JP2000034337A - One-pack type epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a one-pack type epoxy resin composition having rapid curing rate when removed from a vessel and excellent storage stability. SOLUTION: This composition includes (A) a ketimine-group containing compound obtained by reacting the corresponding ketone having a substituent at its α site and a polyamine having at least two amino groups each having a methylene group at its α site, (B) an epoxy resin having at least two intramolecular epoxy groups, and (C) an alkoxysilyl group-containing compound having at least one intramolecular alkoxysilyl group, but, no reactive substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type epoxy resin composition useful as an adhesive, a paint, a coating agent and the like in the field of civil engineering and construction, which has a high curing rate when taken out of a container and has excellent storage stability. About.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used as adhesives or paints in the fields of civil engineering and construction and electronic equipment because of their excellent properties such as adhesiveness and strength. Since this epoxy resin has high reactivity, when mixed with an amine component, it reacts easily and cures.
Therefore, conventionally, the two-pack type was almost used. On the other hand, various studies have been made on one-packing using a latent curing agent mainly composed of a ketimine-based compound, but a system that balances storage stability and curability has not yet been found. For example, JP-A-5-132541 discloses that a skeleton of a ketimine compound is made of long-chain polyoxylen,
Techniques have been disclosed for reducing the reactivity during storage and consequently increasing the storage stability. However, the curing speed at the time of being taken out of the container is too slow to be used as a practical one-pack type epoxy resin composition. On the other hand, a technique using a sterically hindered amine or thiol capped with a trialkylsilyl group as a latent curing agent is also disclosed (JP-A-1-138221, JP-A-2-362).
No. 20, each publication), these curing agents react sensitively even to a very small amount of moisture, and thus are gelled by a small amount of moisture in the system during storage.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a one-pack type epoxy resin composition which has a high curing rate when taken out of a container and has excellent storage stability.

[0004]

That is, the present invention provides:
(A) a ketimine group-containing compound obtained by reacting a ketone having a substituent at the α-position with a polyamine having at least two amino groups having methylene at the α-position in the molecule, and (B) an epoxy compound within the molecule. A one-pack type epoxy resin composition comprising: an epoxy resin having at least two groups; (C) an alkoxysilyl group-containing compound having at least one alkoxysilyl group in the molecule and having no reactive substituent. provide.

It is preferable that the ketone is a compound represented by the following formula (1) and the polyamine is a compound represented by the following formula (2).

Embedded image R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group

Embedded image R ⁴ : organic group (including groups having O, S and N) n: integer of 2 or more

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (A) Ketimine Group-Containing Compound A ketone having a substituent at the α-position serving as a raw material of the ketimine group-containing compound used in the present invention, and having at least two or more amino groups in which α-methylene is in the molecule The compound will be described. The ketone having a substituent at the α-position used in the present invention refers to a ketone having a substituent at the α-position counted from the carbonyl group, such as methyl t-butyl ketone, diisopropyl ketone, methyl isopropyl ketone, and propiophenone. And benzophenone as specific examples. Among them, the compound represented by the formula (1) is particularly preferable, and specific examples include methyl isopropyl ketone and methyl t-butyl ketone. The one-pack type epoxy resin composition of the present invention containing a ketimine group-containing compound (hereinafter, referred to as the composition of the present invention) is preferable because it has an excellent balance between storage stability and curability.

As the polyamine having at least two amino groups having methylene at the α-position in the molecule, a compound represented by the formula (2) is preferable. Specific examples of the compound represented by the formula (2) include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine,
N-aminoethylpiperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, diamine having a polyether skeleton represented by Jeffamine EDR148 manufactured by San Techno Chemical Co., and MPMD manufactured by DuPont Japan Aliphatic polyamine: isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, Mitsui Toatsu Chemicals, Inc. Diamines having a norbornane skeleton typified by NBDA; metaxylylenediamine; polyamidoamines having an amino group at the molecular terminal of polyamide; Among these, 1,3-bisaminomethylcyclohexane, norbornanediamine, meta-xylylenediamine,
Polyamidoamine is particularly preferable because the composition of the present invention containing a ketimine group-containing compound synthesized using the same is excellent in storage stability and particularly excellent in curability.

