JP4500556B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition containing an epoxy silica hybrid having excellent heat resistance.

In recent years, epoxy resin cured products have been required to have high performance depending on the application. For example, in the field of electronic parts such as printed circuit boards and semiconductor sealants, and in the aircraft field, heat resistance has been improved. Is desired.
As an epoxy resin composition having excellent heat resistance, an epoxy-silica hybrid has attracted attention. For example, Patent Document 1 discloses an epoxy resin composition containing an alkoxy group-containing silane-modified epoxy resin obtained by dealcoholizing a bisphenol-type epoxy resin having a hydroxyl group and a hydrolyzable alkoxysilane, and a curing agent. Are listed.

  In addition, the present inventor reacted a ketone with a primary amino group-containing alkoxysilyl compound containing a primary amino group and an alkoxysilyl group as a curable resin composition using an epoxy silica hybrid having better heat resistance. A two-component curable resin composition composed of a first liquid containing the obtained ketimine oligomer and a second liquid containing an epoxy group-containing compound was proposed (see Non-Patent Document 1).

JP 2001-59013 A Hiroyuki Okuhira et al. “Novel Moisture Curvable Epoxy Resins and Epoxy / Silica Hybrids Using Laten Hardeners”, Processeds of the 25th Annual Meeting of The Adhesion. and The Second World Congress on Adhesion and Related Phenomena (WCARP-II), February 10, 2002, p. 48-50

However, in the curable resin composition described in Non-Patent Document 1, the heat resistance determined from the change in the storage elastic modulus is sufficiently good from the viewpoint that the glass transition point (Tg) has disappeared. However, it was necessary to further improve the rate of change in storage modulus (retention rate).
Therefore, the present invention is a curable resin composition using an epoxy silica hybrid, which is superior in heat resistance to a conventional composition, and particularly has no change in storage elastic modulus from low temperature to high temperature. When using as a liquid type, it is an object to provide a curable resin composition having excellent storage stability.

As a result of diligent research on the curable resin composition described in Non-Patent Document 1 in order to solve the above problems, the inventor has obtained a ketimine oligomer and the like described in Non-Patent Document 1 and an epoxy group (oxirane). It has been found that a composition containing a specific silane compound having a ring) is excellent in heat resistance, and in particular, there is no change in storage elastic modulus from low temperature to high temperature.
Furthermore, this inventor discovered that the said composition is excellent in storage stability, when using as a 1 liquid type.
The present inventor has completed the present invention based on these findings. That is, this invention provides the curable resin composition shown to following (1) or ( 2 ), and the cured article shown to following ( 3 ).

(1) Silane compound (A) in which an epoxy group is bonded to a silicon atom via an organic group that may contain a nitrogen atom or an oxygen atom, and an organic group in which the ketimine group may contain a nitrogen atom or an oxygen atom A curable resin composition containing a silane compound (B) bonded to a silicon atom via
Ri at least partially condensate der of the silane compound (A) and / or the silane compound (B),
The condensate of the silane compound (A) is a condensate of 3-glycidoxypropyltrialkoxysilane, a condensate of 3-glycidoxypropylalkyldialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trialkoxysilane condensate or 2- (3,4-epoxycyclohexyl) ethylalkyldialkoxysilane condensate,
The content ratio of the silane compound (A) and the silane compound (B) is such that the epoxy group of the silane compound (A) can generate an active hydrogen of an amino group that can be generated from the ketimine group of the silane compound (B). The curable resin composition (the first aspect) has a ratio of 0.5 to 1.5 times equivalent .

( 2 ) The curable resin composition according to the above (1 ), wherein the condensate of the silane compound (B) is a condensate of a ketimine group-containing alkoxysilane.

( 3 ) A cured article obtained by applying the curable resin composition according to (1) or ( 2) ( second aspect).

  As described below, according to the present invention, the heat resistance is superior to that of the conventional composition, in particular, there is no change in the storage elastic modulus from low temperature to high temperature, and furthermore, storage stability when used as a one-component type. Therefore, it is useful as a printed circuit board, a semiconductor sealing agent, an aircraft resin, a paint, an adhesive, and a sealing agent.

The present invention is described in detail below.
In the curable resin composition according to the first aspect of the present invention (hereinafter sometimes simply referred to as “the curable resin composition of the present invention”), the epoxy group may contain a nitrogen atom or an oxygen atom. A silane compound (A) bonded to a silicon atom via an organic group, and a silane compound (B) bonded to a silicon atom via an organic group in which the ketimine group may contain a nitrogen atom or an oxygen atom. A curable resin composition, wherein at least a part of the silane compound (A) and / or the silane compound (B) is a condensate.
Next, the silane compound (A) and the silane compound (B) used in the curable resin composition of the present invention will be described in detail.

