JP3025782B2 - Curable composition and curing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition and a method for curing the same. More specifically, the present invention relates to a curable composition containing an epoxy resin, a polyurethane prepolymer, a polyfunctional cyclic carbonate compound or a polyfunctional (meth) acrylate, and a method for curing the same.

[0002]

2. Description of the Related Art Conventionally, various photocurable compositions have been widely used in various applications such as printing plates, paints, printing inks, etching resists, plating resists, solder resists, surface coating agents, varnishes, adhesives and potting agents. Used, but most of them are basically radically polymerizable polyfunctional
It is a composition comprising (meth) acrylate and a photo-radical polymerization initiator. Such compositions are characterized by their excellent photocurability, the variety of (meth) acrylate combinations that can be used, and the like.

[0003] However, the (meth) acrylate-based photo-cured product has a large volume shrinkage at the time of curing, and therefore generally has problems in adhesion to a substrate and dimensional stability of the cured product. Reactively, these photoradical polymerization systems also have a problem that the curability of the surface of the cured product is poor due to polymerization inhibition by oxygen. Furthermore, there is a disadvantage that water resistance and alkali resistance are low due to the presence of the ester group. In addition, many polyfunctional (meth) acrylates are highly irritating to human skin and have problems in handling in this aspect.

In order to solve such a problem, an ene-thiol-based photocurable composition comprising a polyfunctional allyl compound, a polyfunctional thiol compound and a photoradical polymerization initiator is also known. It can solve some of the points, but raises the new problem of strong smell of thiols.

A photocurable composition comprising a polyfunctional vinyl ether or epoxy compound using a cationic photopolymerization initiator such as diphenyliodonium hexafluoroantimonate and triphenylsulfonium tetrafluorophosphate is also known. . It has relatively small volume shrinkage at the time of curing, is not affected by polymerization inhibition by oxygen, and has low irritation to the skin, as compared with the acrylate-based photocurable composition. However, it is also important as a chemically amplified photoresist having high sensitivity and high resolution.

[0006] However, such compositions still have many problems that must be solved. For example, when diphenyliodonium hexafluoroantimonate or triphenylsulfonium tetrafluorophosphate is used for the photocuring reaction of a polyfunctional vinyl ether or epoxy compound, the cationic polymerization initiator generated by light irradiation is a strong acid, so the cured product The strongly acidic compound will remain in it.

Therefore, when this composition is used as an adhesive, a solder resist, a paint, a coating agent, etc., corrosion of the substrate by acid becomes a serious problem. In addition, although the cationic photopolymerization system does not hinder the reaction due to oxygen, the reaction is greatly hindered by moisture or the hydroxyl group of the reaction system. , Purity, etc. become very important, and there is a problem that it is difficult to handle industrially.

On the other hand, a curing reaction system of an epoxy resin using various amines as a curing agent has a good adhesion to a cured product due to its excellent mechanical strength, dimensional stability, adhesive strength and chemical resistance. It is widely used in various fields such as agents, potting agents, printed wiring plates, composite materials, paints, and printing inks. However, the reaction between the epoxy resin and the organic amine compound is relatively fast, and the reaction proceeds during handling. Therefore, various studies have been made on the control of this reaction so far, for example, microencapsulation of a curing agent is one of them.

Similarly, polyurethane prepolymers are used for paints, coatings, etc. because of their many characteristics. In this case, as in the case of epoxy resins, polyfunctional amine compounds are used. And crosslinking with alcohols is required. However, the isocyanate group, which is a reactive group of the polyurethane prepolymer, has a higher reactivity than the epoxy group, and therefore requires prompt use and treatment after mixing with a curing agent such as an amine.

As described above, amines are excellent curing agents for epoxy resins and polyurethane prepolymers, and thermosetting reactions using these are widely used industrially.
However, as described above, these resin compositions have problems that must be solved in terms of storage stability, reaction control, and the like.

[0011]

An object of the present invention is to provide a composition of an epoxy resin, a polyurethane prepolymer, a polyfunctional cyclic carbonate compound or a polyfunctional (meth) acrylate using an organic amine compound-based curing agent. To provide excellent storage stability and cured product characteristics.

