JP2003026772A - Curable composition and curing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition exhibiting an excellent catalytic activity in low-temperature curing and an excellent storage stability; and a curing method using the same. SOLUTION: This curable composition contains (a) an amine imide compound generating a base under the irradiation with an active beam of light, (b) a singlet or triplet sensitizer, and (c) a compound having at least two epoxy groups or contains (a) an amine imide compound generating a base under the irradiation with an active beam of light, (b) a singlet or triplet sensitizer, (e) a compound having at least two isocyanate groups, and (f) a compound having at least two hydroxyl groups. In the curing method for the composition, heating is conducted simultaneously with or after the irradiation with an active beam of light, thus giving a cured item.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition containing an amine imide compound which generates a base upon irradiation with actinic rays, a singlet or triplet sensitizer and an epoxy resin or an isocyanate resin, and a curable composition. Regarding the method.

[0002]

2. Description of the Related Art Curing technology using actinic rays can be applied to coatings, resists, etc. by taking advantage of characteristics such as low temperature curing, process shortening, short time curing, and microfabrication as compared with conventional thermosetting technology. Has been planned. Curing systems mainly used for such curing are roughly classified into radical curing and cationic curing. In the case of radical curing, the photo-radical generator and the (meth) acrylate resin are the main components, and the photo-radical generator generates radicals through processes such as cleavage and hydrogen abstraction during light irradiation, resulting in (meth) acrylate resin. It is a system that cures, and is characterized by being capable of rapid curing. In the case of cation curing, it is composed of a photo-acid generator and a cationically polymerizable epoxy resin, oxetane resin, vinyl ether resin, etc., and the photo-acid generator generates an acid upon light irradiation to cure the cation-polymerizable resin. It is a system and has the characteristic of low cure shrinkage during curing.
In addition, these photo-curing systems are characterized by having an excellent pot life by shielding light. However, in the case of a radical curing system, a low adhesive force is obtained, and in the case of a cation curing system, a strong acid remains in the system, so that there is a problem that corrosion is caused when an adherend made of a metal or an inorganic material is used. Conventionally, for applications such as adhesives, a thermal latent catalyst having a tertiary amino group such as imidazole or dicyandiamide and an epoxy resin,
Alternatively, a thermosetting system in which a carboxyl group, a mercapto group, an amino group, a phenolic hydroxyl group or the like having reactivity with an epoxy resin is combined is used. This system has high adhesion to adherends such as inorganic materials, metal materials, organic materials, etc., and also has excellent moisture resistance, weather resistance, and heat resistance, so it can be used for construction materials, electrical / electronic materials, and semiconductor materials. It is used in a wide range of applications. However, when the latent curing agent is used, a curing temperature of 170 ° C. or higher is generally required, and when curing is performed at a temperature of 170 ° C. or lower, it is difficult to construct a curing system that also has a pot life. Considering pot life and low-temperature curability, studies on photobase generators that generate basic compounds by irradiation with actinic rays have been conducted in recent years. Examples of such a photobase generator include, for example, Chemistry & Technology.
gy of UV & EB Formulation
for Coatings, Inks & Paint
s, Ed. by G.A. Bradley, John W
ileyand Sons Ltd. (1998),
The carbamate derivatives and oxime ester derivatives described in p479 to p545 are generally known.
However, most of these compounds have a low generation efficiency, and the basic compound generated by irradiation with actinic rays is a primary or secondary amine, so that the basicity is low, and the catalytic activity for sufficiently curing the epoxy resin is low. There is a problem with not having. Some compounds that generate a tertiary amine upon irradiation with actinic rays have been reported, for example, Japanese Patent Application Laid-Open No. Sho 5
Examples thereof include ammonium carboxylic acid salts described in JP-A 5-22669 and α-aminoacetophenone derivatives described in JP-A No. 11-71450.

[0003]

However, in the case of an ammonium carboxylic acid salt, the bond between the carboxylic acid and the tertiary amine is an ionic bond. Therefore, when dissolved in the epoxy curable composition, dissociation proceeds and the pot It has the disadvantage of inferior life. Further, in the case of α-aminoacetophenone derivative, although the catalyst is inactivated by steric hindrance in the molecule, when dissolved in the epoxy curable composition, free rotation in the molecule becomes possible, resulting in pot life. It is known to be inferior.

The present invention provides a curable composition and a curing method which exhibit excellent catalytic activity upon curing at low temperature and have excellent storage stability.

