TW200815325A - Amine imide compound to be activated by irradiation of active energy ray, composition using the same, and method for curing the same - Google Patents

Abstract

Disclosed is a novel amine imide photobase generator which is more excellent in solubility in resins and curability at low temperatures than the conventional aromatic amine imide photobase generators, while having a sufficient photoactivity. Also disclosed is a novel curable composition using such an amine imide photobase generator, which is applicable to various uses such as reaction systems, adhesive bonding, sealing, casting, molding, paint application, coating or the like. The curable composition can be cured quickly at a lower temperature by irradiation of an active energy ray. Also disclosed are a method for curing the composition and a cured product of the composition. Specifically disclosed is an amine imide compound (A) having one or more structures represented by the general formula (I) below in the molecule. Also specifically disclosed are a composition containing the compound and a method for curing such a composition. In the formula, R1 represents H or an alkyl group and/or aryl group which may have a functional group; and R2, R3 and R4 independently represent an alkyl group and/or aryl group which may have a functional group.

Description

200815325 IX. Description of the Invention: [Technical Field] The present invention relates to a novel amine quinone imine compound which generates a base by irradiation with an active energy ray, and can be polymerized and hardened at a low temperature and rapidly by light irradiation. The composition of the new I member and its hardening method. [Prior Art] Light hardening technology is widely used in adhesives, sealants, coating agents, and anti-friction techniques in comparison with previous thermal hardening techniques, such as low-temperature hardening, shortening of process, short-time hardening, and fine processing. Etch and so on. As a hardening system mainly used for photohardening, it can be largely classified into radical hardening and cationic hardening. In the case of free radical hardening, photoradical generators and (meth) propylene

As an anionic agent for a photobase generator, for example, in recent years, as a solution to such a cationic hard slave, research on the hardening of a basic compound by light irradiation has been conducted. As such a photobase generator

7042-8939-PF 200815325 Aminoformate derivative or a vinegar derivative which produces a grade 1 or 2 amine by light irradiation and is used for polymerization hardening of an epoxy resin (Non-Patent Document 1) . It is known in the art by the technique of generating alkali catalyst by light, and many cases are used for photoresist technology. The narrow line width anti-reagent is used for the development of the edge size stability of the development, and the anionic polymerization type having a small amount of reaction is often used, and the non-patent type is disclosed in Non-Patent Document 2, Patent Document 3). The method of hardening each latex resin by the test substance produced by light is an amine which is representative of the basic compound, and these amines are still the most useful light generation test to date. For example, a substituted benzylamine-based derivative produces i- and 2-grade amines by light irradiation. (Non-Patent Documents 3 to 5). However, most of these compounds are produced with low efficiency and alkaline compounds produced by light irradiation! Grade or grade 2 amines have low alkalinity and do not have the problem of catalyst activity required to sufficiently harden the epoxy resin. As a photochemical generator capable of producing a third amine which is more photochemically detectable, there is a report of an aromatic amine quinone imine compound (Patent Document 4, (8), and an epoxy resin, a polyvalent thiol compound, etc.) The addition hardening reaction is reported as a case where the temperature at the start of heat hardening is lowered after light irradiation. Further, the aromatic amine sulfoxide compound and the singlet. triplet sensitizer: hydrogen extraction type photo radical A combination of the generating agents (Patent Document 5). However, these aromatic amine sulfonamide compounds have high crystallinity, limited solubility to the resin, or the heat curing temperature after light irradiation is not sufficiently low. A known amine-bromide compound is a compound which can be converted to a tertiary amine by Curtlus rearrangement by heat decomposition, and is a compound which can be decomposed by low-temperature heating to produce a tertiary amine (IV) imine. Yuji

7042-8939-PF 6 200815325 Amine quinone imine compound having a carbon-bonded carbon structure (Patent Document 6). However, the photoactivity of the amine quinone imine compound having a low heat decomposition temperature is not known. [Non-Patent Document 1] Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Ed. by G. Bradley, John Wiley and Sons Ltd. (1998, p479-p545) [Non-Patent Document 2] Pure and Appl. Chem., 64, 1239 (1992) f % [Non-Patent Document 3] J. Org. Chem., 55, 59 1 9 (1 990) [Non-Patent Document 4] Polym. Mat. Sci. Eng , 64, 55 (1991) [Non-Patent Document 5] Macromol., 28, 365 (1 9 95) [Patent Document 1] European Patent No. 599571 [Patent Document 2] European Patent No. 555749 [Patent Literature] [Patent Document 5] Japanese Laid-Open Patent Publication No. 20 03-26 772 [Patent Document 6] Japanese Patent Application Laid-Open No. Hei. 00-2 2 9927 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a resin which is superior in solubility and low-temperature hardenability to a resin than a conventional aromatic amide amide imine photobase generator. And a novel photo-active novel amine-bromide-based photobase generator; use: a reaction system; and can be used for subsequent, dense Sealing, casting, forming, coating I, coating, etc.

7042-8939-PF 7 200815325 Various types of applications, novel curable compositions which can be hardened at a lower temperature and faster by irradiation with active energy rays; hardening methods, and hardening [to solve problems] Means] In order to solve the above problems, it has been found that an amine quinone imine compound having a specific structure among the amine quinone imine compounds which are mainly used as a thermosetting catalyst for epoxy resins is used, and energy rays such as ultraviolet rays are used. The activity is high and the present invention is achieved. That is, the present invention provides the following amine quinone imine compound, composition, and polymerization hardening method. σ 1) A photobase generator which is produced by irradiation with an active energy ray and has a structure of the above formula (1) in a molecule, and is represented by the following formula (1): Moon ruthenium compound: Formula (I) )

Wherein 'R1 represents a group, and R2, R3 and R4 are each independently or/and an aryl group. The alkyl group or the aryl group which may also have a functional group independently represents an alkyl group which may also have a functional group. 2) A composition comprising: a functional amount of a line irradiated to produce a base, which is a formula (I) The amidoxime-catalyzed polymerization or rearrangement of the indicated structure is white; and (Β) contains a compound of more than a basic species, έ: (A) a photobase generator, which is acted upon by One or more molecules in the molecule, and the following one imine compound; and (Β) contains one type of alkaloids in the form of a base.

