JP3404378B2 - 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 many techniques are known for a one-pack type epoxy resin composition using a moisture-decomposition type latent curing agent mainly containing a ketimine compound. Has been. 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 are well known as latent curing agents for epoxy resins and isocyanate-terminated urethane prepolymers. The reaction mechanism of the composition containing the ketimine compound and the epoxy resin will be described. The ketimine compound reacts with moisture in the air and decomposes to form an amine compound having active hydrogen. The generated amine compound having active hydrogen reacts with the epoxy resin, and the epoxy resin composition is cured by this mechanism. That is, the most important thing in the composition containing the ketimine compound and the epoxy resin is that the faster the hydrolysis rate of the ketimine compound 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 ketimine compound having a high hydrolysis rate has a contradictory problem that it has 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 conventional technique is that the method using a ketimine compound obtained from an amine compound having high reactivity with an epoxy resin must be used. Since there is a dilemma of impairing storage stability if improving the rapid curing property in this way, in a composition containing a ketimine compound and an epoxy resin, a technique for imparting rapid curing property and achieving storage stability at the same time. Is currently not found at all.

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.

In addition, the above-mentioned Japanese Patent Laid-Open No. 2000-34337.
The compounding amount of the alkoxysilyl group-containing compound disclosed in the publication and the hydrolyzable substance disclosed in the above-mentioned JP 2000-44914 A is the epoxy resin 10
0.1 to 20 parts by mass and 1 to 3 parts by mass for 0 parts by mass, respectively
It is disclosed that 0 parts by weight is suitable. However, even if the compound containing an alkoxysilyl group-containing compound or a hydrolyzable substance in the above range is used, the poor deep-curability, which is one of the curing characteristics that has been a drawback from the past, that is, the adhesive composition layer The fact that the inner cured thickness is small has not been solved. That is, the adhesive composition here has a limit in the thickness of the adhesive layer, and under the present circumstances, an uncured portion may remain in the adhesive layer, which is not practically sufficient.

[0008] 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.

Thus, if a composition which combines a ketimine compound and an epoxy resin and has a rapid curing property and storage stability is found, an adhesive agent, a putty material, a paint or a coating material using these is found. Since it is a basic technology such as potting material, its industrial utility is much improved.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent storage stability, rapid curing property and excellent deep-part curing property, so that the initial adhesive strength and the mechanical strength can be markedly increased. Another object of the present invention is to provide a one-part moisture-curable epoxy resin composition that can be cured at room temperature and that has conflicting performances.

[0011]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a one-component moisture-curable epoxy resin composition containing a specific silyl compound and a specific ketimine compound. It has been found that the products show significantly better storage stability without compromising the markedly faster cure rate, which is an advantage of certain ketimines. It was found that a ketimine compound obtained by reacting a specific carbonyl compound with an amine compound having a primary amino group exhibits remarkably fast hydrolyzability, and attention was focused on this hydrolyzability, and further research was conducted. When piled up, when used in combination with a specific silyl compound, the storage stability is further improved without impairing the adhesive property and the rise in mechanical strength, which are the features of this ketimine compound. I found a thing. In the prior art, there was a dilemma that the fast curing property was 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, the invention of this application consists of two techniques. One is that only a compound in which the structure of a carbonyl compound as a raw material of a ketimine compound is in a very limited range is compounded with an epoxy resin. , It is completely inactive in a container where moisture is blocked, and once it is taken out of the container, it is easily hydrolyzed by moisture in the air, resulting in significantly faster adhesion and mechanical strength. It is based on the function indicating. The other is that the structure of the silyl compound is limited to a compound in a very limited range, and when added to the epoxy resin composition in the limited range described above, it suppresses invasion of moisture during storage in a container. It is based on the function of improving storage stability. Combining these two functions is a technology that achieves both the desired purpose of practical curing characteristics and excellent storage stability.

