JPH05271389A - One pack type flexible epoxy resin composition and sealing material and adhesive comprising the same - Google Patents

Abstract

PURPOSE:To obtain the subject composition having more excellent storage stability and flexibility of cured material comprising an epoxy resin, a specific ketimine as a cold moisture curing agent, a modified silicone resin, a catalyst for the modified silicone resin and a dehydrating agent. CONSTITUTION:The objective composition comprising (A) an epoxy resin, (B) a ketimine of the formula (A is >=5C polyoxyalkylenediamine residue; R2 to R4 are H, 1-6C alkyl, etc.), (C) a modified silicone resin [preferably poly(methyldimethoxysilyl ether), etc.], (D) a catalyst (e.g. dibutyltin oxide) for the component B and (E) a dehydrating agent (e.g. vinyltrimethoxysilane). The component B is usually obtained by condensing a primary amine-containing compound such as polyoxypropylenediamine with a ketone group-containing compound such as methyl ethyl ketone. The composition is obtained by stirring the components A and C in a blending agitator for high viscosity under reduced pressure, adding the components B and D and stirring under reduced pressure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a one-part flexible epoxy resin composition and a sealing material or an adhesive comprising the same, and in particular, it can be cured at room temperature and has excellent storage stability and flexibility of the cured product. The present invention relates to a one-part type flexible epoxy resin composition, and a sealing material or an adhesive comprising the same.

[0002]

BACKGROUND ART Epoxy resins have been conventionally used for their sealing, adhesives, and adhesives in the fields of civil engineering and construction, electronic equipment, etc. by taking advantage of their excellent characteristics such as strength, adhesiveness, chemical resistance, and electrical insulation. Alternatively, it has been widely used as a paint or the like.

However, since this epoxy resin is easily reactive, it has a drawback that the storage stability period in a mixed system with a curing agent is very short. Therefore, most of the epoxy resins are two-component systems that are mixed with a curing agent, etc. immediately before use, and as a matter of course, they are inferior in workability to one-component systems. there were. In addition, even in the case of a one-liquid epoxy resin composition, a latent curing agent such as dicyandiamide or an acid anhydride curing agent is used as a curing agent, or radicals are generated by irradiating with UV. Then, a catalyst for curing the epoxy resin is used, and all of them require troublesome work such as heating and UV irradiation at the time of curing. Moreover, these epoxy resins, whether one-component or two-component, have the drawback that the cured product has poor flexibility. It was extremely inconvenient when used as an agent.

Therefore, in recent years, various epoxy resin compositions which can eliminate these drawbacks have been investigated, and JP-A-63-273629 and JP-A-63-27363 have been investigated.
In JP-A-0, the above-mentioned problems can be solved all at once by using an epoxy resin, a ketimine, a modified silicone resin, a modified silicone resin catalyst, and a silane compound as a dehydrating agent, which can be cured at room temperature. One-part flexible epoxy resin compositions have been proposed. And, in these publications, ketimine contained in such a one-component flexible epoxy resin composition is stable in the absence of water, but a primary amine that cures the epoxy resin due to water in the air, etc. Since the composition is formed, the storage stability of the composition is enhanced, and the composition can be moisture-cured at room temperature. Further, the cured product can be imparted with excellent flexibility by the modified silicone resin. Has been shown.

However, according to the results of the study by the present inventors, the one-component flexible epoxy resin composition disclosed in those publications can be stored even when stored while being protected from moisture from the outside.
It easily gels, and in addition, in the case of containing a large amount of general-purpose epoxy resin, the cured product becomes hard,
It became clear that sufficient flexibility could not be obtained.

[0006]

The present invention has been made in view of such circumstances, and the problems to be solved are storage stability and flexibility of a cured product. The present invention is to provide a more excellent one-part type flexible epoxy resin composition, and a sealing material or an adhesive comprising the same.

[0007]

Under such circumstances, the inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that epoxy resins, modified silicone resins, modified silicone resin catalysts,
A one-part flexible epoxy resin composition comprising a dehydrating agent and a specific polyoxyalkylenediamine or polyoxyalkylenetriamine-derived ketimine, in a sealed state,
It was found that it is stable for a long period of time, and when it is brought into contact with moisture in the air, it begins to cure rapidly, and that the cured product has greater flexibility than conventional products. It was.