[0005]

Means for Solving the Problems The present invention has been intensively studied in view of the above, and as a result, an amine imide compound has excellent storage stability, and a tertiary amine is generated by irradiation with actinic rays to be curable at a low temperature of 170 ° C. or lower. It has been found that the composition can be cured. It is described in JP-A-10-139748 that an amine imide compound generates a tertiary amine by heating, but it does not generate a tertiary amine when irradiated with an actinic ray having excellent low temperature curability and storage stability. Not listed. The present invention provides [1] (a) an amine imide compound which generates a base upon irradiation with actinic rays, (b) a singlet or triplet sensitizer, (c) a compound having at least two epoxy groups in the molecule. It is a curable composition containing. Further, the present invention is characterized in that the singlet or triplet sensitizer [2] (b) is at least one of a naphthalene derivative, an anthracene derivative, a carbazole derivative, a thioxanthone derivative and a benzophenone derivative. ] It is a curable composition of description. Further, the present invention provides the curable composition according to the above [1] or [2], which [3] (d) essentially contains a compound having two or more functional groups reactive with an epoxy group in the molecule. is there.
Further, in the present invention, the functional group reactive with [4] (d) epoxy group is any one or more of a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group. It is the curable composition according to the above [3].
The present invention also provides [5] (a) an amine imide compound which generates a base upon irradiation with actinic rays, (b) a singlet or triplet sensitizer, and (e) two or more isocyanate groups in the molecule. The curable composition essentially comprises a compound having (f) a compound having two or more hydroxyl groups in the molecule. further,
The present invention provides a cured product by [6] curing the curable composition according to any one of the above [1] to [5], by performing irradiation with active light and heating simultaneously or after irradiation with active light. To obtain a curing method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The amine imide compound used in the present invention is represented by the following general formula (1) or (2),

[Chemical 1] In the formula, R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, and a cycloalkyl having 4 to 8 carbon atoms. Group, C4-8 cycloalkenyl group, C1-6 phenoxyalkyl group, phenyl group, electron-donating group and /
Alternatively, a phenyl group substituted with an electron-withdrawing group, a benzyl group, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, and the like can be given. Examples of the alkyl group having 1 to 8 carbon atoms include an alkyl group having a substituent, for example, an isopropyl group, an isobutyl group, a t-butyl group and the like, in addition to a linear alkyl group. Among these substituents, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 1 to 6 carbon atoms, from the viewpoints of ease of synthesis, solubility of amine imide, and the like. Is preferred.
R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. Ar ¹ in the general formula (1) is an aromatic group represented by the general formulas (I) to (XIII),

[Chemical 2] In the formula, R ^{5 to} R ²⁸ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, and carbon. Cycloalkyl group having 4 to 8 carbon atoms, cycloalkenyl group having 4 to 8 carbon atoms, amino group, alkylamino group having 1 to 6 carbon atoms, dialkylamino group having 1 to 3 carbon atoms, morpholino group, mercapto group, hydroxyl group, Hydroxyalkyl group having 1 to 6 carbon atoms, halogen such as fluorine, chlorine and bromine, ester group having 1 to 6 carbon atoms, carbonyl group having 1 to 6 carbon atoms, aldehyde group, cyano group, trifluoromethyl group, cyano group , A nitro group, a benzoyl group, a phenyl group, a phenyl group substituted with an electron-donating group and / or an electron-withdrawing group,
A benzyl group substituted with an electron-donating group and / or an electron-withdrawing group. Further, in the formula, U to Z are carbon, nitrogen, oxygen and sulfur atoms. In addition, Ar in the general formula (2)
² is an aromatic group represented by the following formulas (XIV) to (XXII),

[Chemical 3] R ^{29 to} R ³⁶ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, and 4 carbon atoms.
~ 8 cycloalkyl group, C4-8 cycloalkenyl group, amino group, C1-6 alkylamino group,
A dialkylamino group having 1 to 3 carbon atoms, a morpholino group,
Mercapto group, hydroxyl group, hydroxyalkyl group having 1 to 6 carbon atoms, halogen such as fluorine, chlorine and bromine, and 1 to 1 carbon atoms
6 ester group, carbonyl group having 1 to 6 carbon atoms, aldehyde group, cyano group, trifluoromethyl group, cyano group,
A phenyl group substituted with a nitro group, a phenyl group, an electron-donating group and / or an electron-withdrawing group, an electron-donating group and
Or a benzyl group substituted with an electron-withdrawing group. In the formula, W is carbon, nitrogen, nitrogen substituted with an alkyl group having 1 to 6 carbon atoms, oxygen, and sulfur, and X to Z are independently carbon, nitrogen, oxygen, and sulfur atoms. From the viewpoints of thermal stability and absorption wavelength similar to Ar ¹ , the substituent of R ^{29 to} R ³⁶ is preferably a carbonyl group having 1 to 6 carbon atoms, which is an electron-withdrawing group, a cyano group, or a nitro group. .

