JP2003160634A - Setting compound and resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a setting compound which is easily and safely decomposed after setting (no poisonous gas is generated when its decomposition by heating is carried out) and excellent in physical properties and utility, and also provide a setting resin composition containing the same. <P>SOLUTION: The setting compound has in its molecule at least respective one functional group selected from the group consisting of a nitrogen-containing heterocyclic ring, isocyanate group, block isocyanate group, alkoxysilyl group and epoxy group, and it can be hardened by the functional groups. The hardened products obtained by crosslinking reaction of these functional groups are decomposed by heating which separates positions at which hydrogen bonds are formed by the nitrogen-containing heterocyclic ring. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable compound and a curable resin composition containing the same. More specifically, it relates to a curable compound that is safe (does not generate a toxic gas during thermal decomposition) and can be easily decomposed, has excellent cured physical properties, and is highly practical, and a curable resin composition containing the same.

[0002]

2. Description of the Related Art In recent years, recyclability is required in various fields from the viewpoint of being environmentally friendly and reducing costs. Curable resins widely used in adhesives, sealants, waterproof materials, paints, foams, etc. (eg urethane resin, epoxy resin, silicone resin, etc.) can also be liquefied and cured while maintaining the original properties of those resins. If the above can be repeated, not only the resin can be recycled, but also the members once adhered to each other can be disassembled and the reinforcing material can be easily removed.

Urethane resins widely used for adhesives, sealants, etc. are useful because they are excellent in storage stability and can be moisture-cured with one liquid, but conventional curable urethane resins are polyether polyol type, It is produced by reacting a polyester polyol-based polymer polyol, a polymer polyol-based polyol, or the like with a polyisocyanate. These urethane bonds are relatively stable, and when heated above 200 ° C., toxic gases such as hydrocyanic acid are generated. While it is known to decompose. Therefore, conventionally, from the viewpoint of safety of dismantling work, workability, etc., disassembling of members that have been once adhered with the resin has been rarely performed.

Epoxy resins, silicone resins, etc., which are widely used as adhesives, sealing agents, waterproof materials, etc., are excellent in storage stability, weather resistance and the like and are useful in that they can be cured with one liquid. It is known that the bond (for example, 1-alkylamino-2-hydroxyethyl group and the like) generated by the cleavage (curing) reaction of, the siloxane bond and the like do not decompose unless the temperature is higher than 200 ° C. For this reason, conventionally, from the viewpoints of safety of disassembly work, workability, equipment investment, etc., disassembling of members once adhered with the resin has been rarely performed.

By the way, in the thermoplastic resin, hydrogen is added in order to suppress deterioration of heat resistance or rigidity when a compound having a small molecular weight or a thermoplastic resin having a large fluidity is added as a fluidity improving agent. A method of utilizing a combination has been proposed. For example, a method of improving the fluidity and heat resistance of a thermoplastic resin by adding a compound having a hydroxyl group and a compound having a group capable of forming a hydrogen bond with the group to the thermoplastic resin (Japanese Patent Laid-Open No. 5-33).
9420) or a styrene-based resin having a carboxyl group, and a thermoplastic resin and a compound having a functional group capable of hydrogen bonding with the carboxyl group are added to improve rigidity and fluidity of the styrene-based resin. (JP-A-7
-331002) and the like are disclosed.

Further, regarding the elastomer, an elastomer composition containing an elastomer having a reaction site capable of forming a hydrogen bond and a compound having a reaction site capable of forming a hydrogen bond with the reaction site of the elastomer (Japanese Patent Laid-Open No. H11 (1999) -111945) No. 209524), and a hydrogen-bonding curable compound (Japanese Patent Laid-Open No. 2000-169527) composed of an elastomeric polymer having a carbonyl group-containing group and a heterocyclic amine-containing group in the side chain is formed by hydrogen bond. The applicant has disclosed a method for improving heat resistance, cold flow property, and recycling of an elastomer composition and an elastomer by utilizing cross-linking and de-cross-linking. These techniques introduce a reaction site capable of forming a hydrogen bond into a high molecular weight elastomer and reversibly solidify
It is a technology that can be fluidized.

[0007]

DISCLOSURE OF THE INVENTION In the present invention, by introducing a nitrogen-containing heterocycle capable of forming a hydrogen bond, decomposition after curing by the functional group such as isocyanate group is safe (no toxic gas is generated during thermal decomposition). The first object is to provide a curable compound and a curable resin composition containing the curable compound which can be easily prepared. Further, by introducing the nitrogen-containing heterocycle in a specific ratio, the cured product has a high cross-linking strength and a low decomposition temperature (excellent cured properties), and a highly practical curable compound and curability containing the same. A second object is to provide a resin composition. Furthermore, it is a third object to provide a curable compound having physical properties (performance) according to applications and the like and a curable resin composition containing the same by adjusting the introduction ratio of the nitrogen-containing heterocycle. .

[0008]

Means for Solving the Problems As a result of earnest studies on a curable compound which can be decomposed safely and easily after curing, the present inventor has found that by introducing a site capable of forming a hydrogen bond into the compound, The present invention has been accomplished by finding a curable compound that can be safely and easily decomposed by a functional group such as a group after curing, has high practicability, and can obtain physical properties (performance) according to applications and the like.

That is, 1) the present invention has at least one nitrogen-containing heterocycle in the molecule; and a functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an alkoxysilyl group and an epoxy group. And can be cured by the functional group, and by heating the cured product in which the functional group undergoes a crosslinking reaction, the hydrogen bonding site due to the nitrogen-containing heterocycle or the like is dissociated and the cured product can be decomposed. A curable compound is provided. Thereby, the first and second objects of the present invention can be achieved.

In the nitrogen-containing heterocycle, it is preferred that the nitrogen atom (hereinafter referred to as "ring-constituting nitrogen atom") constituting the heterocycle has no hydrogen atom (tertiary nitrogen atom).
Is one. More preferably, all ring-constituting nitrogen atoms have no hydrogen atoms. It is one of the particularly preferred embodiments that the nitrogen-containing heterocycle is a pyridine ring.

The term "site capable of forming a hydrogen bond" as used herein means a donor hydrogen (hereinafter also simply referred to as "donor") and an acceptor heteroatom (eg, nitrogen, etc.) in the nitrogen-containing heterocycle. Oxygen, etc. (hereinafter, also simply referred to as “acceptor”) site, and a donor and / or acceptor site of a hydrogen atom in the functional group such as the isocyanate group or the blocked isocyanate group after the functional group is cured. . The "hydrogen bond site" is a site that is hydrogen-bonded by a site capable of forming a hydrogen bond, and does not dissociate at a temperature at which a crosslink is formed by the functional group such as an isocyanate group, or cures even if dissociated. A portion that does not participate in the reaction and retains hydrogen bonds before and after the curing reaction, and the bonding site formed by the functional group or the basic skeleton of the curable compound thermally dissociates below the decomposition or dissociation temperature. (Hereinafter, it may be referred to as a “thermal dissociation site”.).