That is, the present invention has been completed on the basis of such findings, and the characteristic features are as follows.
In the one-component flexible epoxy resin composition containing an epoxy resin, a ketimine, a modified silicone resin, a catalyst for a modified silicone resin, and a dehydrating agent, the ketimine is represented by the following chemical formula 9:

[Chemical 9] (However, A represents a residual chain of a polyoxyalkylenediamine having at least 9 carbon atoms, and R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group. In one-component flexible epoxy resin composition using the compound represented by

The present invention also provides an epoxy resin, ketimine, modified silicone resin, modified silicone resin catalyst,
And a dehydrating agent in a one-component flexible epoxy resin composition, wherein the ketimine is represented by the following chemical formula 10:

[Chemical 10] (However, B represents a residual chain of polyoxyalkylene triamine having at least 15 carbon atoms, and R ₅ , R ₆ , R
₇ , R ₈ , R ₉ and R ₁₀ are each hydrogen and a carbon number of 1 to 1, respectively.
A one-part type flexible epoxy resin composition using a compound represented by the formula (6) which represents an alkyl group or a phenyl group of 6) is also featured.

By the way, in such a one-pack type flexible epoxy resin composition according to the present invention, it is advantageous that the modified silicone resin has the following chemical formula:

[Chemical 11] (However, R ₁₁ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₁₂
Is a monovalent hydrocarbon group having 1 to 12 carbon atoms, n is an integer of 0 to 2), and is a polyether polymer having a hydrolyzable silicon functional group at the terminal, or the following chemical formula 12:

[Chemical 12] (However, R ₁₃ and R ₁₄ are the same or different from each other, a substituted or unsubstituted monovalent hydrocarbon group, and R ₁₅ and R ₁₆ are the same or different from each other and are a monovalent group having 1 to 6 carbon atoms. Hydrocarbon radical,
m is the viscosity of this compound at 25 ° C. is 100 to 300.
A linear polyorganosiloxane having a hydrolyzable silicon functional group represented by (indicated by an integer of 00 centipoise) at both ends is used.

In the one-pack type flexible epoxy resin composition according to the present invention, it is preferable that 1 part of the epoxy resin is added to 100 parts by weight of the modified silicone resin.
˜1000 parts by weight will be included.

Further, in the present invention, an epoxy resin,
In a sealing material or adhesive comprising a one-pack type flexible epoxy resin composition containing a ketimine, a modified silicone resin, a catalyst for a modified silicone resin, and a dehydrating agent, the ketimine is represented by the following chemical formula 13:

[Chemical 13] (However, A represents a residual chain of polyoxyalkylenediamine having at least 9 carbon atoms, and R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group. The sealant or adhesive using the compound represented by

Further, according to the present invention, there is provided a sealing material or adhesive comprising a one-pack type flexible epoxy resin composition containing an epoxy resin, ketimine, a modified silicone resin, a modified silicone resin catalyst and a dehydrating agent. As the ketimine, the following chemical formula 14:

[Chemical 14] (However, B represents a residual chain of polyoxyalkylene triamine having at least 15 carbon atoms, and R ₂₁ , R ₂₂ , R
₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each hydrogen and a carbon number of 1 to
A sealing material or an adhesive agent using a compound represented by the formula (6) which represents an alkyl group or a phenyl group of 6) is also featured.

In the above-mentioned sealing material or adhesive according to the present invention, it is advantageous that the modified silicone resin has the following chemical formula 15:

[Chemical 15] (However, R ₂₇ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₂₈
Is a monovalent hydrocarbon group having 1 to 12 carbon atoms, n is an integer of 0 to 2), and is a polyether polymer having a hydrolyzable silicon functional group at the end, or the following chemical formula 16:

[Chemical 16] (However, R ₂₉ and R ₃₀ are the same or different from each other, a substituted or unsubstituted monovalent hydrocarbon group, and R ₃₁ and R ₃₂ are the same or different from each other, and a monovalent C 1 to C 6 group. Hydrocarbon radical,
m is the viscosity of this compound at 25 ° C. is 100 to 300.
A linear polyorganosiloxane having a hydrolyzable silicon functional group represented by (indicated by an integer of 00 centipoise) at both ends is used.

