JP3404385B2 - One-part moisture-curable epoxy resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a one-pack moisture-curable epoxy resin composition which has both excellent curing characteristics and good storage stability. Especially suitable for one-part room temperature-curing hard epoxy adhesives, one-part room-temperature hardening hard putty materials, one-part room-temperature hardening hard coating materials, one-part room-temperature hardening hard coating materials, and one-part room-temperature hardening hard potting materials. The present invention relates to a one-pack moisture-curable epoxy resin composition.

[0002]

2. Description of the Related Art Epoxy resin compositions have been widely used as adhesives, putty materials, paints and coating materials because of their excellent physical strength and adhesiveness. Since the conventional epoxy resin composition uses a highly reactive amine compound as a curing agent, it is a two-pack type in which the epoxy resin and the curing agent component are mixed immediately before they are used. However, the two-pack type epoxy resin composition requires work such as weighing and mixing, and thus is inferior in workability, and due to its complexity, there are various problems such as measurement error and poor mixing. The two-pack type has a drawback that the usable time is limited because a chemical reaction starts when it is mixed.

For this reason, various studies have been made on a one-pack type epoxy resin composition, and a technique for a one-pack type epoxy resin composition using a moisture-decomposition type latent curing agent mainly containing a ketimine compound or an oxazolidine compound. Are known in large numbers. Above all, from an industrial standpoint, various techniques have been disclosed for a one-pack type epoxy resin composition using a ketimine compound obtained from methyl isobutyl ketone as a carbonyl compound.

Ketimine compounds and oxazolidine compounds are well known as latent curing agents for epoxy resins and isocyanate-terminated urethane prepolymers. The reaction mechanism of the composition in which the latent curing agent and the epoxy resin are mixed will be described. The ketimine compound reacts with moisture in the air and decomposes to form a primary amine compound having active hydrogen. In addition, the oxazolidine compound produces a secondary amino alcohol due to the humidity in the air. These produced amine compounds having active hydrogen react with the epoxy resin, and the epoxy resin composition is cured by this mechanism. That is, the most important thing in the composition in which the latent curing agent and the epoxy resin are blended is that the faster the hydrolysis rate of the latent curing agent is, the faster the curability is obtained. Furthermore, the higher the reactivity of the amine compound generated by hydrolysis, the easier the rapid curing and the higher physical properties. Here, the latent curing agent having a high hydrolysis rate is
There was a contradictory problem of poor storage stability. The one-pack type epoxy resin composition containing a well-known ketimine compound obtained from methyl isobutyl ketone has good storage stability, but has a drawback that curing properties such as initial adhesive strength and rise in mechanical strength are slow. is there. Therefore, since the storage stability is taken into consideration, the limit of the prior art is that the method using a ketimine compound or an oxazolidine compound obtained from an amine compound having high reactivity with an epoxy resin must be used. In this way, if there is a dilemma that the storage stability is impaired if the rapid curing property is improved, the epoxy resin composition containing the ketimine compound or the oxazolidine compound provides the rapid curing property to achieve the storage stability. The current situation is that no technology has been found.

Recently, international publication WO98 / 31722
The official gazette discloses a technique of improving storage stability by using a specific ketimine compound obtained from a carbonyl compound having steric hindrance. The ketimine compound here is
Due to its three-dimensional structure, it became difficult for water to come into contact with the hydrolyzable site, and as a result, the hydrolyzability was slow. Therefore, although it has good storage stability, it has a conventional drawback that it has poor curing characteristics such as fast curing property. That is, when the ketimine compound is used here, the curing of the epoxy resin composition is difficult to proceed, and there is a problem that the initial adhesive strength and the mechanical strength are slow to rise.
It was necessary to cure for a long time before the physical properties that could be used were obtained, which was not practically sufficient.

Further, in JP-A-2000-34337 and JP-A-2000-44914, storage stability is improved by using an alkoxysilyl group-containing compound that can be dealcoholized by a hydrolysis reaction or a hydrolyzable substance that can be dealcoholized similarly. A technology for improving performance is disclosed. These are techniques in which the above-mentioned alkoxysilyl group-containing compound and hydrolyzable substance are intended to improve storage stability by reacting with water entering the system of the composition preferentially over the ketimine compound. It was However, in terms of their curability, they have the conventional drawback of inferior curing characteristics such as rapid curing, and are not practically sufficient.

[0007] Therefore, even in these techniques, it is not possible to achieve a technique in which practical curing characteristics and storage stability are compatible with each other. That is, it was a technical means that is an extension of the conventional technology.