The reversible thermal dissociation of the present invention utilizes the fact that a hydrogen bond is a thermotropically reversible equilibrium reaction in general, so that the hydrogen bond is formed at a low temperature and the hydrogen bond is cleaved at a high temperature. And does not mean thermal dissociation by the functional group such as the isocyanate group. In the present invention, by utilizing such a hydrogen bond, the crosslinking due to the formation of a hydrogen bond and the decrosslinking due to the cleavage of the hydrogen bond are reversibly repeated to realize curing and softening or fluidization of the curable compound. There is.

2) In the present invention, a part of the functional group is
There is provided the curable compound according to 1) obtained by reacting with the compound having a nitrogen-containing heterocycle. Thereby, the first to third objects of the present invention can be achieved.

Further, 3) the present invention provides a curable resin composition containing the curable compound described in 1) or 2). Thereby, the first to third objects of the present invention can be achieved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. A first aspect of the present invention has at least one nitrogen-containing heterocycle in the molecule and a functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an alkoxysilyl group and an epoxy group; A curable compound characterized by being capable of being cured by a functional group, and heating the cured product in which the functional group has undergone a crosslinking reaction to dissociate the hydrogen bonding site due to the nitrogen-containing heterocycle or the like to decompose the cured product. Is.

In the present invention, the cured product can be decomposed by decrosslinking by utilizing cleavage of hydrogen bond. Also, having a functional group such as an isocyanate group in the molecule enables curing in the presence of moisture or a curing agent.

The hydrogen bonding site will be described. The "hydrogen bond site" in the present invention is a site that is hydrogen-bonded by a site capable of forming a hydrogen bond, and does not dissociate at a temperature at which a crosslink is formed by the functional group such as an isocyanate group, or dissociates. Does not participate in the curing reaction and retains hydrogen bonds before and after the curing reaction, and the bonding site formed by the functional group or the basic skeleton of the curable compound is thermally dissociated at a temperature lower than the decomposition or dissociation temperature. The part to do. The reversible thermal dissociation of the present invention generally utilizes the fact that a hydrogen bond is a thermotropical reversible equilibrium reaction, and causes the formation of a hydrogen bond at low temperature and the cleavage of the hydrogen bond at high temperature. It does not mean thermal dissociation by the functional group such as the isocyanate group. Further, "a site capable of forming a hydrogen bond" means a donor and acceptor site of a hydrogen atom having a nitrogen-containing heterocycle, and the functional group such as the isocyanate group or the blocked isocyanate group after being cured. It is a donor and / or acceptor site for a hydrogen atom that it has.

At least one of the nitrogen-containing heterocycles forming such a hydrogen bonding site is a donor and / or a hydrogen atom in a functional group after curing of another nitrogen-containing heterocycle or the isocyanate group or the like. Alternatively, it is capable of forming a hydrogen bond with the acceptor. That is,
The curable compound of the present invention is a nitrogen-containing heterocyclic compound capable of forming a hydrogen bond with a donor and / or an acceptor of a hydrogen atom contained in the functional group after curing, without requiring the intervention of other compounds. It has at least one ring.
Such a nitrogen-containing heterocyclic ring may be a hydrogen-bonding ring by itself, that is, a ring having both a donor and an acceptor (hereinafter, also simply referred to as “co-ring”),
Further, it may be a ring having only a donor or a ring having only an acceptor. A ring having only a donor can form a hydrogen bond by being used in combination with a ring having only an acceptor or a combined ring, and a ring having only an acceptor must be used in combination with a ring having only a donor or a combined ring. This is because a hydrogen bond can be formed by That is, the nitrogen-containing heterocycle introduced into the compound may be only a ring having both a donor and an acceptor, or one of a ring having only a donor and a ring having only an acceptor in addition to the co-ring. Both may be present, or both may be a ring having only a donor and a ring having only an acceptor without having a combined ring, or may be only a ring having only an acceptor.

As the nitrogen-containing heterocycle, any heterocycle having a nitrogen atom in the heterocycle may be used which has a heteroatom other than the nitrogen atom in the heterocycle, for example, a sulfur atom, an oxygen atom or a phosphorus atom. be able to. The reason why the heterocyclic compound is used in the present invention is that a heterocyclic structure allows hydrogen bonding, which will be described later, and the bonding force becomes stronger.

Specifically, the ring having both a donor and an acceptor is, for example, pyrrololine, pyrrolidone,
Oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole,
Isatin, indolyl, phthalimidine, β-isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phylloerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzo. Triazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone,
Examples include pyrazolidone, indazole, pyridoindole, purine and cinnoline. Examples of the ring usually having only a donor include, for example, pyrrole, pyrroline, indole, indoline, oxylindole, carbazole,
Examples include phenothiazine. Examples of the ring having only an acceptor include, for example, indolenine, isoindole, oxazoles, thiazoles, isoxazoles, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine. , Pteridine, pyrazine, phenazine, tetrazine,
Examples thereof include benzoxazole, benzisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthazoline, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline and triazine.

The nitrogen-containing heterocycle in the present invention is the stability of the curable resin composition of the present invention (particularly, urethane-based composition and silicone-based composition) described later, ease of introduction of nitrogen-containing heterocycle, and curing. From the viewpoint of physical properties and the like, a ring having no hydrogen atom at the nitrogen atom constituting the heterocycle, that is, a ring having only the above-mentioned normal acceptor is preferable. In particular,
A ring in which all the nitrogen atoms constituting the heterocycle do not have hydrogen atoms is preferable. Among these, pyridine-based nitrogen-containing heterocycles are more preferable, and pyridine is particularly preferable, from the viewpoints of cured properties and availability.

In the present invention, if the functional group such as the isocyanate group and the nitrogen-containing heterocycle are present in the molecule, the functional group and the nitrogen-containing heterocycle are independently introduced into the basic skeleton of the compound. Alternatively, the nitrogen-containing heterocycle may have a substituent capable of reacting with the functional group, and the substituent may be reacted with the functional group to introduce the compound into the compound. From the viewpoint of ease of introduction of the nitrogen-containing heterocycle, ease of adjustment of the introduction ratio, and the like, a part of the functional group such as an isocyanate group is a nitrogen-containing heterocycle having a substituent capable of reacting with the functional group. It is preferably introduced into the polymer by reacting with a ring (hereinafter referred to as “a compound having a nitrogen-containing heterocycle”). The compound having a nitrogen-containing heterocycle is not particularly limited as long as it has the above-mentioned heterocycle. For example, it may have a group capable of chemically (covalently) bonding with carbon or the like forming the basic skeleton of the curable compound. Examples of such groups include alkyl groups such as methyl group, ethyl group, (iso) propyl group and hexyl group, alkoxy groups such as methoxy group, ethoxy group and (iso) propoxy group, halogens such as fluorine, iodine and chlorine. Group consisting of atoms, cyano group, amino group, hydroxyl group, aromatic hydrocarbon group,
Examples thereof include an ester group, an ether group, an acyl group and a thioether group, and these can be used in combination. The substitution position of these groups is not particularly limited, and the number of substituents is also not limited. Further, the heterocycle may be used with or without aromaticity, but it is preferable to have aromaticity because the hydrogen bonding force becomes strong.

