TW200813100A - 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

200813100 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to the rapid polymerization of hard by irradiation of energy rays in the atmosphere or by adhesion, and/or ultraviolet rays. α of a curable resin group containing cyanoacrylate as a main component: It can be widely used in lithography, ceramics, casting, coating sound*, other materials, and various resist materials. J. Grab the seal [Prior Art]: The bismuth propylene adhesive is rapidly anionically polymerized by the moisture adsorbed on the surface of the adherend, and the bodies are firmly adhered to each other in an extremely short time. Therefore, it is widely used as a contact agent for metal, plastic, rubber wood, etc. as a liquid-to-liquid normal temperature type. However, cyanoacrylic acid (4), the agent, when it is adhered to the body phase: the gap is wide, overflowing from the joint or if the coating is not in a pair of The shortcomings of slowness. * Therefore, in order to fill a large gap, or to quickly harden the cyanopropylene H-based adhesive which overflows the adhesive portion, it is generally used to harden it with a modifier or a hardening accelerator (Patent Document 1 and Patent) Document 2, Patent Document 3), but the method steps are complicated and labor-intensive, and the modifier or hardening property of the modifier or the solvent which is hardened into the mold is not good in the working environment. Therefore, it is desirable to have the excellent characteristics of the instant adhesive which is not damaged by the so-called one-liquid type and the rapid hardening at room temperature, and it is possible to simply use the modifier or the hardening accelerator even if the overflow portion or the filling is large. Make it

7042-9039-PF 5 200813100 Hardened α-cyanoacrylate based adhesive. As a method for judging the above problems, it is known that the method of the above-mentioned problems is super-extraordinary, and in Patent Document 4 or Patent Document 5, it is not disclosed that a photocurable α-aroma, a knee, or a sputum, a sputum The addition of a metallocene compound alone or a metallocene compound and a cleavage type light: by a base generating agent, the composition can be hardened by the usual moisture hardening of the surface of the adherend or the like. Light irradiation hardens. Further, in Patent Document 6, an α-cyanoacrylic acid is added to an aromatic azide compound, or a non-patent R 1 is used as a photoanionic polymerization initiator.

Report on the technology of Pt(acac)2. In addition to these, the photoanion generator is a carboxylate ammonium salt (Patent Document 7), an α-aminophenyl benzene derivative (Patent Document 8), a material group amine quinone imine compound (Patent Document 359), A combination of an amine quinone imine compound and a singlet/triplet sensitizer, that is, a hydrogen abstraction type radical generator (Patent Document 1). [Patent Document 1] JP-A-61-176634 (Patent Document 3) JP-A-61-176634 (Patent Document 4) JP-A-9-249708 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. STATEMENT [Patent Document 9] International Publication Patent No. 2〇〇2/〇519〇5 [Patent Document 10] JP-A-200 3-267 72

7042-9039-PF 6 200813100 [Non-Patent Document 1] Macromolecules (28(4) 1 328 (1 995)) However, the addition of a metallocene compound, an aromatic azide disclosed in Patent Documents 4 to 6 and Non-Patent Document i The photocurable α-cyanoacrylate composition of the compound or the platinum complex has a problem that the composition is easily colored, the stability at the time of storage is poor, the photocurability is poor, and the like, and depending on the case, α - The original characteristics of the cyanoacrylate-based composition are caused by adverse effects such as rapid hardening of moisture. On the other hand, in Patent Documents 7 to 1, each of the compounds which generate a base by light irradiation is described, and the polymerization of the compound of the compounds is carried out. The raw compound 'is mainly an epoxy resin, not A cyanoacrylate-based composition is a subject. [Problem to be Solved by the Invention] An object of the present invention is to solve the above problems, that is, to provide a hardening resin composition which maintains the thirst hardening property of a cyanoacrylate vinegar composition or Other characteristics can be rapidly hardened by irradiation with active energy rays such as ultraviolet rays, and can be quickly hydrated and hardened by irradiation of active energy rays with moisture. [Means for Solving the Problem] The present inventors' # consists of a curable resin composition comprising: (Α) α-cyanoacrylate; and (Β) having one or more formulas (I) in the molecule (I) The structure of the amine quinone imine compound 'and/or the amide acetophenone compound' is solved to solve the above problem: 7042-9039-PF 7 200813100 ο ri4^©42 1 R4 In the formula (i), The aryl group R2, R3 in which R1 cannot have a functional group in the main-system table is independently and represents an alkyl group or/and an aryl group which may have a functional group. , : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Therefore, it is possible to reduce the problem of the reduction of the thickness of the thick film hardening Du 2 L when the moisture sclerosing acrylates are used in a large number of weak points of the L ^ α , , , and σ substances. The active energy can be resolved in the quadrant hardening. The curable resin composition containing the above (Α) and (8) as a main component may be used as a liquid composition of the lido, which may be used for applications other than the adapter, such as a coating agent. Or paint. The combination of the curable resin of the present invention of the component (c) can further improve the m energy ray hardenability. Therefore, the component (B) which affects the storage stability of the component (A) can be added, and the curable resin composition having high stability can be stored by using the component (c). [Embodiment] Hereinafter, the present invention will be described in detail. As the acrylate, the above-mentioned conventional one represented by the (Α) α-cyano group (π) used in the present invention can be used. H2C=C(CN) C00R (II)