[0012]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
(A) epoxy resin, (B) polyurethane prepolymer,
This is achieved by a curable composition containing (C) a polyfunctional cyclic carbonate compound or (D) a polyfunctional (meth) acrylate and a blocked amine that generates a free amine upon irradiation with light. However, in the case of epoxy resin
The blocked amine is converted to N-formylation or N-
Acylated monofunctional or polyfunctional aromatic amines
Limited.

The curing of such a curable composition is carried out by applying the composition on a substrate and irradiating with light, preferably ultraviolet light and heating.

The blocked amine which forms a free amine upon irradiation with light may be an N-formylated or N-acylated monofunctional or polyfunctional aromatic amine or [(nitrobenzyl) oxy] carbonylation For example, a polyfunctional aromatic or aliphatic amine is used.

As these blocked amines, for example, the following are used. Di-N- (p-formylamino) diphenylmethane di-N- (p-acetylamino) diphenylmethane di-N- (p-benzoamido) diphenylmethane 4-formylaminotoluylene 4-acetylaminotoluylene 2,4-diformyl Aminotoluylene 1-formylaminonaphthalene 1-acetylaminonaphthalene 1,5-diformylaminonaphthalene 1-formylaminoanthracene 1,4-diformylaminoanthracene 1-acetylaminoanthracene 1,4-diformylaminoanthraquinone 1,5 -Diformylaminoanthraquinone 3,3'-dimethyl-4,4'-diformylaminobiphenyl 4,4'-diformylaminobenzophenone 2,2'-diformylamino-1,1'-dimethyl-4,4 ' -(Perfluoroisopropylidene) biphenyl di- (p-formylaminophenyl)-[4,4 '-(perfluoroisopropylidene) diphenol] bis [[ (2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane 2,4-di [[(2-nitrobenzyl) oxy] amide] toluylene bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine Bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexane-1,6-diamine m-xylylenedi [[(2-nitrobenzyl) oxy] amide] m-xylylenedi [[(2,4-dinitrobenzyl) [Oxy] amide] m-xylylenedi [[(2-nitro-4-chlorobenzyl) oxy] amide] 2,5-di [[(2-nitrobenzyl) oxy] amide] naphthalene 2,4-di [[(2 , 4-Dinitrobenzyl) oxy] amide] toluylene 3,3'-dimethyl-4,4'-di [[(2-nitrobenzyl) oxy] amide] biphenyl

The monofunctional or polyfunctional aromatic amine N-
The formylated or N-acylated product can be obtained by any method, but is generally synthesized by the following method. (1) Reaction of aromatic diisocyanate with formic acid, acetic acid, propionic acid, benzoic acid and the like. The reactivity of the carboxylic acid is generally about 50-150 ° C., preferably about 80-130 ° C., because formic acid is larger and benzoic acid is smaller in this order.
The reaction conditions for about 10 hours are also selected according to the reactivity of the carboxylic acid. (2) A condensation reaction between an aromatic amine and the above carboxylic acid using a dicyclohexylcarbodiimide condensing agent or the like. This reaction is generally carried out at about -10 to 10 ° C, preferably at about 0 ° C for about 3 to 2 ° C.
It is carried out for 0 hour, preferably about 10 to 20 hours. (3) Reaction of an aromatic amine with an acyl halide such as acetic halide, propionic halide, or benzoic halide.
This reaction is generally carried out at about −20 to 10 ° C. for about 2 to 5 hours.

The [(nitrobenzyl) oxy] carbonyl compound of a polyfunctional aromatic amine or aliphatic amine can be obtained, for example, by the following method. Reaction of a polyfunctional aromatic or aliphatic diisocyanate with nitrobenzyl alcohol substituted with a mononitro group, a dinitro group, or the like. The reaction preferably employs a catalyst such as triethylamine, dibutyltin dilaurate, and generally ranges from about 60 to 100.
C. for about 3-6 hours.

These blocked amines act as curing agents for epoxy resins, polyurethane prepolymers, polyfunctional cyclic carbonate compounds or polyfunctional (meth) acrylates.