A known method can be used for the synthesis of the amine imide compound. For example, Encycled
ia of Polymer Science and
Engineering, John Wiley &
Sons Ltd. , (1985), Volume 1, p74
0, it can be obtained from the reaction of the corresponding carboxylic acid ester with a halogenated hydrazine and sodium alkoxide, or the reaction of the carboxylic acid ester with a hydrazine and an epoxy compound. Considering the convenience and safety of the synthesis, the synthetic method from the corresponding carboxylic acid ester, hydrazine and epoxy compound is particularly preferable. The synthesis temperature and the synthesis time are not particularly limited as long as the starting materials used are not decomposed, but generally, the desired amine imide compound is obtained by stirring at a temperature of 0 to 100 ° C. for 30 minutes to 7 days. Obtainable.

As the sensitizer used in the present invention, a known singlet sensitizer or triplet sensitizer can be used as long as it does not adversely affect the curable composition. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, aromatic carbonyl compounds, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. Of these, a naphthalene derivative, an anthracene derivative, a carbazole derivative is most preferable as the singlet sensitizer, and a thioxanthone derivative and a benzophenone derivative are most preferable as the triplet sensitizer. For example,
1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene,
1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene,
9,10-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, 9
-Cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, carbazole, 9-methylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9-propyl -9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol,
9-methyl-3-nitro-9H-carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octanoylcarbazole, 9-carbazolemethanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-decyl-3,6-dinitro-9
H-carbazole, 9-ethyl-3,6-dinitro-9
H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9-allylcarbazole, 9-benzyl-9H-carbazole, 9-carbazole acetic acid, 9-
(2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-
Methyl-propyl) -9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9
H-carbazole, 2-hydroxycarbazole, 3,
6-diacetyl-9-ethylcarbazole, benzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethoxy) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-Benzoylbenzoic acid methyl ester, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, [4- (4- Methylphenylthio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-
Examples include isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 1-chloro-4-propoxythioxanthone. These may be used alone or in combination of two or more. The amount of the sensitizer used is required to refer to the absorption wavelength and the molar extinction coefficient of the sensitizer, but it is generally 0.01 to 10 parts by weight with respect to 1 part by weight of the amine imide compound, 1 to 5 parts by weight is particularly preferred. Sensitizer is 0.01
If it is less than 10 parts by weight, the efficiency of light absorption is low, and if it exceeds 10 parts by weight, actinic rays may not reach the entire curable composition.

A compound (epoxy resin) having at least two epoxy groups in the molecule used in the present invention
There is no particular limitation as long as it has two or more epoxy groups in the molecule, and known ones can be used. Further, among the compounds having an epoxy group used in the present invention, examples of the compound having two epoxy groups in one molecule include the compounds shown below (Me is a methyl group, and the broken line is a methylene group in some cases. Shown).

[0010]

[Chemical 4]

[0011]

[Chemical 5]

Among the compounds having an epoxy group used in the present invention, the compounds having three epoxy groups in one molecule include the compounds shown below (Me
Represents a methyl group, Et represents an ethyl group, and a broken line represents a methylene group in some cases).

[0013]

[Chemical 6]

Further, among the compounds having an epoxy group used in the present invention, examples of the compound having four epoxy groups in one molecule include the compounds shown below.

[Chemical 7]

As the compound having an epoxy group used in the present invention, a compound represented by the general formula (3) can also be used.

[Chemical 8] In the general formula (3), R ^{8 to} R ¹¹ each independently represents a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, or a monovalent group. Examples of the monovalent group include an amino group, an ester group such as a carbomethoxy group, an amide group such as a carboaminomethyl group, a carbamino group such as an aminocarboxymethyl group, a substituted or unsubstituted methyl group, an ethyl group and a propyl group. Examples thereof include an alkyl group such as a butyl group, a hexyl group, and a heptyl group or a substituted or unsubstituted phenyl group, a vinyl group, a 1-propenyl group, an alkenyl group such as a 1-butenyl group, and a silyl group.

