AMINIMIDE COMPOSITION TO BE SOLIDIFICATED BY ACTIVE ENERGY RAY AND METHOD FOR SOLIDIFICATING THE SAME

Disclosed is a solidificable composition containing aminimide photobase generator which is more excellent in solubility in resins and solidificable at low temperatures than the conventional aromatic aminimide photobase generators, while having a sufficient photoactivity, which is applicable to various uses such as reaction systems, adhesive bonding, sealing, casting, molding, paint application, coating or the like. The solidificable composition can be cured quickly at a lower temperature by irradiation of an active energy ray. Also disclosed are a method for solidificating the composition and a solidificated product of the composition. Specifically disclosed is an aminimide compound (A) having one or more structures represented by the general formula (I) below in the molecule,

The present invention relates to an aminimide composition by active energy ray irradiation to generate a base, capable under prior lower temperature than the novel compositions rapidly polymerized and cured by light irradiation, and the composition solidificating method.

BACKGROUND ART

The photosolidificable technology has been widely used in adhesives, sealants, coating agent, resist or the like, as compared with the conventional thermal curing, photocuring technology utilizes characteristics such as low temperature curing, shortening the process short-term curing and precision machining. Curing system is mainly used for light curing is roughly divided into radical curing and cationic curing. In the case of free-radical curing, photo-radical generating agent and (meth) acrylic resin as a main component, and is characterized by curing immediately after the light irradiation, but usually present a low adhesion strength, shrinkage upon curing, resistance heat and poor. In the case of cationic curing, which contain information such as diaryliodonium salts pan or triaryl sulfonium salt photoacid generator having a cationically polymerizable epoxy resins, oxetane resins, vinyl ether resin, and Upon irradiation with light, the light acid generator generates an acid, thereby cationic polymeric resin is cured. In the case of cationic curing, wherein fast curing, high bond strength, small shrinkage upon curing, etc., but when using adherends made of a metal or inorganic material, due to the presence of water and a small amount on the adhering surface basic dyes and that there is no sufficient curing as well as problems caused by residual acid in the system caused by corrosion.

Anion as a means for solving the cationic curing these problems, use photobase generator to generate a basic compound is cured by light irradiation has been studied in recent years. As such photobase generator, such as derivatives and oxime carbamate ester derivatives generally have been you know, and these compounds produce a primary or secondary amine derivative exposure to light, so that they are used in the epoxy resin Polymerization curing (Non-Patent Document 1). Produced by the light of the basic catalyst technology has been well known in the technology and has been frequently used in the photoresist art. Narrow line width of the resist, to be developed in order to obtain the dimensional stability of the edges, which often use rare terminate the anionic polymerization type curing reaction model (Non-Patent Document 2, Patent Documents 1 to magic. By using basic substance cured epoxy resin in the light generation method, the amine may be mentioned as a representative of a basic compound and the amine is by far the most useful of the light generated by the base. For example, substituted benzyl carbamate Derivatives generate primary and secondary amines (Non-Patent Document 3-5).

However, there is a problem: most of these compounds exhibit low generation efficiency, and because the light irradiation by the basic compound is a primary or secondary amine, so its low alkalinity and therefore does not have to make the amine catalytic activity sufficiently cured epoxy resin.

As the tertiary amine to produce a strong alkalinity by photochemical photobase generator, reported an aromatic aminimide (Patent Document 4 and magic, and reported a polyvalent mercaptan compounds having epoxy resins such as an addition curing reaction starting temperature in the case of thermal curing after light irradiation reduced. In addition, reported imide compound in combination with the aromatic amine singlet / triplet sensitizer, i.e., the dehydrogenation type radical generating agent (Patent Document 5).

However, these aromatic aminimide compound has high crystallinity, the solubility of the resin is restricted or after the light irradiation heat curing temperature low enough. To date, we all know, aminimide decomposition by heat generated by Curtius rearrangement of a tertiary amine, and a tertiary amine as produced by thermal decomposition at low temperatures aminimide having a hydroxyl group which is bonded to the carbonyl carbon is bonded aminimide structure of carbon have been you know (Patent Document 6). However, these have low optical active aminimide thermal decomposition temperature is not you know.

Non-patent Wo Ij Document 1: Chemistry & Technology of UV & EB Formulation forCoatings, Inks & Paints, Ed by G. Bradley, John Wiley and Sons Ltd. (1998,479 Mg 545 M)..

Non-Patent Document 2 = Pure and App 1. Chem., 64,1239 (1992)

Non-Patent Document 3 J. Org. Chem., 55,5919 (1990)

Non-Patent Document 4: Polym Mat Sci Eng, 64,55 (1991) [0011] Non-Patent Document 5 = Macromol, 28,365 (1995)….

Patent Document 1: European Patent No. 599571

Patent Document 2: European Patent No. 555749

Patent Document 3 JP-A-4-330444

Patent Document 4: W02002 / 051905

Patent Document 5 JP-A-2003-26772

Patent Document 6 JP-A-2000-2 ^ 927

SUMMARY

The present invention solves the problem

The present invention is to provide a novel aminimide photobase generator, its better solubility and low temperature solidificable resin than conventional aromatic aminimide photobase generator, and it has sufficient photoactive; the novel amine reactive system imide photobase generating agent; applications such as adhesion, sealing, casting, molding a variety of purposes, paint and coating applications and can be lower by energy ray irradiation novel solidificable composition at a temperature fast curing; curing method of the composition; and a cured product.

means to solve the problem

As a result of solving the above problems carried out extensive research and found that the epoxy resin is mainly used as the known aminimide thermosetting catalyst, aminimides having a specific structure, such as by UV The energy ray has a high activation energy, which leads to completion of the present invention.