7042-9039-PF 8 200813100 wherein R is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or an aryl group. The carbon number of the ester residue is not particularly limited, and those having from j to 8 are usually used. Further, an ester residue containing a substituted alkyl group such as an alkoxyalkyl group or a trialkyldecylalkyl group may also be used. Specific examples thereof include methyl α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, and cyclohexyl α-cyanoacrylate. Alkenyl and cycloalkyl cyanopropenyl acrylates; alkenyl and cycloalkenes such as propenyl α-cyanoacrylate, methacrylyl α-cyanoacrylate, cyclohexene α-cyanoacrylate Alkenyl α-cyanoacrylate; alkynyl α-cyanoacrylate such as propynyl α-cyanoacrylate; aryl α-cyanoacrylate such as phenyl α-cyanoacrylate or tolyl α-cyanoacrylate Acrylate, methoxyethyl cyanoacrylate containing a hetero atom, ethoxyethyl α-cyanoacrylate, decyl α-cyanoacrylate, trimethyl decylmethyl α containing hydrazine Cyanoacrylate, tridecylmercaptoethyl α-cyanoacrylate, tridecylmercaptopropyl α-cyanoacrylate, monomethyl vinyl mercaptomethyl α-cyanoacrylate, and the like. In the present invention, there are i or more amine quinone imine compounds having a structure represented by D, and/or an aminoacetophenone compound, which is irradiated with an active energy ray by molecular structure. In the case of a change or a disproportion in a molecule, one or more kinds of basic substances or a compound similar to a basic substance (photobase generator) are rapidly formed. Among them, as one in the molecule, the upper formula ( The amine imine compound of the structure represented by I) may be a compound represented by the formula (I). 7〇42-9039-PF 9 200813100

R1-C-N-N-R3 R4 Formula (I) wherein R1 represents an aryl group which may have a functional group. R2, R3 and R4 are each independently and represent a burnt group or/and an aryl group which may have a functional group. For the synthesis method of the amine quinone imine compound, a conventional method can be used. For example, Encyclopedia of P〇iymer Science and