Further, in the sealing material or adhesive according to the present invention, it is preferable that 1 to 10 parts by weight of the epoxy resin be added to 100 parts by weight of the modified silicone resin.
It will be included in a proportion of 00 parts by weight.

[0016]

SPECIFIC STRUCTURE By the way, as described above, the one-component flexible epoxy resin composition according to the present invention is constituted by containing the epoxy resin, ketimine, modified silicone resin, modified silicone resin catalyst, and dehydrating agent. Among them, as the epoxy resin, the following can be specifically mentioned.

For example, bisphenol A type, bisphenol F type and bisphenol AD type epoxy resins, hydrogenated products thereof, novolac type, glycidyl ester type and glycidyl amine type epoxy resins, and further polyoxypropylene and polyoxyethylene. Glycidyl ether, or a urethane-modified epoxy resin having a urethane bond in the structure, an epoxy resin having a resin modified with NBR, CTBN, or the like in the structure, and the like, and a glycidyl group capable of reacting with active hydrogen of amine. Any epoxy resin having can be used.

In the epoxy resin composition according to the present invention, these epoxy resins are contained singly or in combination of two or more, and the content thereof is 100 parts by weight of the modified silicone resin. On the other hand, 1
The proportion is preferably 1000 parts by weight, more preferably 50 to 200 parts by weight. If its content is less than 1 part by weight, the adhesiveness will decrease, and
This is because if the content exceeds 000 parts by weight, improvement in flexibility of the cured product cannot be expected.

Particularly, in the one-pack type flexible epoxy resin composition according to the present invention, the epoxy resin as described above is contained in an amount of 1 to 100 parts by weight of the modified silicone resin.
When it is used as a sealing material, an adhesive, etc., when it is contained at a ratio of about 7 parts by weight, excellent adhesiveness is obtained without using a primer when used. It will have the advantage.

The ketimine contained in the epoxy resin composition according to the present invention is represented by the chemical formula 9 (wherein A,
R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above or the above chemical formula 10 (wherein B, R ₅ , R ₆ and R ₇ ,
R ₈ and R ₉ R ₁₀ must have the chemical structural formulas shown above). Ketimine in which A in the formula of Chemical Formula 9 above is a polyoxyalkylenediamine having less than 9 carbon atoms, and ketimine in which B in the formula of Chemical Formula 10 above is a polyoxyalkylenetriamine having less than 15 carbon atoms This is because in the epoxy resin composition containing, the cured product becomes hard and sufficient flexibility cannot be obtained. From the viewpoint of preventing the time required for curing from being prolonged, it is desirable that the polyoxyalkylenediamine and polyoxyalkylenetriamine each have 160 or less carbon atoms.

In the present invention, the ketimines having the chemical structural formulas shown in the chemical formulas 9 and 10 are used alone or in combination to prepare a one-component flexible epoxy resin composition. However, in any case, for one epoxy group of the epoxy resin contained in the epoxy resin composition, such ketimine is the active hydrogen in the primary amine generated by moisture. The number is preferably 0.6 to 1.4, more preferably 0.
It is contained so as to be 8 to 1.2. When the relative ratio of these is smaller than 0.6 or larger than 1.4, the epoxy resin composition causes deterioration of curability and water resistance and mechanical strength of the cured product. It

The ketimine according to the present invention can be usually obtained by subjecting a compound having a primary amine in the molecule and a compound having a ketone group in the molecule to a condensation reaction.