As the ketimine group-containing compound used in the present invention, a ketimine group obtained by combining each of the above-mentioned polyamines with each ketone such as methyl t-butyl ketone, diisopropyl ketone, methyl isopropyl ketone, propiophenone and benzophenone is used. Preferred examples include compounds. Among them, the ketimine group-containing compound synthesized from the polyamine, methyl isopropyl ketone, and methyl t-butyl ketone has a particularly excellent balance between the curing speed and the storage stability. In addition, the above ketone and 1,3
A ketimine group-containing compound synthesized from bisaminomethylcyclohexane, norbornanediamine, metaxylylenediamine, or polyamidoamine is also particularly excellent in the balance between the curing speed and the storage stability, but is particularly excellent in the curability.

Specifically, Jeffamine EDR which is a diamine having a polyether skeleton manufactured by San Techno Chemical Co., Ltd.
148 and methyl isopropyl ketone,
One obtained from Jeffamine EDR148 and methyl t-butyl ketone, one obtained from 1,3-bisaminomethylcyclohexane and methyl t-butyl ketone, one obtained from NBDA and methyl isopropyl ketone manufactured by Mitsui Toatsu Chemicals, Inc. One obtained from 1,3-bisaminomethylcyclohexane and methyl isopropyl ketone, one obtained from NBDA and methyl t-butyl ketone, one obtained from MXDA and methyl isopropyl ketone manufactured by Mitsubishi Gas Chemical Company, and one manufactured by Mitsubishi Gas Chemical Company MXDA
And methyl t-butyl ketone, those obtained from X2000 and methyl isopropyl ketone (manufactured by Sanwa Kagaku), those obtained from X2000 and methyl t-butyl ketone (manufactured by Sanwa Kagaku), and the like. Among these, those obtained from NBDA and methyl isopropyl ketone manufactured by Mitsui Toatsu Chemical Co., Ltd., those obtained from NBDA and methyl t-butyl ketone, and those obtained from 1,3-bisaminomethylcyclohexane and methyl isopropyl ketone Those are excellent in curability. In addition, X200
From X and methyl isopropyl ketone, X2
000 and methyl t-butyl ketone are:
Excellent adhesion to wet surfaces.

A ketimine group-containing compound obtained by reacting a ketone having a substituent at the α-position with a polyamine having two or more amino groups having methylene at the α-position is a ketimine group-containing compound.
Having bulky groups near the heavy bond satisfies the conflicting properties of cure speed and storage stability. That is, methyl isobutyl ketone (MI
When a ketimine group-containing compound is synthesized using a ketone having no substituent at the α-position of a ketone carbon, such as BK) or methyl ethyl ketone (MEK), strong basicity is exhibited because the ketimine nitrogen is exposed. . Therefore,
The composition blended with the epoxy resin has a problem in storage stability such as progress of gelation. However, methyl isopropyl ketone having a substituent at the α-position of ketone carbon and methyl t-
A ketimine group-containing compound using butyl ketone or the like as a raw material has ketone amine nitrogen protected by a substituent, that is, its basicity is significantly weakened by steric hindrance.
Therefore, the composition blended with the epoxy resin is kept stable without being affected by the ketimine group-containing compound. On the other hand, when the epoxy resin composition using the ketimine group-containing compound is exposed to the air, the small water molecules that are moisture easily attack ketimine nitrogen without steric hindrance of the substituent, and therefore, hydrolysis is easy. Proceed to Therefore,
The curing time of the epoxy resin composition is fast.

The ketimine group-containing compound used in the present invention is:
The above-mentioned ketone and polyamine can be obtained by refluxing under heating without solvent or in the presence of a solvent such as benzene, toluene and xylene, and reacting while removing elimination water by azeotropic distillation.

The amount of the ketimine group-containing compound to be added to the composition of the present invention is, in equivalent ratio, (imino group of ketimine group-containing compound) / (epoxy group in epoxy resin), preferably 0.1 to 2%. , More preferably 0.3 to 1.5.
Outside these ranges, the curability will be poor. The concentration of the added ketimine group was 1.6 [mmol] in the composition of the present invention.
/ G] or less, preferably from 0.2 to 1.5 [mm
ol / g] is more preferable. Within this range,
This is because they have excellent cured physical properties and storage stability.

