JP2010280880A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition being friendly to the environment and also having a necessary and sufficient curing rate withstanding to real use while assuring safety. <P>SOLUTION: In the curable resin composition containing a curable resin (A) having a group of formula (1): -X-SiR<SP>1</SP><SB>a</SB>(OR<SP>2</SP>)<SB>3-a</SB>in a molecule, a curable resin (B) having a group of formula (2): -W-CH<SB>2</SB>-SiR<SP>3</SP><SB>b</SB>(OR<SP>4</SP>)<SB>3-b</SB>in a molecule, a basic compound (C) and one or more non-tin curing catalysts (D) selected from a group consisting of a metal curing catalyst which does not contain a tin compound and boron trifluoride and/or its complex, the curable resin (A) and the curable resin (B) are mixed in 98/2 to 50/50 (mass ratio), and the basic compound (C) of 0.001-30 pts.mass and the non-tin curing catalyst (D) of 0.001-10 pts.mass are contained to the total 100 pts.mass of the curable resin (A) and the curable resin (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable resin composition containing a hydrolyzable silyl group, which can be cured at room temperature, and more specifically, can reduce the environmental load and ensure safety while ensuring safety. The present invention relates to a curable composition having a necessary and sufficient curing rate capable of withstanding use.

  The curable silicone-based resin whose main chain is an organic polymer and has a hydrolyzable silyl group that can be cross-linked in the molecule is crosslinked by the hydrolysis of the alkoxysilyl group, which is a cross-linkable silyl group, with moisture in the atmosphere. It is a so-called moisture curable polymer and is widely used as a base polymer for sealing materials, adhesives, paints, and the like (Patent Documents 1 to 4). When such moisture curable polymers are used in sealing materials, adhesives, paints, etc., compounds such as amine catalysts and organotin catalysts are blended to promote the curing of the moisture curable polymers (patents). Literature 5, 6). However, amine catalysts have problems such as bleed out, and organotin catalysts have safety problems, and alternative catalysts have been demanded. On the other hand, it has been proposed that halogen compounds such as boron halide compounds represented by boron trifluoride and the like and fluorosilane compounds can be used as curing catalysts for the moisture-curable polymer (Patent Documents 7 to 9).

Japanese Patent Laid-Open No. 52-073998 Japanese Patent No. 3030020 Japanese Patent No. 3343604 JP 2005-514504 Gazette Japanese Patent Laid-Open No. 08-283366 Japanese Patent No. 3062625 JP 2005-054174 A WO2006 / 051799 Publication WO2007 / 123167

In recent years, not only the global environment but also the usage environment of workers, the demand for the safety of chemical substances has become stronger due to the growing interest in the environment.
Some organotin compounds have become problematic in recent years, and the amount used is desired to be suppressed to 1000 ppm or less based on the composition. In particular, among organic tin compounds, those that contain a relatively toxic tributyltin derivative require special attention for its use.
Therefore, as a result of intensive research, the present inventors have a curable resin having a chemical structure near a specific crosslinkable silyl group as described in Patent Document 4 and a conventionally known crosslinkable silyl group. Surprisingly, it was found that when the curable resin was used in combination, the curing performance of the entire system was increased, and this combined system was filed earlier (Japanese Patent Application No. 2008-187669).

However, in the above invention, although a constant curing rate could be obtained, when considering practical application as a sealing material or adhesive mainly composed of a curable resin composition, a further faster curing rate is obtained. I was asked. Further, when only a curable resin having a chemical structure near a specific crosslinkable silyl group as described in Patent Document 4 is used as a resin component, there are problems in terms of storage stability and cost. .
That is, the problem to be solved by the present invention is to obtain a curable composition having a necessary and sufficient curing rate capable of withstanding actual use while ensuring safety while reducing environmental burden. .