As the epoxy resin, for example, an epibis-type epoxy resin having epoxy groups at both ends synthesized from epichlorohydrin and bisphenol A; similarly, epichlorohydrin and bisphenol AF, bisphenol
Bisphenol type epoxy resin synthesized from S etc .;
Novolak type epoxy resin obtained by reacting novolak type phenol resin synthesized from phenol, cresol, etc. with epichlorohydrin; (poly) ethylene glycol, (poly) propylene glycol, 1,4-butanediol, 1,6 Aliphatic diglycidyl ether type epoxy resin obtained by the reaction of polyfunctional polyols such as -hexanediol and trimethylolpropane with epichlorohydrin; reaction of epichlorohydrin with dicarboxylic acids such as isophthalic acid and terephthalic acid Diglycidyl ester type epoxy resin obtained by the following: N, N-diglycidylaniline, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane; alicyclic diepoxy obtained by oxidation of vinylcyclohexene Compound; triglycidyl isocyanurate and the like are used .

Examples of the polyurethane prepolymer include an excess amount of diisocyanate such as tolylene diisocyanate, methylene diphenylene diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and (poly) ethylene glycol, (poly) propylene glycol, , 4-butanediol, 1,6-hexanediol, neopentyl glycol,
A typical example is a polyfunctional polyurethane prepolymer having an isocyanate residue at a molecular terminal obtained by a reaction with a polyol such as trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol.

The polyfunctional cyclic carbonate compound reacts with an epoxy group by reacting various polyfunctional epoxy compounds with carbon dioxide at about 50 to 110 ° C. under normal pressure using tetrabutylammonium salt or the like as a catalyst. Cyclic carbonate group In this case, by controlling the reaction rate with carbon dioxide, it is also possible to obtain a mixture having a cyclic carbonate group and an epoxy group at the terminal, which can also be used as a polyfunctional cyclic carbonate compound. included.

The polyfunctional (meth) acrylate includes, for example, ethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di
(Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth)
Acrylate, bisphenol-type epoxy resin or novolak-type epoxy resin and epoxy (meth) acrylate obtained by addition reaction of (meth) acrylic acid, obtained by reacting 2-hydroxyethyl (meth) acrylate, diol and diisocyanate Polyurethane (meth) acrylate, polyester (meth) acrylate obtained by reacting (meth) acrylic acid, polycarboxylic acid and polyol are used.

Blocked amines which generate free amines by irradiating the epoxy resin or the like with light, preferably with ultraviolet light, are used in the following proportions.

For the epoxy group in the epoxy resin,
The free amine is theoretically used depending on the number of amino groups, for example, a monoamine or diamine has a molar ratio of 1.0 to 0.5, but is practically used in a molar ratio of about 1.1 to 0.1.

For the isocyanate groups in the polyurethane prepolymer, one amino group and one isocyanate group
Since it is a reaction with an individual, an equimolar ratio is optimal, but generally it is used in a molar ratio of about 1.2 to 0.2 as an amino group to an isocyanate group.

The free amine generated by light irradiation reacts with the polyfunctional cyclic carbonate compound as follows. Therefore, in this case, the molar ratio of the amino group to the cyclic carbonate group is optimally equimolar, but generally the molar ratio is about 1.2 to 0.2 relative to the cyclic carbonate group.

In the case of polyfunctional (meth) acrylates,
The amino group is optimally equimolar to the (meth) acryloyl group, but generally about 1.
It is used in a molar ratio of about 2 to 0.2.

The composition can be prepared by simply mixing an epoxy resin or the like with a blocked amine, and it is industrially preferable to use a ball mill or a three-roll mill. Further, if necessary, they can be mixed using a solvent such as dimethylformamide, tetrahydrofuran, methyl ethyl ketone, or ethyl acetate.

The prepared composition is applied to a substrate and cured by irradiation with light and heating. Light irradiation for releasing the blocked amine, preferably ultraviolet irradiation, may be performed by any of industrially available light sources such as a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp. The irradiation time varies greatly depending on the light intensity of the light source, and is as short as about 5 minutes and as long as about 3 hours, but generally about 30 to 60 minutes.

By such light irradiation, an N-formyl group, an N-acyl group or [(nitrobenzyl) oxy] carbonyl group is released from the blocked amine to form a free amine. The free amino groups formed react with epoxy groups, isocyanate groups, cyclic carbonate groups or (meth) acryloyl groups. This curing is done by heating, about 80-200 for epoxy resin
C., preferably about 100-160 ° C., about 50-180 ° C., preferably about 80-120 ° C. for the polyurethane prepolymer, about 30-150 ° C., preferably about 50-120 ° C. for the polyfunctional cyclic carbonate compound, and About 3 for polyfunctional (meth) acrylate
Heat curing is performed at 0 to 150 ° C, preferably at about 50 to 120 ° C.