<Silane compound (A)>
The silane compound (A) used in the curable resin composition of the present invention is not particularly limited as long as the epoxy group is a silane compound bonded to a silicon atom through an organic group that may contain a nitrogen atom or an oxygen atom. Specific examples thereof include a compound represented by the following general formula (1) having a crosslinkable silyl group, a condensate thereof, and the like.

In the formula, m represents an integer of 1 to 3.
R ¹ represents an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group. When R ¹ is more than one, a plurality of R ¹ may each be the same or different.
R ² represents an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group. When R ² is more than one, a plurality of R ² may each be the same or different.
R ³ represents a nitrogen atom or an organic group which may contain an oxygen atom, a C 3-6 divalent acyclic aliphatic group which may contain an oxygen atom, a C 6-10 2 It is preferably a valent cycloaliphatic group.

Specific examples of the silane compound (A) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidyl. 3-glycidoxypropyltrialkoxysilane or 3-glycidoxypropylalkyldialkoxysilane such as Cidoxypropyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 2- (3,4-epoxycyclohexyl) such as -epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane ) Ethyl Triarco Shishiran or 2- (3,4-epoxycyclohexyl) ethyl alkyl dialkoxy silane; and condensates thereof; and the like, may be used in combination of two or more even with these alone.
Specific examples of these condensates include, for example, a chain, ladder, and cage siloxane skeleton represented by the following formulas (2) to (4), or a siloxane skeleton in which these are mixed, and an epoxy group is organic. The thing of the structure couple | bonded through group is mentioned. In the case of forming a chain siloxane skeleton represented by the following formula (2), the silane residue not involved in the siloxane bond and the bond with the epoxy group is an alkoxysilyl group and / or a silanol group. Moreover, it is preferable to produce these condensates using 3-glycidoxypropyltrialkoxysilane as a raw material because the raw materials are easily available and have high reactivity.

In said formula (2), R represents a hydrogen atom or a C1-C3 alkyl group each independently.
Moreover, as said silane compound (A), a commercial item can also be used, for example, A186, A187 (made by Nihon Unicar); KBE-402, KBE-403 (made by Shin-Etsu Chemical Co., Ltd.), for example. ); Etc. can be used.

In the present invention, the condensate of the silane compound (A) can be obtained, for example, by condensing the compound represented by the general formula (1) by hydrolysis. After forming the skeleton, the compound may be synthesized by introducing a compound having an epoxy group into the siloxane skeleton. Further, a silane compound having a functional group such as a vinyl group, an acrylic group, a methacryl group, or an isocyanate group in the molecule, or a tetraalkoxysilane such as tetramethoxysilane or tetraethoxysilane may be condensed together.
In addition, since alcohol produces | generates at the time of formation of the siloxane bond by hydrolysis and a condensation reaction, when manufacturing the condensate of a silane compound (A), it is preferable to remove this alcohol under reduced pressure.

<Silane compound (B)>
The silane compound (B) used in the curable resin composition of the present invention is particularly limited as long as the ketimine group is a silane compound bonded to a silicon atom through an organic group that may contain a nitrogen atom or an oxygen atom. Specific examples thereof include compounds represented by the following general formula (5) having a crosslinkable silyl group, condensates thereof, and the like.
Hereinafter, the silane compound (B) that is not a condensate as exemplified by the following general formula (5) is referred to as “ketimine group-containing silane compound”, and the condensate of this ketimine group-containing silane compound is referred to as “ketimine group-containing silane”. It will be called "condensate".

In the formula, n represents an integer of 1 to 3.
R ⁴ and R ⁵ are basically the same as R ¹ and R ² described in the general formula (1), respectively.
R ⁶ represents an organic group which may contain a nitrogen atom or an oxygen atom, and is preferably a C 2-8 divalent acyclic aliphatic group which may contain a nitrogen atom.

