ 6 alkylcarbonyls Group, aldehyde group, cyano group, trifluoromethyl group, cyano group, nitro group, phenyl group, benzoyl group, benzyl group, phenyl group substituted with electron donating group and / or electron withdrawing group, or electron donating group Base / Or an electron-withdrawing group is a benzyl group or the like substitution. Of these, 4-12 tropenyl groups are preferred from the viewpoint of the balance between stability and curability of the composition, even though substituted phenyl groups are preferred as R1 because of the availability of raw materials. Examples of the carboxylic acid ester compound having 4 12 tropenyl group include methyl 4 12 trobenzoate and ethyl 12 12 trobenzoate. When a polyfunctional carboxylic acid ester compound is used, an aminimide compound having a plurality of aminimide structures in the molecule can be obtained. The hydrazine compound is not particularly limited! However, 1,1-dimethylhydrazine is preferred from the standpoint of availability of raw materials and the high basicity of the generated photobasic substance. Further, the epoxy compound as another raw material may be a compound having one or more epoxy groups in the molecule. For example, in addition to monofunctional epoxy compounds such as propylene oxide, glycylol, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl daricidyl ether, and tertiary butyl phenol glycidyl ether, resorcinol diglycidyl ether, neopentyl diester So-called bis-type liquid epoxy resins such as glycidyl ether, glycerol polyglycidyl ether, diglycidyl ether derived from bisphenol A and epichlorohydrin, derived from aliphatic 'aromatic alcohol and epichlorohydrin Polyglycidyl derived from polyglycidyl ether, polybasic acid and epichlorohydrin Polyfunctional epoxy compounds such as polyglycidyl ethers derived from diyl esters, hydrogenated bisphenol A and epichlorohydrin can also be used. When a polyfunctional epoxy resin is used, an aminimide compound having a plurality of aminimide structures in the molecule can be obtained.

 The alkyl group represented by R2, R3 and R4 in the general formula (I) is more preferably a methyl group, preferably an alkyl group having!

[0018] The α-aminoacetophenone compound, which is another compound that can constitute component (B), is a compound having an α-aminoacetophenone skeleton in the molecule. Specific examples of compounds having an a-aminoacetophenone skeleton include (4 morpholinobenzoyl) 1 Benjirou 1 —dimethylaminopropane (Irgacure 369, trade name of Ciba Specialty Chemicals) and 4 ( A commercially available compound such as methylthiobenzoyl) 1-methyl-1 morpholinoethane (Irgacure 907, trade name of Ciba Specialty Chemicals) or a solution thereof can be used.

 As the above-mentioned aminimide compound or α-aminoacetophenone compound of component (B), at least one of these compounds may be used, but a plurality of these compounds may be used in combination.

 Further, the blending amount of the component (に お け る) in the curable resin composition of the present invention is not particularly limited, but preferably 0.001 to 100 parts by weight of the total of the component (Α). ~; It is desirable to add in the range of 10 parts by weight. When the component (Β) is added within the above range, it is possible to obtain a curable composition having an excellent balance between the curing speed and the strength of the cured product, storage stability, and the like. If the amount is less than 001 parts by weight, the curable composition of the present invention cannot be provided with effective photocurability, and if it exceeds 10 parts by weight, it is difficult to dissolve in the component (v), and storage stability and various physical properties are also provided. May be adversely affected.

[0019] In the present invention, the composition comprising the above components (i) and (ii) as the main component is further added to (C) an active energy linear radical generator (however, as the component (C) of the present invention, Addition of (ii) excluding α-aminoacetophenone compound used as a component can further enhance the photoactivity of the composition. This active energy ray radical generator is a compound that generates radical species upon irradiation with active energy rays such as ultraviolet rays, and is a hydrogen abstraction type radical generator. And the force S that is broadly divided into intramolecular cleavage type radical generators, and the force S that can be used without distinction in the present invention.