[0031]

The curable composition according to the present invention is an N-formylated or N-acylated aromatic amine or [(nitrobenzyl) oxy] carbonylated aromatic or aliphatic amine by ultraviolet irradiation. A free amine is generated from the amine, and the subsequent heating reacts the free amine with a functional group of an epoxy resin, a polyurethane prepolymer, a polyfunctional cyclic carbonate compound or a polyfunctional (meth) acrylate to cure them.

In such a series of curing operations, since the amine is blocked by N-formylation or N-acylation or [(nitrobenzyl) oxy] carbonylation, the curing reaction is accelerated unless irradiated with ultraviolet light. And extremely excellent storage stability.

The present invention also solves the problem that the (meth) acrylate-based photocured product has poor curability on the surface of the cured product due to inhibition of polymerization by oxygen. (Below)

[0034]

Next, the present invention will be described with reference to examples.

Reference Example 1 Synthesis of di-N- (p-formylamino) diphenylmethane After dissolving 2.50 g (10 mmol) of 4,4'-diphenylmethane diisocyanate in 40 ml of dehydrated toluene, 1.01 g of formic acid was obtained.
(22 mmol) and reacted at 80 ° C. for 2 hours. As the reaction proceeds, a white product precipitates. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and then the product was filtered and washed with methanol for reflux. Yield: 2.49 g (yield 98.1%) Melting point: 177.6-178.3 ° C Infrared absorption spectrum: 3200-2880 cm ^-1 (-NH-), 1690 cm
^-1 (C = 0) ¹ H-NMR: 3.8 ppm ( ¹ H, s, -CH _2- ) 7.0 to 7.6 ppm (4 H, m, ArH) 8.25 ppm (1 H, d, -CHO) 10.0 ppm (1 H, s, -NH-)

Reference Example 2 Synthesis of di-N- (p-benzoamido) diphenylmethane 1.98 g (10 mmol) of diaminodiphenylmethane was dissolved in 40 ml of tetrahydrofuran, and 2.23 g (22 mmol) of triethylamine as an acid acceptor was further dissolved. added. While stirring under ice-cooling, 3.09 g (22 mmol) of benzoyl chloride was slowly added dropwise at 0 to 5 ° C. After the completion of the dropwise addition, the reaction was carried out at 5 ° C. or lower for 2 hours and subsequently at room temperature for 4 hours. The product was precipitated by adding the reaction mixture to 400 ml of water, stirred for 1 hour, and then filtered and dried. Thereafter, reflux washing with methanol was performed. Yield: 2.46 g (60.5% yield) Melting point: 253.4-254.6 ° C (Literature value 250 ° C) Infrared absorption spectrum: 3330-3050cm ^-1 (-NH-), 1645cm
^-1 (C = 0) ¹ H-NMR: 3.9 ppm ( ¹ H, s, -CH _2- ) 7.1 to 8.0 ppm (9 H, m, ArH) 10.2 ppm (1 H, s, -NH-)

Reference Example 3 Synthesis of 4-formylaminotoluylene 1.07 g (10 mmol) of p-toluidine and 1 as a condensing agent
2.11 g (11 mmol) of -ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved in 24 ml of methylene chloride. While stirring this solution, formic acid
0.60 g (13 mmol) was slowly added dropwise.
The reaction was continued for 2 hours at room temperature and 16 hours at room temperature. After the reaction mixture was added to 250 ml of water and stirred for 1 hour, the precipitate was filtered, dried and recrystallized with a toluene-n-hexane mixed solvent. Yield: 1.05 g (77.7% yield) Melting point: 49.5-50.4 ° C (Literature 52 ° C) Infrared absorption spectrum: 3310cm ^-1 (-NH-), 1690cm ^-1 (C =
0) ¹ H-NMR: 2.3 ppm (3 H, s, -CH ₃ ) 6.7 to 7.5 ppm (4 H, m, ArH) 8.1 ppm (1 H, s, -CHO) 8.5 ppm (1 H, s, -NH-)