Among the compounds having an epoxy group used in the present invention, compounds containing 2 to 4 epoxy groups in the molecule are preferable because the polymer has an appropriate crosslinking density. When the number of epoxy groups is more than 5, the crosslink density of the polymer is too high, which makes it difficult to handle and also tends to cause intramolecular reaction.

As the compound having an epoxy group according to the present invention, a compound having an epoxy equivalent of 43 to 10,000 may be used. When the epoxy equivalent is 43 or less, a compound having an epoxy group cannot be formed, and when it is more than 10000, the reaction rate tends to decrease. At this time, when not only a single molecule but also an oligomer having a distribution of the number of repeating units (z) as shown below is used, the crystallinity of the composition is lowered and the storage stability is excellent. Therefore, 0 <z is preferable, and 0.5 ≦
z is more preferable, and 1 ≦ z is most preferable.

[0018]

[Chemical 9]

Examples of the compound having at least two epoxy groups in the molecule (such as epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type Epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin There are resins, aliphatic chain epoxy resins, etc. These epoxy resins may be halogenated or hydrogenated, and these epoxy resins may be used in combination of two or more kinds. Among these, different grades of when compared to other various epoxy compounds the molecular weight is widely available, from the point can be arbitrarily set the adhesive and reactivity, etc., a bisphenol type epoxy resin is preferable.

The amine imide compound can be generally used as a curing catalyst for a compound (epoxy resin) having at least two epoxy groups in the molecule,
The amount used is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the compound (epoxy resin) having at least two epoxy groups in the molecule,
More preferably, it is 1 to 30 parts by weight. This amount is
If the amount is less than 0.01 part by weight, the curing acceleration effect tends to be insufficient, and if it exceeds 50 parts by weight, the compatibility tends to decrease.

The present invention provides a compound (epoxy resin) having at least two epoxy groups in the molecule and an amine imide compound, and further a compound having two or more functional groups reactive with the epoxy resin in the molecule. Can be used together. As the functional group having reactivity with the epoxy resin, a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group known to react with the epoxy resin can be used. . Considering three-dimensional curability, it is essential that two or more of these functional groups be contained in one molecule. Further, a polymer having a weight average molecular weight of 10,000 or more and a functional group introduced into a side chain may be used.

The amount of the compound having two or more functional groups reactive with the compound (epoxy resin) having at least two epoxy groups in the molecule is the same as the functional group of the epoxy resin. Of total amount / total amount of epoxy groups (equivalent ratio) is preferably 0.5 / 1.5 to 1.5 / 0.5, and 0.8 / 1.2 to 1.
It is more preferable that the ratio is 2 / 0.8. If this ratio is less than 0.5 / 1.5 and 1.5
If it exceeds /0.5, a large amount of unreacted epoxy groups and functional groups remain in the cured product, which tends to deteriorate the mechanical properties of the cured product.

The compound having an isocyanate group (hereinafter referred to as an isocyanate resin) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule, and a known compound is used. You can. Typical examples of such compounds include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, and hexamethylene diisocyanate. In addition to the low molecular weight compound, an oligomer or a polymer having a weight average molecular weight of 3,000 or more and having an isocyanate group at the side chain or terminal may be used.

The compound having an isocyanate group is usually used in combination with a compound having a hydroxyl group in the molecule. Such an isocyanate resin is not particularly limited as long as it has two or more hydroxyl groups in the molecule,
Known ones can be used. Such compounds include:
In addition to low molecular weight compounds such as ethylene glycol, propylene glycol, glycerin, diglycerin, and pentaerythritol, those having a hydroxyl group at the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more may be used.

The amount of the compound having two or more hydroxyl groups in the molecule is 0.5 / total amount of hydroxyl groups / total amount of isocyanate groups (equivalent ratio) with respect to the above isocyanate resin.
The ratio is preferably 1.5 to 1.5 / 0.5, and more preferably 0.8 / 1.2 to 1.2 / 0.8. This ratio is 0.5
When it is less than /1.5 and exceeds 1.5 / 0.5, a large amount of unreacted epoxy groups and functional groups remain in the cured product, which tends to deteriorate the mechanical properties of the cured product. is there.