Examples of hydrogen abstraction-type radical canore generators include 1-methylnaphthalene, 2-methylnaphthalene, 1-funole ronaftalene, 1 chloronaphthalene, 2-chloronaphthalene, 1 'mouth monaphthalene, 2' mouth monaphthalene, 1-odonaphthalene, 2--naphthonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1, 4--naphthalene derivatives such as dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9, Anthracene derivatives such as 10 diclonal anthracene, 9, 10 dibromoanthracene, 9, 10 diphenylanthracene, 9 cyananoanthracene, 9,10 dicyananthracene, 2, 6, 9, 10 tetracyananthracene, pyrene derivatives, Canolevazole, 9-methylcarbazole, 9 phenylcarbazole , 9 Propyl 2-ynil 9H strength rubazole, 9 propyl-9H—power rubazole, 9-butcarbazole, 9H—force rubazole – 9 ethanol, 9-methyl-3-nitroh 9H—force rubazole, 9-methyl-3, 6— Dinitro 9H—Strength rubazole, 9 Otanoyl carbazole, 9 Strength rubazo, Monoremethanol, 9 Strength rubazole propionic acid, 9 Strength rubazole propionitrile, 9-ethyl-3-6 , 9-Ethyl-3-nitrocarbazole, 9-Ethylcarbazole, 9 Isopropylcarbazole, 9 (Ethoxycarbonylmethyl) carbazole, 9 (Morpholinomethyl) carbazole, 9 Acetylcanole azole, 9-Alinole nore zonore, 9-Benzyl 1 9H-carbazole, 9-force rubazole acetic acid, 9 1 (2 ditro 9- (4-methoxyphenol) carbazole, 9-1 (1 ethoxy-2-methyl-pour pill) 1 9H rubazole, 3 2-trocarbazole, 4-hydroxycarbazole, 3,6-dinitro 9H—Strength rubazole, 3, 6 diphenyl nitro 9H Strength rubazole, 2-hydroxycarbazole, 3,6-diacetyl- 9-ethylcarbazole, rubazole derivatives, benzophenone, 4-phenylbenzophenone, 4, 4'-bis (Dimethoxy) benzophenone, 4,4'-bis (dimethinoleamino) benzophenone, 4,4'-bis (jetylamino) benzophenone, 2 benzoinole benzoic acid methyl ester, 2 methylbenzophenone, 3 methylbenzophenone, 4-me Tylbenzophenone, 3, 3 'dimethyl mono-4-methoxybenzophenone, 2, 4, 6 Methylate Benzophenone derivatives such as rubenzophenone, aromatic carbonyl compounds, [4- (4-methylphenylthio) phenyl] phenylmethanone, xanthone, thixanthone, 2-cyclodithioxanthone, 4-cyclodioxanthone, 2 isopropylthixanthone, 4 isopropylthione Examples include thixanthone derivatives such as xanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, and 1 chloro-4 propoxythixanthone, and coumarin derivatives.

[0020] The intramolecular cleavage type radical generator is a type of radical generator that generates radicals by cleavage of the compound when irradiated with active energy rays. Specific examples thereof include benzoin ether derivatives, (Excluding α-aminoacetophenone compound) Arylphene ketones such as acetphenone derivatives, oxime ketones, acyl phosphine oxides, thiobenzoic acid S phenyls, titanocenes, and high molecular weights thereof Derivatives, but not limited to these. Commercially available cleavable radical generators include 1- (4-dedecylpenzoyl) -1-hydroxy-1-monomethylethane, 1-1- (4-isopropylbenzol) 1-hydroxy-1-methylethane, 1 1-hydroxy-1- 1-methylethane, 1- [4- (2 hydroxyethoxy) monobenzoyl 1-hydroxy 1-methylethane, 1 [4 (ataryloxyethoxy) monobenzoyl] -1- 1-hydroxy 1-methylethane, diphenylketone, phenylolene 1-hydroxycyclohexenoleketone, penzinoresimethinoreketanol, bis (cyclopentageninole) -bis (2, 6 difluoro-1-pyryl-1-phenyl) titanium, (7 ] ⁶ —Isopropylbenzene) 1 (7) ⁵ —Cyclopentaenyl) Iron (鉄) hexafluorophosphate, trim Tinole Benzyldiphenylphosphine oxide, bis (2,6 dimethoxymonobenzoyl) mono (2, 4, 4 trimethyl-pentyl) Phosphine oxide, bis (2, 4, 6 trimethylbenzoyl) 2, 4 di Examples thereof include, but are not limited to, pentoxyphenylphosphine oxide or bis (2,4,6 trimethylbenzoyl) phenylphosphine oxide.