Examples of such compounds having a nitrogen-containing heterocycle include dipyridylamine, 1,2-dimethylimidazole, 2-benzimidazole urea, pyrrole-2-carboxylic acid, 3-methyl-pyrazole, 4 (o).
r2) -hydroxymethylpyridine, 2 (or4)-
(Β-hydroxyethyl) -pyridine, 2 (or4)-
(2-Aminoethyl) -pyridine, 2 (or4) -aminopyridine, 2,6-diaminopyridine, 2-amino-
6-hydroxypyridine, 6-azathymine, acetoguanamine, benzoguanamine, citrazinic acid, 1,2,4
-Triazole, 3-amino-1,2,4-triazole, 3-aminomethyl-1,2,4-triazole, 3
-Methylamino-1,2,4-triazole, 3-methylol-1,2,4-triazole, 3-hydroxy-
1,2,4-triazole, 2-hydroxytriazine, 2-aminotriazine, 2-hydroxy-5-methyltriazine, 2-amino-5-methyltriazine, 2
-Hydroxypyrimidine, 2-aminopyrimidine, 2-
Aminopyrazine, 2-hydroxypyrazine, 6-aminopurine, 6-hydroxypurine, 2-amino-1,3
4-thiadiazole, 2-amino-5-ethyl-1,
3,4-thiadiazole may be mentioned. Among them, 4 (or2) -hydroxymethylpyridine, 2 (or4)-(β-hydroxyethyl) -pyridine, 2 (or4)-(2-aminoethyl) -pyridine,
2 (or4) -aminopyridine, 2-hydroxypyrimidine, 2-aminopyrimidine, 2-aminopyrazine, 2
-Hydroxypyrazine is preferred and 2 (or4) -aminopyridine is particularly preferred.

The curable compound of the present invention has at least one nitrogen-containing heterocycle in the molecule. If you have one,
Hydrogen bonding is possible within or between molecules. When the curable compound of the present invention has two or more nitrogen-containing heterocycles in the molecule as described above, the nitrogen-containing heterocycles may be the same or different. When the curable compound of the present invention has two or more nitrogen-containing heterocycles, two or more nitrogen-containing heterocycles may be present in the same molecule. Moreover, the curable compound of the present invention may have a nitrogen-containing heterocycle that does not form a hydrogen bond with another nitrogen-containing heterocycle.

The position of the nitrogen-containing heterocycle in the curable compound of the present invention is not particularly limited. For example, it may have the above-mentioned nitrogen-containing heterocycle as a side chain of a compound (polymer), may have in the main chain of the polymer, or may have the above-mentioned nitrogen-containing heterocycle at the molecular end of the polymer. You may have. From the viewpoint of ease of introduction, cured physical properties, and thermal dissociation properties, it is preferably on the side chain or molecular end of the polymer.

The site capable of forming a hydrogen bond with the nitrogen-containing heterocycle is the stability of a curable resin composition (particularly a urethane composition or a silicone composition) containing the curable compound of the present invention described later. Since the deterioration and deterioration of physical properties after curing due to the introduction of other nitrogen-containing heterocycle as a donor may occur, the functional group after curing the isocyanate group, blocked isocyanate group, alkoxysilyl group and epoxy group It is preferably a donor and / or an acceptor of a hydrogen atom contained in the group.

Specifically, for example, a hydrogen atom contained in a urethane bond (urea bond) or the like formed by curing an isocyanate group or a blocked isocyanate group; a hydrogen atom contained in, for example, an amino group or a hydroxyl group formed by curing an epoxy group. Etc.

Since at least one functional group of the above-mentioned isocyanate group, blocked isocyanate group, alkoxysilyl group and epoxy group is present in the molecule as will be described later, the sites capable of forming hydrogen bonds derived from these functional groups are After curing, at least one occurs in one molecule before curing. That is, when the curable compound of the present invention is cured by moisture, a curing agent or the like, the hydrogen atom generated thereby and the nitrogen-containing heterocycle are hydrogen-bonded to each other to form a bridge (hydrogen-bonding site).

The hydrogen-bonding site thus generated utilizes the fact that the hydrogen bond is a thermotropically reversible equilibrium reaction in general, and specifically, utilizes the formation and cleavage of the hydrogen bond to form a cross-linking reaction. And the decrosslinking reaction can be repeated. Further, the hydrogen bond site is a site hydrogen-bonded by a site capable of forming a hydrogen bond, and does not dissociate at a temperature at which a crosslink is formed by the functional group such as an isocyanate group, or even if dissociated, a curing reaction does not occur. Has a hydrogen bond bond before and after the curing reaction without involvement, and has a property that the bonding site formed by the functional group or the basic skeleton of the curable compound thermally dissociates at a temperature lower than the decomposition or dissociation temperature. .

Accordingly, the hydrogen bonding force of the nitrogen atom in the nitrogen-containing heterocycle and the donor and / or acceptor of the hydrogen atom generated by the functional group are appropriately selected and the hydrogen bonding force is controlled within a specific range. It is possible to construct a safe curable compound that does not generate poisonous gas during decomposition.

The curable compound of the present invention has a strong cross-linking structure (hereinafter sometimes referred to as "permanent cross-linking") derived from the functional group such as the isocyanate due to the formation of a hydrogen bond (hydrogen bond site), and this. Since it forms a thermally dissociative cross-linking structure different from the above, a curable compound having high cross-linking strength and low decomposition temperature (excellent in cured physical properties) and highly practical can be obtained.

The curable compound of the present invention has at least one functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an alkoxysilyl group and an epoxy group in the molecule together with the nitrogen-containing heterocycle. These groups are preferably at the side chain or the molecular end of the compound. By having at least one of these functional groups, a curing reaction (permanent crosslinking) becomes possible. In addition,
When two or more of these groups are contained, they may be the same or different.

Here, the blocked isocyanate group means
Isocyanate group is blocked by a protective group, for example, a group that can be easily removed by heat or moisture to generate an isocyanate group, for example, blocking agents such as alcohols, phenols, oximes, triazoles, caprolactams, etc. An isocyanate group blocked with is preferably mentioned.

Preferred examples of alcohols include methanol, ethanol, propanol, hexanol, lauryl alcohol, t-butanol, cyclohexanol and the like. Preferred examples of phenols include xylenol, naphthol, 4-methyl-
2,6-di-t-butylphenol and the like can be mentioned. Preferred examples of oximes include 2,6-dimethyl-4-heptanone oxime, methyl ethyl ketoxime, 2-heptanone oxime and the like. In addition, 3,5-dimethylpyrazole, 1,2,4-triazole and the like can be preferably used. Of these, methanol and xylenol are preferable as the blocking agent.