Specific examples of the ketimine group-containing silane compound include, for example, water from which an amino group-containing alkoxysilyl compound containing an alkoxysilyl group having 1 to 3 carbon atoms and an amino group and a ketone are eliminated. Preferable examples include ketimine group-containing alkoxysilanes obtained by reacting while removing by azeotropic distillation.
Since the ketimine reaction is an equilibrium reaction, in general, for example, a ketimine is obtained by heating and refluxing a ketone and a polyamine in the absence of a solvent or in the presence of a solvent such as benzene, toluene, xylene and the like. It can be obtained by reacting with azeotropic removal.
The amount of the amino group-containing alkoxysilyl compound and the ketone mixed during the synthesis of the ketimine group-containing silane compound (ketimine group-containing alkoxysilane) is The carbonyl group is preferably 0.9 to 2.0 times equivalent. If it exceeds 2.0 times equivalent, a large amount of unreacted ketone remains, which is economically disadvantageous, but there is no particular problem because it can be recovered and reused. In addition, when the amount is less than 0.9 times equivalent, an amino group remains, which is not preferable in the case of the one-component type, which may deteriorate storage stability. However, in the case of the two-component type, there is no particular problem.
As such a ketimine group-containing silane compound, a commercially available product can be used. Specifically, for example, KBE-9103 (manufactured by Shin-Etsu Chemical Co., Ltd.) or the like can be used.

  Here, the amino group-containing alkoxysilyl compound is not particularly limited as long as it is a compound having an alkoxysilyl group having 1 to 3 carbon atoms and an amino group in one molecule. Specific examples thereof include the following general formula ( Preferred examples include the compound represented by 6).

In the formula, p represents an integer of 1 to 3.
R ⁷ and R ⁸ are basically the same as R ¹ and R ² described in the general formula (1), respectively.
R ⁹ is basically the same as R ⁶ described in the general formula (5).

Specific examples of such amino group-containing alkoxysilyl compounds include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and compounds represented by the following formulas (7) to (12). Etc. are preferable.
Among these, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and each compound represented by the following formulas (7) and (8) are ketimine group-containing compounds obtained by reaction with ketones. The silane compound is preferable because it can form a three-dimensional silica network at the time of curing and can improve the retention rate of the storage elastic modulus.
Moreover, as said amino group containing alkoxysilyl compound, a commercial item can also be used, for example, A1110, A1100 (made by Nihon Unicar Co., Ltd.); KBM-903, KBE-903 (made by Shin-Etsu Chemical Co., Ltd.) ) Etc. can be used.

  On the other hand, specific examples of the ketone include acetone, methyl ethyl ketone (MEK), methyl butyl ketone, methyl isobutyl ketone (MIBK), methyl propyl ketone, methyl isopropyl ketone (MIPK), methyl-t-butyl ketone, and diethyl. Examples include ketone, ethyl propyl ketone, ethyl butyl ketone, dipropyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexanone, methylcyclohexyl ketone, propiophenone, and benzophenone.

As the ketimine group-containing silane condensate, specifically, for example, the condensate of ketimine group-containing alkoxysilane exemplified above is preferably mentioned.
In the present invention, such a ketimine group-containing silane condensate can be obtained, for example, by condensing the above-mentioned ketimine group-containing silane compound by hydrolysis, but is not particularly limited thereto, and after forming a siloxane skeleton Alternatively, the compound may be synthesized by introducing a compound having an amino group into the siloxane skeleton. Further, a silane compound having a functional group such as a vinyl group, an acrylic group, a methacryl group, or an isocyanate group in the molecule, or a tetraalkoxysilane such as tetramethoxysilane or tetraethoxysilane may be condensed together.

In particular, in the present invention, such a ketimine group-containing silane condensate can also be obtained by reacting the above-described amino group-containing alkoxysilyl compound with the above-described ketone using the desorbed water. Can do.
Specifically, as schematically illustrated in the following formula (13), the amino group of the amino group-containing alkoxysilyl compound and the carbonyl group of the ketone are dehydrated to form a ketimine group, and the reaction Hydrolysis and condensation of the alkoxysilyl group of the amino group-containing alkoxysilyl compound with water liberated in step 1 forms a siloxane bond to give a ketimine group-containing silane condensate. This is useful because a ketimine group-containing silane condensate can be obtained directly without isolating the ketimine group-containing silane compound.
The ketone used in this case has a small molecular weight, which makes it easy to remove excess ketone under reduced pressure in the production of the ketimine group-containing silane condensate, and the ketimine group in the ketimine group-containing silane condensate is hydrolyzed. This is preferable because the volume of the ketone generated by desorption at the time of decomposition becomes small and can be easily removed by heating, and even if the ketone remains in the cured product, the physical properties such as storage elastic modulus are small. Specifically, among the ketones exemplified above, acetone, MEK, MIPK, and diethyl ketone are preferable.