The present invention provides the following aminimide compounds, compositions and polymerization curing method.

  1. An active energy ray solidificable composition comprising:

an aminimide compound (A) having at least one structure represented by the general formula (I) below, which is a photobase generator generating a base by irradiation of an active energy ray:

general formula (I)

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;

at least a compound (B) taking part in the polymerization reaction or being converted to another form by means of a base catalyst; and

an active energy ray radical generating agent (C).

  1. The composition according to item 1, wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises compound(s) containing at least two epoxy groups in the molecule.
  2. The composition according to item 1, wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises a mixture of compound(s) containing at least two epoxy groups in the molecule and compound(s) containing at least two thiol groups in the molecule.
  3. The composition of item 1, wherein the active energy ray radical generating agent (C) is a cleavage type radical generating agent.
  4. The composition according to any one of items 1 to 4, comprising 0.1-50 parts by weight of (A) based on 100 parts by weight of (B) and 0.01 to 10 parts by weight of (C) based on 1 part by weight of (A).
  5. An active energy ray solidificable composition comprising:

an aminimide compound (A) having at least one structure represented by the general formula (I) below, which is a photobase generator generating a base by irradiation of an active energy ray:

general formula (I)

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;

at least a compound (B) taking part in the polymerization reaction or being converted to another form by means of a base catalyst;

wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises a mixture of compound(s) containing at least two epoxy groups in the molecule and compound(s) containing at least two thiol groups in the molecule.

  1. The composition according to item 6, comprising, based on 100 parts by weight of (B), 0.1 to 50 parts by weight of (A).
  2. A method for curing and polymerizing a composition by irradiation of an active energy ray at the same time with thermal treating or irradiating an active energy ray before thermal treating, the composition comprising:

an aminimide compound (A) having at least one structure represented by the general formula (I) below, which is a photobase generator generating a base by irradiation of an active energy ray:

general formula (I)

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;

at least a compound (B) taking part in the polymerization reaction or being converted to another form by means of a base catalyst.

  1. The method of item 8, wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises compound(s) containing at least two epoxy groups in the molecule.
  2. The method according to item 8, wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises a mixture of compound(s) containing at least two epoxy groups in the molecule and compound(s) containing at least two thiol groups in the molecule.
  3. The method according to any one of items 8 to 10, comprising 0.1-50 parts by weight of (A) based on 100 parts by weight of (B) and 0.01 to 10 parts by weight of (C) based on 1 part by weight of (A).
  4. A method for curing and polymerizing a composition by irradiation of an active energy ray at the same time with thermal treating or irradiating an active energy ray before thermal treating, the composition comprising:

an aminimide compound (A) having at least one structure represented by the general formula (I) below, which is a photobase generator generating a base by irradiation of an active energy ray:

general formula (I)

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;

at least a compound (B) taking part in the polymerization reaction or being converted to another form by means of a base catalyst, and

an active energy ray radical generating agent (C).

  1. The method according to item 12, wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises compound(s) containing at least two epoxy groups in the molecule.
  2. The method according to item 12, wherein the at least one compound (B) taking part in the polymerization reaction or being converted to another form of the base catalyst comprises a mixture of compound(s) containing at least two epoxy groups in the molecule and compound(s) containing at least two thiol groups in the molecule.
  3. The method of item 12, wherein the active energy ray radical generating agent (C) is a cleavage type radical generating agent.
  4. The method according to any one of items 12 to 15, comprising 0.1-50 parts by weight of (A) based on 100 parts by weight of (B) and 0.01 to 10 parts by weight of (C) based on 1 part by weight of (A).

in 1) above, it has been found to have an aminimide structure more ⑴ represented by the following formula in the molecule as a light base has enough energy ray (light) base activity generator It is useful, and the resin is excellent in solubility and low temperature curing.

[Formula 4]

Formula (I)

 

wherein R1 represents H or an alkyl group may have a functional group and / or aryl; and R2, R3 and R4 each independently represents an alkyl group having a functional group and / or aryl.

In the above 2), (viii) it has been found to contain the aminimide compound and at least one polymerization ⑶ or converted to another form of the compound occurs through a basic catalyst as an essential component of the reactive composition ( polymeric) by light irradiation changed (improved). Further, in the above-mentioned phantom, having in the molecule at least two epoxy groups in the compound to be used as component (B) and the aminimide (A) composition. In this system, it has been found that when the composition is irradiated with active energy rays, curability (curing at low temperature) at low temperatures better. Further, in the above-mentioned 4), there is provided a composition comprising a compound of the present invention, an aminimide (A) and as component (B) having at least two epoxy groups in the molecule and a compound the mixture having at least two thiol groups in a molecule compounds. In this composition it has been found better after active energy ray irradiation of low temperature curability.

Further, in the above 6) to 10), is provided wherein the composition is further added active energy ray radical generating agent. It has been found thereby obtaining a solidificable composition having excellent active energy ray radical generator. In the above 11) to 19), characterized by active energy ray irradiation and heating performed simultaneously with or after the light irradiation heating.

Advantageous effects of the present invention,

The present invention provides a novel aminimide as a photobase generator, the resin solubility and low activity better than the conventional aromatic aminimide photobase generator; and by light irradiation in the more new energy at low temperature fast curing radiation activity (polymerizable, solidificable) composition, a cured product of the curing method and composition, and they can be used, such as adhesion, sealing, casting, molding, painting and coating applications cloth various applications.

In addition, by using the above-described novel aminimide as a curing catalyst, e.g., by use in combination with an epoxy resin, etc., in addition to heat-solidificable, but also by imparting energy ray (light) irradiation solidificable.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 respectively before and after light irradiation light irradiation 6J / cm2 of the DSC diagram of composition of Comparative Example 11 and the third embodiment.