As the compound having a nitrogen-containing heterocycle and the functional group, a compound obtained by introducing the functional group such as an isocyanate group into a compound having a nitrogen-containing heterocycle; or a compound having a nitrogen-containing heterocycle will be described later. A polyisocyanate compound, a blocked isocyanate compound obtained by protecting all or a part of the isocyanate groups of the polyisocyanate compound with the blocking agent, an alkoxysilyl group-containing compound, an epoxy compound as a raw material for producing an epoxy prepolymer described below, and these groups Compounds obtained by reaction with compounds having two or more kinds; and the like. The latter compound is preferable from the viewpoint of easiness of introduction of nitrogen-containing heterocycle, and the compound having two or more kinds of the functional groups is more preferable from the viewpoint of physical properties of the cured product.

The compound having the nitrogen-containing heterocyclic ring and the functional group such as an isocyanate group introduced therein is not particularly limited, and examples thereof include 3-pyridyl isocyanate and 2
-Pyridyl isocyanate, 4-pyridyl isocyanate, 2-pyridyl methyl isocyanate, 2-pyridyl ethyl isocyanate, 4-pyridyl methyl isocyanate, 4-pyridyl ethyl isocyanate, etc. are mentioned.

The compound obtained by reacting the compound having a nitrogen-containing heterocycle with the functional group is not particularly limited, and the nitrogen-containing heterocyclic compound 1 having a reactive group such as an amino group, a hydroxyl group, a mercapto group, etc. Reaction products of one or more species and one or more species such as epoxysilane and isocyanate silane compounds may be mentioned. Epoxy silanes, isocyanate silane compounds and the like are not particularly limited and include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- ( 3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and other epoxy group-containing silane compounds; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyl Diethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatoethyltriethoxysilane, γ
-Isocyanatoethylmethyldiethoxysilane, γ-
Isocyanate group-containing silane compounds such as isocyanate ethylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-
Amino group-containing silane compounds such as β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-
Mercapto group-containing silane compounds such as mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethyl Phenylbis (2-methoxyethoxy)
Silane, N-β- (carboxymethyl) aminoethyl-
Carboxysilane compounds such as γ-aminopropyltrimethoxysilane; Vinyl group-containing silane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane; γ-methacryloxypropylmethyldimethoxysilane Methacryloxy group-containing silane compounds such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane and γ-methacryloxypropyltriethoxysilane; halogen-containing silane compounds such as γ-chloropropyltrimethoxysilane Can be mentioned.

Among these, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanateethyltrimethoxysilane and γ-isocyanate. Isocyanate group-containing silane compounds such as ethyltriethoxysilane, γ-isocyanate ethylmethyldiethoxysilane and γ-isocyanateethylmethyldimethoxysilane are preferable, and γ
-Isocyanatopropyltrimethoxysilane is particularly preferred.

The compound having a nitrogen-containing heterocycle and the functional group is not particularly limited as long as it is a thermosetting resin or a moisture-curing resin having these groups, in addition to the compounds described above, and the physical properties of the cured product. Urethane prepolymers, epoxy resins, silane compounds and modified polymers thereof are preferable from the viewpoint of (adhesive strength etc.) and handleability. Also,
The number average molecular weight is not particularly limited, but it is preferably liquid at room temperature from the viewpoint of handleability and the like. Further, such polymer compounds may be used alone or in combination of two or more.

As the urethane prepolymer, a commonly used prepolymer can be used, and examples of the polyol used for producing the prepolymer include polyether polyol, polyester polyol, other polyols and mixed polyols thereof. Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4′-dihydroxyphenylpropane, 4,
Dihydric alcohols such as 4'-dihydroxyphenylmethane; polyhydric alcohols such as glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol and pentaerythritol; diamines such as ethylenediamine and aromatic diamines. A polyol obtained by adding one or more saccharides such as sorbitol and one or two or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. .

As the polyester polyol, one or two kinds of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane and other low molecular weight polyols are used. Above, glutaric acid, adipic acid, pimelic acid,
Examples thereof include condensation polymers of suberic acid, sebacic acid, terephthalic acid, isophthalic acid and one or more low molecular carboxylic acids and oligomeric acids; ring-opening polymers such as propionlactone, valerolactone and caprolactone.

Other polyols include polymer polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol,
Examples thereof include low molecular weight polyols such as hexanediol.

The polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups, and specifically, 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tridiene. Diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI),
Aromatic polyisocyanates such as p-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI) and 1,5-naphthalene diisocyanate; aliphatic such as hexamethylene diisocyanate (HDI) and norbornane diisocyanatomethyl (NBDI) Polyisocyanate; isophorone diisocyanate (IPDI), H ₆ XDI
Alicyclic polyisocyanates such as (hydrogenated XDI) and H ₁₂ MDI (hydrogenated MDI); carbodiimide-modified polyisocyanates of the above polyisocyanates, or isocyanurate-modified polyisocyanates thereof. It is also possible to use an isocyanate compound having at least one isocyanate group having a large steric hindrance. Specifically, preferred examples include TMI (monoisocyanate compound), TMXDI (diisocyanate compound), and secene (triisocyanate compound) manufactured by Mitsui Cytec. These may be used alone or in combination of two or more.

In the production of the urethane prepolymer, the raw material amount ratio is the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol (NCO).
/ OH ratio) is 1.4 to 3.0, and it is preferable to set the amount ratio to 1.7 to 2.5. Within this range, the physical properties of the cured product will be good without foaming due to the remaining polyisocyanate compound and without increasing the viscosity of the urethane prepolymer due to molecular chain extension.

The production conditions of the urethane prepolymer are not particularly limited, and the usual production conditions of the urethane prepolymer can be mentioned. That is, the reaction temperature is 50 to 10
The reaction can be carried out under atmospheric pressure at about 0 ° C. Further, a urethane-forming catalyst such as an organic tin compound or an organic bismuth compound can also be used.

Among the urethane prepolymers composed of the compounds exemplified above, polypropylene glycol and TDI are included.
A urethane prepolymer obtained from MDI and / or MDI is preferable because it is easily available and the properties (performance) of the cured product are well balanced.

As the prepolymer having a blocked isocyanate group, the above-mentioned urethane prepolymer in which the isocyanate group is protected by the above blocking agent or the like can be used. In the present invention, the blocking rate is not particularly limited, and all the isocyanate groups may be protected or a part of the isocyanate groups may be protected depending on the use, the physical properties of the cured product and the like. The reaction conditions for blocking are not particularly limited, and the conditions for synthesizing the urethane prepolymer can be used.