In this case, the mixing amount of the amino group-containing silane compound and the ketone is such that the carbonyl group of the ketone is 0 with respect to the amino group of the amino group-containing silane compound, as in the synthesis of the ketimine group-containing silane compound. It is preferably 9 to 2.0 times equivalent.
If it exceeds 2.0 times equivalent, a large amount of unreacted ketone remains, which is economically disadvantageous, but there is no particular problem because it can be recovered and reused. In addition, when the amount is less than 0.9 times equivalent, an amino group remains, which is not preferable in the case of the one-component type, which may deteriorate storage stability. However, in the case of the two-component type, there is no particular problem.
In addition, since alcohol produces | generates at the time of formation of the siloxane bond by hydrolysis and a condensation reaction, it is preferable to remove this alcohol and excess ketone under reduced pressure at the time of manufacture of a ketimine group containing silane condensate.
In addition, in the synthesis of the ketimine group-containing silane condensate using the desorbed water, hydrolysis and / or condensation of the alkoxysilyl group of the amino group-containing alkoxysilyl compound is advanced by adding water separately. You may keep it.

Therefore, specifically, as the ketimine group-containing silane condensate, for example, a condensate obtained by reacting the amino group-containing alkoxysilyl compound exemplified above with the ketone exemplified above is also preferably exemplified. be able to.
Of these, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and each of the compounds represented by the above formulas (7) and (8), respectively, acetone, MEK, MIPK and diethylketone The reason why the condensate obtained by the reaction is that the final silica network of the cured product obtained by curing the condensate is dense, and the reason is that the volume of ketone produced by the reaction is small To preferred.

As described above, the curable resin composition of the present invention contains the silane compound (A) and the silane compound (B), and the silane compound (A) and / or the silane compound (B). At least a part of is a condensate.
Here, “at least a part of the silane compound (A) and / or the silane compound (B) is a condensate” means “at least one of or both of the silane compound (A) and the silane compound (B)”. It is preferable that both of the silane compound (A) and the silane compound (B) are condensates. Specifically, the silane compound (A) is the above-mentioned 3- The combination which is a condensate of glycidoxypropyl trialkoxysilane and the silane compound (B) is a condensate of the above-mentioned ketimine group-containing alkoxysilane is preferably exemplified.
In the present invention, the content ratio of the silane compound (A) and the silane compound (B) is such that the epoxy group of the silane compound (A) is converted from the ketimine group (ketimine group of the silane compound (B)). It is preferably contained at a ratio of 0.5 to 1.5 times equivalent to the active hydrogen of the amino group that can be produced, and contained at a ratio of 0.8 to 1.2 times equivalent. More preferably. If the content ratio of the silane compound (A) and the silane compound (B) is within this range, the retention rate of the storage elastic modulus of the obtained curable resin composition of the present invention becomes very high, and the heat resistance is improved. It is preferable because it is extremely excellent.

  In addition to the silane compound (A) and the silane compound (B), the curable resin composition of the present invention is a filler, plasticizer, antioxidant, anti-aging agent, as long as the object of the present invention is not impaired. Various additives such as pigments, thixotropy imparting agents, adhesion imparting agents, flame retardants, dyes, antistatic agents, dispersants, and solvents can be contained.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products. The content of the filler is 300 parts by mass or less with respect to 100 parts by mass of the total of the silane compound (A) and the silane compound (B) (hereinafter simply referred to as “main agent”) in terms of physical properties of the cured product. Is preferred.

Among these, by containing calcium carbonate, particularly surface-treated calcium carbonate, the viscosity can be easily 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, a urethane compound or a fatty acid ester can be used. Specifically, for example, as calcium carbonate surface-treated with fatty acid, Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Whiten 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), carbonic acid surface-treated with fatty acid ester As calcium, Sealets 200 (manufactured by Maruo Calcium Co., Ltd.) is preferably used.

  Specific examples of the plasticizer include, for example, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; phosphorus Examples include tricresyl acid, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester. These may be used alone or in combination of two or more. The content of the plasticizer is preferably 50 parts by mass or less with respect to 100 parts by mass of the main agent from the viewpoint of workability.

Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the anti-aging agent include hindered phenol compounds.

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone And organic pigments such as pigments, isoindoline pigments, and carbon black.

Specific examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.) and disparon (manufactured by Enomoto Kasei Co., Ltd.).
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide polyether, and brominated polyether.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives; and the like.

The curable resin composition of the present invention may be used as a one-pack type that is cured by moisture in the air, and water is added or the silane compound (A), the silane compound (B), and water are mixed during use. It may be used as a two-component type. In addition, it is necessary to mix | blend the addition amount of the water at the time of using as a 2 liquid type so that the remaining alkoxy silyl group and ketimine group may hydrolyze.
Moreover, since the silane compound (B) has a ketimine group, the curable resin composition of the present invention exhibits excellent storage stability even when used as a one-component type.