[0021] In the composition of the present invention, these (C) active energy ray radical generators, that is, hydrogen abstraction type or cleavage type radical generators can be used alone. You can use a combination of multiple forces, but the stability of the radical generator alone In view of the properties and curability of the composition in the present invention, a combination of two or more containing at least one cleavage type radical generator is preferred. Also, high molecular weight type with the structure of high molecular oligomer / cleavable radical generator in the polymer is preferred because of less outgassing during and after curing!

 Also, depending on the type of (C) active energy ray radical generator, there may be a difference in the effect depending on the structure and type of component (B) to be combined with this, so component (B) and component (C) You can choose the best combination of! / ,.

 The addition amount of the (C) active energy ray radical generator in the curable resin composition of the present invention needs to refer to the absorption wavelength and the molar extinction coefficient, but generally the curable resin composition of the present invention. Component (A) is 100 parts by weight, 0.00;! To 50 parts by weight, preferably 0.01 to 10 parts by weight. If the amount added is small, a sufficient photoactivity improving effect cannot be obtained, and if it is too large, the basic catalytic action of component (B) may be inhibited.

 Furthermore, various additives can be used in combination with the cured composition of the present invention as long as the characteristics of the present invention are not impaired.

 For example, it is possible to use a radical polymerizable compound such as an acrylate ester in combination, and further known anionic polymerization inhibitors, radical polymerization inhibitors, thickeners, curing accelerators, plasticizers, tougheners, fragrances, dyes Specific additives such as pigments, fillers, and heat stabilizers can be added as necessary. Anionic polymerization inhibitors are added to increase stability during storage of the composition. Examples of known inhibitors include sulfur dioxide, sulfur trioxide, nitric oxide, hydrogen fluoride and p-toluenesulfonic acid, etc., generally in the range of 0.;! To lOOOOppm relative to α-cyanate acrylate. It is accompanied. Examples of radical polymerization inhibitors include quinone, hydroquinone, t-butylcatechol, and p-methoxyl phenol, and are generally added in the range of 0.1 to 1000 Oppm with respect to α-cyanacrylate. .

Furthermore, thickeners are added to increase the viscosity of the composition. Examples of thickeners include poly (methyl) metatalylate, metatalylate type copolymers, acrylic rubber, cellulose derivatives, polybutyrate and poly ( _α -cyanacrylate). In addition to this, many conventional polymer additives are also added for toughening. Examples thereof include an acrylic elastomer, an acrylonitrile copolymer elastomer, a fluoroelastomer and a fine silica filler. These substances also function as thickeners.

 [0023] The curable resin composition of the present invention has a long life at room temperature and has a pot life, and in addition to rapid polymerization and curing due to moisture in the atmosphere or the surface of the adherend, it also exhibits active energy rays such as light. Even when irradiated, it cures quickly, forming a tough cured product and developing strong adhesion to metals and plastics.

 In addition, a one-component curable resin composition in which a composition containing component (A) a-cyanoacrylate and a photobase generator as component (B) are mixed can be used, and component (A) and (B) may be separated into two-component compositions and polymerized and cured by a method of mixing or contacting immediately before use. Such a form is arbitrarily selected depending on the types of the components (A) to (C), particularly the combination of the components (B) and (C).

 Example

 [0024] The ability to specifically describe the present invention by way of examples below The present invention is not limited by the following examples. Further, the blending ratios in the following table are based on weight unless otherwise specified.

 [0025] The aminimide compounds used in Examples and Comparative Examples are compounds represented by the structural formulas shown in Table 1, and those synthesized by the following methods were used.