7042-8939-PF 8 200815325 The basic catalyst produced by the above (A) amine quinone imine compound by the active energy ray, is used as & X ρ ^ & Or rearranged into other dissociated catalysts: ~ General formula (I), R2 〇II Θ R1—CH—C—N^N^_R3

OH V R4 where 'R1 is H-vh»!__r a χ.. or may also have an alkyl or/and an aryl group of the g-energy group, R2, R3 and R4, respectively, heterogeneous *main one +, knife It is also possible to independently have an alkyl group or/and an aryl group having a functional group. 3) Intrusion 4 as described in 2) above, wherein the above (β) is one or more compounds which are polymerized by alkaline catalyst or rearranged into other t 刎

There are two or more compounds in the molecule which are prepared as w and A ^ &oxy groups. 4) The compound of the above-mentioned 2), wherein the above (B) is reacted or rearranged by the alkaline catalyst water a into a compound of one or more types of sorrow A mixture of a compound having more than two % mercapto groups and a compound having more than one molecule of a thiol group. Eight 5) The body of the heart as above 2) ~ 4)! The composition according to any one of the preceding claims, wherein the component (B) has a weight of 100 parts, and contains a component (A) having a weight of 50 parts by weight. 6) The έ7, and the mash as described in 2) above, further comprising: Γ) a performance amount line radical generating agent. 7) The group of people in the above-mentioned 6) encounters the person S幡10 from the ΑT (β) by the experimental catalyst mouth reaction or rearrangement to another eight; meat 1 ancient 9 plus one or more The compound is a compound having two or more t &

7042-8939-PF 9 200815325 8) The composition according to the above β), wherein the above (B) is polymerized by alkaline catalyst or rearranged Α ^, and the field test is written in another month. One or more compounds of the form are a mixture of a compound having one or more epoxy groups and a compound having two or more thiol groups in the molecule. In the composition described in ', Free 6', the above (c) active energy ray radical generating agent' is a cleavable photoradical generator. 10) The composition according to the above 6), wherein the component (B) contains 100 parts by weight of the component (B), and each component has a weight of 0·1 to 50 parts (A). For the component (A), the weight portion contains the right η ηι ιλ ^ ; and the shape 3 has a weight component (C) of 0·〇1~1〇. (1) A method for the detection of containing (A) light by the active energy line to produce alkali, .v, you are wrong

The alkali generator has one or more molecules in the molecule, and is represented by the following formula (I) M > AW version of the imine compound; and (β) contains ^L by the basic catalyst polymerization anti-library or tongue秘&,) 3 々 从 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

The composition of the material, at the same time, as shown in Fig., and the work k A ... # this amount of wire and heating, or by the irradiation of the active energy line after the twisting ..., the above composition is polymerized and hardened: I) 〇R2, R4

In the formula OH, R1 represents hydrazine or may also be cis- Gan DO D〇 J, has an alkyl group or/and an aryl group of R-decyl group, and R2, R3 and R4 are each independently or/and an aryl group. (4) 12) The compound described in the above 11), wherein the above (B) is polymerized by alkaline catalyst or rearranged into another shape, and one or more compounds are

7042-8939-PF 10 200815325 A compound having two or more epoxy groups in its molecule. (13) The method according to the above (11), wherein the medium polymerization reaction or rearrangement is a compound having more than two kinds of epoxy groups in the chemical substance or the molecule of the other species And a method according to any one of the above items 11), wherein the component (B) is 100 parts by weight, and contains 〇·b 5 The composition according to the above 11) wherein the composition contains: (C) an active energy ray radical generating agent. Further, the method according to the above 15), wherein the above-mentioned polymerization or rearrangement is a second form of a compound having a compound having two or more epoxy groups in a biololecular molecule, which is 17 The method according to the above 15), wherein the above-mentioned Zen double eight; 5 tongue 4 outer & IB) hunting is performed by an organic solvent reaction or rearrangement to another form of work, and the phase is present in the touch molecule. The vu ^ self-compound is a mixture of two or more epoxy-based compound fish in a compound of more than one thiol group. The knife has 2 18) as described in the above 15) Method, a straight-through radical generating agent, a cleavage type photoradical generating agent) active energy ray 19) The composition of any of the above items 15) to 18) 'for the component (8) (10) by weight method 'where the above ingredients ( A) The component (C) is contained in the weight portion of the component (A) and the weight of the component. υ· 10 parts by weight, as found in the above 1), the following general formula Imine compound (1) is used as an amine brewing line (light) activity having sufficient energy: structure

7042-8939-PF 11 200815325 And excellent in solubility and low temperature hardenability of resin: If Θ @/R2 C-N__N 3 R4 photobase generator Formula (I)

R1—CH

I

In the formula, RH represents an anthracene or an alkyl group or a aryl group which may have a functional group. R2, R3 and R4' each independently represent an alkyl group or/and an aryl group which may have a functional group. According to the above 2), it is found that the ((Α) amine-bromide compound, and (8) the reactivity of the compound which is an essential component by the polymerization of the catalytic catalyst or rearrangement of the compound of the other form or the other form] Polymerization) changes (lifts) by light irradiation. Further, in the above 3), it was found that the component (B) is a compound having two or more epoxy groups in the molecule, and is combined with the (1) amine quinone imine compound. When the active energy ray is irradiated, the curability at low temperature (low-temperature hardenability) is more excellent. Further, in the above 4), the composition contains the amine quinone imine compound of the present invention and the component (8) which is a compound having two or more epoxy groups in the molecule and two or more sulfurs in the molecule. A mixture of alcohol based compounds. In the composition, it was found that the low temperature hardening property after the active energy ray irradiation was better. Further, in the above composition having better linear radical generating property, the composition is further added with active energy. It was found that the active energy ray hardening of the composition was obtained. In the above 11)~19), it is characterized by: simultaneous advancement

7042-8939-PF 12 200815325 Schedule the irradiation and heating of the active energy rays or heat them after light irradiation. [Effect of the Invention] The present invention provides a novel amine ugly imine compound which is a photobase generator which is superior in solubility to a resin and low-temperature hardenability to a resin which is more excellent than the prior aromatic amine quinone imine photoreagent. A novel composition for curing (polymerized, harden) which is hardened at a lower temperature and rapidly hardens, a hardening method thereof and a hard: crucible $' can be used for bonding, sealing, casting, molding, painting, coating A variety of uses. The above-mentioned new retentive amine quinone imine compound is used as a curing catalyst, for example, in combination with an epoxy resin or the like, and heat curability is added to impart curability to irradiation by an energy ray (light).曰 [Embodiment] = The present invention will be described in detail below. The g-shaped g of the present invention is produced by the action of the line-illuminating test, and is obtained in the molecule! One or more of the amine quinone imine compounds having the structure represented by the following formula (1): General formula (I)

N R2 R3 R4 〇 ηΛ II Θ R1—CH—C——Ν-

In the formula OH, R1 represents Η or may be and right is I p9 D0 flying knife J /, having an alkyl or / and aryl group, R2, R3 and R4, is a public 倔 * main - ▲ you are independent The table is also not > lean or / and aryl. The alkyl group having the s group is synthesized in the sigma compound having the above amine quinone imine, and can be used.

7042-8939-PF 13 200815325 The method of knowing. For example, Encyclopedia of Polymer Science and Engineering, John Wiley & Sons Ltd., (1985), Volume 1 'P740' can be reacted with a corresponding carboxylic acid ester with a halogenated hydrazine and a sodium alkoxide or It is obtained by reaction with hydrazine and epoxy compounds. The method for synthesizing the amine quinone imine compound used in the (A) photobase generator of the present invention is not particularly limited, and considering the simplicity and safety of the synthesis, the carboxylic acid ester and the hydrazine and the epoxy compound are used. The synthesis method is preferred. The synthesis temperature and time at this time are not particularly limited, and are generally 〇1 to 〇〇. (: Mixing 30 minutes for 7 days to obtain a compound having the desired amine quinone imine structure. Since the present amine amide imine compound has heat such as an aromatic amine quinone which is previously known as a photobase generator The decomposition temperature is low, the side reaction can be inhibited, and the thermal decomposition of the female imide can be inhibited. Therefore, the temperature in the initial stage of the synthesis reaction is in the range of 〇25 C, which will be in the final stage of temperature adjustment & (9). <丨月市(The sour vinegar of the raw material of the amine ylide imine compound of the invention, as long as it is in the molecule, has Na H) the early functional or polyfunctional tickish western compound of the ruthenium structure. For example, = methyl vinegar: lactic acid B, lactic acid _, 2_ basal n-butyric acid B _, 2 _ = 夂 夂 酉 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁 扁"Different", tartaric acid dimethyl vinegar, etc. 'is not limited thereto. The use of 曰' can be obtained in the molecule of a complex amine amide imine structure of the amine sub-fe compound. There is no original ease of use of the hydrazine compound or The nature of the test substance produced: L: With !, dimethyl dimethylamine is preferred. , another - epoxidation of raw materials ^: to