The ketimine group-containing compound used in the present invention is represented by the formulas (9) and (10) described in International Patent Application No. PCT / JP98 / 00220 on January 21, 1998. A silicon-containing compound having a ketimine group or a silicone compound having an epoxy group, a ketimine group, or an alkoxysilyl group in the same molecule, and specific examples thereof include compounds represented by the formula (21) in the same specification. Anything that can be used can be used.

(B) Epoxy Resin The epoxy resin used in the present invention is not particularly limited as long as it is a polyepoxy compound having two or more epoxy groups in one molecule. For example, glycidyl ether type epoxy resin of bisphenol A and its derivatives, glycidyl ether type epoxy resin of glycerin, glycidyl ether type epoxy resin of polyalkylene oxide, glycidyl ether type epoxy resin of phenol novolak, glycidyl ester type epoxy resin of dimer acid,
A glycidyl ether type epoxy resin of bisphenol F, or an epoxy resin having a sulfur atom in the main chain of an epoxy resin represented by FLEP 10 manufactured by Toray Thiokol, or the like can be used. Of these, bisphenol A
The glycidyl ether type epoxy resin is suitably used as a general-purpose epoxy resin. Epoxy resins having a sulfur atom in the skeleton are preferably used because the resulting composition of the present invention has excellent adhesion to wet surfaces.

(C) Alkoxysilyl Group-Containing Compound The alkoxysilyl group-containing compound used in the present invention has at least one alkoxysilyl group in the molecule and has no reactive substituent other than the alkoxysilyl group. Compound. That is, the alkoxysilyl group-containing compound used in the present invention is an alkoxysilyl group-containing compound excluding the silane coupling agent. As such a silane compound, a monomer represented by the following formula (3): R _4-k —Si (OR) _k (3) (where R is a hydrocarbon group having 1 to 6 carbon atoms) And an organic group excluding a reactive substituent, k is an integer of 1 to 3) or a polymer having four or more alkoxysilyl groups in one molecule and having no reactive substituent. it can. In the alkoxysilyl group-containing compound represented by the formula (3), specific examples of R include the following organic groups.

Embedded image When two or more R and OR are present in the monomer represented by the formula (3), they may be the same or different. Examples of the reactive substituent removed from R include a vinyl group, a methacryl group, an epoxy group, an amino group, a mercapto group, and the like. Specific examples of the alkoxysilyl group-containing compound represented by the formula (3) include C ₆ H ₅ —Si (OCH ₃ ) ₃ .

The polymer contained in the alkoxysilyl group-containing compound used in the present invention, which has four or more alkoxysilyl groups in one molecule and has no reactive substituent,
Four or more alkoxy groups contained in one molecule are represented by
It may be contained in either the main chain terminal or the side chain. The main chain mainly consists of Si—O bonds, and when the alkoxysilyl group is contained in the main chain, Si of the alkoxysilyl group becomes Si in the main chain. The alkoxy group can be represented by -OR, wherein R has the same meaning as R in the above formula (3). 1
The alkoxy groups (OR) contained in the molecule may be the same or different. The Si atom in the main chain may have a group other than an alkoxy group, but these functional groups do not include a reactive substituent. Examples of the group other than the alkoxy group which may be contained in the molecule include a linear alkyl group such as a methyl group, an ethyl group, and a propyl group; a branched alkyl group such as an isopropyl group and an isobutyl group; a cycloalkyl group such as a hexamethyl group An aromatic group such as a phenyl group and a benzyl group. Examples of the excluded reactive substituents are the same as the reactive substituents excluded from R in the above formula (3).
As a specific example of such an alkoxysilyl group-containing compound, the following compound (MS51) can be shown.

Embedded image

The above-mentioned compound containing an alkoxysilyl group is
The composition of the present invention, which has an effect as a dehydrating agent and contains such an alkoxysilyl group-containing compound, has excellent storage stability without impairing the excellent curability of the aforementioned ketimine group-containing compound. At the same time, the alkoxysilyl group-containing compound also has a diluting effect on the composition of the present invention, and together with the above-mentioned effect as a dehydrating agent, makes the storage stability of the composition of the present invention excellent. In the composition of the present invention, the content of the alkoxysilyl group-containing compound is preferably from 0.1 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the epoxy resin.
This is because if the content is within this range, the composition of the present invention will have better storage stability without impairing the curability.

