JP4847704B2 - Curable resin composition - Google Patents

Description

The present invention relates to a curable resin composition and a moisture curable adhesive composition containing the same as a component. More specifically, the present invention relates to a curable resin composition in which a specific curable resin is mixed with an amine complex of boron trifluoride as a curable catalyst.

  Conventionally, as a moisture curable resin, a curable resin having a silicon-containing characteristic group such as a hydrolyzable silyl group in the molecule, particularly an alcohol-eliminated alkoxysilyl group-terminated one, is often used. Alcohol detachable curable resins include methanol detachable curable resins having a trimethoxysilyl group or methyldimethoxysilyl group in the molecule, and ethanol having a triethoxysilyl group or methyldiethoxysilyl group in the molecule. A detachable curable resin is common.

  Of these two, it is preferable to use an environmentally friendly ethanol detachable curable resin. However, since the ethanol detachable curable resin has a drawback that the curing is extremely slow when a curing catalyst such as an organic tin compound, which is a general curing catalyst, is used, a methanol detachable curable resin has been used so far. I had to.

  In addition, there is a method of using a large amount of a curing catalyst such as an organic tin compound in order to accelerate curing when using an ethanol detachable curable resin, but the increase in the curing rate relative to the added amount is not sufficient, and to some extent When the amount exceeds the addition amount, almost no increase in the curing rate is observed. In addition, when a large amount of a curing catalyst such as an organic tin compound is used, there is a problem that the environmental load is very large.

  The present invention has been made in order to solve the above-mentioned problems, and its object is to use an ethanol detachable curable resin and a normal general curing catalyst. An object of the present invention is to provide a curable resin composition that exhibits a curing rate equal to or higher than that of a methanol detachable curable resin. Furthermore, it is providing the curable resin composition with little load with respect to an environment by not using curing catalysts, such as an organotin type catalyst.

In order to achieve the above object, the present inventors have conducted intensive research. As a result, when a specific curing catalyst is used, the curing is very difficult even when a curable resin having an ethanol elimination reactive silyl group is used. We found it fast and completed the present invention. The present invention is composed of the following first to third inventions.

That is, the first invention contains diethoxy alkylsilyl group in the molecule, and does not contain a bond containing a sulfur atom, and the number average molecular weight of 1,000 to 150,000 curable resin (A) , a curable resin composition comprising a compound or compounds is an amine complex of boron trifluoride, the curable resin (a) 100 parts by mass of per amine complex of boron trifluoride 0 It is a curable resin composition characterized by containing 0.001-10 mass parts .

The second invention is the curable resin composition of the first invention, wherein the main chain skeleton of the curable resin (A) is polyoxyalkylene .

According to a third aspect of the invention , the one or more compounds that are an amine complex of boron trifluoride are a boron trifluoride monoethylamine complex and / or a boron trifluoride piperidine complex . It is a curable resin composition of any invention.

The curable resin composition according to the present invention is a curable resin (A) having a specific structure having a diethoxyalkylsilyl group which is an ethanol elimination reactive silyl group in the molecule, and an amine complex of boron trifluoride. Since it is a curable resin composition containing one or more compounds at a specific ratio, it is very environmentally friendly and cures quickly.

  In the curable resin (A) having an ethanol detachable reactive silyl group, since the compound produced by the hydrolysis reaction at the time of curing is ethanol, the environmental load is much higher than that of the methanol detachable curable resin. small.

  One or more compounds (B) selected from Lewis acids and their derivatives are prominent as curing catalysts for heat-curable epoxy resins, but synergistically cure with ethanol-eliminated reactive silyl groups. Increasing effectively is a finding found by the present inventor and is not known. The reason why the curability is synergistically enhanced is, for example, when boron trifluoride piperidine complex is exemplified as a Lewis acid derivative, and boron trifluoride piperidine complex interacts with the above ethanol-elimination-type reactive silyl group. By doing so, it is speculated that the elimination ability of the ethoxy group in the ethanol elimination type reactive silyl group is enhanced, and as a result, the coupling reaction between the silyl groups is promoted.