Engineering, John Wiley & Sons Ltd., (1985), Vol. 1, p740, 'Reaction of the corresponding carboxylic acid ester with a halogenated hydrazine and a sodium alkoxide, or a carboxylic acid ester with a hydrazine and a ring Oxygen compound reaction derived. The method for synthesizing the amine quinone imine used in the present invention is not particularly limited. However, in view of the simplicity and safety of the synthesis, a synthesis method of a carboxylic acid ester, a hydrazine, and an epoxy compound is preferred. The synthesis temperature and time at this time are not particularly limited, and generally the desired amine quinone imine compound is obtained by stirring at a temperature of 〇~1 〇〇 for 3 () minutes to 7 days. The carboxylic acid ester as a raw material of the amine quinone imide compound of the present invention used in the case of the synthesis method may be a monofunctional or polyfunctional carboxylic acid ester compound having R b c - in the molecule. R1 is an aryl group which may have a functional group. Examples of the aryl group include a phenyl group, a naphthyl group, a diphenyl group, a triphenyl group, a behenyl group, a fluorenyl group and the like, but are not limited thereto. Further, examples of the functional group which R1 may have include an alkyl group having 1 to 8 atomic atoms, an alkoxy group having a carbon number of 丨8, an alkylthio group having 1 to 8 carbon atoms, and a subatomic carbon number. An alkyl group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amine group, an alkylamino group having 1 to 6 carbon atoms, a dialkyl group having 2 to 3 carbon atoms Amino, morpholinyl, fluorenyl, 7042-9039-PF 10 200813100 hydroxyalkyl group having a carbon number of 1 to 6, a halogen atom, an ester group having a carbon number of n, and an alkyl group having 1 to 6 carbon atoms a carbonyl group, an aldehyde group, a cyano group, a trimethyl group, a cyano group, a nitro group, a benzylidene group, a benzyl group, a phenyl group substituted with a push electron group and/or an electron withdrawing group, or a push electron group and/or Or a benzyl group substituted with an electron group. Among these, it is preferable that R1 is substituted with a phenyl group from a raw material, and a 4-nitrophenyl group is preferred from the viewpoint of the balance between the stability of the composition and the hardenability. The carboxylic acid ester compound having a 4-nitrophenyl group may be methyl 4-nitrobenzoate or ethyl 4-nitrobenzoate. The use of a polyfunctional carboxy: 酉曰^ mouthpiece can be carried out in the molecule with an amine-imine compound having a complex amine-imine structure. The hydrazine compound is not particularly limited, and it is preferred that the benzylamine is preferably a benzylamine which is derived from a raw material or a basic strength of a photobase which is produced. Further, the epoxy compound of another raw material may be a compound having one or more epoxy groups in the same. Example:,; oxygen, lyCU 〇 K trade name; monofunctional epoxy compound), propylene glyceryl ether, r ρ f ^ ^ propylene cup base fine: butyl - hexyl "glycidyl ether, phenyl glycidol Ether, first butyl hydrazine I® glycerol _ and other mono-shrinkage 廿, T 4 early s Month 匕% milk compound other than 'resorcinol x glycerol _, neopentyl glycidyl ether, glycerol fk # phenol A Life Owner-1 Gan, a condensed diglycidyl ether derived from t-glycidyl ether, double ” 表 醇 所 〆 〆 〆 〆 液 液 液 液 液 液 液 液 液 液 液 液 液 液 液 , , , , , , , , , , — — Glycerol ether, more... "Polymerized by a poly-alkaline acid derived from a gas alcohol and a polyhydric alcohol derived from a surface alcohol, and a polyhydric alcohol derived from epichlorohydrin: a hydroglyceric acid, an added compound. At a — , “ ' A polyfunctional epoxy ruthenium b epoxy resin from the singularity of the succinct, which can be obtained from an alkyl group, an amine amide imine structure. In the knives, there are plural numbers, and as the formula (1), R2 and RUR4 are listed.

7042-9039-PF 11 200813100 It is preferred to use a carbon number of 1 to 6 and a methyl group. The α-aminoacetophenone compound which is another compound which can constitute the component (B) is a compound having an α-aminoacetophenone skeleton in the molecule. Specific examples of the compound having an aminoacetophenone skeleton can be used as follows: (4-morpholinyl benzamidine)-1-benzyl-; [-dimethylaminopropane (irgacure 369, product manufactured by CUa Speciality Chemicals) Name) or 4_(methylthiobenzidine)-1-morpholinylethane (IRGACURE 9〇7, ciba such as """""""""""""""""""""""""""""""""""""""""""""""""""""""" The amine quinone imine compound or the α-amino acetophenone compound 'suppose at least one of the compounds may be used, but these compounds may be used in combination of a plurality of them. Also in the composition of the curable resin composition of the present invention The blending amount of (Β) is not particularly limited. It is preferred that the total amount of the component (1) is the weight portion, and it is preferably added in the range of the weight portion of the U0HG. The component (8) is added in the first step. A combination of a curing rate and a strength of a cured product, and a curable composition excellent in stability such as food stability. If the weight is less than 001·001, the effective curability of the curable composition of the present invention cannot be imparted. 1 Λ ^ ^ tk 1 〇 weight section In addition to the difficulty in dissolving the component (A), it may cause adverse effects on the storage female character or characteristics. In the present invention, it is considered that the above components (A) and (B) are the main components. The (π:) active energy ray radical generating agent (except as the present compound) invented by the group removes the α-aminophenylphenidene assimilating base-derived agent as the component (8), and the light of the composition The active energy line is free from the irradiation of active energy rays such as ultraviolet rays.