[0008] Thus, if a composition containing a ketimine compound or an oxazolidine compound, which is a latent curing agent, and an epoxy resin is given, a composition which imparts a rapid curing property and achieves both storage stability can be found. Agent,
Since it is a basic technology for putty materials, paints, coating materials, potting materials, etc., its industrial utility is greatly improved.

[0009]

DISCLOSURE OF THE INVENTION The object of the present invention is contradictory to the fact that the storage stability is remarkably excellent and the excellent rapid curing property is exhibited, so that the initial adhesive strength and the mechanical strength are remarkably accelerated. It is an object to provide a one-part moisture-curable epoxy resin composition that can be cured at room temperature and has both performances.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a carboxylic acid vinyl ester compound and a latent curing agent such as a ketimine compound or an oxazolidine compound are contained. It has been found that the liquid moisture-curable epoxy resin composition exhibits remarkably excellent storage stability. When a carboxylic acid vinyl ester compound is blended with a one-pack moisture-curable epoxy resin composition containing a latent curing agent such as a ketimine compound or an oxazolidine compound which is hydrolyzed by moisture in the air to form an amine compound, the adhesiveness is improved. It has been found that the storage stability is further improved without impairing the curability such as the rise of mechanical strength and the mechanical strength. In the prior art, there was a dilemma that the curing characteristics were sacrificed when trying to improve the storage stability, but it was confirmed that the technique here is a technique for solving this dilemma.

That is, according to the invention of this application, when a latent curing agent such as a ketimine compound or an oxazolidine compound is mixed with an epoxy resin, it is completely inactive in a moisture-shielded state such as in a container, and once removed from the container. In this case, it is easily hydrolyzed by moisture in the air, and therefore, it is based on the function of exhibiting remarkably fast rise of adhesiveness and mechanical strength. Another is to block the active hydrogen of the amine compound decomposed and produced from the ketimine compound or the oxazolidine compound during storage in a container when the carboxylic acid vinyl ester compound is added to the epoxy resin composition in the limited range described above. Therefore, it is based on the function of further improving the storage stability. Combining these two functions is a technology that achieves both the desired purpose of practical curing characteristics and excellent storage stability.

Based on these findings, the present inventors have
Furthermore, the range of compounds having such characteristics, the blending amount with an epoxy resin, and the synthesis technology were extensively studied. As a result, the initial adhesive strength, the adhesive strength, the rise of mechanical strength is remarkably fast, and it has succeeded in developing a one-part moisture-curable epoxy resin composition that can be used without problems even after long-term storage, and the present invention is achieved. It came to completion.

The means of the present invention for solving the above problems will be described below. In the invention of claim 1, a carboxylic acid vinyl ester compound represented by the following chemical formula (1) and a carbonyl compound represented by the following chemical formula (2):
A ketimine compound represented by the following chemical formula (3) obtained by reacting with an amine compound having a primary amino group, or / and a compound represented by the following chemical formula (4) obtained by dehydration condensation of a carbonyl compound and an amino alcohol compound. A one-part moisture-curable epoxy resin composition comprising an oxazolidine compound as described above and an epoxy resin.

[0014]

[Chemical 7] However, R ₁ is an organic group, R ₂ , R ₃ , and R ₄ are hydrogen atoms or an organic group, and R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, n is an integer of 1 or more.

[0015]

[Chemical 8] However, R ₅ and R ₆ are alkyl groups, and R ₅ and R ₆ may be the same or different.

[0016]

[Chemical 9] However, R ₇ is a residue excluding a primary amino group of an amine compound, R ₅ and R ₆ are alkyl groups, R ₅ and R ₆ may be the same or different, and n is 1 It is an integer above the above.

[0017]

[Chemical 10] However, R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are hydrogen atoms or organic groups.

The ketimine compound herein means a hydrolyzable compound represented by the above chemical formula (3) and having a double bond between a C atom and an N atom. This site reacts with water and is hydrolyzed into an amine compound having a primary amino group and a carbonyl compound having two alkyl groups which are the same or different from each other. In the one-pack moisture-curable epoxy resin composition, after the amine compound is produced, it reacts with the epoxy resin and cures.

The oxazolidine compound herein means a hydrolyzable cyclic compound represented by the above chemical formula (4) having an O atom and an N atom on the same carbon. This part reacts with water and is hydrolyzed to a carbonyl compound having two alkyl groups which are the same as or different from the secondary amino alcohol. In the one-pack moisture-curable epoxy resin composition, after the amine compound is produced, it reacts with the epoxy resin and cures.