The amount of the amine imide compound used as a curing catalyst for the isocyanate resin and the compound having a hydroxyl group is 0.01 to 50 parts by weight based on 100 parts by weight of the total amount of the compound having an isocyanate group and the compound having a hydroxyl group. It is preferable that it is 0.1 to 30 parts by weight. If this amount is less than 0.01 part by weight, the curing acceleration effect tends to be insufficient, and if it exceeds 50 parts by weight, the compatibility tends to decrease.

The curable composition of the present invention may optionally contain additives such as an adhesion improver such as a coupling agent, a leveling agent and an organic or inorganic filler.

Various polymers may be appropriately added to the curable composition of the present invention for the purpose of thickening or forming a film. The polymer to be used is not particularly limited, but it is essential that it does not adversely affect the curability. Examples of such polymers include general-purpose phenoxy resins such as polyimide resins, polyamide resins, bisphenol A-type phenoxy resins and bisphenol F-type phenoxy resins, bisphenol A / bisphenol F copolymerization-type phenoxy resins, polymethacrylate resins, and polyacrylate resins. , Polyimide resins, polyurethane resins, polyester resins, polyvinyl butyral resins, SBS resins and modified epoxy resins thereof, SEBS resins and modified products thereof, and the like can be used. These may be used alone or in combination of two or more. Furthermore, these polymers may contain a siloxane bond or a fluorine substituent. These can be suitably used as long as the resins to be mixed are completely compatible with each other, or microphase separation occurs to cause clouding. The molecular weight is not particularly limited, but as a general weight average molecular weight, 5,000 to 150,000 is preferable and 10,000
~ 80,000 is particularly preferred. This value is 5,000
If it is less than 15, the film formability tends to be inferior.
If it exceeds 50,000, the compatibility with other components tends to deteriorate. The amount used is preferably 20 to 320 parts by weight with respect to 100 parts by weight of a compound (epoxy resin) having at least two epoxy groups in the molecule or an isocyanate resin.

The curable composition of the present invention can be used as a paste when it is liquid at room temperature. When it is solid at room temperature (25 ° C.), it may be used by heating or may be made into a paste by using a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the curability and exhibits sufficient solubility, but a solvent having a boiling point of 50 to 150 ° C. under normal pressure is preferable. Boiling point is 5
If the temperature is 0 ° C. or lower, there is a risk of volatilization when left at room temperature, which limits use in an open system. Also, the boiling point is 150
If it is above ℃, it may be difficult to remove the solvent.

The curable composition of the present invention can be used in the form of a film. A solution obtained by adding a solvent or the like to the curable composition is applied onto a releasable base material such as a fluororesin film, a polyethylene terephthalate film or a release paper, or a base material such as a non-woven fabric is impregnated with the solution. It can be used as a film by removing the solvent and the like by placing it on a peelable substrate. When used in the form of a film, it is even more convenient in terms of handleability.

The curable composition of the present invention can be cured by simultaneous irradiation with active light and heating, or by heating after irradiation with active light. As the actinic ray to irradiate,
There are ultraviolet rays, far ultraviolet rays, visible light, electron beams, X-rays and the like.
In particular, an actinic ray having a wavelength range of 150 to 750 nm is preferable, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a metal halide lamp are used to irradiate 0.01 to 100 J / cm ² . It can be cured in an amount. The heating temperature has a functional group reactive with the compound (epoxy resin) having at least two epoxy groups in the molecule and the compound (epoxy resin) having at least two epoxy groups in the molecule. It is not particularly limited as long as it is at or below the decomposition point of the compound, but a temperature of 30 to 200 ° C. is preferable, and a temperature of 50 to 170.
C is even more preferred. Further, the heating time is 1 second to 3 hours, preferably 30 seconds to 1 hour in order to sufficiently perform the curing.

The curable composition of the present invention comprises a paint, an adhesive,
It can be applied to a wide variety of applications such as inks, photoresists, coating materials, various automobile parts, electric / electronic materials, semiconductor materials, optical materials, optical fibers, adhesives for optical fibers, and optical waveguide materials. Especially regarding adhesives, in addition to adhesion of wood, building materials, plastics, leather, etc.
Used as anisotropic conductive adhesive, circuit paste such as silver paste, silver film, etc., and semiconductor element adhesive material such as flip chip anisotropic conductive material for connecting semiconductor elements such as flip chips and printed wiring boards. can do.
Further, even when the adherend to be adhered itself does not have a light-transmitting property, as represented by an adhesive for DVD, the curable composition of the present invention can be bonded by heating after light irradiation. Can be preferably used.