7042-9039-PF 12 200813100 The compound of the basic species can be broadly classified into a hydrogen abstraction type radical generating agent and an intramolecular cleavage type radical generating agent, but the present invention can be used without distinction. Examples of the scavenging type radical generating agent include i-decylnaphthalene, 2-indenylnaphthalene, fluorofluoronaphthalene, buponaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, and 1- Naphthalene derivatives such as iodine, 2-iodo, 1-naphthol, 2-naphthol, methoxynaphthalene, 2-methoxyl, 1,4-dicyanonaphthalene; anthracene, anthracene, 2-benzene And hydrazine, 9, 1 〇-dichloron, 9,1 〇-dibromo fluorene, 9,1 〇-diphenyl hydrazine, 9-cyano hydrazine, 9,1 〇-dicyandi, 2, 6, 9, Anthracene derivatives such as 10-tetracyanoquinone; anthracene derivatives, carbazole, 9-methylcarbazole, 9-phenyloxazole, 9-propyl-2-alkenyl 9H-carbazole, 9-propyl-(10) Monocarbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, g-methyl-3-nitro-9H-carbazole, 9-fluorenyl-3,6-dinitro- 9H- Carbazole, 9-octoxazole, 9-oxazole methanol, 9-oxazole propionic acid, 9-carbazole propionitrile, 9-ethyl-3,6-dinitro-9H-carbazole, 9- Ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropyl saliva, 9-(ethoxylated oxime, 9-(methylamino)morpholinyl , 9-ethazole, 9-propenylcarbazole, 9-mercapto-9H-carbazole, benzoic acid, 9-(2- surely base) 兮 saliva, 9 bis[4- 曱9-(b-ethoxy-2-methyl-propyl)-9H, 3-nitrozole, keto , 3,6-dimercapto- 9H-, carbaryl, 3,6-diphenyl- 9h-carbazole, carbazole, 3,6-diethylhydrazine-9-ethylcarbazole Azole derivative; diphenylamine, 4-phenyl, 4,4,-bis(dimethoxy)benzophenone, 4,4,: bis(didecylamino)benzonitrile, 4 , 4,-bis(diethylamino)di-S, 2-benzoylbenzoic acid, cis, 2-methyldibenzyl, "fluorenone, 4-methyl-methanone , 3,3'-dimercaptomethoxy dioxin, 2,4,6-trimethylbenzophenone, etc.; diphenyl cis-like derivatives; aromatic 7042-9039-PF 13 200813100 Base compound; [4-(4-methylphenylthio)phenyl phenyl ketone; oxybenzophenone; (iv) ketone, 2-chloro(tetra) ketone, mdontonone, 2-isopropyl thioxanthene a thioxanthene derivative such as a ketone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 1-chloro-propoxythioxanthone or a coumarin derivative. Further, an intramolecular cleavage type free radical generator is obtained by A radical generating agent which cleaves the active energy ray to generate a radical, 'as a specific example thereof, may be a benzoin ether derivative, (except for an aminoacetophenone sulfonate) acetophenone derivative, etc. Base-burning sputum, sputum sulphate, acid-based sulphate, thiobenzoic acid S_stupid, ferrocene, and derivatives of these polymers are not limited thereto. The pyrolysis-type free radical generator sold can be exemplified by 4-guaryl benzoyl ketone + ketone + methyl ethane, pu (4-isopropylbenzhydrazide) small warp group + methyl ethane sulphur, Benzoyl 1 L-based 1 methyl bromide, b [4-(2-ethoxy)-benzhydryl] + benzyl-1-methylethane, 1-[4-(propenyloxy) Ethoxy)benzylpyridinium & keb methyl bromide, diterpene ketone, stupid-bupyridin-cyclohexanone, benzyl dimethyl condensed _, double (cyclopentyl pentenyl) Bis(2,6-difluoro-3-indolyl-phenyl): (η cumene X 77 - cyclopentadienyl iron hexafluorophosphate (II), methyl benzoyl diphenyl phosphine oxide , bis(2,6-dimethoxy-benzoic acid)-(2'4,4-trimethyl-pentyl)-oxygen Phosphine, bis (acyl Yue 2,4,6_ trimethylbenzene) phenyl - phosphine oxide, 'but is not limited thereto. In the composition of the present invention, the enthalpy of the active energy ray-free radical generating or the stimulating radical generating agent may be used alone or in combination of the 'resonant generating monomer'. Or 7042-9039-pf 14 200813100 It is preferred that the composition of the present invention has a lipid-hardening property, and two or more types of cleavage-type radical generating agents are contained in combination. Further, in the polymer oligomer/polymerization The high-molecular-weight type of the cleavage-type radical generating agent is introduced into the high-molecular-weight type of the cleavage-type radical generating agent, and it is preferable that the amount of degassing during hardening and hardening is small. _In addition, according to the type of (C) active energy ray radical generating agent, The structure or type of the component (:6) combined therewith differs in its effect, so that the optimum combination of the component (B) and the component (c) can be arbitrarily selected. f (6) Activity of the curable resin composition of the present invention The amount of energy line added from the bioactive agent needs to be referenced to the absorption wavelength and the Mohr absorption system denier =:;: °01~50 weight part, U 0·01~10 weight part. The addition of the light activity of the addition of (8) The effect is too much to hinder the inspection of the knife (B) Further, in the hardening composition of the present invention, various additives may be used in combination with each other. For the characteristics of s, use: acrylic acid extraction /, α "" * Add known anionic polymerization inhibitors, free A polymerization inhibitors, tackifiers, hardening accelerators, soil materials, dyes, pigments, fillers, etc., and heat stabilizers, primers, and fragrance polymerization inhibitors. In order to increase the specific additive of έ 人 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Scope addition. Examples of the base (4) acid 1 forbidden agent, 醌, p-phenylene-free radical polymerization " dibutyl catechol, pair