The carboxylic acid vinyl ester compound here is C═C—O—C═O represented by the above chemical formula (1).
A compound having a bond. This site reacts with an amine compound to form an amide compound. The carboxylic acid vinyl ester compound reacts with a slight amine compound produced by decomposing from a ketimine compound or an oxazolidine compound by a slight amount of water entering the system of the composition during storage, so that it reacts with the epoxy resin. Storage stability is improved due to the formation of less active amide compounds. Even when the adhesive composition is used, the carboxylic acid vinyl ester compound reacts with the amine compound, but the addition amount is small and the amount of the amine compound that is decomposed and produced is conversely large,
It does not affect the curing properties. That is, it means that the storage stability can be improved without lowering the curability during use.

By combining these vinyl carboxylate compounds with a one-pack type epoxy resin composition, the storage stability could be dramatically improved.

The invention of claim 2 is the one-pack type epoxy resin composition according to claim 1, which contains a silyl compound represented by the following chemical formula (5) or / and chemical formula (6), and has stability. It is a further improved one-component moisture-curable epoxy resin composition.

[0023]

[Chemical 11] However, R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are alkyl groups,
R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ may be the same or different, and n is an integer of 1 or more.

[0024]

[Chemical 12] However, R ₁₇ and R ₁₈ are alkyl groups, R ₁₇ and R ₁₈ may be the same or different, R ₁₉ is an organic group, and n is an integer of 1 to 3.

The silyl compound herein means a hydrolyzable compound having a bond of Si atom and O atom represented by the chemical formula (5) and / or the chemical formula (6). This site undergoes a dealcohol reaction with water and consumes water. During storage, the silyl compound reacts with and consumes a small amount of water that enters the system of the composition faster than the ketimine compound or the oxazolidine compound and prevents hydrolysis of the ketimine compound or the oxazolidine compound. Ketimine compounds and oxazolidine compounds decompose during storage,
Storage stability is improved because the generation of amine compounds is suppressed. Even when the adhesive composition is used, the silyl compound reacts rapidly with water, but since a large amount of water enters the system, the ketimine compound represented by the above chemical formula (3) in the present invention, or the above The oxazolidine compound represented by the chemical formula (4) also reacts rapidly with water due to its fast hydrolyzability. That is, the composition of the present invention is a one-pack moisture-curable epoxy resin composition that does not affect curability and dramatically improves storage stability.

By incorporating these silyl compounds into the one-pack type epoxy resin composition, the storage stability could be dramatically improved.

The invention of claim 3 is the one-pack type epoxy resin composition according to claim 1 or claim 2, wherein R ₅ and R ₆ of the ketimine have 2 to 6 carbon atoms.

The ketimine compound represented by the above chemical formula (2) having an alkyl having 2 to 6 carbon atoms has a rapid hydrolysis. That is, the composition of the present invention is a one-pack moisture-curable epoxy resin composition that does not require long-term curing to develop sufficient strength.

The invention of claim 4 provides the one-pack type epoxy resin composition according to claim 3, wherein the carbon atom at the α-position of R ₅ and R ₆ of the ketimine has a methylene structure.

Since the ketimine compound here does not have a structure that causes steric hindrance in the vicinity of the double bond between the C atom and the N atom, the hydrolyzability is not hindered, and thus the storage stability is not impaired. The curing characteristics could be further improved.

In the invention of claim 5, the ketimine compound is obtained by reacting a carbonyl compound having the same or different alkyl group selected from an ethyl group or a propyl group with an amine compound having a primary amino group. The one-part moisture-curable epoxy resin composition according to claim 4.

Since the ketimine compound here has a higher hydrolyzability due to its molecular structure, the rapid curing property could be further improved without impairing the storage stability.

In the invention of claim 6, the ketimine compound is obtained by reacting a carbonyl compound having two ethyl groups with an amine compound having a primary amino group.
A one-part moisture-curable epoxy resin composition according to claim 5.

The carbonyl compound here means diethyl ketone (3-pentanone), which has the fastest hydrolyzability and therefore does not impair storage stability.
It was possible to have the most excellent rapid curing property.

The invention of claim 7 is the one-pack type epoxy resin composition according to any one of claims 2 to 6, wherein the silyl compound is represented by the chemical formula (6) and has an epoxy group in the organic group.

A silyl compound represented by the chemical formula (6), which has an epoxy group in an organic group and dramatically improves both the deep-curing property and the storage stability, is represented by the chemical formula (3). By combining with a ketimine compound having fast hydrolyzability, it was possible to dramatically improve not only the deep-part curability but also the curing characteristics including the fast curability and the storage stability.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The carboxylic acid vinyl ester compound used in the present invention is represented by the following chemical formula (1):
If it is a compound having a carboxylic acid vinyl ester group,
It can be anything. Specific examples of the compound represented by the following chemical formula (1) include vinyl acetate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, and stearic acid. Examples thereof include vinyl, vinyl cyclohexanecarboxylate, vinyl pavilate, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate and vinyl cinnamate.
Needless to say, the carboxylic acid vinyl ester used in the present invention is not limited to these and may be used in combination of two or more kinds.