DETAILED DESCRIPTION

The present invention will now be described in detail. One form of the present invention is an amine having at least one imide compound represented by the following structural formula (I) in the molecule represented, which is generated by the active energy ray irradiation photobase generator base:

[Chemical formula δ]

Formula (I)

 

wherein R1 represents H or an alkyl group may have a functional group and / or aryl; and R2, R3 and R4 each independently represents an alkyl group having a functional group and / or aryl.

For the above-mentioned amine compound having an imide structure synthesis, a known method may be used. For example, Encyclopedia of Polymer Science and Engineering, JohnWiley & Sons Ltd., (1985), Vol. 1 on page 740 is described by the reaction of the corresponding carboxylic acid ester compound and sodium halide corpus and alcohol or carboxylic acid ester and the corpus and The reaction of the epoxy compound obtained.

The present invention for the synthesis of the photobase generator using aminimide (A) of the method is not particularly limited, but taking into account the synthesis of simplicity and safety, preferably from carboxylic acid esters with corpus and synthetic epoxy compound. In this case, there is no particular limitation on the temperature and the time for synthesis, but usually, the target amine compound having an imide structure can be stirred at temperature of 0 to 100 ° C for 30-7 minutes is obtained. Preferably, since the aminimides of the present invention is known as a conventional photobase generator aromatic aminimide thermal decomposition temperature is low as compared with the characteristics, the preferred initial temperature regulating synthesis reaction to 0-25 Range ° C and the end of the temperature control to below 60 ° C.

The synthesis method used, as the aminimide starting material of the present invention, carboxylic acid esters having -CH (OH) COO- structure in the molecule any monofunctional or polyfunctional carboxylic acid ester. For example, there may be mentioned methyl lactate, ethyl lactate, butyl, 2-hydroxy – n-butyric acid ethyl ester, 2-hydroxy – n-hexyl acetate, ethyl mandelate, ethyl alcohol, methyl alcohol White isopropyl, dimethyl tartrate, etc., but the ester is not limited to this. When polyfunctional carboxylate, aminimide having a plurality of obtained aminimide structure in the molecule. There are no specific restrictions corpus of material, but the easy availability of raw materials, the light alkaline substances produced high alkalinity viewpoint, it is preferred 1,1_ dimethyl corpus. Further, as another starting material of the epoxy compound is any compound having at least one epoxy group in the molecule. For example, monofunctional epoxy compounds may be used, such as propylene oxide, glycerol, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and t-butylphenol glycidyl ether, and isophthaloyl phenol diglycidyl ether, neopentyl diglycidyl ether, glycerol polyglycidyl ether, such as bisphenol A and epichlorohydrin diglycidyl ether derived from a so-called dual-type table (India i-bis type) liquid ring epoxy resins, and multifunctional epoxy compounds such as aliphatic / aromatic epichlorohydrin ether derived more from the polyacid and epichlorohydrin, polyglycidyl esters derived from bisphenol A and epichlorohydrin hydrogenated more alcohol derived ether. When using the multifunctional epoxy resin obtained aminimide having a plurality of aminimide structure in the molecule.

Since the compounds of the present invention, the aminimide (A) to generate a base by irradiation of an energy ray, so as the reaction rate by which the light activated catalyst or a basic catalyst retarder changing reaction system is effective. In addition, in one embodiment of the present invention, by the above aminimide compound (A) with at least one basic catalyst by the polymerization reaction or converted to another form of the compound (B) mixing occurs, is formed The polymerizable (solidificable) composition.

Examples of the basic catalyst by the at least one occurrence of the polymerization reaction or converted to another form of the compound (B), can be used a basic catalyst by known polymerization reaction system (resin composition). For example, the system comprises a Michael (Michael) addition reaction, a basic catalyst by homopolymerization of the epoxy compound, epoxy compound and / or (meth) acrylic acid ester compound and / or a cyclic sulfide with the sulfur-containing alcohol, polymeric compounds, amino phenol, isocyanate, carboxyl and / or acid anhydride groups, polymeric compounds containing hydroxyl and / or thiol groups and isocyanate-containing compound, polymerization of cyanoacrylate compound, but is not limited to this.

In the case of (light) solidificable composition of the present invention is the use of aminimide obtained activation energy ray, as the component (B), it is suitable to use an epoxy resin comprising as a main component or composition, or epoxy resin and a polythiol compound as the main component of the composition, but the component is not limited thereto.

The polymerization reaction or converted to another form of the compound [0080] In addition, in the compositions of the present invention, the mixing amount of the aminimide compound (A) with the at least one basic catalyst occurs by (B) of the kind of change. For example, when selecting an epoxy resin as component (B) in the case, it is desirable in an amount based on 100 parts by weight of the epoxy resin is 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight. When the amount is less than 0.1 parts by weight, the curing is insufficient, and when it exceeds 50 parts by weight, the cured product properties such as heat resistance and strength worse.