7042-9039-PF 15 200813100 Methoxy groups are generally added to cyanoacrylates in the range of 1 〇〇〇〇 ppm. r Further, the tackifier is added to increase the viscosity of the composition. Examples of tackifiers are 'poly(meth)decyl acrylate, methacrylate type copolymer, acrylic acid, cellulose derivative, polyvinyl acetate and poly(α-nitrogen acrylate) )Wait. In addition, most polymer additives are usually added toughness. Examples thereof include an acrylic elastomer, an acrylonitrile copolymer elastomer, a fluoroelastomer, and a fine cerium oxide filler. These substances also function as tackifiers. The curable resin composition of the present invention has a long room temperature and can be rapidly polymerized and hardened by moisture in the atmosphere or on the surface of the body, and can also be activated by active energy rays such as light. The irradiation hardens rapidly, forming a hardened object of a strong early edge' and exhibits a strong adhesion to the metal or plastic. Further, it may be a liquid curable resin composition in which a composition of the component g (Α) α-cyanoacrylic acid vinegar and a photobase generator of a knife (Β) are mixed; the component (Α) and the component (Β) The composition may be a two-component type, and it may be polymerized and hardened by mixing or contacting before use. Such a form can be arbitrarily selected from the types of components (Α) to (C), particularly the combination of components (8) and (6). [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the following: a detailed example. X ′ The blending ratio in the following table is based on weight unless otherwise specified. The amine quinone imine compounds used in the examples and comparative examples are used to express