1. About curable resin (A) The curable resin (A) which is one component of the composition of the present invention is a curable resin having a diethoxyalkylsilyl group which is an ethanol-elimination-type reactive silyl group in the molecule. is there. The ethanol-eliminated reactive silyl group is a hydrolyzable silyl group in which the compound that is eliminated when the silyl group undergoes a coupling reaction due to the effect of a catalyst or the like is ethanol. Specifically, is shown Ru group by the following general formula (1). Such an ethanol-elimination-type reactive silyl group-containing curable resin is a compound that is generated and volatilized upon curing, and is a commonly used methanol-elimination-type reactive silyl group-containing curable resin. In comparison, the environmental impact is overwhelmingly small.

X represents an ethoxy group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 1 .

The main chain skeleton of the curable resin (A) is not particularly limited, and may be appropriately selected according to required performance and use. Examples of the main chain skeleton include polyoxyalkylene, saturated hydrocarbon polymer, vinyl polymer (for example, (meth) acrylic acid ester monomer copolymer), polythiol, polyester, organopolysiloxane, and polycarbonate. is there. Of these, polyoxyalkylene, saturated hydrocarbon polymer and vinyl polymer are preferable, and polyoxyalkylene and vinyl polymer are more preferable. As the method of introducing ethanol detachable reactive silyl groups to these backbone skeleton, you can use the hydrosilylation reaction with hydrosilane compounds. Hereinafter, it illustrates the preparation method of these curable resin.

  Examples of the curable resin (A) whose main chain skeleton is a polyoxyalkylene polymer include curable resins described in JP-A Nos. 55-137129 and 5-59267. Specific examples of the polyoxyalkylene polymer as the main chain skeleton include copolymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, and polyoxytetramethylene. Among these, a polyoxypropylene copolymer is particularly preferable.

  Examples of the curable resin (A) whose main chain skeleton is a hydrocarbon-based polymer include curable resins as described in JP-A No. 64-22904. Examples of the hydrocarbon polymer as the main chain skeleton include polymers having 1 to 6 carbon monoolefins such as ethylene, propylene, 1-butene, isobutene and 1-hexene as main monomers, butadiene, isoprene and the like. Examples include homopolymers of diolefins, hydrogenated products of copolymers of these diolefins and the above monoolefins, and the like. Among these hydrocarbon polymers, polymers with isobutene as the main monomer and hydrogenated products of butadiene polymers are easy to introduce functional groups at the terminals and adjust the molecular weight. Can be increased, which is preferable.

  Examples of the curable resin (A) whose main chain skeleton is a vinyl polymer include a polymer of a compound having at least one polymerizable alkenyl group in the molecule. For the reaction of polymerizing a compound having at least one polymerizable alkenyl group in the molecule to form the main chain skeleton of the vinyl polymer, conventionally known reactions and methods are used. Among these vinyl polymers, a copolymer of (meth) acrylic acid ester monomers is particularly preferable. Furthermore, you may carry out in presence of curable resin (A) and / or another curable compound as described in this invention.

Further, the curable resin (A) suitably used in the present invention includes a curable resin containing a polar element portion in the molecule. Here, the polar component parts, a urethane bond, urea bond, location換尿containing bond, A bromide binding, human Dorokishiru group, primary amino group, secondary amino group and a tertiary oxygen atom or an amino group , refers to binding or functional group containing ChissoHara child, it does not include binding containing a sulfur atom. When the polar element part is contained in the molecule of the curable resin (A), curing is further promoted, which is preferable.

Further, among these polar component parts, a urethane bond, urea bond, location換尿containing bond, A bromide coupling, primary amino groups, nitrogen-containing polar moieties such as secondary amino groups and tertiary amino group It is preferable to have a material because curing is further accelerated. The reason why the curing is further promoted is that the polar element portion present in the molecule of the curable resin becomes a domain having good molecular compatibility with the amine complex of boron trifluoride, and the amine of boron trifluoride in the present invention By further improving the effect of the complex interacting with the hydrolyzable silyl group in the above silicon-containing characteristic group, the ability to desorb the hydrolyzable group in the hydrolyzable silyl group is further increased. This is presumably because the coupling reaction between groups is further promoted.

  Examples of a method for producing a curable resin in which a polar element portion is contained in the molecule include a method described in Japanese Patent No. 3030020.

  The molecular weight of the curable resin (A) is not particularly limited, but the number average molecular weight is preferably 500 to 150,000, more preferably 1,000 to 60,000, and particularly preferably 2,000 to 20,000.