7042-8939-PF 14 200815325 . It is a compound which has one epoxy propylene appearance, glycyrrhizin, and propylene methyl group in Molecular Yin. For example, licorice% propylene glycidyl ether, glyceryl ether, phenyl glycidyl ether, methyl hexyl water-reducing epoxy compound, or mono-pentyl diglycidyl ether such as glycidyl bond, 0-phenol may be used. Glycidyl ether, alcohol-derived - condensed ...% water Gan (4), bispan A and epichlorohydrin - hydrazine glyceryl ether, etc. so-called ring _ lipid, aliphatic. aromatic alcohol and epichlorohydrin: epoxy The MIS water derived from the alkali acid and epichlorohydrin, the MIS water derived from the polyol, the water-added A and the epi-chlorinated epoxy age can be obtained as follows: A polyamine quinone compound is used. The (A) amine quinone imine compound of the present invention having an internal and an imine structure, which is capable of effectively reacting as a reaction speed by reactive light, by the irradiation of energy rays Active catalyst or retarder. Further, in one aspect of the present invention, the above-mentioned (A)feg&imine and (B) are mixed by a basic catalyst polymerization reaction or rearranged into a compound of another form or more. A polymerizable (curable) composition. ^ As the above (β) by a basic catalyst polymerization reaction or rearrangement to one or more other compounds, a reaction system (known as a composition) which is polymerized by a known basic catalyst can be used. . For example, a Mi chae i addition reaction, a separate polymerization of an oxygen compound with a basic catalyst, an epoxy compound and/or a (meth) acrylate compound and/or an episulfide compound, and a thiol, Polymerization of a compound of an amine group, a phenol, an isocyanate, a carboxyl group and/or an acid anhydride group, polymerization of a cyanoacrylate compound, etc., but is not limited thereto.

7042-8939-PF 15 200815325 For human use: the amine of the invention is made of an active energy ray (light) hard U 曰) composition, the oxygen tree wax or the main form of eight points (8), can be good The composition of cyclodextrin/the main component is used, and the composition of the crucible & compound as a main component and the polythiol air knife is used, but it is not limited thereto. In the composition of the present invention, the amount of ^ ^ ^ ^ ^ is based on (8) by the combination of an initiating catalyst poly 2 = compound to add (4) "reaction or rearrangement into a different form of the chemical 5 The type varies, for example, two kisses, for the epoxy resin _ weight portion, with .... weight = soil with 0. 5~30 weight portion is better. Not full (K1 weight #1 in ',,, foot, and beyond 50 parts of weight °, 丨 hardenability does not deteriorate. The characteristics of the hardened material of the 漉 寺 寺 寺 Π Π 使用 使用 使用 使用 使用 使用 使用 使用 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 寺 寺Phenol a disk # (4) Derived diglycidyl hydrazone and its derivatives, etc. The main and phenotype liquid ring pediatrics t: 丨 is the ring - double age... ί月曰, phenolic epoxy block type Epoxy resin, isocyanic acid, material type oxygen resin, epichlorohydrin-derived shrinkage = (4) fat, fat, aromatic alcohol and water glycerin, polychloric acid and epichlorohydrin-derived glycerin, and materials Biological, adding water (hydrogenation) double W shrinking glycidol _, 3,4_epoxy I 甲其's derivative I methylcyclohexyl slow acid brewing, double ... methyl ~ 3, 4, oxygen W and H 4-% fluorenyl- 6-methyl ketone is good -: aliphatic cyclic epoxide such as oxime ester, and its derivative: soil methyl) methyl double-resistive epoxy resin, Li Yi, 5, 5-dioxa+%, bismuth hydrazine glyceride, butyl aryl α / t epoxide, etc., but not limited to those = imitation oxime resin products, can be, As a market

For example, Japan Epoxy Co., Ltd. JER

7042-8939-PF 16 200815325

Coat 828, 1001, 801, 806, 807, 152, 604, 630, 871, YX80 00, X8034, YX4000; EPICR0N 830, 835LV, HP4032D, 703, 720, 726, HP820 manufactured by Dainippon Ink Industries Co., Ltd.; EP4100, EP4000, EP4080, EP40 85, EP4088, EPU6, EPR4023, EPR1 309, EP49-20, Nagase ChemteX Co., Ltd., Denar Co., Ltd., EX411, EX314, EX201, EX212, EX252, etc., but not Limited to those who are. These compounds may be used singly or in combination of two or more. Among these, a ring-shaped epoxy resin can obtain a composition having a good balance between the price and the curability, the adhesion of the cured product, and the physical strength. Further, when an aliphatic or cyclic aliphatic epoxy compound is used, a composition having excellent flexibility, transparency, and weather resistance of the cured product can be obtained. The polythiol compound to be used in combination with the above epoxy resin may be a compound having two or more thiols in the molecule. Specific examples thereof include trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate, propylene glycol dithioglycolate, and 1,4-butanediol dithioglycol. Alcohol ester, trihydrocarbyl propane trithioglycolate, pentaerythritol tetrathioglycolate, bis(2-mercaptoethyl)ether, anthracene, 4-butanedithiol, anthracene , 3, bistridecyl benzene, 4,4'-thiodiphenyl thiol, ι, 3,5-trimethylmethyl- 2 4 6-trimethyl benzene, 2, 4, 6- Trisyl-s_triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, polyether containing terminal thiol group, polythioether containing terminal thiol group, ring The thiol compound obtained by the reaction of the oxygen compound and hydrogen sulfide, and the reaction of the polythiol compound with the epoxy compound are obtained by a thiol compound having a thiol group at the terminal, but are not limited thereto. Commercially available mercaptan