7042-9039-PF 16 200813100 The compound represented by the structural formula is synthesized by the following method. Table 1 Amine quinone imine compound ------------------- Θ/〇Η3 r6 R5-C-Ν-Ν-CH3 〇Η R5 R6 Amine quinone imine compound a 4-Ν〇2-ΟθΗ4- ---------------- 1""""" ·—·— -CH2OC6H5 Amine quinone imine compound bd - CHs Amine quinone imine compound C CHrCH(OH) - —----------- ---— CH2〇CH2CH=CH2 Amine Imine Compound d (C6H5)2-C(0H) - --------_ """"----- - CHs Amine imidate compound e CH3CH2- ------------- - -CHs Amine quinone imine compound f CH2=C(CH3) - -CHa Amine quinone imine compound g CFs- -ch3 Amine quinone imine compound h n-C3F7 - --~-----CHa -------- (Synthesis of Amine-Amine Compound a) According to the method disclosed in International Publication No. WO 02 02/051 905, an amine quinone imine is obtained. a compound; [, bis-methyl-hydrazine-^-hydroxy-phenoxypropyl)amine-based succinyl phenyl hydrazine. (Synthesis of amine imine compounds b to h) According to the method disclosed in J. Polym. Sci. part A, 38, 18, and JP-A-200-229 927, corresponding methyl carboxylate or bismuth citrate The ester, and the dimethyl hydrazine and the epoxy compound respectively give an amine quinone imine compound. Examples of the present invention and comparative examples 7042-9039-PF 17 200813100 Other materials used in the present invention are commercially available products or reagents as shown below. • Ethyl oc-amino acrylate (·) ThreeBond product, high-grade grade) • Acetone: Tokyo Chemical Industry Co., Ltd. • IRGACURE 369, 907: α-Aminobenzene manufactured by Ciba Speciality Chemicals Co., Ltd. Ethyl ketone compound • IRGACURE 184, 651, 819 · Ciba Speciality Chemicals Co., Ltd. cleavage type photoradical generator ・ One ketone · Tokyo Chemical Industry Co., Ltd. reagent hydrogen abstraction photoradical generator • BF3 ether mismatch : Morita Chemical Industry Co., Ltd., three-fluidized boron diethyl ether salt, R805, Japan AER0SIL Co., Ltd., surface treatment gas phase dioxide, [Examples 1 to 16., Comparative Examples 1 to 7] In the weight ratio, each raw material other than ethyl acrylate was stirred and dissolved in acetone in a shading device. The acetone solution was added dropwise to ethyl acrylate in a light-shielding container, and the mixture was stirred and dissolved to obtain each composition. Next, each of the obtained compositions was subjected to the following tests, and the results are shown in Table 2. [Measurement test of usable time of 2 5 ° C] Each composition was i〇g卩25. The room temperature is sealed and stored in a light-shielding container until the time when the whole becomes gelatinous. Again, marked as. In some cases, the gelatinizer is reacted violently after mixing. 7042-9039-PF 18 200813100 [Photohardenability test] Each composition 〇·5g was dropped into a plastic cup having an inner diameter of 24 mm, and the active energy was irradiated with a focus ultraviolet irradiation device (365 nm illuminance: 100 mW/cm2) manufactured by Hamamatsu ΡΗ0Τ0ΝΙΧ. Line, amount of light. It is not possible to determine from the table after mixing, which is violently reversed from the table. From the time until the hardening of the whole, the person who is smashed and smashed is unable to measure

[Color determination of hardened material] The color tone of the cured product of the above light hardening is visually observed