The epoxy resin is not particularly limited, and specifically, an epoxy resin can be used. For example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, tetramethylbisphenol G, glycidyl ether type obtained by reaction of polyphenols such as F and bixylenol with epichlorohydrin; aliphatic such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol Polyglycidyl obtained by reaction of polyhydric alcohols with epichlorohydrin Ether type; p-oxybenzoate, beta-glycidyl ether ester type obtained by reacting hydroxycarboxylic acid with epichlorohydrin, such as oxy-naphthoic acid; phthalic acid, methyl phthalic acid, isophthalic acid,
Terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid,
Endomethylene hexahydrophthalic acid, trimellitic acid, polyglycidyl ester type derived from polycarboxylic acid such as polymerized fatty acid; glycidyl aminoglycidyl ether type derived from aminophenol, aminoalkylphenol, etc .; derived from aminobenzoic acid Glycidylaminoglycidyl ester type; aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-
Glycidyl amine type derived from diaminodiphenyl sulfone; further epoxidized polyolefin, glycidyl hydantoin, glycidyl alkyl hydantoin,
Triglycidyl cyanurate and the like; butyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, benzoic acid glycidyl ester, monoepoxy compounds such as styrene oxide, and the like, and one or a mixture of two or more thereof may be used. it can. In this case, the mixing ratio can be any mixing ratio depending on the use, storage stability, low temperature storability and physical properties of the cured product.

Of these, a reaction product of bisphenol A glycidyl ether and aminopyridine is preferable because it is easily available and the properties (performance) of the cured product are well balanced. The production conditions of the prepolymer are not particularly limited, and the prepolymer may be produced under the conditions usually used. For example, it can be obtained by heating and stirring at a temperature of 150 ° C. or lower.

The polymer containing an alkoxysilyl group is not particularly limited, and examples thereof include condensation products of the above silane compounds or alkoxysilane-containing polyethylene or polypropylene. Of these, the condensate of the silane compound is preferable because it can be easily prepared. The production conditions of the prepolymer are not particularly limited, and the prepolymer may be produced under the conditions usually used. For example, the condensate of the silane compound can be obtained by stirring in the presence of water.

The modified polymer is not particularly limited, and examples thereof include alkoxysilyl group-modified (block) urethane prepolymer, epoxy-modified (block) urethane prepolymer, isocyanate-modified epoxy prepolymer, alkoxysilyl group-modified epoxy prepolymer, and isocyanate-modified. Examples thereof include silane compounds and alkoxysilyl group-modified silane compounds.

Alkoxysilyl group-modified (block) urethane prepolymers and epoxy-modified (block) urethane prepolymers are prepared, for example, by using alkoxysilyl group-containing polyols, epoxy group-containing polyols, etc. as raw materials for urethane prepolymers. It can be manufactured under the conditions
It can also be produced by grafting a urethane prepolymer with a compound having these groups. Further, an isocyanate-modified epoxy prepolymer, an alkoxysilyl group-modified epoxy prepolymer, an isocyanate-modified silane compound and an alkoxysilyl group-modified silane compound can be similarly produced.

The compound of the present invention comprises an isocyanate group, a blocked isocyanate group,
A compound having at least one functional group selected from the group consisting of an alkoxysilyl group and an epoxy group in its molecule, and in addition to these functional groups, an acid anhydride group, an amino group, a latent amino group, a mercapto It is also possible to further have at least one group selected from the group consisting of a group and a carboxyl group in the molecule. If it further has a group capable of reacting with an isocyanate group or the like to crosslink, the crosslink density is improved and the physical properties of the cured product are excellent.

Here, the latent amino group means a group in which the amino group is blocked by a protecting group and can be easily removed by, for example, moisture or heat to generate an amino group. For example, an aliphatic polyamine and a ketone are used. Reaction product ketimine; n
-Hexylamine, monoethylamine, benzylamine, diethylamine, piperidine, triethylamine,
Boron trifluoride-amine complex, which is a compound of an amine such as aniline and boron trifluoride; dicyandiamide or o-tolyl biguanide, α-2,5-dimethyl biguanide, α, ω-diphenyl biguanide, 5-hydroxynaphthyl- Derivatives of dicyandiamide such as 1-biguanide; succinic acid hydrazide, adipic acid hydrazide, isophthalic acid hydrazide, p-oxybenzoic acid hydrazide,
Acid hydrazides such as salicylic acid hydrazide and phenylaminopropionic acid hydrazide; diaminomaleonitrile or derivatives thereof; melamine derivatives such as diallyl melamine; amine imides synthesized by carboxylic acid ester, dimethylhydrazine and epoxy compound; ethylenediamine, hexamethylenediamine, Salts of diamines such as piperidine with dicarboxylic acids such as benzoic acid, phthalic acid, adipic acid, sebacic acid, 2,4,4-trimethyl-2,
Polyamines such as 4,7-trihydroxyflavan and N,
Salts of polyhydroxyphenols such as N′-dimethyl 1,3-propanediamine, phenylphosphonates of polyamines, phenylphosphates of polyamines; ester compounds of sulfonic acid and primary alcohol, monoesters of phosphoric acid or Examples thereof include a diester or a mixture thereof, and an ester compound obtained by an addition reaction between a sulfonic acid and an epoxy compound. Further, an ultraviolet curing agent such as an aromatic diazonium salt or an aromatic sulfonium salt may also be used.

In the curable compound of the present invention, a functional group selected from the group consisting of the above-mentioned isocyanate group, blocked isocyanate group, alkoxysilyl group and epoxy group and a nitrogen-containing heterocycle may be introduced into the compound independently. However, it is preferable to introduce a part of the functional group such as an isocyanate group by reacting with a compound having a nitrogen-containing heterocycle.
In this case, the functional group is first introduced and then 20-
80 mol% (based on the amount of the functional group including the content of these acid anhydride groups, hydroxyl groups, amino groups, latent amino groups, mercapto groups, and carboxyl groups in the case of having these groups in the molecule. Is preferably obtained by reacting and blocking with a substituent capable of reacting with the functional group of the compound having a nitrogen-containing heterocycle.

The blocking rate can be adjusted to an arbitrary ratio to satisfy the physical properties (performance) according to the application etc., but is preferably 30 to.
It is 70 mol%, particularly preferably 40 to 60 mol%.
Here, the blocking rate is 20 to 80 mol% of the functional group,
The total amount of the functional groups contained in the molecule (including the acid anhydride group, the hydroxyl group, the amino group, the latent amino group, the mercapto group and the carboxyl group described above in the molecule is included). 20 when molar
It is said that 80 moles are reacted with the above substituents to introduce a nitrogen-containing heterocycle. Within this range, the crosslinked strength of the cured product is high due to the formation of crosslinks (permanent crosslinks) by the functional groups that are not blocked by the nitrogen-containing heterocycle,
Since the hydrogen bond site is easily dissociated, the decomposition temperature is low, and it becomes a highly practical curable compound having both cross-linking strength and low temperature decomposability.