Epoxy resin is preferably used as the component (B), having at least two epoxy groups in the molecule compounds. As specific examples, there can be mentioned a so-called dual-type liquid epoxy resin as the table from bisphenol A and epichlorohydrin diglycidyl ether and derivatives thereof derived from bisphenol F and epichlorohydrin diglycidyl derivatives ethers and derivatives thereof, phenol novolak type epoxy resin, cresol novolac type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic / aromatic alcohol and Table chlorohydrin ethers derived from polycarboxylic acid and epichlorohydrin ether and derivatives thereof derived from hydrogenated bisphenol A and epichlorohydrin, glycidyl ethers derived from aliphatic cyclic epoxy compound such as 3, 4- epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexyl carboxylate, bis (3,4_-epoxy-6-methyl-cyclohexylmethyl) hexyl terephthalate and derivatives thereof, 5,5 ‘- dimethyl hydantoin the epoxy resin, triglycidyl isocyanate, epoxy substituent derived from isobutylene, etc., but not limited to an epoxy resin . Examples of commercially available epoxy resin product, there may be mentioned by the Japan Epoxy Resin Co., Ltd. manufactured JER coat 828,1001,801,806,807,152,604,630,871, YX8000, YX8034, YX4000, the DainipporHnk And Chemicals Ltd. made Epiclon830,835LV, HP4032D, 703,720,726, HP820, the Asahi Denka Kogyo K. K manufacture of EP4100, EP4000, EP4080, EP4085, EP4088, EPU6, EPR4023, EPR1309, EP49-20, manufactured by the Nagase ChemteX Ltd. Denacol EX411, EX314, EX201, EX212, EX252, etc., but the product is not limited to this. These compounds may be used alone or as a mixture of two or more. When using one of the tables double type epoxy resin obtained in cost and curability, adhesion, physical strength of the cured product of the other aspects of a well-balanced composition. In addition, when using an aliphatic or alicyclic epoxy compound, obtained flexibility, transparency and weather resistance of the cured product excellent in composition.

Polythiol compound to be used in combination with the above-mentioned epoxy resin may have at least two thiol groups in a molecule compounds. As specific examples thereof, may be mentioned trimethylolpropane trithiol propionate, pentaerythritol tetra thiol propionate, ethylene glycol dithiol acetate, butylene glycol dithiol acid 1,4_ ester, trimethylol propane tri thiol acetate, pentaerythritol tetra thiol acetate, bis (2-mercaptoethyl) ether, 1,4_ butane dithiol, 1,3,5_ three mercapto toluene , 4,4’-thio thiophenol, 1,3,5-mercapto-2,4,6-trimethylbenzene, 2,4,6-mercapto – s-triazine, 2-dibutylamino _4 amino, 6-mercapto – triazine, terminal thiol group-containing polyethers, terminal thiol group-containing polythioethers, thiol compounds and hydrogen sulfide by reacting an epoxy compound obtained by polysulfide thiol compound with an alcohol compound obtained by reaction of an epoxy-containing terminal thiol group and the like, but not limited to the thiol compound. Examples of commercially available products and the thiol compounds may be mentioned manufactured JER mate QXl 1, QX12, JER cureQX30, QX40, QX60, QX900, Capcure CP3-800, manufactured by Yodo Kagaku KK by the Japan Epoxy Resin Co., Ltd The OTG, EGTG, TMTG, PETG, 3_MPA, TMTP, PETP, the iTorayFine Chemical Co., Ltd. manufactured guar phenol sulfonate, potassium LP-2, LP-3, polythiol QE-340M, etc., but the product It is not limited thereto. These compounds may be used alone or in combination of two or more thereof. From the viewpoint of storage stability, the thiol compound is more preferably a compound comprising a thiol minimal amount of basic impurities. Moreover, taking into account the heat resistance of the cured product, and more preferably a thiol compound containing in the molecule an aromatic ring. On the composition of the present invention, the mixing amount of the thiol compound, there is no particular limitation on its scope, but as with respect to the epoxy equivalent of the composition is a thiol equivalent ratio of the epoxy compound, the thiol compound may be 0.5 2. O to the range, and more preferably is added in the 0.8 to 1.3 range. When the thiol compound is added to the above range is obtained in balance between strength and heat resistance of a cured product of the curing speed and better composition.

In the present invention, when the energy ray radical generator (C) is further added to the composition comprising the above components (A) to (B) as a main component, optical activity of the composition may be enhanced. As energy ray radical generator, using known dehydrogenation type radical generator and / or cleavage type radical generating agent. Examples of dehydrogenation type radical generating agent, there may be mentioned naphthalene derivatives such as 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoro-naphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodo-naphthyl, 2-iodo-naphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene and 1,4_-dicyano naphthalene; anthracene derivatives such as anthracene, 1,2-anthracene, 9,10-dichloro-anthracene, 9,10-dibromo-anthracene, 9,10-diphenyl anthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene and 2,6,9,10- tetracyanoanthracene; pyrene derivatives; carbazole derivatives such as carbazole, carbazole-9-methyl, 9-phenyl carbazole, 9-prop-2-ynyl -9H- carbazole, 9- propyl -9H- carbazole, 9-vinylcarbazole, 9H- carbazol-9-ethanol, 9-methyl-3-nitro -9H- carbazole, 9- methyl -9H–3,6-dinitro-carbazole, 9- octanoyl carbazole, 9-carbazolyl methanol, 9-carbazolyl acid, 9- propionitrile carbazole, 9-ethyl-3,6 – dinitro -9H- carbazole, 9-ethyl-3-nitro-carbazole, 9-ethylcarbazole, 9-isopropyl carbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholine meth) carbazole, 9-acetyl-carbazole, 9-allylcarbazole, 9-benzyl -9H- carbazole acetic acid, 9- (2-nitrophenyl) carbazole , 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl – propyl) -9H- carbazole, 3-nitro-carbazole, 4-hydroxy carbazole , 3,6-dinitro -9H- carbazole, 3,6-diphenyl–9H- carbazole, carbazole and 2-hydroxy-3,6-diacetyl-9-ethylcarbazole; phenone derivatives such as benzophenone, 4-phenyl benzophenone, 4,4 ‘- bis (dimethoxy) benzophenone, 4,4’ – bis (dimethylamino) benzophenone, 4, 4 ‘- bis ( diethylamino) benzophenone, 2-benzoyl benzoate, 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 3,3 ‘- dimethyl-4- methoxybenzophenone and 2,4,6-trimethylbenzene ketone; aromatic carbonyl compounds; [4-methylphenyl) phenyl] – phenyl methane; xanthone; thioxanthone derivatives such as thioxanthone , 2-chloro thioxanthone, 4-chloro-thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl-thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxy thioxanthone; and coumarin derivatives.