[0038]

[Chemical 13] However, R ₁ is an organic group, R ₂ , R ₃ , and R ₄ are hydrogen atoms or an organic group, and R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, n is an integer of 1 or more.

All of these carboxylic acid vinyl esters have high reactivity with amines. Therefore, the amine compound that is hydrolyzed and generated by the moisture that has entered during storage reacts with the carboxylic acid vinyl ester before reacting with the epoxy resin and suppresses thickening.

The specific ketimine compound used in the present invention is a hydrolyzable C represented by the following chemical formula (3).
A compound having a double bond between an atom and an N atom. This ketimine compound is a compound obtained by reacting a carbonyl compound having the same or different alkyl group at the C atom of the carbonyl group with an amine compound having a primary amino group. Any structure may be used as long as it has the structure of the chemical formula (3). For example, N, N′-di (1-ethylpropylidene) -1,3-bisaminomethylcyclohexane of the following chemical formula (7), the following chemical formula N shown by (8),
N'-di (1-ethyl propylidene) -meta xylylene diamine etc. are mentioned. They are a dehydration condensation product of 1,3-bisaminomethylcyclohexane and diethyl ketone, and a dehydration condensation product of metaxylylenediamine and diethyl ketone, respectively.

[0041]

[Chemical 14] Provided that R ₇ is a residue of the amine compound excluding the primary amino group, R ₅ and R ₆ are any one selected from the group consisting of alkyl groups, and R ₅ and R ₆ are the same. May be different, and n is an integer of 1 or more.

[0042]

[Chemical 15]

[0043]

[Chemical 16]

The carbonyl compound which is a raw material of the ketimine compound used in the present invention is represented by the following chemical formula (2):
Any carbonyl compound having the same or different alkyl group at the C atom of the carbonyl group may be used. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, ethyl propyl ketone and ethyl butyl ketone. It is preferable that the carbon atom of the carbonyl group has an alkyl group having 2 to 6 carbon atoms because hydrolysis is fast. Specific examples include diethyl ketone, ethyl butyl ketone,
Examples include dipropyl ketone.

[0045]

[Chemical 17] However, R ₅ and R ₆ are alkyl groups, and R ₅ and R ₆ may be the same or different.

In the case of a double bond between a C atom and an N atom which has a steric hindrance in the vicinity which prevents contact with a water molecule, the hydrolyzability is lowered. The α-position carbon atom of the carbonyl compound is preferably a methylene structure because it does not have a structure that causes steric hindrance in the vicinity of the double bond between the C atom and the N atom, and thus hydrolyzability is not hindered. Carbonyl compounds having the same or different alkyl groups having 2 or 3 carbon atoms are more preferable because they have high hydrolyzability among these carbonyl compounds. Among these,
Diethyl ketone having the same alkyl group having 2 carbon atoms has the highest hydrolyzability, and thus is most preferable when it is compounded in the epoxy resin, since it gives the fastest curability.

The amine compound which is a raw material of the ketimine compound used in the present invention may be any compound as long as it has a primary amino group.
Ethylenediamine, diethylenetriamine, 1,3-bisaminomethylcyclohexane, norbornanediamine, metaxylylenediamine, isophoronediamine,
Polyamine having polyoxylene skeleton, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N
-Β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane,
Examples thereof include, but are not limited to, γ-aminopropyltriethoxysilane. Those having two or more primary amino groups in one molecule are preferable because excellent mechanical strength can be obtained.

From the above, a ketimine compound obtained from diethyl ketone having the same alkyl group having 2 carbon atoms and an amine compound having two or more primary amino groups in one molecule,
When compounded with epoxy resin, the fastest curing, and
It is the most preferred composition because it gives excellent mechanical strength.

The ketimine compound may be produced by any method, for example, the carbonyl compound and the amine compound in the absence of a solvent or in a nonpolar solvent (hexane, cyclohexane, toluene, benzene, etc.). It can be obtained by mixing in the presence, refluxing with heating and removing the water formed azeotropically. As the carbonyl compound and / or amine compound used, two or more kinds of compounds may be used as raw materials.

The specific oxazolidine compound used in the present invention refers to a compound represented by the following chemical formula (4) having N atom and O atom on the same hydrolyzable C atom. This oxazolidine compound is a compound obtained by reacting a carbonyl compound having the same or different alkyl group at the C atom of the carbonyl group with a secondary amino alcohol compound. Any structure may be used as long as it has the structure of chemical formula (4).