The composition of the present invention can be obtained by mixing an epoxy resin, the above-mentioned ketimine group-containing compound and the above-mentioned alkoxysilyl group-containing compound under a nitrogen atmosphere. If necessary, a curing accelerator may be used in combination. May be. Phosphite esters are very effective as curing accelerators. This is because phosphites do not increase the viscosity of the epoxy resin composition or other adverse effects during the storage of the epoxy resin composition.

The phosphites used in the present invention include triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, and the like. Tris (tridecyl) phosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphos Phyto, trilauryl trithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, Stearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di -t - butyl phenyl) phosphite, hydrogenated bisphenol A · pentaerythritol phosphite triester such polymers. Further, di- or monoesters obtained by partially hydrolyzing these triesters are also exemplified. Among them, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, hydrogenated bisphenol A.penta Erythritol phosphite polymer and the like have a particularly high accelerating effect and are preferably used.

When a triester is used among these phosphites, the amount of the phosphite is 0.005 mol% or more based on the epoxy group of the epoxy resin.
Preferably it is 0.005 to 1.0 mol%. When a di- or monoester obtained by partially hydrolyzing a triester is used, the amount of the di- or monoester is 0.005 to 50 mol%, preferably 0.005 to 10 mol, based on the epoxy group of the epoxy resin. %. 0.005
When the amount is less than mol%, there is no effect as an accelerator, while when the amount of the diester is more than 50 mol%, the storage stability deteriorates. Further, the composition of the present invention may contain an accelerator other than the phosphite as the accelerator.

The composition of the present invention may contain a compound having a silyl ester group represented by the following formula (4).
By containing a specific amount of such a compound having a silyl ester group, the curing time can be shortened without impairing the storage stability of the composition of the present invention.

Embedded image In the formula, R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group include linear hydrocarbon groups such as a methyl group, an ethyl group, a vinyl group, a propyl group, an octyl group, a lauryl group, a palmityl group, a stearyl group, an allyl group, and an eicosyl group; And a branched hydrocarbon group such as an isobutyl group; an alicyclic hydrocarbon group such as a hexamethyl group; an aromatic group such as a phenyl group and a benzyl group. As R ′, a hydrocarbon group having 1 to 17 carbon atoms is particularly preferable because it is excellent in storage stability and the effect of accelerating the curing reaction.
This is because when R ′ is a hydrogen atom, storage stability is somewhat difficult, and when the carbon number is 18 or more, the effect of accelerating the curing reaction is slightly reduced.

The compound having a silyl ester group used in the present invention is not particularly limited as long as the silyl ester group is a compound represented by the above formula (4). , In any of the side chains,
Also, one or two or more may be included. When two or more silyl ester groups represented by the formula (4) are contained in the compound, only one kind may be contained,
Each may be different. The main chain of such a compound having a silyl ester group mainly comprises Si—O bonds.
The main chain may be used alone or in combination of two or more. Equation (4)
When the silyl ester group represented by is contained in the main chain, Si of the silyl ester group becomes Si in the main chain.

As the compound having such a silyl ester group, a compound represented by the following formula can be specifically mentioned.

Embedded image In the formulas (5) to (7), the number j of repeating units of the silyl ester group is an integer of 1 or more.

The method for producing the compound having a silyl ester group includes, for example, polyhydrogensiloxane having an Si—H group such as poly (methylhydrogen) siloxane; and linear saturated fatty acid such as formic acid and stearic acid. An unsaturated fatty acid such as caproleic acid, an aromatic carboxylic acid such as benzoic acid, and a carboxylic acid such as an alicyclic carboxylic acid such as naphthoic acid, or a copolymer of the above-described polyhydrogensiloxane and alkene, The above-mentioned carboxylic acids can be synthesized by dehydration-condensation using a simple substance of a transition metal of Group VIII such as Pt or Ru or a chloride of these metals as a catalyst. In the composition of the present invention, the content of the compound having a silyl ester group is as follows:
0.05 to 1 with respect to 100 parts by weight of the epoxy resin.
0 parts by weight is preferred. This is because the curing time is shortened without impairing the storage stability when the content is in the above range. In particular, it is preferably 0.1 to 8.0 parts by weight.