[0033]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

(Example 1) <Synthesis of amine imide> p-Cyanobenzoic acid methyl ester (2.00 g, 12 mmol), N, N-dimethylhydrazine (0.75 g, 12 mmol), phenylglycidyl ether (1.86 g, 12 mmol)
-Butanol (10 g) was added, and the mixture was stirred at 50 ° C for 72 hours and then at room temperature for 48 hours. After removing tert-butanol from the obtained reaction solution with a rotary evaporator, 10 g of ethyl acetate was added for recrystallization to obtain a white amineimide compound. Yield 2.74
g, yield 65%, melting point 148-149 ° C. In addition, the thermal decomposition start temperature in an oxygen atmosphere is TG-D.
When measured by TA, the decomposition start temperature was 200 ° C.

Example 2 As a compound (epoxy resin) having at least two epoxy groups in the molecule, 1.00 g of an epoxy resin (DER736; trade name of Dow Chemical Co., Ltd., epoxy equivalent 172), Pentaerythritol tetra (mercaptoacetate) as a compound having two or more functional groups having reactivity with a compound (epoxy resin) having at least two epoxy groups in the molecule (SH group manufactured by Tokyo Kasei Kogyo Co., Ltd. Equivalent 108, reactive functional group is mercapto group)
0.614 g, amine imide of Example 1 0.016
g and 0.008 g of anthracene (manufactured by Wako Pure Chemical Industries, Ltd.) as a singlet sensitizer were mixed at room temperature (25 ° C.) to obtain a uniform solution. This was sampled in a DSC sample pan so as to have a concentration of 3 mg, and after irradiating with light, DSC (heating rate 10 ° C./min) was measured. The light irradiation was performed using a UV irradiation device AEL 1B / M (365 nm illuminance: 21.5 mW / cm ² ) manufactured by Fusion Co., Ltd. at 1 J / cm ² .

Example 3 The DSC measurement was carried out in the same manner as in Example 2 except that the triplet sensitizer was replaced with benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.).

Comparative Example 1 The DSC measurement was carried out in the same manner as in Example 2 except that the sensitizer was not used.

Comparative Example 2 The DSC measurement was carried out in the same manner as in Example 2 except that the light irradiation was not carried out.

Table 1 shows the measurement results of Examples 3 and 4 and Comparative Examples 1 and 2.

[0040]

[Table 1]

The curable compositions of Examples 2 and 3 had a maximum exothermic temperature of 40 to 50 ° C. lower than that of Comparative Examples 1 and 2, and had a maximum exothermic peak at a temperature lower than the decomposition temperature of the amine imide compound. The temperature was indicated. This result indicates that the amine imide compound generated a basic compound by light irradiation, and the low temperature curing became possible.

(Example 4) When the solutions formulated in Examples 2 and 3 were placed in a light-shielding bottle and allowed to stand at room temperature for 3 days, gelation was not observed, and it was confirmed that the storage stability was excellent.

Example 5 As a compound having an epoxy group (epoxy resin), 50 g of a bisphenol A type epoxy resin (Epicoat 828; trade name of Yuka Shell Epoxy Co., Ltd., epoxy equivalent 184) was dissolved in methyl ethyl ketone. This was used as a solution having a solid content of 40% by weight. As the polythiol, 13.5 g of pentaerythrithiol (SH equivalent 50) was used. As the photobase generator, 2.0 g of the amine imide compound of Example 1 was used. Also, 0.5 g of anthracene as a singlet sensitizer
Using. Further, 1.5 g of an epoxysilane compound (A-187; trade name of Nippon Unicar Co., Ltd.) was used as a silane coupling agent. As a phenoxy resin, bisphenol A, bisphenol F (1/1) and epichlorohydrin were used to prepare 50 g of a bisphenol A, F copolymer type phenoxy resin (average molecular weight 20,000) by a general method, and this was converted into methyl ethyl ketone. This was used as a solution having a solid content of 40% by weight when dissolved. As the conductive particles, on the surface of particles having polystyrene as a nucleus,
A nickel layer having a thickness of 0.2 μm is provided, and a gold layer having a thickness of 0.02 μm is provided on the outer side of the nickel layer, and the average grain size is 10
Particles having a μm and a specific gravity of 2.0 were prepared and used. 3 parts of conductive particles were added to a solution (50 g of solid epoxy resin, 13.5 g of polythiol, 2.0 g of amine imide compound, 1.5 g of silane coupling agent, 50 g of phenoxy resin) containing the above components except for the conductive particles. The mixture is dispersed by volume% and applied to a fluororesin film having a thickness of 80 μm by using a coating device, and dried by hot air at 70 ° C. for 10 minutes to form a film having a thickness of 25 μm made of a composition for circuit connection on the fluororesin film. did.