As the compound having a primary amine in the molecule, for example, polyoxyalkylene diamine and triamine obtained by homopolymerization, random polymerization, or block polymerization of propylene oxide or ethylene oxide, or in the molecular chain is used. Examples include amines such as polyoxyalkylene polyamines having polyester polyols, and examples of compounds having a ketone group in the molecule include, for example, methyl ethyl ketone, methyl isobutyl ketone,
A ketone solvent such as cyclohexanone or a ketone resin obtained by cross-linking cyclohexanone, acetophenone, phenol or the like with formalin can be used. In addition, the amines and ketone resins exemplified as the raw materials of these ketimines are used alone or in combination,
It will be used for the synthesis reaction of ketimine.

Since the ketimine according to the present invention as described above has the characteristic that the nitrogen in the molecule is weakly basic and the epoxy group in the epoxy resin is difficult to undergo anionic polymerization, it does not react with the epoxy resin in the absence of water. It hardly reacts, but when water is given, it easily forms a primary amine, which makes it possible to cure the epoxy resin by a polyaddition reaction and effectively prevent the cured product from becoming hard. Therefore, a system in which such a ketimine and an epoxy resin are mixed is stable for a long period of time unless moisture is mixed, and is rapidly cured at room temperature by being brought into contact with moisture in the air. In addition, the cured product does not become hard unlike the conventional one.

That is, as described above, the ketimine according to the present invention is extremely useful as a room temperature moisture curing agent for a one-pack type epoxy resin composition, and furthermore, the storage stability of the epoxy resin composition and its cured product. To improve the flexibility of
It is a great contribution.

Further, in the one-component flexible epoxy resin composition according to the present invention, the modified silicone resin is hardened by moisture in the air in the presence of the modified silicone resin catalyst to give a hardened epoxy resin. On the other hand, in order to impart flexibility to the cured product, the modified silicone resin in the present invention is a compound represented by Chemical Formula 11 (wherein, R ₁₁ , R ₁₂ , and n have the same meanings as described above, and are preferably polyether polymers having a hydrolyzable silicon functional group at the terminal.
And, as such a polyether polymer, for example, poly (methyldimethoxy ether) and the like can be mentioned.

Further, in the present invention, as the modified silicone resin, in addition to the above-mentioned ones, it is advantageous that the above-mentioned chemical formula 12 (wherein R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and m are:
A linear polyorganosiloxane having a hydrolyzable silicon functional group represented by the same meaning as described above) at both ends is used. The one-component flexible epoxy resin composition according to the present invention has excellent flexibility after curing, exhibits excellent mechanical strength, and has good workability. Chain polyorganosiloxane has 2
It preferably has a viscosity in the range of 100 to 30,000 centipoise at 5 ° C., more preferably 100 to 10,000 centipoise, and is represented by R ₁₃ and R _{14 in the} above formula (12). As the substituted or unsubstituted monovalent hydrocarbon groups which are the same or different from each other, a methyl group which is easy to synthesize and has a low viscosity before curing is preferable. From this point of view, as such a linear polyorganosiloxane, for example, polydimethylsiloxane, terminal ethoxy and the like can be preferably used.

In the present invention, the polyether polymer and the linear polyorganosiloxane preferably used as the modified silicone resin are generally commercially available as long as they satisfy the respective conditions. It is acceptable, and even if they are used alone or in a mixture of two or more kinds, it does not matter at all, and the amount used is relative to the epoxy resin as described above. It will be decided accordingly.

As described above, the modified silicone resin catalyst is a catalyst for curing the modified silicone resin as the flexibility-imparting agent, and the cured product of the epoxy resin composition has excellent flexibility. In order to obtain, it is essential in the present invention. And as such a modified silicone resin catalyst, specifically, a tin compound such as dibutyltin oxide, a metal salt of a carboxylic acid such as lead octylate, or dibutylamine-2-ethylhexoate. Amines can be exemplified. The content of the modified silicone resin catalyst in the one-component flexible epoxy resin composition according to the present invention is preferably modified silicone resin 100.
It is 0.1 to 10 parts by weight with respect to parts by weight.

Further, the dehydrating agent contained in the one-part type flexible epoxy resin composition according to the present invention plays a role of absorbing the water that has penetrated into the epoxy resin composition during storage. That is, this dehydrating agent prevents the epoxy resin and the modified silicone resin from being cured by the reaction of such water with ketimine and the modified silicone resin, except when the epoxy resin composition is used. However, in the present invention, it is indispensable for maintaining the storage stability of the one-component flexible epoxy resin composition satisfactorily for a longer period of time.