On the other hand, it has been found that among the epoxy resin compositions containing a silyl compound, the epoxy resin composition containing a silyl compound having an epoxy group has a uniquely excellent deep curability. It was confirmed that the technique here does not impede compatibility between the practical curing characteristics and the storage stability, but is an added function. That is, the invention of this application is limited to compounds in which the structure of the silyl compound is further limited, and in the compounding of the ketimine compound and the epoxy resin, in order to participate in the crosslinked structure of the epoxy resin and the ketimine compound, It is based on the function of adding excellent deep curability without impeding compatibility between practical practical curing characteristics and storage stability. This function is the technology that achieves both the desired 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, it was decided to develop a one-part moisture-curable epoxy resin composition that has a significantly faster initial adhesive strength, adhesive strength, and mechanical strength, has excellent deep-curing properties, and can be used without problems even after long-term storage. It succeeded and came to complete this invention.

The means of the present invention for solving the above problems will be described below. In the invention of claim 1, a silyl compound represented by the following chemical formula (1) and / or a silyl compound represented by the following chemical formula (2), a carbonyl compound represented by the following chemical formula (3), and an amine having a primary amino group. It was to mix a ketimine compound represented by the following chemical formula (4) obtained by reacting with a compound with an epoxy resin, and dramatically improved compatibility between curing characteristics such as fast curing and storage stability. It is a one-part moisture-curable epoxy resin composition.

[0016]

[Chemical 5] However, R ₁ , R ₂ , R ₃ , and R ₄ are alkyl groups,
R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and n is an integer of 1 or more.

[0017]

[Chemical 6] However, R ₅ and R ₆ are alkyl groups, R ₅ and R ₆ may be the same or different, R ₇ is an organic group,
n is an integer of 1 to 3.

[0018]

[Chemical 7] However, R ₈ and R ₉ are any one selected from the group consisting of alkyl groups having 2 to 6 carbon atoms, and R ₈ and R ₉ may be the same or different.

[0019]

[Chemical 8] However, R ₁₀ is a residue excluding a primary amino group of the amine compound, R _8, R ₉ is any one selected from the group consisting of alkyl group having 2 to 6 carbon atoms, R _8, R ₉ may be the same or different, and n is an integer of 1 or more.

The ketimine compound herein means a hydrolyzable compound having a double bond between a C atom and an N atom represented by the above chemical formula (4). 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. That is, the rate of hydrolysis of the ketimine compound affects the curability of the epoxy resin composition. The curability here refers to the rise in adhesive strength and mechanical strength, and the fast curability does not require long-time curing to obtain practical physical properties that can withstand use. It shows that. In the present invention, the chemical formula (4)
The ketimine compound represented by means that the C atom having a double bond between the N atom and the C atom has the same or different alkyl group selected from the group consisting of alkyl groups having 2 to 6 carbon atoms. The composition was remarkably fast curable because it was hydrolyzed to an amine compound having a primary amino group.

Further, the silyl compound herein means a hydrolyzable compound having a bond of Si atom and O atom represented by the chemical formula (1) and / or the chemical formula (2). This site undergoes a dealcohol reaction with water,
Consume water. During storage, the silyl compound reacts with and consumes a small amount of water entering the system of the composition faster than the ketimine compound and consumes it to prevent hydrolysis of the ketimine compound. The storage stability is improved because the ketimine compound is prevented from decomposing during storage to generate the amine compound. Even when the adhesive composition is used, the silyl compound reacts quickly with water, but since a large amount of water enters the system,
The ketimine compound represented by the above chemical formula (4) in the present invention also reacts rapidly with water due to its fast hydrolyzability. That is, it means that the composition of the present invention has fast curing property and does not require long-term curing to obtain practical physical properties that can withstand use.

By combining these silyl compounds and the ketimine compounds, it was possible to dramatically improve both the fast curability and the storage stability.

According to the second aspect of the present invention, the silyl compound represented by the chemical formula (2) and having an epoxy group in the organic group (R ₇ ) is blended with the ketimine compound and the epoxy resin. It is a one-part moisture-curable epoxy resin composition that dramatically improves both curing characteristics such as properties and storage stability.