Reference Example 4 Synthesis of 2,4-diformylaminotoluylene 0.87 g (5 mmol) of 2,4-tolylenediisocyanate was dissolved in 20 ml of dehydrated toluene, and 0.51 g (11 mmol) of formic acid was added. At 80 ° C. for 2 hours. After the reaction was completed, the product precipitated in the reaction solution was filtered and washed with methanol for reflux. Yield: 0.85 g (94.9% yield) Melting point: 168.8-170.4 ° C (Literature 176-177 ° C) Infrared absorption spectrum: 3250-2890cm ^-1 (-NH-), 1690cm
^-1 (C = 0) ¹ H-NMR: 2.2 ppm (3 H, s, -CH ₃ ) 6.7 to 7.6 ppm (3 H, m, ArH) 8.0 ppm (1 H, s, -CHO) 8.28 ppm (1 H, s , -CHO) 9.6ppm (1H, s, -NH-) 10.1ppm (1H, s, -NH-)

Reference Example 5 Synthesis of 1-acetylaminonaphthalene 1.43 g (10 mmol) of α-naphthylamine was dissolved in 30 ml of tetrahydrofuran, and 1.12 g (11 mmol) of triethylamine as an acid acceptor was added thereto. While stirring under ice-cooling, 0.86 g (11 mmol) of acetyl chloride was added to 0 to
Drip slowly at 5 ° C, and after dropping at 5 ° C or less for 2 hours,
The reaction was continued at room temperature for 4 hours. After the reaction mixture was added to 300 ml of water and stirred for 1 hour, the precipitate was filtered, dried and recrystallized from toluene. Yield: 1.13 g (61.0% yield) Melting point: 160.1-161.0 ° C (literature value 160 ° C) Infrared absorption spectrum: 3270cm ^-1 (-NH-), 1655cm ^-1 (C =
0) ¹ H-NMR: 2.2 ppm (3 H, s, -CH ₃ ) 7.0 to 8.2 ppm (7 H, m, ArH) 8.8 ppm (1 H, s, -NH-)

Reference Example 6 Synthesis of 1,5-diformylaminonaphthalene 1.27 g (8 mmol) of 1,5-diaminonaphthalene and 3.37 g (17.6 g) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride Mmol) in 32 ml of methyl ethyl ketone
Dissolved in. To this solution, 0.96 g (20.8 mmol) of formic acid was slowly added dropwise while stirring at 0 ° C. or lower.
After completion of the dropwise addition, the reaction was carried out at 0 ° C. or lower for 2 hours and subsequently at room temperature for 15 hours. The reaction mixture was added to 350 ml of water to precipitate the product, stirred for 1 hour, filtered, dried, and washed with methyl ethyl ketone. Yield: 0.90 g (52.7% yield) Melting point: 268.3-269.2 ° C (literature value 280 ° C) Infrared absorption spectrum: 3220-3280cm ^-1 (-NH-), 1650cm
^-1 (C = 0) ¹ H-NMR: 7.2 to 8.3 ppm (3H, m, ArH) 8.6 ppm (1H, s, -CHO) 10.4 ppm (1H, s, -NH-)

Reference Example 7 Preparation of 3,3'-dimethyl-4,4'-diformylaminobiphenyl
2.64 g (10 mmol) of synthetic o-tolidine diisocyanate were dissolved in 40 ml of dehydrated toluene, to which 1.01 g (22 mmol) of formic acid and a catalytic amount of triethylamine were added.
The reaction was performed for 6 hours. The product precipitated in the reaction solution was filtered and reflux washed with methanol. Yield: 2.51 g (93.5% yield) Melting point: 260.7-262.6 ° C (literature value 254 ° C) Infrared absorption spectrum: 3300-3200cm ^-1 (-NH-), 1665cm
^-1 (C = 0) ¹ H-NMR: 2.3 ppm (3 H, s, -CH ₃ ) 7.2 to 8.0 ppm (3 H, m, ArH) 8.3 ppm (1 H, s, -CHO) 9.6 ppm (1 H, s , -NH-)