7042-8939-PF 17 200815325 For example, Jer Mate QXll, QX12, JER Cure QX3G, QX40, QX6q, qX9qq, Capcure CP3-800, 〇TG, manufactured by Japan Chemical Co., Ltd., EGTG, TMK, pETG, 3-MPA, TMTP, PETP, TORAY Fine Chemical Co., Ltd. TM〇k〇i LP-2, LP-3, Polythiol QE-340M, etc., but are not limited thereto. These compounds may be used singly or in combination of two or more. As the thiol compound, it is preferred that the surface of the storage stability be as small as possible. Further, the heat-resistant surface of the cured product is more preferably a thiol compound containing an aromatic ring in the molecule. The range of the thiol equivalent ratio of the epoxide in the composition of the thiol compound is 0. 5~2. Good, add 〇. 8~丨.3 to the range is better. When a thiol compound is added in the above range, a composition having a better curing rate and a balance of strength or heat resistance of the cured product can be obtained. In the present invention, when the (C) active energy ray radical generating agent is further added to the composition containing the components (A) and (B) as a main component, the photoactivity of the composition can be further improved. As the active energy ray radical generating agent, a conventional hydrogen extracting type photoradical generating agent and/or a cleavable type photoradical generating agent can be used. Examples of the hydrogen extraction type photoradical generator include 1-methylamine, 2-methylnaphthalene, 1-fluoronaphthalene, 1-naphthalene, 2-naphthalene, and [monobromonaphthalene, 2-bromine]. Naphthalene derivatives such as naphthalene, 1-indolene, 2-mothene, 1-naphthol, 2-naphthyl alcohol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanophthalene; 1,2 - benzopyrene, g 1 〇 - monochloro, 9, 10-dibromoindole, 9, 10-diphenyl hydrazine, 9-cyano hydrazine, 9, 1 cyano cyano, 2 , 6,9,1 0-tetracyanoquinone isomer derivative; anthracene derivative; 啼7042-8939-PF 18 200815325 oxazole, 9-methylcarbazole, 9-phenylcarbazole, 9-propan-2 1-yl- 9H-carbazole, 9-propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole_9__ethanol, g-mercapto-3-nitro-9H-carbazole, 9 -methyl-3,6-dinitro-9H-carbazole, 9-octoxazole, 9-oxazole methanol, 9-oxazolidine acid, 9-carbazole propionitrile, 9-ethyl-3 ,6-dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9-(ethoxycarbonylindenyl)carbazole , 9-(morpholinylfluorenyl)carbazole, 9-ethazole, 9-propenylcarbazole, 9-benzyl -9H - oxazole, 9-carbazole acetic acid, 9-(2-nitrophenyl)carbazole, 9-(4-mercaptophenyl)carbazole, 9-(ethoxymethyl-2-methyl-propane -9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxyl Carbazole derivatives such as carbazole, 3,6-diethyl-9-ethylcarbazole; benzophenone, 4-phenylbenzophenone, 4,4'-bis(dimethoxy) Benzophenone, 4,4,-bis(dimethylamino)benzophenone, 4,4,-bis(diethylamino)benzophenone, 2-benzoic acid benzoic acid methyl ester , 2-methyl dimethyl quinone dibenzoquinone dimethyl 4-yloxy bis- 2, 4, 4, 6-dimethylbenzhydrazide and other diphenylmethyl-street organisms; aromatic compounds ; [4-(4-methylphenylthio)phenyl phenyl ketone; oxygen: benzoquinone. (iv) ketone, 2-chloro-, 4-chloro-, her, 2-isopropyl primone, 4 — Isopropyl thiox ig, 2, 4-dimethyl thioxanthene, 2, [diethyl thioxanthone, chloro- 4-propoxy (tetra) ketone, etc. (tetra) ketone derivatives or coumarin derivatives Things. Further, the cleavable photoradical generator is a radical generating agent which is formed by pulverizing the compound to generate a radical, and is exemplified by two specific examples, and examples thereof include a stimulating (tetra) derivative and a styrene-butadiene derivative. = Meijiu (4); ketone phosphine oxide; thiobenzoic acid S, benzene;

7042-8939-PF 19 200815325 Titanocenes and derivatives of these polymers are not limited thereto. As a commercially available cleavage type photoradical generator, 1 - (4-11 alkyl benzoquinone) - hydroxy-1-methylethane, 1-(4-isopropylbenzhydrazide) 1-hydroxy-1-methylethane, 1-benzylidene-1-hydroxy-1-methylethene, benzo[4-(2-hydroxyethoxy)-benzamide]-1-hydroxyl I-methylethene, benzo[4-]propenyloxyethyl)-benzhydrazide]-1-hydroxy-1-methylacetamidine, diphthoquinone, benzyl-1-carbyl-cyclohexyl Ketone, mercapto dimethyl dimethyl homo, bis(cyclopenta-diyl)-bis(2,6-difluoro-3-indenyl-phenyl)titanium, (776-cumene)-(々5 ~ cyclopentanyl)-iron hexafluoroate (II), trimethylphenylphosphonium phosphine oxide, cone (2,6-monodecyloxy-benzoinyl)-(2, 4, 4-three Methyl-pentyl)-oxidized scale, bis(2,4,6-trimethylphenylhydrazinyl)-2,4-dipentyloxyphosphine oxide or bis(2,4,6-trimethylphenylhydrazine Phenyl phosphine oxide, (4-cylinyl strepto) - ι ~ benzyl-1-dimethylaminopropane, 4-(methylthiobenzimidyl monomethyl-1 - The morphyl ethane or the like is not limited thereto. In the present invention, the (C) active energy The linear radical generating agent, that is, the hydrogen extracting type or the cleavable type photoradical generating agent may be used singly or in combination of plural kinds, only in the stability of the radical generating monomer, or the composition of the present invention. The sclerosing surface is preferably a combination of one or more types of cleavable photoradical generators, and a high molecular weight type having a structure in which a cleavage type photoradical generator is introduced into a polymer oligo/polymer. It is preferable because there is little deflation during hardening and hardening. Further, depending on the type of the radical generating agent, there is a possibility that the effect is different depending on the structure of the combined (A) amine quinone imine compound. Is absorbed by the amine quinone compound and the free radical generator

7042-8939-PF 20 200815325 Line = wavelength combination, so the optimum combination of (A) amine quinone imine compound and (c) radical generator can be arbitrarily selected. In the radical generating state of the composition of the present invention, it is necessary to consider the absorption wavelength of the radical generating agent and the molar absorption constant of the moiré, and generally the weight of the (A) amidoximine compound 1 is 10 It is better to use 〇· 〇5~5 weights. If it is too small, the photo-activity enhancement effect of the filling knife cannot be obtained, and if it is too much, it will hinder the action of the alkali catalyst. The combination of the invention may be added to a compound containing one epoxy group in the molecule and/or a compound having one thiol group in the molecule. These are used for the improvement of the totality of the composition (2), the improvement of workability, the adjustment of reactivity, and the like. When these rings = compounds and thiol compounds are added, it is preferable to consider the blending ratio of the epoxy compound and the thiol compound in the entire epoxide equivalent and the thiol equivalent adjusting group σ. ° Further, in the composition of the present invention, the coloring agent such as pigments and dyes may be blended in an appropriate amount without damaging the target of the present invention; calcium carbonate, talc, emulsified stone, and oxidation Inorganic filler such as silver hydroxide, conductive particles such as silver; flame retardant; preservative enhancer such as boric acid ester or phosphate ester, inorganic acid or organic acid; organic filler such as acrylic rubber and rubber knee; I: amine a wide range of phenoxy polydecyl acrylate resins such as a resin, a polyamide resin, a bis-A phenoxy resin or a bis(tetra) fluorene-bis 19F copolymerized phenoxy resin; a polyacrylate resin. Amine resin; polyamine vinegar resin; poly-resin resin; % ethylene shrink; (iv) grease '· SBS resin and epoxy resin denatured body; resin and stereotyped polymer or thermoplastic elastomer; plastic Additives, organic solvents, anti-foaming agents, coupling agents, smoothing agents, rheology modifiers, etc.