Examples of such dehydrating agents include silane compounds such as vinyltrimethoxysilane, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and aminopropyltrimethoxysilane, and orthoformic acid. Ethyl etc. are mentioned. Further, such a dehydrating agent may be contained in the epoxy resin composition according to the present invention in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin contained therein. ,preferable.

Further, in the one-pack type flexible epoxy resin composition according to the present invention, in addition to the main components as described above, an antioxidant such as titanium oxide, a pigment such as carbon, a filler such as calcium carbonate, The inclusion of various additives such as ultraviolet absorbers and plasticizers is acceptable. It should be noted that these additives are added in various combinations in various amounts depending on the application of the one-component flexible epoxy resin composition.

Thus, the one-pack type flexible epoxy resin composition according to the present invention contains the epoxy resin, ketimine, modified silicone resin, modified silicone resin catalyst, dehydrating agent,
Various additives are mixed and produced according to a conventional method, but generally, they are obtained by the following method.

That is, first, a predetermined amount of each of an epoxy resin, a modified silicone resin and, if desired, various additives such as an antioxidant and a filler is put into a high-viscosity mixing stirrer or the like, and then at room temperature. And preferably 700 to 760
Stir under reduced pressure at Torr to obtain a mixture. Then, a predetermined amount of ketimine, a dehydrating agent and a catalyst for modified silicone resin is added to a high-viscosity mixing stirrer in which the mixture thus obtained is accommodated, and advantageously, the mixture is further stirred under reduced pressure at 700 to 760 Torr. Thus, the intended epoxy resin composition is obtained.

The epoxy resin composition thus obtained exhibits more excellent properties than the conventional ones in storage stability in one liquid and flexibility of the cured product. And glass, concrete, metal,
It will be extremely advantageously used as a sealing material or adhesive for wood and the like.

Examples of the present invention will be shown below to clarify the present invention more specifically, but the present invention is not limited by the description of such examples. It goes without saying that. Further, in the present invention, in addition to the following examples, further, in addition to the above specific description, various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention,
It should be understood that improvements and the like can be added.

[0037]

EXAMPLES First, epoxy resins A and B as shown below are used.
, Two kinds of modified silicone resins A and B, one kind of modified silicone resin catalyst, one kind of dehydrating agent, and six kinds of ketimines A to E synthesized as shown below, respectively. Got ready. Here, except for ketimines D to E, each is in accordance with the present invention, wherein ketimine D has the carbon number of the polyoxyalkylenediamine represented by A in the formula of the above chemical formula 9 is 8, In terms of the number of carbon atoms, it is outside the scope of the present invention, and ketimine E is also outside the scope of the present invention, in which A in the formula (9) is different from the residual chain of polyoxyalkylenediamine. In any case, the ketimines D and E are completely different from the ketimine according to the present invention. It is confirmed that these ketimines A to E are ketimine compounds because all of them have sharp absorption at around 1650 cm ^-1 according to the IR spectrum. Epoxy resin A epibis type epoxy resin (Asahi Denka Kogyo KK, trade name: EP-4100) Epoxy resin B bisphenol A type polyoxypropylene modified epoxy resin (Asahi Denka Kogyo KK, trade name: EP-400)
0) Modified silicone resin A poly (methyldimethoxysilyl ether) (Kanefuchi Chemical Industry Co., Ltd., trade name: MSP20A) Modified silicone resin B polydimethylsiloxane, terminal ethoxy (Chisso Co., Ltd., trade name: PS-393) Dioctyl tin oxide dioctyl phthalate solution for modified silicone resin (manufactured by Sansha Machinery Co., Ltd., trade name: No918) Dehydrating agent vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.,
Product name: KBM1003) Ketimine A (manufactured by Asahi Denka Kogyo Co., Ltd.) Polyoxypropylene diamine (molecular weight: 400) and methyl isobutyl ketone were used as raw materials and synthesized by dehydration reaction. Ketimine B (manufactured by Asahi Denka Kogyo Co., Ltd.) Polyoxypropylene triamine (molecular weight: 400) and methyl isobutyl ketone were used as raw materials and synthesized by dehydration reaction. Ketimine C (manufactured by Asahi Denka Co., Ltd.) Polyoxypropylene diamine (diamine of random polymer of propylene oxide / ethylene oxide = 1 (weight ratio), molecular weight: 400) and methyl isobutyl ketone were used as raw materials and synthesized by dehydration reaction. .. Ketimine D (manufactured by Asahi Denka Co., Ltd.) Polyoxyalkylenediamine (molecular weight: 208, carbon number 8) and methyl isobutyl ketone were used as raw materials and synthesized by dehydration reaction. Ketimine E (manufactured by Asahi Denka Co., Ltd.) Synthesized by dehydration reaction using hexamethylenediamine and methyl isobutyl ketone as raw materials.