Reference Example 8 2,2'-Diformylamino-1,1'-dimethyl-4,4 '-(part
Synthesis of 2,2'-diformyl-1,1'-dimethyl-4,4 '-(perfluoroisopropylidene) biphenyl 1.09 g (3 mmol) and 1-ethyl-3- (3-dimethyl Aminopropyl) carbodiimide hydrochloride 1.27 g (6.6 mmol), methylene chloride 15 ml
Dissolved in. While stirring this solution, 0.36 g (7.8 mmol) of formic acid was slowly added dropwise at 0 ° C. or lower. After completion of the dropwise addition, the reaction was carried out at 0 ° C. or lower for 2 hours and subsequently at room temperature for 16 hours. The reaction mixture was added to 200 ml of water, stirred for 1 hour, and the precipitate was filtered and dried. Yield: 0.91 g (72.7% yield) Melting point: 222.4-223.3 ° C Infrared absorption spectrum: 3350-3300 cm ^-1 (-NH-), 1690 cm
^{-1 (C = 0) 1 H} -NMR: 2.3ppm (3H, s, -CH 3) 6.8~8.1ppm (3H, m, ArH) 8.3ppm (1H, s, -CHO) 9.7ppm (1H, s , -NH-)

Reference Example 9 bis [[(2-nitrobenzyl) oxy] carbonyl] diamid
Synthesis of nodiphenylmethane After dissolving 1.53 g (10 mmol) of 2-nitrobenzyl alcohol in 30 ml of dehydrated toluene, 1.25 g (5 mmol) of 4,4′-diphenylmethane diisocyanate was added and dissolved, and a catalytic amount of dibutyl was further added. Add tin dilaurate and add 80
The reaction was carried out at 3 ° C. for 3 hours. The yellow-white product precipitated in the reaction solution was filtered and washed with toluene. Yield: 2.59 g (93.0% yield) Melting point: 195-197 ° C Infrared absorption spectrum: 3370 cm ^-1 (-NH-), 1730 cm ^-1 (C =
0) ¹ H-NMR: 3.8 ppm ( ¹ H, s, -CH _2- ) 5.5 ppm (2 H, s, -CH ₂ -O-) 6.4 to 8.2 ppm (8 H, m, ArH) 9.8 ppm (1 H, s , -NH-)

Reference Example 10 bis [[(2-nitrobenzyl) oxy] carbonyl] hexa
Synthesis of 1,6-diamine 1.53 g (10 mmol) of 2-nitrobenzyl alcohol was dissolved in 30 ml of dehydrated toluene, and 0.84 g (5 mmol) of hexamethylene diisocyanate and a catalytic amount of dibutyltin dilaurate were added thereto. At 80 ° C. for 3 hours. The product precipitated in the reaction solution was filtered and washed with toluene. Yield: 2.17 g (91.5% yield) Melting point: 136-138 ° C (literature 139-141 ° C) Infrared absorption spectrum: 3330 cm ^-1 (-NH-), 1700 cm ^-1 (C =
^{0) 1 H-NMR: 1.3ppm} (4H, s, - (CH 2) 4 -) 2.97ppm (2H, d, -CH 2H -) 5.4ppm (2H, s, -CH 2 -O-) 7.3 to 8.2 ppm (4H, m, ArH) 10.0 ppm (1H, s, -NH-)

REFERENCE EXAMPLE 11 Bisphenol A di (2-oxy-1,3-dioxysolan-4-
Yl) ether synthesis bisphenol A type epoxy resin (Shell product Epikote -828) 4.75 g (25 mmol of epoxy groups) toluene
It was dissolved in 30 ml, and 0.81 g (2.5 mmol) of tetrabutylammonium bromide as a catalyst was added thereto. While blowing carbon dioxide at a flow rate of 40 ml / min, 9
The reaction was performed at 0 ° C. for 70 hours. The product precipitated in the reaction solution was filtered, washed with water, and then washed with n-hexane. Yield: 4.73 g (81.2% yield) Infrared absorption spectrum: 1790cm ^-1 (-O-CO-O-)

Example 1 0.51 g (2 mmol) of di-N- (p-formylamino) diphenylmethane obtained in Reference Example 1 and 1.52 g of bisphenol A type epoxy resin (Epicoat-828) (8 as an epoxy group)
(Millimol) was applied to a glass plate to a thickness of about 10 μm, and irradiated with light from a 500 W ultra-high pressure mercury lamp from a distance of 35 cm for 10 minutes. Thereafter, the mixture was heated at 140 ° C. for 20 minutes to obtain a cured product insoluble in an organic solvent such as tetrahydrofuran.