The blocking can be carried out by reacting the functional group with a substituent having at least one active hydrogen contained in the compound having a nitrogen-containing heterocycle. For example,
The isocyanate group can be blocked by an addition reaction, the alkoxysilyl group by a dealcoholization reaction, the epoxy group by an epoxy cleavage reaction (addition reaction), and the like. In these cases, the blocking conditions can be those usually used.

The crosslinking and decrosslinking (thermal dissociation) reaction of the curable compound of the present invention will be described by taking a urethane prepolymer as an example. In the urethane prepolymer, when an isocyanate group forms a urethane bond (urea bond) with moisture or a curing agent and is cured, a hydrogen atom in the urethane bond (urea bond) serves as a donor and serves as a ring-constituting nitrogen atom in the nitrogen-containing heterocycle. It forms a hydrogen bond with an atom to form a separate bridge (hydrogen bond site). The cured urethane polymer 12
When heated to 0 to 200 ° C., hydrogen bonding sites undergo a dissociation reaction. That is, the site (permanent crosslink) crosslinked by the urethane bond is not dissociated, but the hydrogen bond sites independently crosslinked are decrosslinked by heating and can be easily decomposed.

The techniques described in JP-A Nos. 11-209524 and 2000-169527 described above introduce a reaction site capable of forming a hydrogen bond into an elastomer having a high molecular weight and reversibly solidify. In contrast to being fluidizable, the present invention provides a compound or oligomer having a reaction site capable of forming a hydrogen bond and a cross-linking part such as an isocyanate group, and cross-links at the cross-linking part to form a hydrogen bond. This is a technique for thermal dissociation at the reaction site.

When the curable compound of the present invention is a compound having a functional group such as an isocyanate group introduced into a compound having a nitrogen-containing heterocycle, a known method (for example, a monomer having a nitrogen-containing heterocycle and the functional group) is used. It is also possible to use a commercially available compound obtained by copolymerization with a monomer having a group). In the case of a compound obtained by reacting a part of the functional group with the nitrogen-containing heterocycle,
According to the method described above, at least one functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an alkoxysilyl group and an epoxy group is introduced into the molecule.
It is obtained by reacting a compound having a nitrogen-containing heterocycle with a part of the functional group.

In the curable compound of the present invention, a nitrogen-containing heterocycle is introduced into the molecule, and the nitrogen-containing heterocycle forms a hydrogen bond site (thermal dissociative site) by hydrogen bond, thereby decomposing after curing. It is a highly practical curable compound that is safe (does not generate toxic gas during thermal decomposition) and can be easily produced, and has a high cross-linking strength and a low decomposition temperature.
In the present invention, the curable compound has a nitrogen-containing heterocycle, but if necessary, it may be a composition of a nitrogen-containing heterocycle compound and a urethane prepolymer.

The second aspect of the present invention is a curable resin composition containing the curable compound. The curable compound of the present invention may be a resin component or a curing agent component. The following are mentioned as a suitable example of the composition of this invention.

(1) Urethane-Based Composition When a urethane-based compound having a nitrogen-containing heterocycle introduced therein is used as the curable compound of the present invention, it can be cured only by moisture (one-component curable resin composition), A hydroxyl group capable of forming a crosslink with the isocyanate group, an amino group, a latent amino group, a mercapto group and a carboxyl group may be introduced into the skeleton, and a crosslink with the isocyanate group may be formed as a curing agent component. It is also possible to contain a compound having a hydroxyl group, an amino group, a latent amino group, a mercapto group and a carboxyl group, which is commonly used in urethane-based compositions. The curing agent component may be used alone or in combination of two or more. The same applies to a compound in which a nitrogen-containing heterocycle is introduced into the skeleton of a block-type urethane compound in which a part or all of the isocyanate group of the urethane compound is blocked by the blocking agent.

(2) Silicone-based composition When a silane compound having a nitrogen-containing heterocycle introduced therein is used as the curable compound of the present invention, it can be cured only by moisture (one-component curable resin composition). A hydroxyl group, an amino group, a latent amino group, a mercapto group and a carboxyl group capable of forming a crosslink with the alkoxysilyl group may be introduced into the skeleton, and a crosslink with the alkoxysilyl group may be formed as a curing agent component. A hydroxyl group, an amino group, a latent amino group, a mercapto group and a carboxyl group,
It may also contain compounds commonly used in silicone-based compositions. The curing agent component may be used alone or in combination of two or more. When a nitrogen-containing heterocycle having no hydrogen atom as a nitrogen atom constituting the heterocycle is used, a group having (producing) a hydrogen atom capable of forming a hydrogen bond with the nitrogen-containing heterocycle (for example, an isocyanate group) is necessary.

(3) Epoxy-based composition When an epoxy-based compound having a nitrogen-containing heterocycle introduced therein is used as the curable compound of the present invention, a hydroxyl group, an amino group capable of forming a cross-link with the epoxy group in its skeleton, A latent amino group, a mercapto group, a carboxyl group and an acid anhydride group may be introduced, and as a curing agent component, a hydroxyl group capable of forming a crosslink with the epoxy group, an amino group, a latent amino group, a mercapto group. It is also possible to contain a compound having a carboxyl group and an acid anhydride group, which is commonly used in epoxy compositions. The curing agent component may be used alone or in combination of two or more. When used as a one-pack type curable resin composition, a latent group or curing agent component generally used is used. Further, one or more thermosetting resins and their prepolymers may be contained depending on the adjustment of cured properties.

(4) Mixed system composition "Mixed system" means a curable composition having two or more different functional groups selected from the group consisting of isocyanate groups, blocked isocyanate groups, alkoxysilyl groups and epoxy groups in the molecule. Refers to a compound. As the curable compound of the present invention,
When using a mixed compound containing a nitrogen-containing heterocycle,
Even if it can be cured only with moisture, a hydroxyl group capable of forming a cross-link with any of the functional groups, an amino group, a latent amino group, a mercapto group, a carboxyl group and an acid anhydride group is introduced into its skeleton like the composition. The system composition may have a hydroxyl group, an amino group, a latent amino group, a mercapto group, a carboxyl group and an acid anhydride group capable of forming a crosslink with any of the functional groups as a curing agent component. It is also possible to contain compounds commonly used in. The curing agent component may be used alone or in combination of two or more. In addition,
When used as a one-pack type curable resin composition, a latent group or curing agent component that is generally used is used. Further, one or more thermosetting resins and their prepolymers may be contained depending on the adjustment of cured properties.
In addition, the "mixed composition" refers to a composition containing two or more kinds of the above-mentioned curable compounds, in addition to the composition containing the above-mentioned curable compound containing two or more kinds of functional groups. For example, a composition containing two or more urethane type curable compounds and a composition containing a urethane type curable compound and an epoxy type curable compound may be mentioned.