In addition, cleavage type radical generating agent is of the following type radical generating agent: a compound thereof by the active energy ray irradiation to produce free radicals induced cleavage. As specific examples thereof, may be mentioned benzoin ether derivatives, arylalkyl ketones such as acetophenone derivative, an oxime ketone, acylphosphine oxide, S- phenyl thiobenzoate, titanocene, and by so that their higher molecular weight derivatives obtained, but the examples are not limited thereto. Examples of commercially available cleavage type radical generating agent, there may be mentioned 1- (4-dodecyl-benzoyl) -1-hydroxy-1-methyl-ethane, 1- (4-isopropyl-benzoyl ) -1-hydroxy-1-methyl-ethane, 1-benzoyl-1-hydroxy-1-methyl ethane, 1- [442_ hydroxyethoxy) _ benzoyl] -1-hydroxy – 1-methyl-ethane, 1- [4_ (acryloyloxyethoxy) _ benzoyl] -1-hydroxy-1-methyl-ethane, benzophenone, 1-hydroxy-phenyl – ring cyclohexanone, benzyl dimethyl ketal, bis (cyclopentadienyl) _ two (2,6_-difluoro-3-yl-pyran (pyryl) – phenyl) titanium, (n6- cumene) – (η5- cyclopentadienyl) – iron (II) hexafluorophosphate, trimethylbenzoyl diphenylphosphine oxide, bis (2,6_ dimethoxy – benzoyl) -½, 4,4_ trimethyl – pentyl) – phosphine oxide, two 0,4,6_ trimethyl benzoyl) -2,4-pentyloxy-phenyl phosphine oxide or bis (2,4 , 6_ trimethylbenzoyl) phenyl phosphine oxide, (4-morpholinyl-benzoyl) -1-Benzyl-1-dimethylamino propane, 4- (methylthio benzoyl) -1-methyl-1-morpholino ethane, etc., but the radical generator is not limited thereto.

In the compositions of the present invention, the (C) i.e. active energy ray radical generator or a radical generator type dehydrogenation cleavage type radical generating agents may be used alone or in combination of more kinds. Considering the radical generating agent of the present invention is its stability and solidificable composition, and more preferably a combination of one or more cleavage type radical generating agent. Further, since the curing is less and degassing, wherein the cleavage-type structure is preferably a radical generating agent is introduced into the cured high molecular weight oligomers / polymers of high molecular weight cleavage type radical generating agent.

In addition, according to the type of free-radical initiator, there are aminimide according to the structure to be caused by a combination of the effect of the possibility of differences. Seems to be due to the combined effects of aminimide radical generating agent with wavelength, so aminimide (A) and the radical generator (C) the most suitable combination can optionally be selected. While considering the absorption wavelength of the radical generator and the molar extinction coefficient is necessary, but the amount of 1 part by weight based on the aminimide (A), the composition of the present invention to be added free-radical initiator is usually 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight. When the amount is too small, no adequate effect of improving light activity, and when the excessive basic catalysis is inhibited.

The compound containing an epoxy group in the molecule and / or a thiol group in the molecule containing compound may be added to in the present invention does not impair the performance of the scope of the compositions of this invention. These compounds are used to reduce the viscosity of the composition as a whole, to improve the workability, reactivity, etc. regulation. In the case of adding such an epoxy compound and a thiol compound, and an epoxy equivalent of taking into account the thiol equivalent weight, the mixing ratio of the desired regulation of the thiol compound and the epoxy compound.

In addition, additives may be mixed into an appropriate amount of the composition of the present invention, the additive such as a pigment or dye comprising a colorant, an inorganic filler such as calcium carbonate, talc, silica, alumina or aluminum hydroxide conductive particles such as silver, flame retardants, such as boric acid or phosphoric acid ester, inorganic or organic acids storage improver, organic fillers such as acrylic rubber or silicone rubber, polyimide resin, polyamide resin, multifunctional resin such as a bisphenol A type phenoxy phenoxy resin, a bisphenol F type phenoxy resin or a bisphenol F type bisphenol A- total polyphenylene oxide resin, such as polymethacrylate resins, poly acrylate resin, polyimide resin, polyurethane resin, polyester resin, polyvinyl butyral resins, SBS resins and modified epoxy resins, and their modified or SEBS polymer or a thermoplastic resin an elastomer, a plasticizer, an organic solvent, an antioxidant, an antifoaming agent, a coupling agent, leveling agent, rheology control agent. By adding it to obtain a resin strength, adhesion strength, flame resistance, thermal resistance, storage stability, processability, etc. better composition and its cured product.

The aminimide of the present invention, (A) is a photobase generator, the photobase generator by the activation energy ray such as ultraviolet radiation is generated by a base, and the activation energy usable herein rays include electron beam, ultraviolet rays, visible light. Its dose may be sufficient to activate the aminimide (A) is not particularly limited, and the dose. As an example of the case where, in a mixture of epoxy resin and polythiol compound is used as component (B), the dose of ultraviolet ray irradiation may be 0. lj / cm2 or more. In addition, the compositions of the present invention may be by UV irradiation and heating simultaneously and in a shorter period of time to a smaller dose provides an energy cured product.