Examples 1 to 5 Then, the respective composition components were weighed so that the blending ratios shown in Table 1 below were obtained. First, epoxy resin, modified silicone resin, calcium carbonate and titanium oxide were used for high viscosity. The mixture was put into a mixing stirrer and stirred under a reduced pressure of 20 Torr at room temperature to obtain a mixture thereof.
Then, in a high-viscosity mixing stirrer containing the mixture thus obtained, the previously weighed ketimine, the dehydrating agent, and the modified silicone resin catalyst were respectively charged, and the mixture was further stirred under reduced pressure in the same manner as above, Various epoxy resin compositions were obtained. Then, the epoxy resin compositions were subjected to evaluation tests for storage stability, mechanical properties and adhesiveness, respectively, as described below. The results are also shown in Table 1 below. Storage stability: The epoxy resin composition was placed in a nitrogen-substituted sample bottle with a sealed stopper, and the state of the composition was observed after standing in an atmosphere of 50 ° C for 7 days. Mechanical Properties: The epoxy resin composition was cured at 25 ° C. for 4 weeks, and the tensile strength and elongation after curing were measured. Adhesiveness: The epoxy resin composition was applied to a mortar piece, allowed to cure at 25 ° C for 4 weeks, and then cured, and then subjected to a uniaxial adhesive strength tester to determine the state when the adhesive surface layer with mortar was destroyed. I observed.

[0039]

[Table 1]

Examples 6 to 9 Further, the blending ratios shown in Table 2 below were obtained.
Each of the compositional components was weighed and they were measured in Examples 1-5.
The mixture was stirred under reduced pressure in the same manner as in 1. to prepare various epoxy resin compositions. Then, with respect to these epoxy resin compositions, evaluation tests were carried out for storage stability, mechanical properties and adhesiveness in the same manner as described above. The results are also shown in Table 2 below.

[0041]

[Table 2]

Examples 10 to 17 Further, the composition components were weighed so that the blending ratios shown in Tables 3 and 4 below were obtained, and the ingredients were mixed in Example 1
Various kinds of epoxy resin compositions were prepared by stirring under reduced pressure in the same manner as in Nos. 5 to 5. Then, using the epoxy resin composition as an adhesive, for the storage stability, an evaluation test is conducted in the same manner as above, and with the following test materials and conditions, pulling of the test materials after bonding An evaluation test for strength, flexibility and adhesiveness was performed by measuring the strength and the elongation of the adhesive surface layer and observing the broken state of the adhesive surface layer. The results are also shown in Tables 3 and 4 below. (1) Test material Adhered material: Colorcon mosaic tile (porcelain) 4.5 cm in length and 4.5 cm in width, JIS-A
According to -5209, it is used as an adherend. Base material: mortar board A mortar board having a length of 7.0 cm, a width of 7.0 cm and a height of 2.0 cm and used as a base according to JIS-A-5548. (2) Test conditions Environmental conditions: 20 ± 1 ° C, 60 ± 5% RH Adhesive coating amount: Approx. 1.6 kg / m ² Sticking time: Within 5 minutes Clamping: 30 seconds with a 1 kg load Adhesive layer thickness Length: 1 mm Curing: 168 hours depending on environmental conditions (3) Measuring conditions Measuring method: Uniaxial tensile test Measuring instrument: Tensilon UTM-10T Pulling speed: 1 mm / min