2. About one or more compounds which are amine complexes of boron trifluoride One or more compounds which are amine complexes of boron trifluoride which is one component of the composition of the present invention is a curing catalyst for the curable resin (A). The curable resin (A) is cured in a very short time.

Among one or more compounds selected from the above Lewis acids and derivatives thereof , Lewis acids include titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, antimony chloride, etc. Metal halides such as boron trifluoride, boron trichloride, boron tribromide, etc., metal triflate compounds such as trimethylsilyl trifluoromethanesulfonate, scandium triflate, yttrium triflate, zinc triflate, etc. . The effect on the curable resin (A) is considered to be influenced by the acid strength of the Lewis acid.

  Examples of Lewis acid derivatives include complexes of the above Lewis acids and Lewis bases, such as amine complexes, alcohol complexes, ether complexes of the above Lewis acids, thiol complexes, sulfide complexes, carboxylic acid complexes, water complexes, and the like. .

Amine compounds used for the amine complex include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2,2,6,6-tetra Methylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N-methyl-3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,2-diaminopropane, 1 , 3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa Spyro[ .5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenyl ether, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, tolidine base, m-toluylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, di-o-tolylguanidine, 1, 1,3,3-tetramethylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether, Jeffamine manufactured by Sun Techno Chemical Co., Ltd. Multiple primary amino A compound having: piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine, 2-aminomethylpiperidine, 4-amino Methylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'-diethylthiourea, N-methyl-1,3 A compound having a plurality of secondary amino groups such as propanediamine, methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethylaminopropylamine, 1- (2- Aminoethyl) piperazine, N-aminopropylpiperazine, 3- Aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamineethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, compounds of the formula _{H 2 n (C 2 H 4} NH) n H (n ≒ 5) ( trade name: Porieito, manufactured by Tosoh Corporation), N- alkyl morpholine, 1,8-diazabicyclo [5.4.0] Undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5, 1,4-diazabicyclo [2.2 .2] Octane, pyridine, N-alkylpiperidine, 1,5,7-triazabicyclo [4.4. In addition to bicyclic tertiary amine compounds such as deca-5-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, γ-aminopropyltri Ethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ- Aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -11-aminoundec Examples thereof include aminosilane compounds such as rutriethoxysilane.

  Examples of alcohols used in the alcohol complex include primary alcohols such as methanol, ethanol, n-propanol and n-butanol, and secondary alcohols such as isopropanol and 2-butanol. Examples of ethers used in the ether complex include dimethyl ether, diethyl ether, and di-n-butyl ether.

  Among the above Lewis acids, titanium chloride (IV), tin chloride (IV), zirconium chloride (IV), aluminum chloride (III), scandium triflate, yttrium triflate, trimethylsilyl trifluoromethanesulfonate, boron trichloride, trifluoride Boron is preferred. Of these, zirconium (IV) chloride, trimethylsilyl trifluoromethanesulfonate, and boron halide are preferable, and boron trifluoride is particularly preferable from the viewpoint of catalytic activity and availability. Further, as the Lewis acid complex, a boron halide complex is preferable, and among them, a boron trifluoride complex is particularly preferable in terms of easy handling.

  Of the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferred. As the Lewis acid and derivatives thereof, commercially available products containing the above compounds as components can be used. Examples of commercially available products include Air Products Japan, trade names: Anchors 1040, 1115, 1170, 1222, BAK1171, and the like. It is done.

Adding and mixing method for the curable resin (A) one or more compounds is an amine complex of boron trifluoride is not particularly limited, for example, may be added at room temperature, added with heating under However, it is preferable to add and mix through a heating step because dispersibility increases.

One or more compounds that are the boron trifluoride amine complex may be used alone or in combination of two or more. The mixing ratio of the amine complex and one or more compounds of the boron trifluoride is above Symbol curable resin (A) 0.001 to 10 parts by weight per 100 parts by weight, particularly preferably 0.01 ~ 5 parts by weight.

The curable resin composition of the present invention contains the curable resin (A) and an amine complex of boron trifluoride as essential components. In addition to these components, other curable catalyst, silane A coupling agent, a filler, various additives, etc. can be mix | blended according to the performance requested | required.