Comparative Example 1 In Example 1, when the light irradiation step was omitted, the coating film was uncured and was soluble in an organic solvent such as tetrahydrofuran.

Example 2 In Example 1, when 1.10 g (8 mmol as an epoxy group) of an alicyclic epoxy resin (Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd.) was used as the epoxy resin, a cured product insoluble in an organic solvent such as tetrahydrofuran was used. was gotten.

Example 3 In Example 1, 0.36 g (2 mmol) of 2,4-diformylaminotoluylene obtained in Reference Example 4 was used instead of di-N- (p-formylamino) diphenylmethane. Thus, a cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Comparative Example 2 In Example 1, m-xylylenediformamide (HCO) was used in place of di-N- (p-formylamino) diphenylmethane.
When 0.38 g (2 mmol) of NHCH _2- [mC ₆ H ₄ ] -CH ₂ NHCOH) was used, the coating film was uncured and was soluble in an organic solvent such as tetrahydrofuran.

Example 4 A mixture of 0.25 g (1 mmol) of di-N- (p-formylamino) diphenylmethane and 3.91 g (4 mmol as isocyanate groups) of a polyethylene adipate-based polyurethane prepolymer (DC-4978, a product of Nippon Polyurethane) was prepared. After applying to the glass plate and performing light irradiation in the same manner as in Example 1,
The mixture was heated at 120 ° C. for 10 minutes to obtain a cured product insoluble in an organic solvent such as tetrahydrofuran.

Comparative Example 3 In Example 4, when the light irradiation step was omitted, the coating film was uncured and was soluble in an organic solvent such as tetrahydrofuran.

Example 5 In Example 4, 2.61 g (4 mmol as an isocyanate group) of a polytetramethylene glycol-based polyurethane prepolymer (Adiprene L-167 manufactured by Uniroyal Co.) was used as the polyurethane prepolymer (however, For 20 minutes, a cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Example 6 In Example 4, 0.37 g (2 mmol) of 1-acetylaminonaphthalene obtained in Reference Example 5 was used instead of di-N- (p-formylamino) diphenylmethane (provided that
(The heating time was 20 minutes), and a cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Example 7 1,5-Diformylaminonaphthalene obtained in Example 6
43 g (2 mmol) and bisphenol A type epoxy resin
(Epicoat-828) A mixture of 1.52 g (8 mmol as epoxy group) was applied to a glass plate to a thickness of about 5 to 10 μm, and light irradiation (for 1 hour) and heating were performed as in Example 1. went. A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Comparative Example 4 In Example 7, when the light irradiation step was omitted, the coating film was uncured and was soluble in an organic solvent such as tetrahydrofuran.

Example 8 0.42 g (1 mmol) of 2,2'-diformylamino-1,1'-dimethyl-4,4 '-(perfluoroisopropylidene) biphenyl obtained in Reference Example 8 and bisphenol A A mixture of 0.76 g (4 mmol as epoxy group) of a type epoxy resin (Epicoat-828) was applied to a thickness of about 15 μm on a glass plate, and light irradiation and heating were performed in the same manner as in Example 1. A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained. The above mixture was applied onto a KBr plate, light irradiation and heating were performed in the same manner, and the infrared absorption spectrum before and after the irradiation was measured. As a result, 2,2′-diformylamino-1,1′-dimethyl A decrease in the characteristic absorption of the amide group of -4,4 '-(perfluoroisopropylidene) biphenyl and a sharp decrease in the characteristic absorption of the epoxy group during heating were confirmed.

Comparative Example 5 In Example 8, when the light irradiation step was omitted, the coating film was uncured and soluble in an organic solvent such as tetrahydrofuran.