In the epoxy resin composition, the silyl compound having an epoxy group in the organic group is not limited to the hydrolyzable reactive site of the bonding site of the Si atom and the O atom. Since the epoxy group also becomes a reactive site, it has more crosslinking sites in one molecule.
Therefore, the cross-linked structure becomes faster and more complicated, and even after curing for a certain period, it hardens to a deeper depth. That is, it means that it has excellent deep-part curability.

By blending this silyl compound having an epoxy group in the organic group, it was possible to dramatically improve the compatibility between the deep-part curability and the storage stability.

In the invention of claim 3, the silyl compound having an epoxy group of the means of claim 2 and the means of claim 1
A compound of formula (4), which has a fast hydrolysis rate and is incorporated into an epoxy resin,
It is a one-part moisture-curable epoxy resin composition that dramatically improves both curing characteristics such as fast-curing property and deep-curing property and storage stability.

A silyl compound represented by the above chemical formula (4), 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 above chemical formula (4). 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.

In the invention of claim 4, the ketimine compound is obtained by reacting a carbonyl compound having a methylene structure at the α-position carbon atom with an amine compound having a primary amino group. The one-part moisture-curable epoxy resin composition according to the means of 3, which is further improved in curing characteristics such as fast-curing property and deep-curing property.

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. It was possible to further improve the curing characteristics such as fast curing and deep curing.

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. A one-component moisture-curable epoxy resin composition according to any one of claims 1 or 3 or 4, which has curing characteristics such as fast curing and deep curing and storage stability. It is a one-pack moisture-curing type epoxy resin composition having improved compatibility.

Since the ketimine compound here has a higher hydrolyzability due to its molecular structure, it is possible to further improve the curing characteristics such as fast curing and deep curing without impairing the storage stability. did it.

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.
The one-part moisture-curable epoxy resin composition according to claim 5, wherein the one-part moisture-curable epoxy resin composition has the most improved compatibility between curing characteristics such as fast curing and deep-curing and storage stability. It is a thing.

The carbonyl compound as used herein 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 curing characteristics such as fast curing and deep curing.

According to the invention of claim 7, the total amount of the silyl compound is 30 parts by mass or more based on 100 parts by mass of the epoxy resin, and the one-component moisture curing according to any one of claims 1 to 6 is performed. -Type epoxy resin composition, which is a one-pack moisture-curable epoxy resin composition having further improved storage stability.

The compounding amount here is such that the amount of the ketimine compound which is decomposed during storage is large because the amount of the silyl compound that can react with a small amount of water entering the system of the composition during storage is large. Due to the decrease, there is long-term storage stability. That is, the storage stability could be further improved without impairing the curing characteristics such as the rapid curing property and the deep region curing property.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. Claim 1 or any one of claims 4 to 7
As the silyl compound used in the invention of the above item, any compound having an alkoxysilyl group represented by the following chemical formula (1) and / or the following chemical formula (2) may be used. 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 (1). Examples of the compound represented by the following chemical formula (2) include silane coupling agents 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. Triethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, γ-
Isocyanate propyl triethoxy silane etc. are mentioned. Needless to say, the present invention is not limited to these and two or more kinds may be used in combination.

[0037]

[Chemical 9] However, R ₁ , R ₂ , R ₃ , and R ₄ are alkyl groups,
R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and n is an integer of 1 or more.

[0038]

[Chemical 10] However, R ₅ and R ₆ are alkyl groups, R ₅ and R ₆ may be the same or different, R ₇ is an organic group,
n is an integer of 1 to 3.

The silyl compound having an epoxy group in the organic group used in the invention of any one of claims 2 to 7 is represented by the above chemical formula (2), and the epoxy group and the alkoxysilyl group are both 1 Any compound may be used as long as it is a compound contained in the molecule. Specific examples thereof include γ-glycidoxypropyltrimethoxysilane represented by the following chemical formula (5) and γ-glycidoxypropyltriethoxysilane represented by the following chemical formula (6). Commercially available products include: KBM403 and KBE403 respectively
(The above are manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these. 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 (1) or the chemical formula (2).