The composition of the present invention may contain calcium carbonate as long as the object of the present invention is not impaired. In particular, by containing the surface-treated calcium carbonate, the viscosity can be adjusted, and good initial thixotropy and storage stability can be obtained. As such calcium carbonate, conventionally known surface-treated calcium carbonate surface-treated with a fatty acid, a resin acid, or a fatty acid ester can be used. Specifically, as calcium carbonate surface-treated with a fatty acid, as Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), white in 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), and as calcium carbonate surface-treated with a fatty acid ester And Sealets 200 (manufactured by Maruo Calcium Co., Ltd.) are preferably used.

In the case of a one-pack type room temperature curable resin composition using surface-treated calcium carbonate as calcium carbonate, when a compound represented by the following formula (8) or (9) is used as ketimine, the thixotropic property is particularly improved. Excellent storage stability.

Embedded image R ⁹ : an organic group having at least one of O, S, N and an aromatic ring

Embedded image R ⁴ : organic group (including groups having O, S, and N)

Since the surface-treated calcium carbonate has a low surface polarity, if ketimine having the same low polarity is used, wetting occurs and the thixotropy is reduced. In order to prevent this wetting, it is preferable to use ketimine having a relatively high polarity. In the ketimine represented by the formula (9), the substituents near the imine moiety are a methyl group and an isopropyl group, which are small to lower the polarity of the highly polar imine moiety. Therefore, good thixotropy and storage stability can be maintained without being affected by the ketimine skeleton (R ⁴ ). On the other hand, in the ketimine represented by the formula (8), the polarity of the imine moiety is lowered due to the methyl group and the t-butyl group. Therefore, the ketimine skeleton (R ⁹ ) must be highly polar. Such ketimines having relatively high polarity include Jeffamine EDR manufactured by San Techno Chemical Co., Ltd.
148, diamines having a xylylene skeleton represented by MXDA manufactured by Mitsubishi Gas Chemical Company, methyl isopropyl ketone, methyl t
-Ketimine synthesized from -butyl ketone, diamines having a norbornane skeleton represented by NBDA manufactured by Mitsui Toatsu Chemicals, diamines having a cyclohexane skeleton represented by 1,3-BAC manufactured by Mitsubishi Gas Chemical Company, and methyl isopropyl ketone And ketimines synthesized from methyl t-butyl ketone.

The addition amount of calcium carbonate is preferably 30 to 300 parts by weight based on 100 parts by weight of the epoxy resin.
80 to 200 parts by weight are more preferred. If the amount is less than 30 parts by weight, appropriate initial thixotropy and workability cannot be obtained. If the amount is more than 300 parts by weight, viscosity increases and workability deteriorates.

The composition of the present invention may further comprise a filler, a plasticizer, a thixotropy-imparting agent, a pigment, a dye, an antioxidant, an antioxidant, in addition to the above-mentioned compounds, as long as the object of the present invention is not impaired. , An antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, a solvent, a curing agent, and the like.

The filler which can be used in the present invention includes various forms of organic or inorganic fillers, such as fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; Zinc, titanium oxide,
Barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; limestone clay, kaolin clay, calcined clay; or carbon black, or a fatty acid, resin acid, or fatty acid ester-treated product thereof. The amount of the filler is preferably from 10% by weight, based on the properties of the cured product obtained after curing the composition of the present invention.
The amount is preferably from 30 to 300 parts by weight, more preferably from 80 to 200 parts by weight, based on 0 parts by weight.

The plasticizer which can be used in the present invention includes dioctyl phthalate (DOP), dibutyl phthalate
(DBP); dioctyl adipate, isodecyl succinate;
Diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like are used. These plasticizers may be used alone or in combination of two or more. The compounding amount is 100 parts by weight based on 100 parts by weight of the epoxy resin, from the viewpoint of physical properties and workability of the cured product.
It is preferably at most 50 parts by weight, more preferably at most 50 parts by weight.

The thixotropic agent which can be used in the present invention includes Aerosil (Nippon Aerosil Co., Ltd.)
) And Disparon (manufactured by Kusumoto Kasei Co., Ltd.). Examples of the antistatic agent include quaternary ammonium salts and hydrophilic compounds such as polyglycol and ethylene oxide derivatives.