[0043]

[Table 3]

[0044]

[Table 4]

Comparative Examples 1 to 8 Furthermore, the respective composition components were weighed so that the blending ratios shown in Tables 5 and 6 below were obtained, and the same operations as in Examples 1 to 5 were performed on them. , Respectively, an epoxy resin composition consisting of an epoxy resin, ketimine and an additive, and a modified silicone resin composition containing no epoxy resin and ketimine were prepared, and the former was compared with Comparative Examples 1 and 6 and the latter was compared. Example 2 is given. Also, different from ketimine according to the present invention, ketimine D and ketimine E were used, and each composition component was weighed so as to have a mixing ratio as shown in Tables 5 and 6 below. Example 1
The same operation as in 5 was performed to obtain an epoxy resin composition. Among them, the epoxy resin compositions obtained using ketimine D were designated as Comparative Examples 3 and 7, and the epoxy resin composition prepared using ketimine E was designated as Comparative Example 4. Furthermore, as shown in Table 5 below, ketimine C according to the present invention, in an amount relative to the epoxy resin,
The epoxy resin composition obtained in the same manner as in Examples 1 to 5 was used as Comparative Example 5 in an amount outside the preferred range of the present invention. Then, the same evaluation tests as in Examples 1 to 5 were performed on Comparative Examples 1 to 5, respectively, and in Comparative Examples 6 to 8, Examples 10 to 17 were used as an adhesive.
An evaluation test similar to the above was performed. The results are also shown in Tables 5 and 6 below.

[0046]

[Table 5]

[0047]

[Table 6]

As is apparent from those tables, Examples 1 to 4, which are epoxy resin compositions according to the present invention, are Comparative Example 1 consisting of the same amounts of epoxy resin A and ketimine A, and other additives. In comparison with the above, the results are that the elongation of the cured product is large and the flexibility is excellent. In addition, the epoxy resin composition according to the present invention, Example 4 ~
Comparative Example 2, which is a modified silicone resin composition containing the same amount of the modified silicone resin A, the catalyst for the modified silicone resin, and the dehydrating agent, but containing no epoxy resin and ketimine, Results inferior.

Further, in Examples 1 to 9 according to the present invention, compared with Comparative Examples 3 and 4 containing ketimine D or E which is not suitable for the present invention, the elongation percentage of the cured product is very high. As shown, the flexibility is extremely excellent. In Comparative Example 4, gelation occurred 7 days after preparation, and it was confirmed that the storage stability was poor. In Comparative Example 5, a decrease in ketimine content resulted in a decrease in adhesiveness. Have been shown to cause.

Furthermore, even in Examples 10 to 17 which are the adhesives according to the present invention, all of them adhere to Comparative Examples 7 and 8 containing ketimine D different from ketimine according to the present invention. The elongation of the surface layer shows a value of 2 to 3 times or more, and it is recognized that the surface layer is remarkably excellent in flexibility, and in Comparative Example 6 which is an adhesive composed of the modified silicone resin composition. , The result of poor adhesion is shown.

[0051]

As is apparent from the above description, the one-component flexible epoxy resin composition according to the present invention, as a curing agent, is almost free from the epoxy resin when contact with water is blocked. Since it comprises a ketimine having a non-reactive property, storage stability can be advantageously increased, and the cured product thereof is modified with a modified silicone resin as a flexibility-imparting agent. Not only can it be imparted with excellent flexibility, but it can be effectively prevented from being hardened like a conventional one by the curing agent ketimine as a curing agent. Compared with other products, it has even greater flexibility.