[0040]

[Chemical 11]

[0041]

[Chemical 12]

The ketimine compound used in the invention of claim 2 or claim 7 is any compound which is a hydrolyzable compound represented by the following chemical formula (7) and which has a double bond between a C atom and an N atom. It may be something like this. For example, N, N′-di (1,3-dimethylbutylidene) -1,3-bisaminomethylcyclohexane represented by the following chemical formula (8), N, N′-di (represented by the following chemical formula (9). 1,
3-dimethylbutylidene) -meta-xylylenediamine and the like. They are a dehydration condensate of 1,3-bisaminomethylcyclohexane and methyl isobutyl ketone, and a dehydration condensate of metaxylylenediamine and methyl isobutyl ketone, respectively.

[0043]

[Chemical 13] However, R ₁₀ is a residue of the amine compound excluding a primary amino group, R ₁₁ and R ₁₂ are alkyl groups, R ₁₁ and R ₁₂ may be the same or different, and n is 1 It is an integer above the above.

[0044]

[Chemical 14]

[0045]

[Chemical 15]

Claim 1 or any one of claims 3 to 7
The specific ketimine compound used in the invention of the above item means a hydrolyzable compound having a double bond between a C atom and an N atom, which is represented by the chemical formula (4). This ketimine compound is obtained by reacting a C atom of a carbonyl group with a carbonyl compound having the same or different alkyl group selected from the group consisting of an alkyl group having 2 to 6 carbon atoms and an amine compound having a primary amino group. The resulting compound. The same or different, selected from the group consisting of a hydrolyzable double bond between a C atom and an N atom, represented by the chemical formula (4), wherein the C atom is an alkyl group having 2 to 6 carbon atoms. Although any ketimine compound having an alkyl group may be used, for example, N, N′-di (1-ethylpropylidene) -1,3-bisaminomethylcyclohexane having a structure represented by the following chemical formula (10) is used. Alternatively, for example, N, N′-di (1-ethylpropylidene) -metaxylylenediamine represented by the following chemical formula (11) and the like can be 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.

[0047]

[Chemical 16] However, R ₁₀ is a residue excluding a primary amino group of the amine compound, R _8, R ₉ is any one selected from the group consisting of alkyl group having 2 to 6 carbon atoms, R _8, R ₉ may be the same or different, and n is an integer of 1 or more.

[0048]

[Chemical 17]

[0049]

[Chemical 18]

The carbonyl compound as a raw material of the ketimine compound used in the invention of claim 2 or 7 is
Any carbonyl compound represented by the following chemical formula (12) may be used as long as it has the same or different alkyl group at the C atom of the carbonyl group. Specific examples include methyl ethyl ketone and methyl isobutyl ketone.

[0051]

[Chemical 19] However, R ₁₃ and R ₁₄ are alkyl groups, and R ₁₃ and R ₁₄ may be the same or different.

Claim 1 or any one of claims 3 to 7
The carbonyl compound used as the raw material of the ketimine compound used in the invention of Item is the same or different from the group consisting of an alkyl group having 2 to 6 carbon atoms in the C atom of the carbonyl group, which is represented by the following chemical formula (3). Any carbonyl compound having an alkyl group may be used. Specific examples include diethyl ketone, dipropyl ketone, dibutyl ketone, ethyl propyl ketone, ethyl butyl ketone, and the like.

[0053]

[Chemical 20] However, R ₈ and R ₉ are any one selected from the group consisting of alkyl groups having 2 to 6 carbon atoms, and R ₈ and R ₉ 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 non-polar 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. In addition, it goes without saying that the one-pack type epoxy resin composition may use two or more kinds of the ketimine compounds, as long as the curability and the storage stability are not impaired. Other latent curing agents such as ketimine compounds and aldimine compounds synthesized from the compounds 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 blending 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 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. When the content is lower than this proportion, the amount of the silyl compound is small, and even a small amount of water entering the system of the composition during storage cannot be completely consumed, and hydrolysis of the ketimine compound cannot be suppressed, so that it is practical. Storage stability cannot 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 comprises, in addition to the above-mentioned compounds, a filler such as calcium carbonate and titanium oxide, a plasticizer, a thixotropy-imparting agent, 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 that the composition is sufficiently kneaded in a nitrogen atmosphere or under reduced pressure using a stirrer such as a mixing mixer. 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.
Thereafter, the ketimine compound is finally blended and homogeneously mixed to obtain a one-part moisture-curable adhesive composition. The final product is obtained by housing the one-component moisture-curable adhesive composition in a closed container that has been subjected to nitrogen substitution. 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.