  As the curing catalyst that can be blended in the curable resin composition according to the present invention, a known catalyst compound can be used within a range that does not impair the effects of the present invention. Specific examples include organic tin compounds, organic bismuth compounds, organic metal compounds such as organic titanium compounds, basic compounds such as amine compounds, and acidic compounds such as phosphoric acid compounds.

  A known silane coupling agent can be used as the silane coupling agent that can be blended in the curable resin composition according to the present invention. Specific examples include silane coupling agents having an ethoxysilyl group in the molecule, such as aminosilane compounds, epoxy silane compounds, mercaptosilane compounds, (meth) acryl silane compounds, isocyanate silane compounds, and vinyl silane compounds.

  Although the said silane coupling agent may be used independently and may be used together 2 or more types, it is preferable to use an aminosilane compound especially. The blending ratio of the silane coupling agent is preferably 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of the curable resin (A).

  As the filler that can be blended in the curable resin composition according to the present invention, known fillers can be used. Specifically, calcium carbonate filler, various treated calcium carbonate filler, magnesium carbonate filler. Agents, organic polymer fillers, clay fillers, talc fillers, silica fillers, fumed silica fillers, various balloon fillers such as glass balloons and plastic balloons, aluminum hydroxide, hydroxylation Examples thereof include metal hydroxide fillers such as magnesium, fibrillated fiber fillers, and the like.

  Examples of the silica-based filler include hydrophilic silica-based powders, hydrophobic silica-based powders, and fused silica glass-based powders. Among these, hydrophobic silica-based powders are particularly preferable. The said filler may be used independently and may be used together 2 or more types. The filler preferably has a particle size of 10 nm to 500 μm, preferably 100 nm to 200 μm, particularly preferably 1.0 to 100 μm. Furthermore, the blending ratio of the filler is preferably 1 to 500 parts by weight per 100 parts by weight of the curable resin (A), preferably 1 to 300 parts by weight, particularly preferably 1 to 1 part by weight. 200 parts by weight.

  The various additives that can be blended in the curable resin composition according to the present invention include a tackifier, a thixotropic agent, a dehydrating agent, a diluent, a plasticizer within a range not impairing the effects of the present invention. Well-known raw materials such as agents, flame retardants, oligomers, anti-aging agents, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents, and tung oil, but are not limited thereto. .

  The curable resin composition of the present invention can be used, for example, for adhesives, sealants, paints, coating agents, sealants (for example, repairing cracks in concrete) used for electrical and electronic products, building materials, households, and various constructions. Can be effectively used as a sealing agent for covering cracks so as not to leak the injection agent), a casting agent, a coating agent, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples.

(Synthesis of curable resin (A))
(Synthesis Example 1)
To the reaction vessel, 220.4 g of 3-aminopropyltriethoxysilane was added dropwise over 1 hour while stirring at 80 ° C. under a nitrogen atmosphere, and further reacted at 80 ° C. for 10 hours. By reacting at 50 ° C. for 7 days, a reaction product (SE-1) having a triethoxysilyl group and a secondary amino group in the molecule was obtained.

  In another reaction vessel, 900 g of PMLS 4012 (trade name: manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene diol, number average molecular weight 10,000), PR3007 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene diol) , 100 g of number average molecular weight 3,000) and 43.0 g of tolylene diisocyanate were added, followed by reaction at 90 ° C. for 8 hours while stirring and mixing in a nitrogen atmosphere, so An oxyalkylene resin (PB-1) was obtained. Thereafter, 121.6 g of the reaction product (SE-1) was added, and the mixture was reacted at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, thereby curable resin (SB) having a triethoxysilyl group in the molecule. -1) was obtained. The viscosity of the curable resin (SB-1) at 23 ° C. was 60,000 mPa · s (BH viscometer, No. 7 rotor, 10 rotations). Hereinafter, all viscosities were measured under the same conditions.