[0051]

[Chemical 18] However, R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are hydrogen atoms or organic groups.

The carbonyl compound used as a raw material for the oxazolidine compound used in the present invention may be any carbonyl compound represented by the following chemical formula (2) as long as it has the same or different alkyl group at the C atom of the carbonyl group. Good. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diethyl ketone,
Examples thereof include dipropyl ketone, dibutyl ketone, ethyl propyl ketone and ethyl butyl ketone.

[0053]

[Chemical 19] However, R ₅ and R ₆ are alkyl groups, and R ₅ and R ₆ may be the same or different.

The aminoalcohol compound used as a raw material for the oxazolidine compound used in the present invention may be any compound having a secondary ethanolamine structure, and specific examples thereof include N-methylethanolamine and N-methylethanolamine. -Ethylethanolamine, N-propylethanolamine, N-ethyl-2-methylethanolamine, diethanolamine and the like can be mentioned, but the invention is not limited thereto. Among these, N-methylethanolamine and N-ethylethanolamine are preferable because they have high reactivity with the epoxy resin.

Any method for producing the oxazolidine compound may be used. For example, the carbonyl compound and the aminoalcohol compound may be used in the absence of a solvent or in a nonpolar solvent (hexane, cyclohexane, toluene, benzene, etc.). ) Mixing in the presence, heating under reflux, and azeotropic removal of the water formed. The carbonyl compound and / or amino alcohol compound used is
You may use two or more types of compounds as a raw material.

Needless to say, the one-pack type epoxy resin composition may use two or more kinds of the ketimine compound and the oxazolidine compound as long as the curability and the storage stability are not impaired. Other latent curing agents may be used together.

The epoxy resin may be any one as long as it has an epoxy group capable of reacting with an amine compound obtained by hydrolysis of a ketimine compound at the time of use. For example, biphenyl type epoxy resin obtained by reacting biphenyl, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, etc. with epichlorohydrin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type Epoxy resin and the like, hydrogenated or brominated epoxy resin, glycidyl ester type epoxy resin, novolac type epoxy resin, urethane modified epoxy resin having a urethane bond, and nitrogen-containing epoxy resin obtained by epoxidizing metaxylene diamine or hydantoin. , A rubber-modified epoxy resin containing polybutadiene or NBR, and the like. It is not limited to these, and two or more kinds of epoxy resins may be used in combination.

The silyl compound used in the invention of any one of claims 2 to 6 may be any compound having an alkoxysilyl group represented by the following chemical formula (5) and / or the following chemical formula (6). It may be something like this. Specific examples thereof include monomers and multimers such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane as long as they are compounds represented by the following chemical formula (5). Examples of the compound represented by the following chemical formula (6) include a silane coupling agent having an organic group such as an alkyl group, a vinyl group, an epoxy group, an isocyanate group and a ketimine group. Specific examples of the silane coupling agent include dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl. Examples thereof include triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane. Needless to say, the present invention is not limited to these and two or more kinds may be used in combination.

[0059]

[Chemical 20] However, R₁₃, R₁₄, R₁₅, R₁₆Is an alkyl group,
R₁₃, R₁₄, R₁₅, R ₁₆Are the same but different
Also, n is an integer of 1 or more.

[0060]

[Chemical 21] However, R ₁₇ and R ₁₈ are alkyl groups, R ₁₇ and R ₁₈ may be the same or different, R ₁₉ is an organic group, and n is an integer of 1 to 3.

The silyl compound having an epoxy group in the organic group used in the invention of claim 7 is a compound represented by the above chemical formula (6) and having both an epoxy group and an alkoxysilyl group in one molecule. As long as it is anything, Specific examples include γ-glycidoxypropyltrimethoxysilane represented by the following chemical formula (9), γ-glycidoxypropyltriethoxysilane represented by the following chemical formula (10), and the like. Examples thereof include KBM403 and KBE403 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited thereto. It goes without saying that two or more kinds may be used in combination and may be used in combination with the silyl compound represented by the chemical formula (5) or the chemical formula (6).

[0062]

[Chemical formula 22]

[0063]

[Chemical formula 23]

The blending ratio of the vinyl carboxylate of the present invention to the epoxy resin is preferably 1 to 30 mol% with respect to 1 mol of the epoxy group. If higher than this blending ratio, the carboxylic acid vinyl ester is
It reacts with an amine compound produced from a ketimine compound or an oxazolidine compound to inhibit the reaction with an epoxy resin. When it is low, the storage stability is not improved because the slight amount of water that enters the composition during storage cannot sufficiently react with the amine compound formed by decomposition from the ketimine compound or the oxazolidine compound. Within this blending ratio, practical storage stability is obtained, and it is more preferable that the blending ratio is 5 to 15 mol% because more ideal storage stability is obtained.