[0026] [Table 1]

table 1

[0027] (Synthesis of aminimide compound a)

 According to the method disclosed in International Patent Publication No. WO2002 / 051905, 1,1 dimethyl-11- (2-hydroxy-3phenoxypropyl) amine paranitrobenzimide was obtained as an aromatic aminimide compound.

 (Synthesis of aminimide compounds b to h)

 According to the method disclosed in J. Polym. Sci. Part A, 38, 18, 3428 (2000) and JP 2000-229927 A, from the corresponding carboxylic acid methyl ester or carboxylic acid ethyl ester, dimethylhydrazine and an epoxy compound. Each amine imide compound was obtained.

 Aminimides a and are amine imides of the present invention, and aminimides c to h are aminimide compounds that are not included in the amine imide compounds of the present invention.

[0028] In addition to the amine imide compounds, the materials used in the examples and comparative examples of the present invention are commercially available products or reagents shown below.

'Ethyl _α — Cyanacrylate: ThreeBond Co., Ltd., Highly refined grade

• Acetone: Reagents of Tokyo Chemical Industry Co., Ltd. 'Inore Gacure 369, 907, α-aminoacetophenone compound manufactured by Ciba Specialty Chemicals Co., Ltd.

 'Irgacure 184, 651, 819: Ciba Specialty Chemicals, Inc. Cleavage type photo radical generator

 • Benzophenone: Tokyo Chemical Industry Co., Ltd. Reagents Hydrogen abstraction type photo radical generator BF ether ether complex: Boron trifluoride manufactured by Morita Chemical Co., Ltd.

Three

 Chill ether complex salt

 R805: Nippon Aerosil Co., Ltd. surface-treated fumed silica

[0029] [Examples;! To 16, Comparative examples;! To 7]

 In the weight ratio shown in Table 2, each raw material excluding ethyl cyanoacrylate is stirred and dissolved in acetone in a light-shielding container. This acetone solution was dropped into ethyl acetate and dissolved in a light-shielding container to obtain each composition. Next, each test described below was performed on each of the obtained compositions, and the results are also shown in Table 2.

 [25 ° C pot life measurement test]

 10 g of each composition was hermetically stored in a light-shielding container in a room at 25 ° C., and the time until the whole gelled. The one marked as 0 minutes is a gel that reacts vigorously immediately after mixing.

 [Photocurability test]

0.5 g of each composition is dropped into a plastic cup with an inner diameter of 24 mm and irradiated with active energy rays using a spot ultraviolet irradiation device (365 nm illuminance: 100 mW / cm ² ) manufactured by Hamamatsu Photonics Co. From this, the integrated light quantity was obtained. Those that reacted vigorously immediately after mixing and gelled were marked as impossible to measure in the table.

 [Color judgment of cured product]

 The color tone of the cured product photocured as described above was visually observed.

実施例;!〜 5から、本発明のァミンイミドを使うと、長い可使時間を有し、光で瞬時に 硬化することがわかる。実施例 6〜； 12から、任意のラジカル発生剤を添加することに より光硬化性が向上し、特に開裂型ラジカル発生剤が光硬化性の向上に特に優れる こと力 ^sゎカゝる。 [0030] [Table 2]

From Examples 5 to 5, it can be seen that when the aminimide of the present invention is used, it has a long pot life and is instantly cured by light. From Examples 6 to 12, the photocurability is improved by adding an arbitrary radical generator, and the cleavage type radical generator is particularly excellent in improving the photocurability. This and the force ^s Wakakaru.

 Examples 13 to 15 show that the storage stability can be improved while maintaining sufficient photocurability by adding an organic acid derivative. Further, Example 15 shows that the amine imide compound b of the present invention having a structure other than the amine imide compound a is also effective. In Example 16, it can be seen that there is no adverse effect even if a filler is added.

 Examples 17 to 18 show that when the α-aminoacetophenone compound of the present invention is used, it has a long pot life and is instantly cured by light. From Example 19, it can be seen that photocurability is improved by adding an arbitrary radical generator. From Examples 20 and 21, it can be seen that the amine imide compound of the present invention and the a-aminoacetophenone compound can be used in combination, and the photocurability is further improved by adding a radical generator.