[0063]

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.)
Then, 258 g of 3 times mol equivalent of diethyl ketone and 200 g of toluene are put in a flask and the produced water is removed by azeotropic distillation, and the reaction is continued for 20 hours at a temperature (120 to 150 ° C.) at which toluene and diethyl ketone are refluxed. It was Then, excess diethyl 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 342 g of ethyl butyl 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 154 g of nobornanediamine (manufactured by Mitsui Chemicals, trade name NBDA) was used as the amine compound.

(Synthesis Example 4) A ketimine compound D was obtained in the same manner as in Synthesis Example 1 except that 300 g of methyl isobutyl ketone was used as the carbonyl compound. .

(Example 1) 100 parts by weight of epoxy resin (Okaka Shell Epoxy, trade name Epicoat 828), heavy calcium carbonate (Nitto Koka, trade name NS100) 4
0 parts by mass, 80 parts by mass of surface-treated calcium carbonate (manufactured by Maruo Calcium, trade name MS700) at 100 ° C.
Reduce pressure and heat under the conditions of torr and 2 hours, and mix with stirring until uniform. When uniform, cool to room temperature and add 45 parts by mass of ketimine compound A as a curing agent for epoxy resin, ethyl silicate (TSL manufactured by Toshiba Silicone Co., Ltd.
8124) 40 parts by mass was added, and the mixture was stirred under reduced pressure to obtain a one-pack moisture-curable adhesive composition.

Example 2 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 1 except that the ketimine compound B was used as the curing agent for epoxy resin.

Example 3 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 1 except that the ketimine compound C was used as the curing agent for epoxy resin.

Example 4 A one-part moisture-curable adhesive composition was prepared in the same manner as in Example 1 except that a vinylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM1003) was used instead of ethyl silicate. Got

(Example 5) The same procedure as in Example 1 was carried out except that ketimine compound D was used as a curing agent for epoxy resin and an epoxy silane coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of ethyl silicate. hand,
A one-pack moisture-curable adhesive composition was obtained.

Example 6 Instead of ethyl silicate, an epoxy silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.,
A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 1 except that KBM403) was used.

Example 7 A one-part moisture-curable adhesive composition was obtained in the same manner as in Example, except that the amount of ethyl silicate compounded was changed from 40 parts by mass to 20 parts by mass.

Comparative Example 1 A one-pack moisture-curable adhesive composition was obtained in the same manner as in Example 3 except that ethyl silicate was omitted.

The following tests were conducted using the adhesive compositions according to Examples 1 to 4 and Comparative Example 1. The results are shown in Table 1.

[0077]

[Table 1]

(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). In order to evaluate the fast-curing property of the adhesive composition, in particular, the rising of the adhesive property was measured by curing at 23 ° C. for 1 day, and at 23 ° C. for 2 days.
The adhesive strength test was conducted under the conditions of 3 ° C. for 3 days. The unit is N / mm ² , and the fracture state at that time was shown.

(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.

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

As is clear from comparison between Examples 1 to 7 and Comparative Example 1, the one-part moisture-curable adhesive composition according to the example is the same as the one-part moisture-curable adhesive composition according to the comparative example. By comparison, it can be seen that it shows excellent storage stability. Further, as is clear from comparing Examples 1 to 6 and Example 7, the one-component moisture-curable adhesive composition according to Examples 1 to 6 is the one-component moisture-curable adhesive composition according to Example 7. It can be seen that the storage stability is further superior to that of the product.