In the curable resin composition of the present invention, the curing agent contained in the composition is 1 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the curable compound.
Parts by mass, particularly preferably 20 to 40 parts by mass. 1
If it is more than 00 parts by mass, the curing agent may be too soft and the cured product may be too soft. If it is less than 1 part by mass, the crosslinking density may be high due to the large amount of the main agent and the cured product may be hard and brittle, or the curing agent may be small It may not be crosslinked and may not cure.

The curable resin composition of the present invention may contain one kind or two or more kinds of polymers other than the compound of the present invention within a range not impairing the object of the present invention. Plasticizer, filler, catalyst, solvent, UV absorber, dye, pigment, flame retardant, reinforcing agent, antioxidant, antioxidant, thixotropic agent, surfactant (including leveling agent), dispersant, A compounding agent such as a dehydrating agent, an anticorrosive agent, an adhesion-imparting agent, an antistatic agent or the like may be contained. As these compounding agents, those usually used can be used.

The method for producing the curable resin composition of the present invention is as follows:
There is no particular limitation, and a resin component, a curing agent component, and the above additives and the like, if necessary, are added to a kneading machine filled with nitrogen gas, and each component is sufficiently kneaded under normal pressure to uniformly disperse the product. . The curable resin composition thus obtained can be used in a liquid state as it is, or can be stored in a container after cooling and sealing after injection.

The curable resin composition of the present invention thus obtained is capable of dissociating hydrogen bonding sites at a relatively low temperature after being cured by a crosslinking reaction resulting from the curing reaction of isocyanate groups and the like, and Since the cured product is stable below the temperature, it can be suitably used for adhesives, sealing agents, sealants, etc. in the field of automobiles or civil engineering and construction, and members bonded together using the composition of the present invention are:
It can be easily disassembled. Further, the curable resin composition of the present invention is highly practical because it can be applied as a liquid to an adherend or the like.

The curable resin composition of the present invention can be decomposed after curing safely (no toxic gas is generated during thermal decomposition) and easily by introducing a nitrogen-containing heterocycle capable of forming a hydrogen bond. Further, by introducing the nitrogen-containing heterocycle in a specific ratio, the crosslinked strength of the cured product is high, the decomposition temperature is low (the cured property is excellent), and the practicality is high. further,
By adjusting the introduction ratio of the nitrogen-containing heterocycle, it has physical properties (performance) depending on the intended use.

[0072]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. As the curable compound of the present invention, various prepolymers and low molecular weight compounds were synthesized by the following method and various tests were conducted.

4-aminopyridine is a reagent manufactured by Kanto Chemical Co., Inc., bisphenol A type epoxy resin is manufactured by Asahi Denka Kogyo Co., Ltd. (EP-4100E, epoxy equivalent 190),
m-xylylenediamine is a reagent manufactured by Kanto Chemical Co., Inc., γ
-Isocyanate propyltrimethoxysilane was manufactured by Nippon Unicar Co., Ltd. (Y-5187), and dibutylamine used for titration of isocyanate group was a reagent manufactured by Tokyo Kasei Co., Ltd.

As the urethane prepolymer, 100 g of polypropylene triol (molecular weight 5000), 100 g of polypropylene diol (molecular weight 3000) and 56.3 g of diisononyl adipate (DINA) as a plasticizer were placed in a reaction vessel and dehydrated under reduced pressure at 110 ° C. for 12 hours. , 50
NCO% 1. After cooling to 80 ° C., 25.3 g of MDI was added thereto with stirring and reacted at 80 ° C. for 36 hours.
2258 urethane prepolymer was used.

<Introduction of nitrogen-containing heterocycle> 1) 0.246 g (2.618 mmol of 4-aminopyridine) of 32.88 g (isocyanate group content 9.595 mmol) of the urethane prepolymer described above was 0. 2729 equivalents) was added, and the mixture was stirred at 160 ° C. for 3 hours to obtain a nitrogen-containing heterocycle-containing urethane prepolymer 1 (referred to as “HBU-1” in Table 1). Here, the isocyanate group of the furan-modified urethane prepolymer was quantified with dibutylamine by the back titration method according to the standard method. As a result, the content of the isocyanate group was 0.87% by mass based on the urethane prepolymer, and 29 mol% of the isocyanate group reacted (including the isocyanate group reacted with water. The same applies hereinafter).

2) The above urethane prepolymer 15.1
4 to 3 g (isocyanate group content 4.42 mmol)
-Aminopyridine 0.2078 g (2.21 mmol,
0.500 equivalent to the isocyanate group), and add 1
The mixture was stirred at 60 ° C. for 3 hours to obtain a nitrogen-containing heterocycle-containing urethane prepolymer 2 (referred to as “HBU-2” in Table 1). Here, the isocyanate group of the furan-modified urethane prepolymer was quantified with dibutylamine by the back titration method according to the standard method. As a result, the content of isocyanate groups is
It was 0.60% with respect to the urethane prepolymer, and 51 mol% of the isocyanate groups had reacted.

3) The above-mentioned urethane prepolymer 35.3
4-aminopyridine 0.7632 g (7.780 mmo) in 2 g (isocyanate group content 10.30 mmol)
1, 0.7553 equivalents relative to the isocyanate group) were added, and the mixture was stirred at 160 ° C. for 13 minutes to obtain a nitrogen-containing heterocycle-containing urethane prepolymer 3 (referred to as “HBU-3” in Table 1). Here, the isocyanate group of the furan-modified urethane prepolymer was quantified with dibutylamine by the back titration method according to the standard method. As a result, the content of the isocyanate group was 0.29% with respect to the urethane prepolymer, and 76 mol% of the isocyanate group was reacted.

4) Bisphenol A type epoxy resin 19
4 to 0.0 g (1.000 mol based on epoxy group)
-Aminopyridine 47.06 g (0.500 mmol)
Was added, and the mixture was heated and stirred at 160 ° C. for 1 hour to obtain a nitrogen-containing heterocycle-containing epoxy polymer (referred to as “HBE” in Table 1). 50 mol% of the epoxy groups have reacted.

5) To 205.3 g (1.000 mol) of γ-isocyanatopropyltrimethoxysilane, 47.06 g (0.500 mmol) of 4-aminopyridine was added, and the mixture was heated and stirred at 160 ° C. for 1 hour to contain a nitrogen-containing heterocycle. Alkoxysilane (referred to as "HBS" in Table 1) was obtained. 100 mol% of the isocyanate groups of the alkoxysilane reacted completely (the introduction rate of the nitrogen-containing heterocycle was 50%).

6) The above urethane prepolymer 15.1
0.4157 g (4.417 mmo) of 4-aminopyridine in 3 g (isocyanate group content 4.417 mmol)
1, and 1.000 equivalents relative to the isocyanate group) were added and stirred at 160 ° C. for 3 hours to obtain a nitrogen-containing heterocycle-containing urethane prepolymer 4 (referred to as “HBU-4” in Table 1). Here, the isocyanate group of the urethane prepolymer was quantified with dibutylamine by the back titration method according to the standard method. As a result, the content of the isocyanate group was 0% with respect to the urethane prepolymer, and 100 mol% of the isocyanate group was completely reacted.