[0032] From Comparative Example 1, it can be seen that when the aminimide compound and / or α-aminoacetophenone compound of the present invention is not included, no photocurability is exhibited. From Comparative Examples 2 to 5, not included in the present invention! / Aminoimide compounds having a substituent having a relatively large electron donating property to the carbonyl carbon are added with cyanoacrylate. At the same time, it is hardened, so it can be seen that it lacks practicality. This is thought to be due to the large basicity before light irradiation.

 Comparative Examples 6 and 7 are aliphatic aminimides not included in the present invention, and a compound having a substituent having a very strong electron-withdrawing property to carbonyl carbon has a long pot life, but has a photoactivity. It can be seen that low enough photocurability cannot be obtained. This may be because the basicity before light irradiation is sufficiently low, but the photoactivity is also low.

[Example 22]: Adhesion test and confirmation test of whitening phenomenon

 Using the compositions of Example 7, Example 19, and Comparative Example 1, adhesion curability, curability of the protruding portion, and the presence or absence of a whitening phenomenon were confirmed by the following measurement method, and are shown in Table 3.

[0034] [Measurement method]: Iron (SPCC—SD), glass (slide glass), silicon rubber (light white translucent, 2 mm thick) is used for the adherend, and it is placed in a 25 ° C '55% RH chamber. Then, one drop of each composition was dropped onto each adherend with a dropper, and the same adherends were bonded together. At that time, cyanoacrylate protruded intentionally from the end.

Immediately after the divination of shellfish, spot ultraviolet irradiation device (365nm illuminance: 10) manufactured by Hamamatsu Photonicus OmW / cm ² ) When active energy rays are irradiated for 10 seconds (lj / cm ² ), the time until the adhesive interface hardens and does not move immediately after bonding The time until the whole is cured, the whitening phenomenon around the protruding part (a phenomenon in which the uncured α-cyanacrylate compound hardens and drops due to moisture in the air after volatilization and adheres as a white cured product to the periphery) The presence or absence was confirmed.

 [Table 3]

 Table 3

 [0036] Even if the composition of V and deviation is not irradiated with light! /, Even if it is a case, the adhesive interface can be seen to cure and bond in a short time. It can be seen that it occurs. It can be seen that the compositions of Examples 7 and 19 are cured immediately after light irradiation for a short time even on an adherend that is relatively slow to cure, such as silicon rubber, when irradiated with light. Further, in all the adherends, when the light is not irradiated, the protruding portion is slowly cured and whitening occurs, but the compositions of Examples 7 and 19 are cured immediately after the light irradiation is completed by irradiating the light. It can be seen that no whitening phenomenon occurs.

 [0037] Although the 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. It is.

 This application is based on Japanese Patent Application No. 2006-210519 filed on August 2, 2006, the contents of which are incorporated herein by reference.

 Industrial applicability

[0038] The curable resin composition of the present invention can be used for a known application in which an α-cyanacrylate-based adhesive is conventionally used, that is, an adhesive utilizing moisture curability. Because it cures and cures quickly even when irradiated with energy rays such as ultraviolet rays, It can also be used for adhesive bonding and coating applications, paints, paints, and various resist materials.

Claims

Claims (A) a-cyanoacrylate (B) —contains an aminimide compound having at least one structure represented by the general formula (I) in the molecule and / or an α-aminoacetophenone compound Curable resin composition.  [Chemical 1] General formula (I)

 (In the formula, R1 represents an aryl group which may have a functional group. R2, R3 and R4 each independently represents an alkyl group which may have a functional group or Z and an aryl group. ) [2] The curable resin composition according to claim 1, comprising 0.001 to 10 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). [3] The curable resin composition according to claim 1, wherein the component (B) is an aminimide compound having one or more structures represented by the general formula (I) in the molecule. [4] The curable resin composition according to claim 1, wherein the component (B) is an α-aminoacetophenone compound.  [5] The curable resin composition according to claim 1, further comprising (C) an active energy ray radical generator.  [6] The component (C) is contained in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the component (i).  5. The curable resin composition according to 5. [7] The curable resin composition according to [1], which is active energy ray curable.