(Synthesis Example 2)
In a reaction vessel, 900 g of PMLS4012 (trade name: manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylenediol, number average molecular weight 10,000), PMLS3011 (trade name: manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene triol, number average molecular weight 10,000) ) After adding 100 g and 56.1 g of 3-isocyanatopropyltriethoxysilane, further add Neostan U-600 (trade name: manufactured by Nitto Kasei Co., Ltd., bismuth compound) to 100 ppm and stir in a nitrogen atmosphere. A curable resin (SB-2) having a triethoxysilyl group in the molecule was obtained by reacting at 90 ° C. for 4 hours while mixing. The viscosity of the curable resin (SB-2) at 23 ° C. was 10,000 mPa · s.

(Synthesis Example 3)
In a reaction vessel, 185.1 g of N-β (aminoethyl) -γ-aminopropyltriethoxysilane and 70.3 g of N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane were stirred at 80 ° C. in a nitrogen atmosphere. Then, 172.2 g of methyl acrylate was added dropwise over 1 hour, and further reacted at 80 ° C. for 10 hours, followed by reaction at 50 ° C. for 7 days, so that a triethoxysilyl group and methyldiethoxysilyl in the molecule. And a reaction product (SE-3) having a secondary amino group.

  In another reaction vessel, 900 g of PMLS4012 (trade name: manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene diol, number average molecular weight 10,000), PR5007 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene diol) In addition, 100 g of a number average molecular weight of 5,000) and 52.3 g of isophorone diisocyanate are added, and dioctyltin dilaurate is further added to 50 ppm, and the mixture is reacted at 90 ° C. for 5 hours while stirring and mixing in a nitrogen atmosphere. Thus, a polyoxyalkylene resin (PB-3) having an isocyanate group in the molecule was obtained. Thereafter, 107.3 g of the reaction product (SE-3) was added and reacted at 90 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere, so that triethoxysilyl group and methyldiethoxysilyl group were formed in the molecule. A curable resin (SB-3) was obtained. The viscosity of the curable resin (SB-3) at 23 ° C. was 53,000 mPa · s.

(Synthesis Example 4)
In a reaction vessel, 100 g of the curable resin (SB-1) was added, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Separately, 40 g of methyl methacrylate, 30 g of lauryl methacrylate, 10 g of stearyl methacrylate, 3 g of 3-acryloxypropyltriethoxysilane, 8 g of 3-mercaptopropyltriethoxysilane, and 2,2′-azobis (2,4 -Dimethylvaleronitrile) A monomer mixture mixed with 0.7 g was added dropwise over 30 minutes to conduct a polymerization reaction. Furthermore, after reacting at 90 ° C. for 30 minutes, a mixed solution of 0.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after reacting at 90 ° C. for 30 minutes, a mixed solution of 0.1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after making it react at 90 degreeC for 30 minutes, unreacted various components were depressurizingly distilled and curable resin (SB-4) which has a triethoxysilyl group in a molecule | numerator was obtained. The viscosity of the curable resin (SB-4) at 23 ° C. was 160,000 mPa · s.

(Synthesis Example 5)
While stirring 234.4 g of N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane at 80 ° C. in a nitrogen atmosphere, 172.2 g of methyl acrylate was added dropwise to the reaction vessel over 1 hour. After reacting at 10 ° C. for 10 hours, the reaction product (SE-5) having a methyldiethoxysilyl group and a secondary amino group in the molecule was obtained by reacting at 50 ° C. for 7 days.

  In another reaction vessel, 900 g of PMLS4012 (trade name: manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene diol, number average molecular weight 10,000), PR5007 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene diol) Polyoxyalkylene having an isocyanate group in the molecule by adding 100 g of a number average molecular weight of 5,000) and 41.0 g of tolylene diisocyanate and reacting at 90 ° C. for 10 hours while stirring and mixing in a nitrogen atmosphere. Resin (PB-5) was obtained. Thereafter, 92.2 g of the reaction product (SE-5) was added, and the mixture was allowed to react at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, whereby a curable resin having a methyldiethoxysilyl group in the molecule ( SB-5) was obtained. The viscosity of the curable resin (SB-5) at 23 ° C. was 55,000 mPa · s.

(Preparation of catalyst solution)
Each compound was mixed in the ratio (mass part) shown in Table 1, and catalyst solution (CS-1)-(CS-5) was prepared.

( Reference Example 1)
In a sealed container, 100 g of the curable resin (SB-1) and 4.2 g of the catalyst solution (CS-1) were added and kneaded under reduced pressure to obtain a curable resin composition.