<Curing Method> I) Urethane-based composition (Examples 1 to 3 and Comparative Example 1,
2) Examples 1 to 3 and Comparative Example 1: Each nitrogen-containing heterocycle-containing urethane prepolymer was allowed to stand in the air at 20 ° C. and 65% humidity for 24 hours for moisture curing. Comparative Example 2: The above-prepared urethane prepolymer (first
In the table, "UP"), 20 ℃, humidity 65%,
It was left in the air for 24 hours for moisture curing.

II) Epoxy Composition (Example 4 and Comparative Example 3) Example 4: Nitrogen-containing heterocycle-containing epoxy polymer (HB
17 g of m-xylylenediamine as a curing agent
(0.5 mol) was used and cured at room temperature (20 ° C.) for 24 hours. Comparative Example 3: Bisphenol A type epoxy resin (referred to as "BFE" in Table 1) 190.0 g (1.0 mo)
34 g of m-xylylenediamine as a curing agent
(1.0 mol) was used and cured at room temperature (20 ° C.) for 24 hours.

III) Silicone Composition (Example 5 and Comparative Example 4) Example 5: Nitrogen-containing heterocycle-containing alkoxysilane (HB)
S) was moisture-cured at 20 ° C. and 65% humidity for 24 hours. Comparative Example 4: 20.5 g of γ-isocyanatopropyltrimethoxysilane (referred to as “IPS” in Table 1)
(0.100 mol) at room temperature (20 ° C.) and humidity 65
%, And allowed to stand in the air for 24 hours for moisture curing.

In Table 1, "introduction rate of nitrogen-containing heterocycle" means that in the urethane-based compositions (Examples 1 to 3 and Comparative Examples 1 and 2), 4-aminopyridine was added to each urethane prepolymer. It is the ratio (mol%) added to the isocyanate group of the polymer, and does not include the ratio of the isocyanate group reacted by water. In the epoxy composition (Example 4 and Comparative Example 3), the ratio (mol%) of the pyridine compound in which 4-aminopyridine was added to the epoxy group of the epoxy prepolymer was the epoxy group reacted with water. Is not included. In the silicone compositions (Example 5 and Comparative Example 4), the ratio (mol%) of the amount of 4-aminopyridine introduced and the amount (mol) of 4-aminopyridine introduced to the sum (mol) of alkoxysilyl groups was used. is there.

<Surface Condition of Cured Product> The surface condition of each cured product was visually confirmed and evaluated. The results are shown in Table 1.
In Table 1, "◎" indicates that surface tack was not confirmed, "○" indicates that almost no surface tack was confirmed, and "△" indicates that only a small amount (no problem at practical level) was confirmed. When it was possible, it was indicated by "x".

<Softening Temperature and Thermal Dissociation Test> A cured product (sheet) obtained by sufficiently curing each composition under the above conditions.
Was heated at 20 ° C. intervals for 15 minutes at each temperature, and the softened or liquefied temperature was measured. The results are shown in Table 1.
Further, the softened state at this temperature is good, "○" when disassembling the adhered member can be safely and easily, "○" when the member can be disassembled, "X" when the member cannot be disassembled. "

<Gas Generation Test> In the above softening temperature measurement, it was confirmed whether gas was generated during softening of each composition. The results are shown in Table 1.

<Adhesion Test> Each composition obtained was cooled to be molded into a sheet having a thickness of 2 mm, the sheet was pressure-bonded to an adherend (glass), and cured by each of the above-mentioned methods to obtain a sample. . The adhesiveness to glass was evaluated by a peel test. As for the test method, in the test sample adhered by the above-mentioned method, a notch of about 30 to 50 mm was made along the adhesion interface. Fix this sample with a vise,
While strongly pulling the end of the cured product at an angle of 90 degrees or more so as not to break it with pliers or the like, a notch was quickly made at an angle of about 60 degrees with a knife. At this time, the cutting with the knife was made to reach the surface of the adherend (glass). This operation was repeated 10 times or more, with the intervals between the cuts being set to about 3 to 5 mm. Depending on the state of the notched cured product, the case of interfacial peeling is represented by AF, the case of thin layer cohesive failure is represented by TCF, and the case of cohesive failure is represented by CF. The results are shown in Table 1.

[0089]

[Table 1]

[0090]

INDUSTRIAL APPLICABILITY According to the present invention, by introducing a nitrogen-containing heterocycle capable of forming a hydrogen bond, a curable compound which can be decomposed after curing safely (no toxic gas is generated during thermal decomposition) and easily A curable resin composition containing it can be provided. Further, by introducing the nitrogen-containing heterocycle in a specific ratio, the cured product has a high cross-linking strength and a low decomposition temperature (excellent cured properties), and a highly practical curable compound and curability containing the same. A resin composition can be provided. Furthermore, by adjusting the introduction ratio of the nitrogen-containing heterocycle, it is possible to provide a curable compound having physical properties (performance) according to the use and the like and a curable resin composition containing the same.

Continued front page    F-term (reference) 4J034 CA04 CA13 CB03 CB07 CC03                       CC08 CC33 CC45 CC52 CC61                       CC65 CE01 DA01 DA03 DA05                       DA07 DA08 DA10 DB03 DB07                       DF01 DF02 DF11 DF12 DF16                       DF20 DF22 DG03 DG04 DG05                       DG08 DG09 DG14 DG18 DG23                       DP18 GA02 GA06 GA23 GA33                       HA01 HA04 HA06 HA07 HA08                       HB06 HC03 HC12 HC13 HC17                       HC22 HC24 HC32 HC35 HC45                       HC46 HC52 HC54 HC61 HC63                       HC64 HC67 HC71 HC73 HD03                       HD04 HD05 HD07 HD12 JA42                       LA08 LA33 QB12 QB17 RA08                 4J035 BA01 BA11 CA052 CA082                       CA092 CA18N CA181 CA192                       CA212 CA262 EA01 LB02                 4J036 AA01 CB22 DA01 JA07

Claims (5)

[Claims] 1. A molecule having at least one nitrogen-containing heterocyclic ring and a functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an alkoxysilyl group and an epoxy group;
A curable compound characterized by being capable of being cured by the functional group, and by heating the cured product in which the functional group has undergone a crosslinking reaction, the hydrogen bonding site by the nitrogen-containing heterocycle can be dissociated to decompose the cured product. . 2. The curable compound according to claim 1, wherein the nitrogen-containing heterocycle has a tertiary nitrogen atom in which a nitrogen atom constituting the heterocycle has no hydrogen atom. 3. The curable compound according to claim 1, wherein the nitrogen-containing heterocycle is a pyridine ring. 4. The curable compound according to claim 1, which is obtained by reacting a part of the functional group with a compound having the nitrogen-containing heterocycle. 5. A curable resin composition containing the curable compound according to claim 1.