7042-9039-PF 19 200813100 ί L\ 细列 14 g 0.08 CN1 0.0001 LO OO None (four) Bright butterfly 7 g rH CO CD 1 7天社丨| 30 or more 1 | Unhardened | Chowder J13 g 0.05 CN1 0.0002 LO 3.3⁄4 CD No outline 6 S τ—Η CO CD & Η—Η 30 or more unhardened Example 12 g 0.03 0.15 1 0.15 inch lS CO No discussion 丨 歹丨 J5 1 g rH T—H CD CO CD 0.001 inch Φ cz> 丝不不议 tmu gi-i 0.03 0.15 1 0.15 inch LO CD No secret money deleted 4 g τ—( 1 o.oi 1 CO 0.001 ◦ silk is not allowed to do 10 g 0.03 CO LO cS OO ◦·1 无纤1 | _column 3 B ◦· CO 0.001 inch CD no έ ί! 0月御列 9 g 0.03 oo 寸 lS OO 丨 no Μ 0 month 1 can J2 gr—< ◦· CO 0.001 inch Φ CD Mm no outlines 8 I g 0.03 CO inch eg CD no moons tbfef column 1 g CO inch 1 7 days to 1 30 or more I uncured series 7 g 0.03 CO inch [S LO CD 1 no fiber 1 | Paste 21 1 g 0.02 1 0.02 1 CO 03 τ—Η 〇· 无议瓣J 6 S r—* 0· 03 CO inch ifi m <=> 1 no_month 1 | flap J20 | S [0.02 1 1 0.02 1 CNI cS LO s no secret valve J5 g rH czi LO 0.5h | CD 1无_月1 |Implement ί列19 | g 1 0.03 1 CO CO r—ί 无秘明修 J4 g 0.05 LO | 2.5h | CO 1 无纲1 | Implementation Η18 | B 1 0.03 1 CO LO 1 gr—H 0.04 呀LO CD 1 colorless transparent 1 | flap J17 | g I 0.01 | rH 0.3ι LO od without lion column 2 g rH 0.03 CO lS CJ^ CD 1 ignoring 1 丨 Example 16 8 1 0.03 1 T—H LO ΙΟ [S LO a colorless transparent surface 'J1 g 0.02 CN1 s LO CO 1 ignoring 1 | Example 15 I g 1 0.02 1 〇q 0.0005 LO 0.3⁄4 CO Aluminium (A) a-amino acrylate (B) Amino quinone imine compound a (B) Amine imipenem compound b (C) IRGACURE 184 I (C) IRGACURE 651 (C) IRGACURE 819 (c) Diphenyl fluorenone BF3 ether complex R805 Acetone 25〇C can be shed time s «□ t55 $ hard 彳b#; color (A) a-amino acrylate (B) amine fine imine compound a (8) amine quinone imine compound b (B) IRGA CURE 369 (B) IRGACURE 907 Amine fine azosole C C amine lion ya jump fine do not d amine fine Asian 匕 匕 。. Amine fine azosin 匕 green f amine fine 匕 匕 g ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ^"^Do not R805 丙明^〇C can be shed time IM JD i hardened yarn-dyed project weaving project

7042-9039-PF 20 200813100 / From Examples 1 to 5, it is understood that the use of the amine quinone imine of the present invention can be instantaneously hardened by using a time of use. From the examples, it is known that the addition of an arbitrary radical generating agent enhances the photocurability, and particularly the cracking type radical generating agent is particularly excellent for the photohardening.

From Examples 13 to 15, it can be seen that the sergeant and the gentleman M J know that the organic acid derivative can be added, and the sufficient photocurability can be maintained and the enthalpy can be preserved. Further, from Example 15, it is understood that the amine quinone imine compound b of the present invention having a structure other than the amine quinone imine compound is also effective. As far as the implementation 6, it is understood that there is no adverse effect even if a filler is added. From Examples π to 18, it is understood that the α-aminostyrene compound of the present invention has a long usable time and is instantly hardened by light. From the actual palladium case 19', it is understood that the photocurability can be improved by adding an arbitrary radical generating agent. It is also known from Examples 20 and 2 that the amine quinone imide compound of the present invention can be combined with the cx-aminophenylidene compound, and the photocurability can be improved by adding a radical generator.