A line width of 50 μm, a pitch of 100 μm, and a thickness of 1 were obtained using the film adhesive obtained by the above-mentioned manufacturing method.
Flexible circuit board (FPC) having 500 8 μm copper circuits and 0.2 μm indium oxide (ITO)
Glass with a thin layer (thickness 1.1 mm, surface resistance 2
0 Ω / □) was heated and pressed at 160 ° C. and 4 MPa for 60 seconds and connected over a width of 2 mm. At this time, the adhesive surface of the film-like circuit connecting material was preliminarily heated and pressed at 70 ° C. and 0.5 MPa for 5 seconds to temporarily connect to the ITO glass, and then the fluororesin film was peeled off to form the circuit connecting composition. 3.0 J / c by using an ultraviolet irradiation device (manufactured by Ushio Inc.) having a high pressure mercury lamp on the film surface.
It was irradiated with m ² of ultraviolet rays. Then, the other adherend was connected to FPC to obtain a connected body. When the resistance value between the adjacent circuits of this connection body was measured, the resistance value between the adjacent circuits was 15
The average of 0 points was 2.8 Ω, indicating good connection characteristics. In addition, the adhesive strength of this connector is JIS-Z0237.
According to the above, it was measured and evaluated by the 90 degree peeling method. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as the measuring device for the adhesive strength. The adhesive strength of the connection body, which was performed as described above, is
It was 650 N / m and showed sufficient adhesive strength.

Example 6 As an isocyanate resin,
Hexamethylene diisocyanate (manufactured by Kanto Chemical Co., Inc.) 0.672 g, polytetrahydrofuran (polytetrahydrofuran 250: BAS) as a resin having a hydroxyl group
A uniform varnish consisting of 1.00 g of F Japan Co., Ltd.), 0.016 g of the amine imide compound of Example 1 as a photobase generator, and 0.008 g of benzophenone as a triplet sensitizer was prepared. Add this to the sample pan of DSC 10
It was sampled so as to obtain mg, and a UV irradiation device AEL 1B / M (365 nm illuminance: 21.21.
The light irradiation of 1 J / cm ² was performed using 5 mW / cm ² ). After this, using a hot plate, at 10O 0 C for 10
After heating for minutes and cooling to room temperature (25 ° C),
It was confirmed that a low-elasticity solid substance was obtained, and the curing of the isocyanate group and the hydroxyl group proceeded.

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, a compound (epoxy resin) having at least two epoxy groups in the molecule at low temperature by irradiating with actinic rays alone, or at least two epoxy groups in the molecule. It is possible to provide a curable composition which can be cured at a low temperature with a compound (epoxy resin) having an epoxy group and a curing agent and an isocyanate resin and an alcohol, and which is excellent in storage stability.

Claims (6)

[Claims] 1. (a) an amine imide compound which generates a base upon irradiation with actinic rays, (b) a singlet or triplet sensitizer,
(c) A curable composition containing a compound having at least two epoxy groups in the molecule. 2. The curing according to claim 1, wherein (b) the singlet or triplet sensitizer is at least one of naphthalene derivative, anthracene derivative, carbazole derivative, thioxanthone derivative and benzophenone derivative. Sex composition. 3. The curable composition according to claim 1, which essentially comprises (d) a compound having two or more functional groups reactive with an epoxy group in the molecule. 4. The functional group having reactivity with an epoxy group (d) is any one of a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group. Curable composition. 5. (a) an amine imide compound which generates a base upon irradiation with actinic rays, (b) a singlet or triplet sensitizer, (e) a compound having two or more isocyanate groups in the molecule, ( f) A curable composition essentially containing a compound having two or more hydroxyl groups in the molecule. 6. A curing method for obtaining a cured product by curing the curable composition according to any one of claims 1 to 5 at the same time with or after irradiation with active light rays. .