The mixing ratio of the ketimine compound of the present invention and the epoxy compound may be determined by the equivalent amount of active hydrogen of the amine compound generated by hydrolysis of the ketimine compound and the equivalent amount of the epoxy group of the epoxy compound. That is, the active hydrogen equivalent of the amine compound generated by hydrolysis of the ketimine compound is 0.5 to 0.5 as compared with the equivalent of the epoxy group.
It is preferably 2.0 times. When the content is lower than this proportion, the epoxy groups become excessive, and the cured product does not undergo satisfactory crosslinking, and practical mechanical strength cannot be obtained.
When it is high, the amount of amine compound generated by hydrolysis becomes excessive, that is, active hydrogen becomes excessive, and in this case also, practical mechanical strength cannot be obtained for the same reason. Within this blending ratio, a cross-linked structure that gives practical mechanical strength is obtained, which is preferred.
It is more preferable that the ratio is 1.2 times, because an ideal crosslinked structure is obtained and the mechanical strength as an adhesive composition is further excellent.

The mixing ratio of the oxazolidine compound of the present invention and the epoxy compound is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin having an equivalent amount of epoxy groups of 190. If it is lower than this proportion,
The epoxy group becomes excessive, and the cured product does not undergo satisfactory crosslinking, so that practical mechanical strength cannot be obtained. When it is high, the amine compound generated by hydrolysis becomes excessive,
That is, the amount of active hydrogen becomes excessive, and in this case as well, practical mechanical strength cannot be obtained for the same reason. Within this blending ratio, a crosslinked structure that gives practical mechanical strength is obtained, and therefore, it is preferably 20 to 30 parts by mass.
It is more preferable because it has an ideal crosslinked structure and further has excellent mechanical strength as an adhesive composition.

The mixing ratio of the silyl compound of the present invention and the epoxy resin varies depending on the kind of the silyl compound used, but 1 part of the silyl compound is added to 100 parts by mass of the epoxy resin.
It is preferably 0 part by mass or more. If it is lower than this mixing ratio, the amount of the silyl compound is small, and even a small amount of water that enters the system of the composition during storage cannot be completely consumed, so that the hydrolysis of the ketimine compound or the oxazolidine compound cannot be suppressed, No practical storage stability can be obtained. Within this blending ratio, practical storage stability can be obtained, and a blending ratio of 30 parts by mass or more is more preferable because the most excellent storage stability can be obtained.

The composition of the present invention contains, in addition to the above-mentioned compounds, fillers such as calcium carbonate and titanium oxide, plasticizers, thixotropy-imparting agents, as long as the effects of the present invention are not impaired.
Pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, adhesion promoters, dispersants, solvents and the like may be added. In this case, removing the influence of the water content of the above-mentioned components as much as possible gives good results on the storage stability.

The method for producing the composition of the present invention is not particularly limited, but it is preferable to knead the composition sufficiently under a nitrogen atmosphere or under reduced pressure using a stirrer such as a mixing mixer to obtain a composition. An example is as follows.
Using a closed processing pot equipped with a stirrer, a condenser, a heating device, a vacuum dewatering device, and a nitrogen stream device, the epoxy resin is charged into the pot. Using a nitrogen gas stream, under nitrogen reflux, if necessary, a modifier or an additive is blended and homogeneously mixed.
Then, finally, a ketimine compound and / or an oxazolidine compound are blended and homogeneously mixed to obtain a one-pack moisture-curable adhesive composition. Then, if this one-component moisture-curable adhesive composition is stored in a closed container subjected to nitrogen substitution,
It will be the final product. If the modifier or additive contains water, it will be easily cured during storage and the storage stability will decrease. Therefore, it is recommended to dehydrate and remove the water content of the modifier or additive. preferable. Dehydration of water may be performed before blending the modifier or additive, or after blending these with the epoxy resin, it may be dehydrated by means such as heating or reduced pressure.

[0070]

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

(Synthesis of Ketimine Compound) (Synthesis Example 1) 142 g of 1,3-bisaminomethylcyclohexane (trade name: 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Inc.)
And 3 times mol equivalent of methyl isobutyl ketone 300g
In a flask while removing the water produced by azeotropic distillation,
The reaction was continued for 20 hours at a temperature (120 to 150 ° C.) at which toluene and methyl isobutyl ketone refluxed. Then, excess methyl isobutyl ketone and toluene were distilled off to obtain ketimine compound A.