7042-8939-PF 21 200815325 agent. By such addition, it is possible to obtain a resin composition, a strength, a flame retardancy, a heat conductivity, a storage stability, and a workability and a cured product. The (A) amine quinone imine compound of the present invention is an active energy line used for activation of an alkali photobase generator by irradiation with an active energy ray such as ultraviolet rays, and is an electron beam, an ultraviolet ray, a visible ray or the like. Further, the amount of irradiation is only a sufficient amount to activate the (A) amine quinone imine compound, and is limited. For example, when the mixture of the epoxy resin and the polythiol compound is used as the component (8), the ultraviolet irradiation amount is as long as possible. .lj/cm2 or more. Further, the composition of the present invention can be heated by irradiation with an active energy ray at the same time, can be irradiated with less energy rays, and hardened in a short time, and the (1) amine quinone imine compound of the present invention, It is also possible to greatly enhance the polymerization hardenability by the activation of the active energy, such as heat, by using only the active energy ray in combination with activation only by heating.

= It is very useful for the polymerization hardening of this hair styling because it is a light-emitting hot wire at the same time as ultraviolet rays. , σ The hardened material of the resin obtained by the treatment of the composition of the present invention is cured by the treatment of the composition of the present invention, and is irradiated with the composition of the present invention as long as it is placed at room temperature. Without using this property, it can be used for photopolymerization to obtain a cured product. Die, coating, coating == forming, or subsequent, sealing, soil laundering, various uses. Moreover, the combination in the present invention can be used for energy irradiation, "the object is not hard immediately after the irradiation, or can be placed after a short time at room temperature or under heating.

7042-8939-PF 22 200815325 It is hardened, such as the latter's sexual f, or as represented by the adhesive of DVD, even if it is built and does not penetrate the light awkward ^, at the temple, the composition After the energy is irradiated, it can be applied by coating. [Examples] Hereinafter, the present invention will be specifically described by way of a member's example, but the present invention is not limited to the following examples. Further, the blending ratio in the following table does not specifically mention the basis weight basis. The amine quinone imine compounds used in the examples and the comparative examples were synthesized by the following methods using the compounds ' represented by the structural formulas shown in Table 1. [Table 1 ]

(Synthesis of Amineimine Compounds A to I) According to the method disclosed in J. Polym. Sci, Part A, 38, 18, 3428 (2000) and JP-A-200-229927, corresponding carboxylic acid Methyl ester or ethyl carboxylate, and dimethyl hydrazine and epoxy compound give each 7042-8939-PF 23 200815325 amine S & imine compound (the amine quinone imine compound A~d of the present invention, excluding The aliphatic amine-containing imine compounds E to H of the present invention are not contained in the #香族胺醯iamine compound I) of the present invention. Formula (Synthesis of Amine Yttrium Compound J) #遌照国际专利专利w〇2002/05 1 905 The method disclosed in the method of obtaining a fragrant amphoteric amine compound, j dimethyl hydrazine? - hydroxy-3 phenoxy propyl amide imipenem (not contained in the aryl of the invention; amine: imine compound J). The amine quinone imine compound is used in the present invention. The materials of the π and %% and the comparative examples are commercially available products or reagents as shown below. • Methanol··Tokyo Chemical Industry Co., Ltd. Pharmacopoeia: Phenyl glycidol ϋ ϋ 合 合 合 U U U U U U U U U U U U U U U U U U U ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO ISO胄-denatured diphenylmethane diisocyanate • EPICRON 835LV: Dainippon ink industry name 斗 a bisphenol epoxy resin made by Toki Industry Co., Ltd. • Dina Kao EX-911 ·· Nagase ChemteX H ^ a aliphatic ring made by the company Oxygen resin • JER Cure QX30: Japan's ring gas, pepper, surname, eucalyptus, and other three-functional aliphatic polythiol. JER Cure QX40: Japan's epoxy resin, q-type compound, 4-functional aliphatic polythiol • IRGACURE 184 : Ciba Specialitv r,. a Chemical Co., Ltd. 7042-8939-PF 24 200815325 Fracture type photoradical generator made by IRGACURE 651 : Fracture photoradical generator made by Ciba Speciality Chemical Co., Ltd. • DAR0CURE 1173 : Ciba Speciality Chemical Fracture type photoradical generator manufactured by the company: Lucirirn TPO: Fracture type photoradical generator manufactured by BASF Japan Co., Ltd. Acetylene ketone, Dongfang, Chemical Industry Co., Ltd. reagent hydrogen extraction type photoradical generator [Example 1] 15 § Amine imipenem compound A, 55 g methanol was added to a transparent vial having an inner diameter of 33 _ 55_ And 3.0 g of pure water, the amine quinone imine compound A was dissolved. The side of the vial was stirred with a stirrer under a nitrogen atmosphere, and a UV irradiation apparatus was manufactured by Hamamatsu ΡΗ0Τ0ΝΙΧ, and an active energy ray of 365 nm illuminance: 10000 mW/cra2 was irradiated, and after a predetermined second irradiation, a pH meter manufactured by Horiba Co., Ltd. was used. D22, pH was measured. The pH before the irradiation of the active energy ray was 8.5 〇, and the enthalpy after the irradiation of the active energy ray for 10 seconds was 8. 53. The pH after exposure for 2 sec. was 8.54, and the pH after irradiation for 30 seconds was 8 55. The pH after exposure to 5 sec. was 8.56, and the alkalinity was enhanced by irradiation with an active energy ray, indicating that the amine quinone imine compound A was a photoreceptor. [Example 2] Phenyl glycidyl ether······················································ g) Mix at room temperature to obtain a homogenous solution. The solution

7042-8939-PF 25 200815325 The amount of 7. 5mg was measured by a differential scanning calorimeter (DSC) in a sample container, and the active energy ray was irradiated by a UV-ray irradiation device (365mn illuminance: 100 mW/cm2) manufactured by Hamamatsu ΡΗ0Τ0ΝΙΧ. The reaction start temperature after irradiation with 9 J/cm 2 before irradiation was measured by measurement DSC. For DSC measurement, DSC (DSC11O) manufactured by Seiko Instruments Inc. was used, and the temperature was measured at a temperature increase rate of 10 ° C /min in a sealed container in a nitrogen atmosphere to 25 to 280 ° C. From the obtained DSC chart, the heat rise temperature (DSC Onset) was determined, and this was taken as the reaction start temperature. The reaction starting temperature before the irradiation of the active energy ray is 1 53. 7 ° C, and the reaction starting temperature after the irradiation of the active energy ray is 1 丨 5 · 丨, the polymerization of the epoxy resin, the amine oxime of the present invention The imine compound exhibits a high catalytic action by irradiation with an active energy ray, and is shown to be effective as a photobase generator. [Example 3] In UR IC Η3 0 : 1 〇g mixed amine quinone imine compound a : 〇 · 5g and IRGACURE 651 : 0.2g was stirred at room temperature to form a homogeneous solution. After the solution was mixed with ISONATE 143LP: 4·5g and stirred at room temperature to form a homogeneous solution,

Immediately, it was applied to a glass plate at a thickness of 1 〇 0 # m, and the active energy ray was irradiated with a spot ultraviolet irradiation device (365 nm illuminance: 1 〇〇 mW/cm 2 ) manufactured by Hamamatsu PHOTONIX Co., Ltd., and compared before irradiation and after irradiation at 6 J/cm 2 . The coating film is "it is hardenable. The time before the coating film is hardened to the non-viscous elastomer before the active energy ray irradiation is 40 minutes, and the coating film after the active energy ray irradiation hardens to the non-viscous elastomer. The polymerization time of the polyol and the polyisocyanate is 30 minutes, and the amine quinone imine compound A of the present invention is also effective as a photobase generator which exhibits a high catalytic action by irradiation with an active energy ray.