As is clear from comparison between Examples 1, 2, 3, 4, 5, 6, 7 and Comparative Example 1, Examples 1, 2,
The one-liquid moisture-curable adhesive composition of 3, 4, 5, 6, 7 is
Compared to the one-part moisture-curable adhesive composition of Comparative Example, the adhesive strength under each curing condition is large and the fracture state is excellent. Regarding the adhesiveness after curing at 23 ° C. for 1 day, Example 5 is inferior to Examples 1, 2, 3, 4, 6, and 7, but the adhesiveness after curing at 23 ° C. for 3 days is not inferior. Especially 23 ° C
With respect to the adhesiveness after curing for one day, the results are remarkably different, and the one-pack moisture-curable adhesive compositions according to Examples 1, 2, 3, 4, 6, and 7 are comparative examples 1. It can be seen that, as compared with the one-pack moisture-curable adhesive composition according to the present invention, it exhibits excellent curability.

As is clear from comparison between Examples 5 and 6 and Comparative Example 1, the one-pack moisture-curable adhesive compositions of Examples 5 and 6 are the one-pack moisture-curable adhesive compositions of Comparative Examples, respectively. It can be seen that, as compared with the product, it exhibits excellent deep-part curability.

[0084]

As described above, the adhesive composition according to the present invention markedly accelerates the rise of initial adhesive strength and mechanical strength without impairing storage stability, and improves even deep-part curability. That has the conflicting performance of
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.

─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kentaro Suzuki 4-7-9 Tsurumi, Tsurumi-ku, Osaka City Konishi Corporation Osaka Research Institute (72) Inventor Nobuteru Matsuura 4--7 Tsurumi, Tsurumi-ku, Osaka No. 9 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) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 59/40 C08G 59/50 C09J 163/00-163/10

Claims (7)

(57) [Claims] 1. A silyl compound represented by the following chemical formula (1) and / or a silyl compound represented by the following chemical formula (2), a carbonyl compound represented by the following chemical formula (3), and an amine compound having a primary amino group. A ketimine compound represented by the following chemical formula (4) obtained by reacting
A one-pack moisture-curable epoxy resin composition comprising an epoxy resin. [Chemical 1] However, R ₁ , R ₂ , R ₃ , and R ₄ are alkyl groups,
R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and n is an integer of 1 or more. [Chemical 2] However, R ₅ and R ₆ are alkyl groups, R ₅ and R ₆ may be the same or different, R ₇ is an organic group,
n is an integer of 1 to 3. [Chemical 3] However, R ₈ and R ₉ are any one selected from the group consisting of alkyl groups having 2 to 6 carbon atoms, and R ₈ and R ₉ may be the same or different. [Chemical 4] However, R ₁₀ is a residue excluding a primary amino group of the amine compound, R _8, R ₉ is any one selected from the group consisting of alkyl group having 2 to 6 carbon atoms, R _8, R ₉ may be the same or different, and n is an integer of 1 or more. 2. A silyl compound having an epoxy group in the organic group (R ₇ ) of the chemical formula (2), a ketimine compound, and
A one-pack moisture-curable epoxy resin composition comprising an epoxy resin. 3. The ketimine compound according to claim 2, obtained by reacting the carbonyl compound represented by the chemical formula (3) with an amine compound having a primary amino group, represented by the chemical formula (4). The one-part moisture-curable epoxy resin composition according to claim 2, which is a ketimine compound. 4. The one-part moisture-curable epoxy resin composition according to claim 1, wherein the carbon atom at the α-position of the carbonyl compound has a methylene structure. 5. The carbonyl compound according to claim 1, wherein the carbonyl compound has the same or different alkyl group selected from an ethyl group and a propyl group. A one-part moisture-curable epoxy resin composition. 6. The one-pack moisture-curable epoxy resin composition according to claim 5, wherein the carbonyl compound has two ethyl groups. 7. The epoxy resin 10 as the silyl compound.
The one-part moisture-curable epoxy resin composition according to any one of claims 1 to 6, which is blended in an amount of 30 parts by mass or more based on 0 part by mass.