(Synthesis Example 2) A ketimine compound B was obtained in the same manner as in Synthesis Example 1 except that 258 g of diethyl ketone was used as the carbonyl compound.

(Synthesis Example 3) A ketimine compound C was obtained in the same manner as in Synthesis Example 1 except that 342 g of ethyl butyl ketone was used as the carbonyl compound.

Example 1 100 parts by mass of epoxy resin (Epicote 828, trade name, manufactured by Yuka Shell Epoxy Co., Ltd.),
Heavy calcium carbonate (Nitto Koka Co., Ltd., trade name NS10
0) 40 parts by mass, surface-treated calcium carbonate (manufactured by Maruo Calcium Co., trade name MS700) 80 parts by mass at 100 ° C.
Reduce pressure and heat under conditions of 15 Torr and 2 hours, and stir and mix until uniform. If it becomes uniform, cool to room temperature, add 30 parts by mass of an oxazolidine compound (manufactured by San-Apro, trade name MS-PLUS) as a curing agent for epoxy resin, and add 6.6 parts by mass of vinyl butyrate as a stabilizer,
The mixture was stirred under reduced pressure to obtain a one-pack moisture-curable adhesive composition.

Example 2 Ethyl silicate (manufactured by Toshiba Silicone, trade name TSL8124) 40 as a dehydrating agent
A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 1 except that parts by mass were added at the same time as the stabilizer.

Example 3 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 2 except that 45 parts by mass of the ketimine compound A was used as the curing agent for the epoxy resin.

Example 4 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 3 except that 13.1 parts by mass of vinyl laurate was used as a stabilizer.

Example 5 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 3 except that 45 parts by mass of the ketimine compound B was used as a curing agent for epoxy resin.

Example 6 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 3 except that 45 parts by mass of the ketimine compound C was used as the curing agent for the epoxy resin.

Example 7 Epoxy silane coupling agent as a dehydrating agent (trade name: KBM40, manufactured by Shin-Etsu Chemical Co., Ltd.)
3) In the same manner as in Example 5 except that 40 parts by mass was used,
A one-pack moisture-curable adhesive composition was obtained.

Comparative Example 1 A one-part moisture-curable adhesive composition was obtained in the same manner as in Example 1 except that vinyl butyrate was removed.

Comparative Example 2 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 3 except that vinyl butyrate was removed.

The following tests were conducted using the adhesive compositions according to Examples 1 to 7, Comparative Example 1 and Comparative Example 2. And
The results of Examples 1 to 7 are shown in Table 1, and the results of Comparative Examples 1 and 2 are shown in Table 2.

[0084]

[Table 1]

[0085]

[Table 2]

(Adhesiveness) Adhesiveness was measured according to JIS A6024 (see Adhesiveness) of the mortar bending adhesion test under each curing condition. That is, it was performed in accordance with the standard condition (curing for 7 days at 23 ° C.) of the adhesive strength test in JIS A6024 (injected epoxy resin for building repair). The unit is N / mm ² , and the fracture state at that time was shown.

(Stability) Regarding the stability, the viscosity was measured when the sample was put in a bottle tightly stoppered and stored under each temperature condition. That is, a one-part moisture-curable adhesive composition,
The cartridge was filled and sealed, left at 40 ° C. or 20 ° C. for each period, and then the viscosity was measured. Then, the stability was compared with the viscosity immediately after blending, and evaluated in the following four stages.
Viscosity was measured at 23 ° C with a BH viscometer of 10 r / mi.
n. I went there. ◎ ... (viscosity after standing) / (viscosity immediately after compounding) <
1.5 ○ ... 1.5 ≦ (viscosity after standing) / (viscosity immediately after compounding) <
2 Δ ... 2 ≦ (viscosity after standing) / (viscosity immediately after compounding) <
3 × ... 3 ≤ (viscosity after standing) / (viscosity immediately after compounding)

(Deep curability) A one-part moisture-curable adhesive composition was placed in a container having a depth so as not to mix air,
Cure at 23 ° C for 1 week to cure. The thickness of the cured product layer from which the uncured composition was removed was measured.

As is clear from comparison between Examples 1 and 2 and Comparative Example 1, the one-part moisture-curable adhesive composition according to the example is similar to the one-part moisture-curable adhesive composition according to the comparative example. It can be seen that the adhesiveness is equivalent. In addition, the one-component moisture-curable adhesive composition according to the example shows excellent storage stability as compared with the one-component moisture-curable adhesive composition according to the comparative example, and thus the adhesive performance. It can be seen that only the storage stability is improved without impairing the storage stability. In particular, in the one-part moisture-curable adhesive composition according to Example 2, the viscosities after standing at 20 ° C. for 6 months and 40 ° C. for 1 month were both 1.5 times or less than the viscosity immediately after compounding, It can be seen that it shows a fairly good storage stability.