7042-8939-PF 26 200815325 [Examples 4 to 9 and Comparative Example 1] The materials were placed in a light-shielding container at room temperature (25 〇 mixed mixing) in the weight ratio shown in Table 2 to prepare Examples 4 to 9 and Comparative Examples. Further, the amine oxime imide compound A is usually liquid at room temperature, and is dissolved at 55 ° C in the case of crystallization, and then stirred and mixed. The obtained composition is evaluated as follows. The results of the test are shown in the respective tables. The methods of the evaluation tests are as follows: • Solubility test of the amine quinone imine compound The material was mixed and stirred at room temperature (25 〇c) in the weight ratio shown in Table 2, visually observed. To observe whether all of the amine imine compound was dissolved. • Determination of reaction initiation temperature and reaction peak temperature. 7.5 mg of each composition was weighed into a sample container of a differential scanning calorimeter (DSC), and a UV irradiation apparatus manufactured by Hamamatsu ΡΗ0Τ0ΝΙΧ was used (365(10) Illumination: l〇0mW/cm2) Irradiation of a specified amount of active energy ray. The reaction start temperature of the composition after irradiation with a specified amount of accumulated light was measured by DSC. The dsc (DSCIIO) manufactured by Seiko Instruments Co., Ltd. was used for DSC measurement. , The sealed container was subjected to a heating rate of 1 (rc /min, temperature was measured to 25 to 280 C °, and the obtained DSC chart was used to determine the hardening temperature (DSC Onset) in the nitrogen atmosphere. This was taken as the reaction starting temperature. The maximum temperature is taken as the peak temperature of the reaction. • The measurement of the hardening time is carried out by dropping 0.5 g of each composition onto a glass slide, and irradiating the specified amount with a UV irradiation apparatus (365 nm illuminance: 1 〇〇 mW/cm 2 ) manufactured by Hamamatsu ΡΗ 0Τ0ΝΙΧ. Active energy line. Test before irradiation and after specifying the amount of acid light

7042-8939-PF 27 200815325 The test piece is placed in a constant temperature oven set to the specified temperature, and the surface of the composition is hardened until it is not sticky. • Storage stability test The composition was sealed in a 10 ml light-shielded bottle and stored in a dark place in a 25 ° C constant temperature chamber, and the composition gelled to lose fluidity [Table 2] Example 4 Example 5 Example 6 Implementation Example 7 Example 8 Example 9 Comparative Example 1 EPICRON 835LV 100 100 100 100 100 100 100 Amino quinone compound A 7 12 15 15 15 15 Amino quinone compound J 12 DAR0CURE 1173 2 2 2 2 LUCIRIN TP0 2 IRGACURE 184 4 benzophenone 3.64 Amine ylide compound solubility (25 ° C) Good good good good good good good insoluble reaction start temperature light non-irradiation 152.9 152.2 151.5 153.3 151.5 153.1 rc) after irradiation 9 J / cm 2 149.1 146. 1 144.8 149.7 143.5 149.4 Unable to react to peak temperature Light not irradiated 178 175.8 174.3 174.9 174.3 174.8 Obtained uniform α) After irradiation of 9 J/cm 2 177. 1 173.8 170.5 173.1 170.3 173.2 Composition hardening time ooo°c) Light not irradiated 160 120 90 120 90 90 without measurement (minutes) After irradiation at 9 J/cm2 140 100 60 60 60 70 25 ° C preservation stability for more than 1 month, more than 1 month, 1 month From the last month or more, one month or more, one month or more, one month or more, from Examples 4 to 9, it is known that the epoxy resin, the amine quinone imine compound of the present invention and the radical generating agent are combined by light. Irradiation can be hardened at a lower temperature for a short time. On the other hand, in Comparative Example 1, it is understood that the aromatic amine quinone imine compound which is not the amine quinone imine compound of the present invention is inferior in solubility to the resin, and a uniform composition cannot be obtained. [Examples 10 to 13 and Comparative Examples 2 to 4] The materials were mixed and stirred at room temperature (25 ° C) in a light-shielding container at a weight ratio shown in Table 3 to prepare Examples 10 to 13 and Comparative Examples 2 to 4. An epoxy/thiol resin composition. If it is not dissolved at room temperature, it is dissolved by stirring at 40 °C. Again, 28

7042-8939-PF 200815325 The weight of the amine imine compound is equivalent to the amount of each amine imine compound 〇·0 05mol, and the weight of the radical generator is equivalent to each radical generator O.Olmol The weight of the quantity. Each of the obtained compositions was subjected to an evaluation test of the following items, and the results thereof are shown together in the respective tables. Further, the DSC chart of the composition of Example I and Comparative Example 3 is shown in Fig. 1. The methods of each evaluation test are as follows. - Solubility test of amine quinone imine compound The material was mixed and stirred at room temperature (25 〇c) in the weight ratio shown in Table 2, and whether or not the amine quinone imine compound was completely dissolved was visually observed. At room temperature (25. ^), the solubility was poor, and the mixture was stirred at 40 ° C to visually observe whether or not the amine quinone compound was completely dissolved. • Measurement of reaction start temperature and reaction peak temperature Each sample was weighed 7 to 5 mg in a sample container of a differential scanning calorimeter (DSC), and irradiated with a UV-ray irradiation apparatus (365 nm illumination: l〇〇mW/cm2) manufactured by Hamamatsu ΡΗ0Τ0ΝΙΧ. A specified amount of active energy line. The reaction temperature of the composition after irradiation with the specified amount of accumulated light is irradiated by the DSC. DSC (DSC110) manufactured by Seiko Instruments Co., Ltd. was used for the DSC measurement, and the temperature was raised at a temperature of 1 Torr in a sealed container under a nitrogen atmosphere. 〇 /miη, the temperature is measured to 25~280 °C. The hardening heat rise temperature (DSC Onset) was determined from the obtained DSC chart, and this was taken as the reaction start temperature. Further, the temperature at the maximum value of the DSC curve was taken as the reaction peak temperature. • Preservation stability test The composition was sealed in a 10 ml light-shielded bottle and stored in a refrigerator at 5 ° C, and the composition gelled to lose fluidity. 7042-8939-PF 29 200815325 [Table 3] Example 10 Example 11 Example 12 Example 13 Comparative Example 2 Comparative Example 3 Comparative Example 4 Denacoel EX-911 100 100 100 100 100 100 100 EPICURE QX40 73 73 73 73 73 73 73 Amidoxime compound A 1.232 1.232 1.232 1.232 Amine quinone imine compound J 1.797 1.797 1.797 DAR0CURE 1173 1.64 1.64 IRGACURE 651 2.56 benzophenone 1.82 1.82 Amidoxime compound 25t Good, good, good, difficult to dissolve Solubility insoluble solution 40 ° C Soluble soluble soluble reaction start temperature light not irradiated 12.7.7 123.9 123.7 123.2 163.6 163.4 163.8 (°C) After irradiation 9J/cm2 124.0 109.5 110.0 110.3 127.1 127.1 126.0 Reaction peak temperature light Not irradiated 140.5 137.4 137.4 136.6 225.7 225. 1 225.5 α) After irradiation 9J/cm2 137.0 123.4 123.9 124.6 189.5 192.1 193.4 5°C storage stability 7 days or more 7 days or more 7 days or more 7 days or more 7 days or more 7 days or more 7 From the above, it is known from Example 10 that a composition comprising an epoxy resin, a polythiol, and an amine quinone imine compound of the present invention is irradiated by light. More low-temperature hardening reaction. Further, from Examples 11 to 13, it is understood that the radical generating agent is further added, and the reaction can be cured at a lower temperature. Further, from Examples 10 to 13, it is understood that the amine-bromide compound of the present invention can be easily dissolved in a resin. On the other hand, in Comparative Examples 3 and 4, it is understood that the aromatic amine quinone imine compound which is not the amine il imine compound of the present invention has a problem of poor solubility in the resin, and the composition thereof is used for the reaction temperature after light irradiation. The peak temperature of the reaction was higher than that of Examples 10 to 13 and the low-temperature hardenability was poor. It is understood that the composition of the present invention exhibits a sharp exothermic peak at a low temperature and a hardening at a lower temperature for a shorter period of time than the composition of the prior aromatic amide imidate compound. [Examples 14 to 17 and Comparative Examples 5 to 10] The materials were mixed in a light-shielding container at room temperature (25 ° C) in a weight ratio shown in Table 4