From Comparative Example 1, it was found that the photocurability was not exhibited when the amine quinone imine compound and/or the α-aminoacetophenone compound of the present invention were not contained. From the comparative examples 2 to 5, an amine quinone imine compound which is not contained in the aliphatic amide quinone imide of the present invention and which has a relatively large electron-donating substituent to the carbonyl stone, may be added with a cyano group. The acrylate hardens at the same time and lacks practicality. This is considered to be due to the large alkalinity before light irradiation. Further, from Comparative Examples 6 and 7, it is understood that the aliphatic amine quinone imine which is not contained in the present invention has a compound having a strong electron withdrawing substituent to the carbonyl carbon, and although it can be used for a long time, the photoactivity is low. Unable to get sufficient 7042-9039-PF 21 200813100 photohardenability. This is considered to be because the alkalinity before irradiation is sufficiently low, but the light activity is also low. [Bei Shi Example 2 2 ] · Adhesion test and confirmation test of whitening phenomenon The composition of Example 7, Example 19, and Comparative Example 1 was used to confirm the subsequent hardenability, the hardenability of the overflow portion, and the presence or absence of whitening by the following measurement methods. , shown in Table 3. [Measurement method] • Use iron (spcc_SD), glass (loaded, slide), enamel rubber (thin white translucent, thickness 2_) on the adherend, and 25%·55% rh to medium' A drop of each of the adherends is dropped by a dropper and the adherends are adhered to each other. At this time, the amino acrylate was intentionally overflowed from the end. Immediately after the adhesion, the active energy ray was irradiated with a focus ultraviolet ray irradiation device (365 nm illuminance: i 〇〇 mw/cm 2 ) manufactured by Hamamatsu PHOTON IX Co., Ltd. for 1 〇 second (1 J/cm 2 ) and when it was not irradiated, it was confirmed that after pasting, Then, the interface is hardened until it is not moving until the time when the overflow portion is hardened, and whether there is whitening around the overflow portion (unhardened cyanoacrylate compound [hardened by evaporation in the air after evaporation, falling, It becomes a phenomenon that white hardened matter adheres to the periphery). Table 3 Composition of Example 7 of Adhesive Test Item Composition of Example 19 Comparative Example 1 Composition was not irradiated with UV Irradiation UV Irradiation UV Irradiation UV Irradiation UV Irradiation UV Next interface hardening 10 sec 10 Seconds 10 seconds 10 seconds 10 seconds 10 seconds Iron overflow part liquefaction PS 20 minutes 10 seconds 20 minutes 10 seconds 20 minutes 20 minutes whitening phenomenon Whether there is any interface hardening time 2 seconds 2 seconds 2 seconds 2 seconds 2 seconds 2 seconds glass When the overflow part is liquefied, ask 15 minutes, 10 seconds, 15 minutes, 10 seconds, 15 minutes, 15 minutes, whitening, there are some, there are some, then there is a hardening of the interface Pd 50 seconds ^ 10 seconds 50 seconds 10 seconds 60 seconds 60 seconds 矽 rubber overflow part of the liquefaction 瞎Asked 20 minutes, 10 seconds, 20 minutes, 10 seconds, 20 minutes, 20 minutes, whitening, nitrogen, whether or not there is any. 7CM2-9039-PF 22 200813100 It can be seen that for any composition, when no light is irradiated, R Shi asked the child η. Inch 3 is followed by a hardening image in the overflow section. The composition of the embodiment ... 9 can be used by the teacher; there will be a white ash now known as "hunting" by the light, even if the hardening of the stone is as slow as the cement, it can be hardened after a short time . In addition, in all the adherends, when the light is not irradiated, although the hardening of the overflow portion is slow and whitening occurs, the composition of the seventh embodiment and the "the composition can be known that the light can be hardened after the end of the light irradiation without light. The present invention has been described in detail with reference to the specific embodiments of the present invention. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention. Japanese Patent Application No. 2〇〇6_21〇519 is a priority. The date of the application is 2GG6彳August 2nd, and the entire contents thereof are incorporated herein by reference. [Industrial Applicability] The curable resin of the present invention The composition can be used for a known use of a previously used α-mur acrylate-based adhesive, that is, an adhesive which is hardened by moisture, and can be rapidly polymerized and hardened by irradiation with an energy ray such as ultraviolet rays. Therefore, it can also be used for large-area application or coating applications, other coatings, ceramics, castings, sealants, and various resist materials. None element SIGNS LIST 7042-9039-PF 23

Claims (1)

200813100 X. Patent Application Range: 1 · A curable resin composition comprising: (A) α-cyanoacrylate; and (Β) an amine having one or more structures represented by the formula (I) in a molecule & imine compound, and / or α-aminoacetophenone compound: 〇Θ, R2 R1 - C - N - N - R3 R4 Formula (I) wherein R1 represents an aryl group which may have a functional group . R2, R3 and R4 are each independently and represent an alkyl group or/and an aryl group which may have a functional group. The curable resin composition according to the first aspect of the invention, wherein the component (A) has a component weight portion. 3. The curable resin composition according to the first aspect of the invention, wherein the component (B) is an amine quinone imine compound having one or more structures represented by the above formula (I) in a 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, wherein t further comprises (C) an active energy ray radical generating agent. The curable resin composition according to claim 5, wherein the component (A) has a weight fraction of 100 parts by weight of the component (C) of 0.1 to 10 parts by weight. 7. The sclerosing 7042-9039-PF 24 200813100 resin composition according to any one of claims 1 to 6, which is active energy ray hardening 7042-9039-PF 25 200813100 VII. Designation Representative diagram: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 7042-9039-PF 4