Therefore, in the sealing material or adhesive made of such a one-component flexible epoxy resin composition, excellent strength and adhesiveness are ensured, and storage stability superior to conventional ones is obtained. Property and more excellent flexibility of the cured product can be obtained, thereby improving workability such as sealing and bonding to a substrate such as concrete, wood, and metal.
It can be effectively achieved.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09J 163/00 JFL 8830-4J JFP 8830-4J C09K 3/10 LG

Claims (10)

[Claims] 1. A one-part flexible epoxy resin composition containing an epoxy resin, ketimine, a modified silicone resin, a catalyst for a modified silicone resin, and a dehydrating agent, wherein the ketimine is represented by the following chemical formula 1: (However, A represents a residual chain of a polyoxyalkylenediamine having at least 9 carbon atoms, and R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group. The one-component flexible epoxy resin composition is characterized by using the compound represented by 2. A one-component flexible epoxy resin composition containing an epoxy resin, a ketimine, a modified silicone resin, a catalyst for a modified silicone resin, and a dehydrating agent, wherein the ketimine is represented by the following chemical formula 2: (However, B represents a residual chain of polyoxyalkylene triamine having at least 15 carbon atoms, and R ₅ , R ₆ , R
₇ , R ₈ , R ₉ and R ₁₀ are each hydrogen and a carbon number of 1 to 1, respectively.
6 represents an alkyl group or a phenyl group), and a one-pack type flexible epoxy resin composition is used. 3. The modified silicone resin has the following chemical formula: (However, R ₁₁ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₁₂
Is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 2), and is a polyether polymer having a hydrolyzable silicon functional group at the terminal. Item 3. A one-pack type flexible epoxy resin composition according to Item 2. 4. The modified silicone resin is represented by the following chemical formula: (However, R ₁₃ and R ₁₄ are the same or different from each other, a substituted or unsubstituted monovalent hydrocarbon group, and R ₁₅ and R ₁₆ are the same or different from each other and are a monovalent group having 1 to 6 carbon atoms. Hydrocarbon radical,
m is the viscosity of this compound at 25 ° C. is 100 to 300.
The one-component flexible epoxy resin according to claim 1 or 2, which is a linear polyorganosiloxane having a hydrolyzable silicon functional group represented by (indicated by an integer of 00 centipoise) at both ends. Composition. 5. The one-component system according to claim 1, wherein the epoxy resin is contained in an amount of 1 to 1000 parts by weight with respect to 100 parts by weight of the modified silicone resin. Flexible epoxy resin composition. 6. A sealing material or an adhesive comprising a one-pack type flexible epoxy resin composition containing an epoxy resin, a ketimine, a modified silicone resin, a catalyst for a modified silicone resin, and a dehydrating agent. 5: (However, A represents a residual chain of polyoxyalkylenediamine having at least 9 carbon atoms, and R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are each hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group. The sealant or adhesive is characterized by using a compound represented by 7. A sealing material or an adhesive comprising a one-pack type flexible epoxy resin composition containing an epoxy resin, a ketimine, a modified silicone resin, a catalyst for a modified silicone resin, and a dehydrating agent. 6: (However, B represents a residual chain of polyoxyalkylene triamine having at least 15 carbon atoms, and R ₂₁ , R ₂₂ , R
₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each hydrogen and a carbon number of 1 to
A compound represented by the formula (6), which represents an alkyl group or a phenyl group of 6, is used. 8. The modified silicone resin has the following chemical formula: (However, R ₂₇ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ₂₈
Is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 2), and is a polyether polymer having a hydrolyzable silicon functional group at the terminal. Item 7. A sealing material or an adhesive according to Item 7. 9. The modified silicone resin has the following chemical formula: (However, R ₂₉ and R ₃₀ are the same or different from each other, a substituted or unsubstituted monovalent hydrocarbon group, and R ₃₁ and R ₃₂ are the same or different from each other, and a monovalent C 1 to C 6 group. Hydrocarbon radical,
m is the viscosity of this compound at 25 ° C. is 100 to 300.
The sealing material or the adhesive according to claim 6 or 7, which is a linear polyorganosiloxane having a hydrolyzable silicon functional group represented by (indicated by an integer of 00 centipoise) at both ends. 10. The sealing material according to claim 6, wherein the epoxy resin is contained in a ratio of 1 to 1000 parts by weight with respect to 100 parts by weight of the modified silicone resin. adhesive.