The pigments that can be used in the present invention include inorganic pigments and organic pigments. Examples of the inorganic pigments include titanium dioxide, zinc oxide, ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, and the like. Hydrochloride, sulfate and the like can be mentioned. Examples of the organic pigment that can be used in the present invention include an azo pigment and a copper phthalocyanine pigment.

Examples of the antioxidants which can be used in the present invention include compounds such as hindered phenols. Antioxidants that can be used in the present invention include:
Butylhydroxytoluene (BHT), butylhydroxyanisole (BHA) and the like can be mentioned. Examples of the flame retardant which can be used in the present invention include chloroalkyl phosphate, dimethyl methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide polyether, brominated polyether and the like. Examples of the adhesion imparting agent that can be used in the present invention include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like. The composition of the present invention contains the aforementioned ketimine group-containing compound as a latent curing agent, but may contain other curing agents as long as the object of the present invention is not impaired.
Aldimine compounds and oxazolidine ring-containing compounds obtained by reacting an aldehyde with an amine can be exemplified.

The method for producing the composition of the present invention is not particularly limited. Preferably, the above-mentioned components are sufficiently kneaded under reduced pressure, particularly under a reduced-pressure nitrogen atmosphere, using a stirrer such as a mixing mixer. To make an epoxy resin composition.

The one-pack type epoxy resin composition of the present invention, having the above-described constitution, has a high curing rate when taken out of a container and has excellent storage stability. Therefore, the composition of the present invention can be suitably used as an adhesive, paint, and sealing agent for concrete, wood, metal, and the like.

[0037]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. <Synthesis of ketimine compound> 100 g of a diamine having a norbornane skeleton (NBDA; manufactured by Mitsui Toatsu Chemical Co., Ltd.), 200 g of methyl isopropyl ketone, and 3.6 equivalents thereof,
And 200 g of toluene were placed in a flask, and the reaction was continued for 20 hours while removing generated water by azeotropic distillation to obtain ketimine compound A.

Embedded image

(Examples 1 and 2, Comparative Examples 1 and 2)
Were mixed at the compounding ratio described in Example 1 to obtain the resin compositions described in Examples 1 and 2 and Comparative Examples 1 and 2, and their evaluation was performed. The evaluation results are shown in Table 1 below.

[0039] The units of the compounds in the table are parts by weight.

1) Tack free time (curability): 20
Time under which the polyethylene film does not adhere to the surface of the resin composition under conditions of 55 ° C. and 55% humidity 2) Increase in viscosity (storage stability); The value obtained by dividing the viscosity after storage by the viscosity at the time when one day has passed at 20 ° C. after the compounding.

<Each component in the table> Epoxy resin; YD128 (manufactured by Sumitomo Chemical Co., Ltd.) Alkoxysilyl group-containing compound A; MS51 (manufactured by Mitsubishi Chemical Corporation) Alkoxysilyl group-containing compound B; phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Ketimine group-containing compound B; EH235R (Asahi Denka)

[0042]

The one-pack type epoxy resin composition of the present invention comprises:
The composition has a high curing rate when taken out of the container, has excellent storage stability, and is well-balanced. Therefore, the one-pack type epoxy resin composition of the present invention can be effectively used as an adhesive, paint, or sealing material for concrete, wood, metal, and the like.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Naoya Adachi 2-1 Oiwake, Hiratsuka-shi, Kanagawa F-term in Hiratsuka Factory of Yokohama Rubber Co., Ltd. (Reference) 4J002 CD001 ER006 EW138 EX039 FD017 FD156 GH01 GJ01 GQ05 4J036 AA01 AA02 DC28 DD01 DD07 DD08 FA01 JA01 JA06 JA07

Claims (2)

[Claims] (A) a ketone having a substituent at the α-position;
A ketimine group-containing compound obtained by reacting a polyamine having at least two or more methylene amino groups in the molecule, (B) an epoxy resin having at least two epoxy groups in the molecule, (C) an intramolecular One-pack type epoxy resin composition comprising an alkoxysilyl group-containing compound having at least one alkoxysilyl group and no reactive substituent. 2. The one-pack type epoxy resin composition according to claim 1, wherein the ketone is a compound represented by the following formula (1), and the polyamine is a compound represented by the following formula (2). Embedded image R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group R ⁴ : organic group (including groups having O, S and N) n: integer of 2 or more