In this regard, the aminimides of the present invention (A) by a method other than the active energy ray, for example, heating is activated, but compared with activation by a separate heating, curing by polymerization combination of active energy ray irradiation is significantly improved. Because the average ultraviolet radiation device while ultraviolet radiation and heat rays, so the polymerization solidificable compositions of the present invention is very useful.

A cured product obtained by curing the resin composition of the present invention is obtained by having such excellent properties of toughness and transparency, and the composition of the present invention is irradiated with a predetermined dose of the active energy ray can be placed only by the ambient temperature and no further special treatment (heating, etc.) polymerization reaction to provide a cured product. The use of performance, such as the formation and adhesion of optical parts, sealing, casting, molding, painting various uses and applications used in the coating composition. Further, the present solidificable composition immediately after energy irradiation, or immediately after the energy irradiation solidificable but not thereafter allowed to stand at room temperature or by heating for a short time and curing. Due to the latter property, as shown by a DVD with an adhesive, the adhesion member is not transmitted even when such light energy, may be irradiated by the energy of the composition and the subsequent adhesion of the coating and adhesion is achieved.

Example

Reference to the following examples illustrate the present invention will be specifically described, but the present invention should not be construed as limiting thereto. In addition, the mixing ratio in the table below are on a weight basis unless otherwise indicated.

Examples and Comparative Examples for the implementation of aminimide compound shown in Table 1, represented by the structural formula, and those compounds were synthesized by the following methods to use.

Table 1

 

(Synthesis of aminimide A through I)

According to disclosed in J. Polym. Sci. Part A, 38,18,3428 (2000) and JP-A-2000-229927 method, aminimide (imide amine compound of the invention A to D, does not fall within the aliphatic aminimide E of the present invention to the H, the aromatic aminimide does not fall within the present invention I) from the corresponding carboxylic acid or carboxylic acid ethyl ester dimethyl ester and epoxy compound obtained corpus.

(Synthesis of aminimide J)

According disclosed in W02002 / 051905. The method of obtaining the imide compound as the aromatic amine (the present invention does not fall aromatic aminimide J) is 1,1-dimethyl-1- (2-hydroxy-3-phenoxy-propyl) amine – nitrophenyl azomethine.

In addition to the aminimide, a reagent shown below for examples and comparative examples in embodiments of the present invention are commercially available materials or products.

methanol: from Tokyo Chemical Industry Co., Ltd manufactured reagent.

phenyl glycidyl ether: from Wako Pure Chemical Industries Ltd. reagent manufactured

URIC H30: By the Itoh Oil Chemicals Co., Ltd polyols manufactured

ISONATE 143LP: manufactured by the Dow Chemical Japan Ltd. modified diphenyl methane diisocyanate

Epiclon 8 35LV:! By the Dainippon Ink And Chemicals Ltd. bisphenol type epoxy resin manufactured

Denacol EX-911: aliphatic epoxy resin manufactured by the Nagase ChemteX Ltd.

JER cure QX30: the Japan Epoxy Resin Co., Ltd aliphatic trifunctional mercaptan produced.

JER cure QX40: the Japan Epoxy Resin Co., Ltd aliphatic trifunctional mercaptan produced.

Irgacure 184: manufactured by the Ciba Specialty Chemical Ltd. cleavage type photo-radical-generating agent [0111] Irgacure 651: manufactured by the Ciba Specialty Chemical Ltd. cleavage type photo-radical generator

Darocur 1173: manufactured by the Ciba Specialty Chemical Ltd. cleavage type photo-radical generator

Lucirin TPO: manufactured by BASF Japan Ltd. cleavage type photo-radical generating agent

benzophenone by: Tokyo Chemical Industry Co., Ltd manufactured dehydrogenation optical radical generating agent.

Example 1

The aminimide 1. 5g compound A, 55g of methanol and 3. Og purified water was added to the inner diameter of 33mm and height of 55mm transparent sample vial, followed by the aminimide A was dissolved. Wherein under a nitrogen atmosphere while stirring with a stirrer, ultraviolet irradiation apparatus useful in the point by the Hamamatsu PhotonicsK. K manufactured in luminance 365nm 100mW / cm2 of the active energy ray irradiation of the sample vial from the outside of the sample vial. Specified number of seconds after irradiation with the Horiki Ltd. PH meter manufactured D22 pH measurements. PH pH pH value of the active energy ray irradiation is 8.50 before, and the active energy ray irradiation for 10 PH value of 8.53 seconds after, 20 seconds after the irradiation 8. M, value after 30 seconds irradiation 8 55 and 50 seconds after the irradiation of PH value of 8.56. Therefore, by increasing the alkalinity and active energy rays showed the discovery of the aminimide A light alkali generating agent.

Example 2

The phenyl glycidyl ether: 0 lmol (15 017g.), Aminimide A: 0.003mol (0 739g.) And Darocurl 173:.. 0 OOlmol (0. 164g) were mixed at room temperature to obtain a homogeneous solution. 7. 5mg was weighed into a differential scanning calorimeter (DSC) sample container, followed by the point of use ultraviolet irradiation apparatus manufactured by Hamamatsu Photonics K. K (365nm Brightness: 100mW / cm2) is irradiated with active energy rays The sample container. Measurement by DSC measurement before irradiation of the reaction 9J / cm2 after the irradiation with the starting temperature. For the DSC measurement, used by Seiko Instruments Ltd. manufactured by DSC (DSCllO) and performs the measurement under a nitrogen atmosphere in a sealed container, while the heating rate 10 ° C / min and the temperature was raised to 25 ° C by the ^ 0 ° C. Curing the exotherm starting temperature (DSC Onset) determined by the obtained DSC chart, and the temperature of the reaction initiation temperature considered.