  The curable resin composition of this invention can be used suitably for uses, such as a coating material, a rust preventive coating material, an adhesive agent, and a sealing agent. In particular, it can be suitably used for applications such as printed circuit boards, semiconductor encapsulants, and aircraft resins that require excellent heat resistance.

  The cured article according to the second aspect of the present invention is a cured article obtained by applying the curable resin composition according to the second aspect described above, and specific examples thereof include a printed circuit board and a semiconductor encapsulation. Preferable examples include a coating obtained by applying the curable resin composition to an adherend such as an agent and an aircraft resin.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
<Synthesis of Silane Compound (A)>
After dissolving 100 g of tetrahydrofuran (THF) in 236 g of 3-glycidoxypropyltrimethoxysilane (A187, manufactured by Nihon Unicar), 54 g of water was added, and a catalytic amount of dibutyltin dilaurate was further added at 80 ° C. Stir for 8 hours. Thereafter, THF and desorbed methanol were removed under reduced pressure to obtain 180 g of viscous epoxysilane condensate A (epoxy equivalent 180).

<Synthesis of Silane Compound (B)>
200 g (1.12 mol) of γ-aminopropyltrimethoxysilane (A1110, manufactured by Nihon Unicar) and 106 g (1.23 mol) of MIPK were mixed in a flask in the presence of a tin catalyst (dibutyltin dilaurate), and 40 ° C. And stirred for 24 hours. At this time, the amount of the carbonyl group of MIPK with respect to the amino group of γ-aminopropyltrimethoxysilane was 1.1 times equivalent. Thereafter, the desorbed methanol and excess MIPK were removed under reduced pressure to obtain 225 g of ketimine group-containing silane condensate B (ketimine equivalent 201).

Example 1
100 g of the epoxysilane condensate A obtained above, 56 g (1.0 eq) of the ketimine group-containing silane condensate B obtained above, and 10 g of water are mixed, cured at 25 ° C. for 2 weeks, and cured at room temperature. Got.
Furthermore, the room temperature cured product was heated from 60 ° C. to 200 ° C. over about 12 hours and cured to obtain a heat cured product.

(Comparative Example 1)
100 g of bisphenol A type epoxy resin (EP4100E, manufactured by Asahi Denka Kogyo Co., Ltd.), the ketimine group-containing silane condensate B53 g (1.0 eq) obtained above and 9.5 g of water are mixed and mixed at 25 ° C. with 2 Cured for a week to obtain a room temperature cured product.
Furthermore, the room temperature cured product was heated from 60 ° C. to 200 ° C. over about 12 hours and cured to obtain a heat cured product.

The heat-cured product obtained in Example 1 and Comparative Example 1 was heated from 30 ° C. to 250 ° C. at a rate of temperature increase of 2 ° C./min, and the storage elastic modulus (E ′) and loss tangent (tan δ) The temperature dependence of was investigated.
The results are shown in FIG. 1 and Table 1 below. From FIG. 1 and Table 1, the heat-cured product (Example 1) of the curable resin composition of the present invention is a heat-cured conventional curable resin composition obtained by simply mixing an epoxy resin and a ketimine group-containing silane condensate. Compared with the cured product (Comparative Example 1), it can be seen that the retention rate of the storage modulus is high and the loss tangent is small. That is, the curable resin composition of this invention is excellent in heat resistance compared with the conventional curable resin composition.

It is a graph which shows the temperature dependence of the storage elastic modulus (E ') and loss tangent (tan-delta) of the heat-cured material obtained in Example 1 and Comparative Example 1.

Claims (3)

A silane compound (A) in which an epoxy group is bonded to a silicon atom through an organic group which may contain a nitrogen atom or an oxygen atom; and an organic group in which the ketimine group may contain a nitrogen atom or an oxygen atom. A curable resin composition containing a silane compound (B) bonded to a silicon atom,
Ri at least partially condensate der of the silane compound (A) and / or the silane compound (B),
The condensate of the silane compound (A) is a condensate of 3-glycidoxypropyltrialkoxysilane, a condensate of 3-glycidoxypropylalkyldialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trialkoxysilane condensate or 2- (3,4-epoxycyclohexyl) ethylalkyldialkoxysilane condensate,
The content ratio of the silane compound (A) to the silane compound (B) is such that the epoxy group of the silane compound (A) can be generated from the active hydrogen of the amino group that can be generated from the ketimine group of the silane compound (B). A curable resin composition having a ratio of 0.5 to 1.5 times equivalent . The curable resin composition according to claim 1, wherein the condensate of the silane compound (B) is a condensate of a ketimine group-containing alkoxysilane. Cured articles obtained by coating a curable resin composition according to claim 1 or 2.

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