( Reference Example 2)
In a sealed container, 100 g of the curable resin (SB-1) and 7.2 g of the catalyst solution (CS-2) were added and kneaded under reduced pressure to obtain a curable resin composition.

( Reference Example 3)
In a sealed container, 100 g of the curable resin (SB-2) and 4.2 g of the catalyst solution (CS-1) were added and kneaded under reduced pressure to obtain a curable resin composition.

Example 4
In a sealed container, 100 g of the curable resin (SB-3) and 4.2 g of the catalyst solution (CS-1) were added and kneaded under reduced pressure to obtain a curable resin composition.

( Reference Example 5)
In a sealed container, 100 g of the curable resin (SB-4) and 4.2 g of the catalyst solution (CS-1) were added and kneaded under reduced pressure to obtain a curable resin composition.

(Example 6)
In a sealed container, 100 g of the curable resin (SB-5) and 5.0 g of the catalyst solution (CS-4) were added and kneaded under reduced pressure to obtain a curable resin composition.

( Reference Comparative Example 1)
In a reaction vessel, 100 g of the curable resin (SB-1) and 4.2 g of the catalyst solution (CS-3) were added and kneaded to obtain a curable resin composition.

( Reference Comparative Example 2)
In a reaction vessel, 100 g of the curable resin (SB-2) and 4.2 g of the catalyst solution (CS-3) were added and kneaded to obtain a curable resin composition.

(Comparative Example 3)
In a reaction vessel, 100 g of the curable resin (SB-3) and 4.2 g of the catalyst solution (CS-3) were added and kneaded to obtain a curable resin composition.

( Reference Comparative Example 4)
In a reaction vessel, 100 g of the curable resin (SB-4) and 4.2 g of the catalyst solution (CS-3) were added and kneaded to obtain a curable resin composition.

(Comparative Example 5)
In a reaction container, 100 g of the curable resin (SB-5) and 5.0 g of the catalyst solution (CS-5) were put and kneaded to obtain a curable resin composition.

(Reference Example 1)
A curable resin (RB-1) was obtained in the same manner as in Synthesis Example 1 except that 3-aminopropyltrimethoxysilane was used instead of 3-aminopropyltriethoxysilane. In a reaction vessel, 100 g of the curable resin (RB-1), 4 g of toluene, and 1.0 g of 918 was added and kneaded to obtain a curable resin composition.

(Measure skinning time)
The curable resin compositions obtained in the above Examples, Comparative Examples, Reference Examples, Reference Comparative Examples and Reference Example 1 were each allowed to stand at 50 ° C. for 7 days, and then the skinning time was measured. Each skinning time is shown in Table 2. The skinning time was determined as the time until the cured film stretched on the surface by finger touch was not transferred to the finger after leaving the curable resin composition in an atmosphere of 23 ° C. and 50% relative humidity. The following skinning time was also obtained by the same method. In the table, for example, “2′30” ”indicates that the skinning time was 2 minutes and 30 seconds.

  From the results shown in Table 2, the curable resin composition of the present invention is not only environmentally friendly because it uses an ethanol detachable curable resin, but also compensates for the disadvantage of slow curing, and has a conventional methanol detachable curable property. It turns out that it has curability more than resin.

  The curable resin composition according to the present invention can be suitably used for applications such as adhesives, sealants, paints, coating agents, sealants, casting agents, coating agents, and the like, and is also environmentally friendly. Despite the use of an ethanol detachable curable resin, a curing rate and adhesiveness suitable for practical use can be achieved, which is very useful industrially.

Claims (3)

Containing diethoxy alkylsilyl group in the molecule, and does not contain a bond containing a sulfur atom, and the number average molecular weight of 1,000 to 150,000 curable resin (A), the
A curable resin composition comprising at least one compound which is an amine complex of boron trifluoride ,
A curable resin composition containing 0.001 to 10 parts by mass of an amine complex of boron trifluoride per 100 parts by mass of the curable resin (A). The curable resin composition according to claim 1, wherein the main chain skeleton of the curable resin (A) is polyoxyalkylene. One or more compounds is an amine complex of boron trifluoride, curability of claim 1 or 2, characterized in that a boron trifluoride monoethylamine complex and / or boron trifluoride piperidine complex Resin composition.