It is found that after the energy ray irradiation reaction starting temperature was 115. 1 ° C, and in the beginning of the reaction before the energy ray irradiation temperature of 153. 7 ° C. So, it shows the aminimide polymerization aspect of the present invention as photobase generator epoxy compound is effective, the photobase generator by active energy ray irradiation exhibit high catalytic activity.

Example 3

The URIC H30 = IOg with aminimide A:. 0 5g and Irgacure651:. 0 2g mixed and the whole was stirred at room temperature to obtain a homogeneous solution. The IS0NATE143LP:. 4 5g mixed into the solution, and the whole mixture was stirred at room temperature to form a homogeneous solution. Then, the solution was immediately applied to a glass plate to a thickness of 100 μ m, and the point of use by the ultraviolet irradiation apparatus manufactured HamamatsuPhotonics K. K (365nm, brightness: 100mW / cm2) was applied to the active energy ray irradiation board. Compared before and after irradiation 6J / cm2 irradiation at 25 ° C, a solidificable coating film. Before active energy ray irradiation of the coating film cured to non-tacky elastomers time required for 40 minutes, and after active energy ray irradiation time of the coated film to solidify into non-sticky elastomeric it required 30 minutes. Thus, the aminimide show the present invention as by active energy ray irradiation exhibit high catalytic activity photobase generator is effective even in the polymeric polyol and isocyanate in.

Examples 4-9 and Comparative Example 1 [0122] Example

The following Table 2 shows the weight ratio of the light-shielding container to mix the material at room temperature (25 ° C) and stirred under Examples 4-9 and Comparative Example Example 1 to prepare an epoxy resin-based compositions. Although an aminimide is generally liquid at room temperature, but in the case of the compound crystal, is first melted and then stirred them next and mixed. Each test was evaluated according to the following composition obtained. The results are shown in the tables. The method of each evaluation test is as follows.

* aminimides solubility test

The following Table 2 shows the weight ratio of each material at room temperature (25 ° C) and stirred under, and aminimide was observed with the naked eye is completely dissolved.

* reaction starting temperature and the reaction peak temperature measurement

Each composition was weighed 7. 5mg sample container into a differential scanning calorimeter (DSC), the point is then used by the ultraviolet irradiation apparatus manufactured by Hamamatsu Photonics K. K (365nm, brightness: 100mW / cm2 ) to specify the amount of active energy ray irradiation of the sample container. DSC measuring method by irradiation before the reaction starting temperature after a specified dose irradiation. For the DSC measurement, used by Seiko Instruments Ltd. manufactured by DSC (DSCllO) and performs the measurement under a nitrogen atmosphere, while heating rate 10 ° C / min so that the temperature of 25 ° C to 280 ° C. Curing the exotherm starting temperature (DSC Onset) determined by the obtained DSC chart, and the temperature of the reaction initiation temperature considered. In addition, the maximum temperature of a DSC curve is considered the peak reaction temperature.

* measured curing time

Each composition (0. Ig) was added dropwise to a slide glass, then an ultraviolet irradiation apparatus using the dot HamamatsuPhotonics K. K manufactured (365nm, brightness: 100mW / cm2) to specify the amount of active energy rays exposure. The integrated irradiation dose of preoperative irradiation and after a specified test piece is placed in the specified temperature in the thermostatic oven, and measured the surface of the solidificable composition until the viscosity and loses all the time required to be cured.

* Storage stability test

The composition was placed in a vial IOml opacity and the vial was sealed. Then, the vials were stored in a dark place 25 ° C thermostatic chamber. Time lost mobility measurements required by gelation.

Table 2

Example 4-9, and show that an epoxy resin composition comprising an aminimide by light irradiation in a short time at a lower internal temperature cure. On the other hand, in Comparative Example 1, it was found as the aromatic amine compound of the present invention, the aminimide imide resin in the poor solubility and could not obtain a uniform composition.

Examples 10-13 and Comparative Example [0135] Example 2-4

The following Table 3 shows the weight ratio of the light-shielding container to mix the material at room temperature (25 ° C) and stirred under Production Example 10-13 and Comparative Examples 2-4 based on epoxy / mercaptan the resin composition. Those stirring at room temperature insoluble material in the 40 ° C to effect dissolution. By weight of each of the corresponding aminimide weight of each compound in the aminimide 0. 005mol, and a radical generating agent each by weight corresponding to the weight of each 0. Olmol radical generator. According to the following items for each composition was subjected to evaluation tests. All results are shown in the tables. In addition, the composition of the DSC diagram of 11 and Comparative Example 3 are shown in Figure 1. [0137] The method of evaluation test is as follows.

* aminimides solubility test

The following Table 2 shows the weight ratio of each material at room temperature (25 ° C) and stirred under, and aminimide was observed with the naked eye is completely dissolved. In at 40 ° C the solubility of those compounds dissolve travel (25 ° C) at room temperature display, and aminimide was observed with the naked eye is completely dissolved.

* reaction starting temperature and the reaction peak temperature measurement

Each composition was weighed 7. 5mg sample container into a differential scanning calorimeter (DSC), the point is then used by the ultraviolet irradiation apparatus manufactured by Hamamatsu Photonics K. K (365nm, brightness: 100mW / cm2 ) to specify the amount of active energy ray irradiation of the sample container. DSC measuring method by irradiation before the start of integrated temperature response specified dose irradiated. For the DSC measurement, used by Seiko Instruments Ltd. manufactured by DSC (DSCllO) and performs the measurement under a nitrogen atmosphere, while heating rate 10 ° C / min so that the temperature of 25 ° C to 280 ° C. Curing the exotherm starting temperature (DSC Onset) determined by the obtained DSC chart, and the temperature of the reaction initiation temperature considered. In addition, the maximum temperature of a DSC curve is considered the peak reaction temperature.