[0059]

[0060]

Example 9 0.55 g (1 mmol) of bis [[(2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane obtained in Reference Example 9 and 3.91 g of a polyethylene adipate-based polyurethane prepolymer (DC-4978) (isocyanate) (4 mmol as a base) was applied on a glass plate, and irradiated with light (for 15 minutes) and heated (for 120 minutes) in the same manner as in Example 1.
C. for 10 minutes). A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Example 10 0.47 g (1 mmol) of bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine obtained in Reference Example 10 and bisphenol A diamine obtained in Reference Example 11 (2-oxy
A mixture of 0.47 g of (-1,3-dioxysolan-4-yl) ether (2 mmol as a cyclic carbonate group), 0.38 g of bisphenol A type epoxy resin (Epicoat-828) (2 mmol as an epoxy group) and a small amount of tetrahydrofuran was added to a glass. After coating on a plate and drying, light irradiation and heating were performed in the same manner as in Example 1. A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained. In addition, the above mixture was applied on a KBr plate, and was similarly irradiated with light and heated.
By measuring the infrared absorption spectrum before and after that,
Bisphenol A di (2-oxy-1,3-dioxysorane-4-
It was confirmed that the absorption of cyclic carbonate group of yl) ether and the absorption of epoxy group of bisphenol A type epoxy resin were reduced. However, the aliphatic amine bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine was changed to the aromatic amine bis [[(2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane As a result, no decrease in the characteristic absorption of the carbonate group was observed, and only a decrease in the characteristic absorption of the epoxy group was confirmed.

Example 11 0.51 g (2 mmol) of di-N- (p-formylamino) diphenylmethane obtained in Reference Example 1, 1.52 g of bisphenol A type epoxy resin (Epicoat-828) (8 mmol as epoxy group) A mixture of 0.30 g of bisphenol A-type epoxy acrylate (Kyoeisha oil and fat product epoxy ester 3000A) and 0.05 g of photoinitiator (Circa Geigy product Irgacure 651) was applied on a glass plate, and irradiated with light in the same manner as in Example 1. (But for 5 minutes) and heating. A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Example 12 0.55 g (1 mmol) of bis [[(2-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane obtained in Reference Example 9, 3.91 g of a polyethylene adipate-based polyurethane prepolymer (DC-4978) (isocyanate 4 mmol), pentaerythritol triacrylate (Nippon Kayaku product PET-30) 0.30 g and photoinitiator (Irgacure 651) 0.0
5 g of the mixture was applied on a glass plate, irradiated with light (for 5 minutes) and heated (for 10 minutes at 120 ° C.) as in Example 1.
Min). A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Example 13 Bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine 0.47 g (1 mmol) obtained in Reference Example 10 and bisphenol A diamine obtained in Reference Example 11 (2-oxy
A mixture of 0.94 g of (-1,3-dioxysolan-4-yl) ether (4 mmol as a cyclic carbonate group), 0.90 g of pentaerythritol triacrylate (PET-30) and 0.15 g of a photoinitiator (Irgacure 651) was placed on a glass plate. It was coated on top and irradiated with light (for 5 minutes) and heated (for 140 minutes at 140 ° C.) as in Example 1. A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Example 14 1.41 g (3 mmol) of bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine obtained in Reference Example 10 and 0.3 of trimethylolpropane triacrylate
0 g (1 mmol) of the mixture was applied on a glass plate, irradiated with light and heated as in Example 1 (but at 60 ° C. for 20 minutes).
Was done. A cured product insoluble in an organic solvent such as tetrahydrofuran was obtained.

Claims (6)

(57) [Claims] 1. A curable composition comprising (A) an epoxy resin and an N-formylated or N-acylated monofunctional or polyfunctional aromatic amine which forms a free amine upon irradiation with light. 2. A composition comprising (B) a polyurethane prepolymer, (C) a polyfunctional cyclic carbonate compound or (D) a polyfunctional (meth) acrylate and a blocked amine which forms a free amine upon irradiation with light. Curable composition. 3. A curing method comprising applying the curable composition according to claim 1 on a substrate and irradiating the substrate with light. 4. The curable composition according to claim 2, wherein the blocked amine is an N-formylated or N-acylated monofunctional or polyfunctional aromatic amine. 5. The curable composition according to claim 2, wherein the blocked amine is a [(nitrobenzyl) oxy] carbonylated polyfunctional aromatic or aliphatic amine. 6. A curing method comprising applying the curable composition according to claim 4 on a substrate and irradiating the substrate with ultraviolet light.