As is clear from comparison between Examples 3 to 7 and Comparative Example 2, the one-component moisture-curable adhesive composition according to the example is similar to the one-component moisture-curable adhesive composition according to the comparative example. It can be seen that the adhesiveness is equal or higher. In addition, the one-component moisture-curable adhesive composition according to the example shows excellent storage stability as compared with the one-component moisture-curable adhesive composition according to the comparative example, and thus the adhesive performance. It can be seen that only the storage stability is improved without impairing the storage stability. In particular, the one-component moisture-curable adhesive compositions according to Examples 5 to 7 have high adhesiveness values and have become mortar fractures, which indicates that they have even better adhesiveness.

Comparing Examples 3 to 6 with respect to deep-part curability, the one-pack moisture-curable adhesive composition according to Example 7 was treated in Examples 3 to 6 without impairing storage stability.
It was cured 2 to 2.5 times deeper than the one-pack moisture-curable adhesive composition. Further, since the value of the adhesiveness is high, it can be seen that the adhesiveness is further excellent.

[0092]

As described above, the adhesive composition according to the present invention achieves the contradictory performance of significantly improving the storage stability without impairing the rapid curing property,
A one-part moisture-curable epoxy resin composition that can be cured at room temperature. Therefore, the adhesive composition according to the present invention can be effectively used for adhesives, putty materials, paints, coating materials, potting materials and the like using these.

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hisaichi Horii 4-7-9 Tsurumi, Tsurumi-ku, Osaka City Konishi Co., Ltd. Osaka Research Institute (72) Nobuteru Matsuura 4-7-9 Tsurumi, Tsurumi-ku, Osaka No. Konishi Co., Ltd. Osaka Research Institute (56) Reference JP-A-11-21532 (JP, A) JP-A-8-217859 (JP, A) JP-A-2000-44773 (JP, A) JP-A-11- 349663 (JP, A) JP-A-8-157563 (JP, A) JP-A-10-60227 (JP, A) JP-A-10-60095 (JP, A) International Publication 98/31722 (WO, A1) (JP 58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 59/40 C08G 59/50 G09D 163/00-163/10 C09J 163/00-163/10

Claims (7)

(57) [Claims] 1. A carboxylic acid vinyl ester compound represented by the following chemical formula (1), a carbonyl compound represented by the following chemical formula (2), and an amine compound having a primary amino group. ) The ketimine compound or / and the carbonyl compound and / or the amino alcohol compound, which are obtained by dehydration condensation, and an oxazolidine compound represented by the following chemical formula (4), and an epoxy resin are contained. Moisture curable epoxy resin composition. [Chemical 1] However, R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms or organic groups, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and n is 1 or more. It is an integer. [Chemical 2] However, R ₅ and R ₆ are alkyl groups, and R ₅ and R ₆ may be the same or different. [Chemical 3] However, R ₇ is a residue excluding a primary amino group of an amine compound, R ₅ and R ₆ are alkyl groups, R ₅ and R ₆ may be the same or different, and n is 1 It is an integer above the above. [Chemical 4] However, R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are hydrogen atoms or organic groups. 2. The following chemical formula (5) or / and the following chemistry
Characterized by containing a silyl compound represented by the formula (6)
The one-pack type epoxy resin composition according to claim 1. [Chemical 5] However, R₁₃, R₁₄, R₁₅, R₁₆Is an alkyl group,
R₁₃, R₁₄, R₁₅, R ₁₆Are the same but different
Also, n is an integer of 1 or more. [Chemical 6] However, R₁₇, R₁₈Is an alkyl group, R₁₇, R₁₈Is
May be the same or different, R₁₉Is an organic group
And n is an integer of 1 to 3. 3. The ketimine wherein R ₅ and R ₆ have 2 to 6 carbon atoms.
The one-pack type epoxy resin composition according to claim 1 or 2, wherein 4. The one-pack type epoxy resin composition according to claim 3, wherein the α-position carbon atom of R ₅ and R ₆ of the ketimine has a methylene structure. 5. The one-pack type epoxy resin composition according to claim 4, wherein R ₅ and R _{6 of the} ketimine have the same or different alkyl groups selected from an ethyl group or a propyl group. 6. The one-pack type epoxy resin composition according to claim ₅ , wherein R ₅ and R _{6 of the} ketimine both have an ethyl group. 7. The one-pack type epoxy resin composition according to claim 2, wherein the silyl compound is represented by the chemical formula (6) and has an epoxy group in an organic group.