* Storage stability test

The composition was placed in a vial IOml opacity and the vial was sealed. Then, the vials were stored at 5 ° C in the refrigerator compartment. Time lost mobility measurements required by gelation.

Example 10, show that epoxy resin compositions, polyhydric alcohols and aminimide composition cured by light irradiation at lower temperatures. Further, Example 11-13, show by further adding a radical generator compound cured at lower temperatures. Further, the embodiments 10-13, showed aminimides of the present invention are easily dissolved in the resin. On the other hand, the aromatic aminimide compound 3 and 4, the present invention is not aminimide resin of Comparative Example has poor solubility problems, as compared with the case of Example 10 to 13, indicating that even in the light after irradiation using the compound compositions also exhibit higher reaction starting temperature and the reaction peak temperature, so the low-temperature curability is poor.

Showed that compared with the conventional compositions aromatic aminimide compound, the compositions of the present invention exhibit a relatively low temperature in sharp exothermic peak, and in a shorter time at lower Under temperature curing is completed.

Example 14-17 and Comparative Examples 5-10

Table 4 below shows the ratio of the weight of the light-shielding container to mix the material at room temperature (25 ° C) and stirred under Examples 14-17 and Comparative Examples 5-10 was prepared based on the implementation of the epoxy / mercaptan the resin composition. Those stirring at room temperature, the solubility of the material shows poor in the 40 ° C to effect dissolution. By weight of each of the corresponding aminimide weight of each compound in the aminimide 0. 005mol. According to the following items for each composition was subjected to evaluation tests. All results are shown in the table. The method used for each evaluation test in Example 10-13 and Comparative Example 2-4 in the same.

Example 14 to 17, showed that the aminimides and aminimide A of the present invention has another structure also easily dissolved in the resin, and the composition by light irradiation at a lower temperature cured. Comparative Example 5-8, Table

Resin solubility of which it does not have the chemical structure of the aminimide compound of the present invention is good, but the effect was not observed by light irradiation. From Comparative Examples 9 and 10, show that the solubility of the aromatic aminimide resin difference after light irradiation and curing temperature low enough.

Example 18-23 and Comparative Examples 11 and 12

The following Table 5 shows the weight ratio of each of the light-shielding material mixing vessel at room temperature (25 ° C) and stirred at 18 to 23 and Comparative Examples 11 to 12 and a composition prepared in Example. Stirring and mixing those materials at room temperature, not dissolved in the 40 ° C. According to the following items for each composition was subjected to evaluation tests. All results are shown in the tables. The method of each evaluation test is as follows.

* aminimides solubility test

The following Table 5 shows the weight ratio of each material at room temperature (25 ° C) and stirred under, and aminimide was visually observed whether complete dissolution. In the case of insoluble compounds at room temperature, and stirred for 1 hour at 60 ° C and visually observed whether complete dissolution of the aminimide.

* measured curing time

Each composition (0. Ig) was added dropwise to a slide glass and then used by Ushio Inc. manufactured ultraviolet curing oven UVL-4001-N (365nm, brightness: 200mW / cm2) to specify the amount of energy ray irradiation. The integrated dose irradiation before irradiation and after the specified test piece is placed in a chamber of 25 ° C, or set to a constant temperature of 60 ° C oven and measuring the solidificable composition until the surface tack and lost time required to fully cured.

Example 18-23, showed that the composition of the present invention after light irradiation even at room temperature in a short time can be cured. In addition, it shows the curing time is shortened by energy irradiation after heating. In addition, it shows the curing time, hardness of the cured product and the like can be controlled. Comparative Example 11 and 12 show a conventional resin soluble aromatic aminimide poor, and when the mixing amount is large, the compound is not soluble resin and unable to obtain a uniform composition. In addition, exposure to ultraviolet light show in low-temperature fast curing is also poor.

In addition, the implementation of the 19 cases the tensile shear bond strength measurements. On the resin thinly coated onto iron test sheet (SPCC-SD, 25X50X 1.6mm) of IOmm ends and is used by Ushio Inc. manufactured UV curing oven UVL-4001-N (365nm, brightness: 200mW / cm2) to specified energy ray irradiation dose. Then, another piece of the iron test piece was laminated thereon and fixed with spring clips, and using a universal tensile tester (Instron) at a tensile rate of IOmm / min measured is placed in a chamber of 25 ° C for 24 hours Tensile shear bond strength. Tensile shear bond strength 3J / cm2 energy ray irradiation and 24 hours after the laminate samples was 17. OMPa, in 6J / cm2 after active energy ray irradiation of the laminate samples and left for 24 hours The tensile shear bond strength was 17. 2MPa. In all cases, the situation occurred in the face of the destruction of both adhered to the adhesion failure. It shows that even after the adhesion member as in the case of iron, such as the case of not transmitting light energy, the compositions of the present invention may also be in the composition is irradiated with energy in a short time by adhering firmly adhered at low temperatures.

While there has been described in detail and with reference to specific embodiments of the present invention will be described, but for skilled staff, without departing from the spirit and scope thereof may be various changes and modifications It is obvious.

This application is based on Japanese Patent June 26, 2006 filed No. 2006-175008, and the entire contents of which are incorporated herein by reference.

Industrial Applicability

The present invention mentioned above provides a novel aminimide photobase generator, its better solubility and low temperature solidificable resin than conventional aromatic aminimide photobase generator, and it has sufficient photoactive; reaction system using the novel aminimide photobase generator; and a cured product and curing methods. By active energy ray irradiation can achieve rapid cure at low temperatures and can be used in the present invention such as adhesion to various uses sealing, casting, molding, painting and coating of applications.

Related Posts

Leave a Reply

Your email address will not be published. Required fields are marked *