7042-8939-PF 200815325 The epoxy/thiol resin compositions of Examples 14 to 17 and Comparative Examples 5 to 10 were prepared by stirring. If it is not dissolved at room temperature, it is dissolved by stirring at 40 °C. Further, the weight of the amine quinone imine compound is 0. 0 05 mol, the weight of the radical generating agent is equivalent to each radical generating agent 0. 0 05πιο 1 amount The weight. Each of the obtained compositions was subjected to an evaluation test of the following items, and the results thereof are shown together in the table. The evaluation test method was the same as the methods of Examples 1 to 10 and Comparative Examples 2 to 4. [Table 4] Example 14 Example 15 Example 16 Example 17 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Denacol EX-911 100 100 100 100 100 100 100 100 100 100 JER CURE QX40 73 73 73 73 73 73 73 73 73 73 Amine quinone compound A 1.232 Amino quinone compound B 1.031 Amino phthalimide compound C 1.162 Amino phthalimide compound D 1.262 Amidoxime compound E 0.871 Amine醯imine compound F 0.931 Amino quinone compound G 1.021 Amine quinone compound Η 1.642 Amino quinone compound I 1.262 Amine quinone compound J 1.797 DAROCURE 1173 2 2 2 2 2 2 2 2 2 2 Amidoxime Combination 25〇C Good Good Good Good Good Good Good Soluble Solubility Solubility 40°C Good Soluble Soluble Reaction Start Temperature Light Irradiation 137.5 136 136.7 139.3 144.8 149.4 148.2 151 167.2 163 rc) Irradiation 9J/ After cm2 111.6 120.3 113.3 114.2 147. 1 157.7 154.2 153.8 145.6 130 reaction peak temperature light is not irradiated 149 146.3 148 150.5 168.3 178.3 159.6 160 200.5 222.7 rc) After irradiation 9J/cm2 124.9 106.5 125.8 128. 1 175.9 183 163.9 162.7 201.2 189.4 5°C preservation stability 7 days or more 7 days or more 7 days or more 7 days or more 7 days or more 7 days or more, 7 days or more, 7 days or more, 7 days or more, 7 days or more, from the examples 14 to 17 7 , it is understood that the amine sulfoximine compound oxime and the amine quinone imine compound of the present invention having the other structures are easily dissolved in the resin. The composition can be hardened by a low temperature reaction by light irradiation. From Comparative Examples 5 to 8, 31

7042-8939-PF 200815325 It is understood that the aliphatic amine quinone imine compound having the chemical structure of the present invention has good solubility in a resin, but has no effect of light irradiation. According to Comparative Examples 9 and 1, it is understood that the aromatic amine quinone imine compound has poor solubility in the resin, and the curing temperature after the irradiation is not sufficiently low. [Examples 1 to 8 and 23, and Comparative Examples 11 and 1 2] The materials were mixed in a light-shielding container at room temperature (25 ° C) in a weight ratio of Table 5 to modulate the respective examples 18 to 2 3 and compare The compositions of Examples 11 and 12. For those who are not dissolved in the room temperature, stir and dissolve at 4 °C. Each of the obtained compositions was subjected to an evaluation test of the following items, and the results thereof are shown together in the respective tables. The methods of each evaluation test are as follows. - Solubility test of amine si imine compound The material was mixed and stirred at room temperature (25 ° C) in a weight ratio shown in Table 5 to visually observe whether or not the amine quinone compound was completely dissolved. When it was not dissolved at room temperature, it was stirred at 60 ° C for 1 hour to visually observe whether or not the amine quinone compound was completely dissolved. - Measurement of the hardening time: Each of the compositions was dropped onto a glass slide, and the active energy ray was irradiated with an ultraviolet curing oven UVL-40 (nN (365 nm illuminance: 200 mW/cm 2 ) manufactured by USHIO Electric Co., Ltd.) before irradiation and irradiation. The test piece after specifying the amount of acid light was placed in a room at 25 ° C and set in a constant temperature oven at 6 (TC), and the time at which the surface of the composition was hardened until it was not adhered was measured. [Table 5] Example 18 Example 19 Implementation Example 20 Example 21 Example 22 Example 23 Comparative Example 11 Comparative Example 12 EPCRON 835LV 100 100 100 100 100 100 100 Denar Cole EX-911 100 JER CURE QX30 80 80 80 80 110 75 80 80 7042-8939-PF 32 200815325 Amidoxime compound A 2 10 10 15 10 10 Amine quinone compound J 2 10 DAR0CURE 1173 1 2 2 1 2 LUCIRIN ΤΡ0 2 2 2 Amine amide imine 25 〇C Good good Good good Good Good insoluble and insoluble Solubility of the substance 40 ° C Soluble insoluble light After 24 hours without irradiation Hardening time After irradiation 2J/cm 2 360 90 80 45 90 180 (25 °〇 irradiation 6J/cm2 after 300 60 60 40 90 180 24 hours later twenty four Hardened afterwards (minutes) Hardened appearance Colorless, transparent, hard, strong, colorless, transparent, hard, strong, pale yellow, transparent, hard, strong, pale yellow, transparent, hard, strong, colorless, transparent, transparent, colorless, transparent, rubbery, still not hardened. Unirradiated 240 180 160 120 200 200 300 or more hardening time after irradiation 2J/cm2 70 20 14 12 23 30 360 or more (24 (60°〇6J/cm2 after 60 15 10 360 7 20 30 hours later hardening) (minute) Colorless Transparent light yellow transparent light ΐ ΐ 日 day: name is A; know B day -------- 300 hardened appearance hard and strong hard and strong hard and strong and strong and strong colorless transparent transparent colorless transparent ηΦ9 :»« t « Light yellow transparent light yellow i Hard and strong by the implementation of the warehouse 18~23', the composition of the present invention can be hardened at room temperature for a short time after light irradiation. The post-force heat can make the hardening time shorter. In addition, it can be seen that the hardness and hardening time can be adjusted by the type and quantity of each 调 战 战. From the comparative example ii^ 2, it is known that the previously known aromatic amine quinone imine compound is against Jiang + yesterday; the solubility of the knife to the resin is poor, and the amount of the blend is not dissolved in the resin, and the group of characters cannot be obtained. The low temperature hardenability is also poor. Further, with respect to Example 19, the tensile shearing joint 1 w was measured for spatter. The resin was thinly applied to the end portion 10_ of the iron test piece (SPCC-SD' 25x50x1·6mm), and the UVB-40 (HN (365nm illuminance··20〇mW) was used by USH10 Electric Co., Ltd. /cm2) Irradiation activity At Once " 1 Tuyue 1ϊ: After the line, another iron test piece is pasted and fixed by a clip, and after being placed for 24 hours within 2 5 Τ '^ u, the tensile sheet is cut and then Strength 'Use the universal tensile test cry (INSTR0N) to measure the tensile speed of 1 〇 _ / min. Show body + q τ / ? ... shoot dJ / cm2 active energy line and paste, placed for 24 hours, pull and cut Strong acoustic helmet | Extinction is 17·〇MPa, 33

7042-8939-PF 200815325 After 6J/Cm2 active energy ray was applied, the tensile strength was 17.2 MPa. The failure modes of the following faces are all condensed damage. The composition of the present invention can be firmly followed by a low temperature for a short period of time even if the member is subjected to energy such as iron that does not penetrate light or the like by adhering the energy ray to the composition. The present invention has been described in detail and with reference to the specific embodiments of the invention, and it is understood that the invention may be modified or modified without departing from the spirit and scope of the invention. The Japanese Patent Application No. 2006-1 75008 is preferred. The filing date is June 26, 2006, and the entire contents thereof are incorporated herein by reference. [Industrial Applicability] The present invention provides a novel amine which is superior in solubility to a resin and low-temperature hardenability to a resin, and which has sufficient photoactivity, in comparison with the prior aromatic aminimine photobase generator. An imide-based photobase generator, and a reaction system using the above-mentioned reaction system and hardener method; by irradiation with an active energy ray, it can be hardened at a lower temperature and rapidly, and can be used for subsequent sealing, sealing, molding, and molding. , coating, coating and other various uses. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the Dsc of each of the compositions of the yoke yoke 11 and the comparative example 3 before light irradiation and 6 J/cm 2 of light. [Main component symbol description] None

7042-8939-PF 34

Claims (1)

200815325 X. Patent application range · 1 · A photoreceptor has one or more amines in the molecule. Amine compound: Amine which is formed by the following general formula (1) by irradiation with an active energy ray. General formula (I) 〇Θ R1—CH—C—N—N: OH R2 R3 R4 where R 1 represents H or a aryl or/and aryl group which may have a functional group, and It may also have a functional group or/and an aryl group. 2. A composition comprising: (4) a photoinitiator which is an amine which is formed by the following general formula (I) by irradiation with an active energy ray; An imine compound; and (8) a compound containing more than one species by a basic catalyst polymerization or rearrangement to another form: General formula (I) 〇Θ R1—CH—C—N—N— OH \ R2 R3 In the formula R4, RH represents Η < and may also have a functional group succinyl group or/and an aryl group 'R2, R3 and R4' each independently represent an alkyl group or/and an aryl group which may have a functional group. 3. The above-mentioned (Β) form of one or more kinds of 7042-8939-PF 35 200815325 compound by the alkaline catalyst polymerization reaction or rearrangement as another composition as described in the second paragraph of the patent application. A compound having two or more epoxy groups in a molecule. The composition according to the second aspect of the invention, wherein the above (8) bad catalyst polymerization or rearrangement is a compound of a different form and is more than a compound in the molecule, which is a right shed, and/ a compound of an epoxy group and a mixture of compounds having two or more thiol groups in the molecule. = Zhongming Patent is a combination of components 2 to 4 of the t-term. The composition according to claim 2, further comprising (C) an active energy ray radical generating agent. 7. The invention as recited in claim 6 The composition wherein the above-mentioned organic solvent is polymerized or rearranged into another morphological compound, and is a compound having two or more epoxy groups in the genus of the meat. The composition according to claim 6, wherein the molecule is conjugated to another molecule by an inductive catalyst. a compound having two phospho-oxygen compounds and a compound having two or more thiol groups in the molecule Compounds. 9. The composition of claim 6, wherein the active energy ray radical generating agent is a cleavable photoradical generator. 10. The object according to any one of claims 6 to 9, wherein the component (10) (10) has a weight portion containing Q. 5Q weight = component (1), and is contained in the weight portion of the product. . . . Bu : Ingredient (C).里里口P11 · A method that contains: 7042-8939-PF 36 200815325 (A) Photobase generator, which is produced by the active energy 飨 〃 & One or more of the amine quinone imine compounds having the structure represented by the following formula (1); and (B) containing one or more of the forms of the polymerization by the basic catalyst or the weight of the powder The composition of the compound 'is simultaneously irradiated with the active energy ray and heated, or by heating after the active energy ray is irradiated, and then the polymer is hardened by the composition: (0) θ - R2 R1 - CH - C - N —N^-R3 〇H R4 where R1 represents fluorene or aryl group which may or may have a functional group, and R2, R3 and R4, respectively, independently represent that J. / and aryl. .兀卷12. The method of applying the patent scope n item #丄上人u, wherein the above (Β) 聚合 is polymerized by alkaline catalyst or rearranged to others 仏" The compound is a compound having two or more J-indenyl groups in the molecule. • As described in Article 11 of the patent application scope, _ by means of an experimental touch, G 々 々 / , /, above (B) (four) ^ catalyst polymerization or rearrangement to other (four) chelates, #认八" The above-mentioned chemical system is a compound of two or more compounds having a mercapto group in the knives and a compound having two or more thiol groups in the molecule. The method according to any one of the items 1 to 1 of the present invention, wherein the component of the item (1) of the bean material is at a weight of 100 parts of the component (β), and comprises a component of the right η Τ 3 (Α). The method of claim 11, wherein the composition further comprises a (C) active energy ray radical generating agent. 16. The method according to claim 15, wherein the (b) one or more compounds in another form by an organic solvent polymerization reaction or rearrangement have two or more molecules in the molecule. An epoxy group compound. 17. The method according to claim 15, wherein the above (b) is polymerized by alkaline catalyst or rearranged into a different form, and the compound has more than two rings in the silk molecule. A compound of an oxy group is a mixture of compounds having two or more thiol groups in the molecule. 18. The method according to claim 15, wherein the active energy ray radical generating agent is a cleavable photoradical generating material. 19 pursuant to claims 15 to 18: In the above composition, the component (1) of the combined weight portion of the component (8) and the component of the weight of the component of (1), and the component (C) of the weight of the component of 50 parts. P contains 0.0 Bu 10 7042-8939-PF 38