The inventors of the present invention paid attention to the invention for which the above patent application was filed, further deepened the technique, and completed the present invention. The present invention is composed of the following first to twelfth inventions.
The first invention is a curable resin (A) having a hydrolyzable silyl group represented by the formula (1) in the molecule, and a cure having a hydrolyzable silyl group represented by the formula (2) in the molecule. One or more types of non-tin cured selected from the group consisting of a conductive resin (B), a basic compound (C), a non-tin metal-based curing catalyst (d1), boron trifluoride and / or a complex thereof (d2) A curable resin composition containing a catalyst (D), wherein the curable resin (A) and the curable resin (B) are (A) / (B) = 98/2 to 50/50 (mass ratio). The basic compound (C) is 0.001 to 30 parts by mass with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). The present invention relates to a curable resin composition containing 0.001 to 10 parts by mass of a catalyst (D).
-X-SiR ¹ _a (OR ² ) _3-a Formula (1)
(However, X is a hydrocarbon group having 2 or more carbon atoms, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a phenyl group, an alkyl group having 1 to 20 carbon atoms, and 2- ( (Butoxy) One or more groups selected from organic groups having 1 to 20 carbon atoms, such as an ethyl group, a represents 0, 1 or 2, respectively.
—W—CH ₂ —SiR ³ _b (OR ⁴ ) _3-b (2)
(W is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silyl group, and R ³ is a carbon atom having 1 to 20 carbon atoms. A hydrogen group, R ⁴ is one or more groups selected from a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms such as 2- (butoxy) ethyl group. , B represents 0, 1 or 2, respectively.
By using the non-tin curing catalyst (D) in combination with the curable resin (A) having a hydrolyzable silyl group, the necessary and sufficient curing rate capable of withstanding actual use. Can be obtained.

The second invention relates to the curable resin composition according to the first invention, characterized in that the main chain of the curable resin (A) is polyoxyalkylene and / or poly (meth) acrylate. It is.
The third invention relates to the curable resin composition according to the first or second invention, wherein the hydrolyzable silyl group of the curable resin (A) is a dialkoxysilyl group. is there.
Moreover, 4th invention is characterized by the curable resin (A) not containing a urethane bond or a urea bond in the molecule | numerator, The curable resin composition concerning any one of the 1st-3rd invention characterized by the above-mentioned. It is about things.
It is preferable that the curable resin (A) has such a structure because it is easier to balance the necessary and sufficient curing rate that can withstand actual use and the physical properties of the cured product.

The fifth invention relates to the curable resin composition according to any one of the first to fourth inventions, wherein the main chain of the curable resin (B) is polyoxyalkylene.
It is preferable that the curable resin (B) has the above-described structure from the viewpoints of easy availability and physical properties of the cured product.
According to a sixth invention, in any one of the first to fifth inventions, the basic compound (C) is an aminosilane compound (C1) having an amino group and a hydrolyzable silyl group in the molecule. It relates to the curable resin composition described. The basic compound (C) is preferably an aminosilane compound (C1) because the adhesiveness is improved.
The seventh invention relates to the curable resin composition according to any one of the first to sixth inventions, wherein the content of the organotin catalyst is 0 to less than 100 ppm.
If the organotin-based catalyst is in the above range, it is preferable because it is possible to reduce environmental burden and to ensure safety.

The eighth invention relates to a curable resin composition according to any one of the first to seventh inventions, characterized by not containing a halogen-containing compound.
If no halogen-containing compound is contained, it is preferable because it is possible to further reduce the environmental load and to ensure safety.
A ninth invention is characterized in that the non-tin curing catalyst (D) is one or more selected from the group consisting of a zirconium compound, a titanium compound, an aluminum compound, and a bismuth compound. The present invention relates to a curable resin composition described in the invention.
When the non-tin curing catalyst (D) is at least one selected from the group consisting of a zirconium compound, a titanium compound, an aluminum compound, and a bismuth compound, it is possible to reduce the environmental burden and to ensure safety. It is preferable in that a curing rate that can withstand use is easily obtained.

A tenth invention relates to a sealing material composition mainly comprising a curable resin composition according to any one of the first to ninth inventions as a curable component.
The eleventh invention relates to an adhesive composition mainly comprising the curable resin composition according to any one of the first to ninth inventions as a curable component.
The twelfth invention relates to a pressure-sensitive adhesive precursor composition mainly comprising a curable resin composition according to any one of the first to ninth inventions as a curable component.
The curable resin composition according to the present invention can be particularly suitably used as a sealing material composition, an adhesive composition, and a pressure-sensitive adhesive precursor composition.

  The present invention relates to a curable resin composition containing a hydrolyzable silyl group, which can be cured at room temperature, and more specifically, can reduce the environmental load and ensure safety while ensuring safety. The effect is that a curable composition having a necessary and sufficient curing rate that can withstand use can be obtained.

Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.
[About curable resin (A)]
The curable resin (A) in the present invention is a curable resin having a hydrolyzable silyl group represented by the following formula (1) in the molecule.
-X-SiR ¹ _a (OR ² ) _3-a Formula (1)
(However, X is a hydrocarbon group having 2 or more carbon atoms, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a phenyl group, an alkyl group having 1 to 20 carbon atoms, and 2- ( (Butoxy) One or more groups selected from organic groups having 1 to 20 carbon atoms, such as an ethyl group, a represents 0, 1 or 2, respectively.

In the hydrolyzable silyl group, a hydrocarbon group (X) having 2 or more carbon atoms is bonded to a silicon atom, and this is bonded to the main chain skeleton. In addition to the bond with the hydrocarbon group X, 1 to 3 alkoxyl groups (OR ² ) are bonded as hydrolyzable groups, and the remaining hydrogen bond is a hydrocarbon group (R ¹ ). 2 to 0 are bonded.
Here, R ¹ and R ² are each a hydrocarbon group having 1 to 20 carbon atoms. The alkoxyl group (OR ² ) is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group. The hydrocarbon group (R ¹ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a methyl group or an ethyl group.
In addition, the hydrolyzable silyl group of the curable resin (A) is preferably an alkyl dialkoxysilyl group (a = 1) when a cured product having a relatively low modulus and high elongation as represented by a sealing material is desired. It is preferable because desired performance is easily obtained. On the other hand, in particular, when a cured product having a relatively high modulus and fast curing as represented by an adhesive is desired, a trialkoxysilyl group (a = 0) is preferable because desired performance can be easily obtained.

  As the main chain skeleton of the curable resin (A), polyoxyalkylene, vinyl polymer (for example, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester, polycarbonate, polydimethyl Those generally used for silicone resins such as siloxane and modified silicone resins are adopted, but in particular, polyoxyalkylene and / or poly (meth) acrylic acid esters must be able to withstand practical use. A sufficient curing rate is obtained, which is preferable from the viewpoint of the film properties of the cured product. In the present application, acrylic acid and methacrylic acid may be collectively referred to as “(meth) acrylic acid”, and acrylate and methacrylate may be collectively referred to as “(meth) acrylate”.

  Many commercially available curable resins (A) are sold as silicone resins or modified silicone resins. For example, Kaneka Co., Ltd. Silyl series, MS polymer series, MA series, SA series, OR series, Epion series; Asahi Glass Co., Ltd. ES series, ESGX series; Degussa Japan silane modified polyalphaolefin; Examples include the XPR series manufactured by Gosei Co., Ltd., the ARUFON US series, and the Actflow series manufactured by Soken Chemical Co., Ltd.

Further, as the curable resin (A), a curable silicone resin containing a polar group such as a urethane bond or a urea bond in the molecule may be used. The curable resin (A) containing a polar group in the molecule may be synthesized by a conventionally known method. For example, a method of reacting an isocyanate group-terminated polymer with an amino group-containing alkoxysilane compound (or a mercapto group-containing alkoxysilane compound), a method of reacting an hydroxyl group-terminated organic polymer with an isocyanate group-containing alkoxysilane compound, etc. are known. . More specifically, it can be easily synthesized by the methods described in Japanese Patent No. 3030020, Japanese Patent No. 3343604, Japanese Patent Application Laid-Open No. 2005-054174, and the like. In the present invention, the active hydrogen in the urethane bond and / or urea bond that the curable silicone resin (A) has in the molecule may be substituted with an organic group. Therefore, in the present invention, allophanate bonds also belong to the category of urethane bonds, and burette bonds also belong to the category of urea bonds.
As the curable resin (A), when a cured product having a relatively low modulus and high elongation, such as a sealing material, is desired, the resin may not contain urethane bonds or urea bonds in the molecule. From the viewpoint of easy adjustment of the modulus.

[Curable resin (B)]
The curable resin (B) in the present invention is a curable resin having a hydrolyzable silyl group represented by the following formula (2) in the molecule.
—W—CH ₂ —SiR ³ _b (OR ⁴ ) _3-b (2)
(W is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silyl group, and R ³ is a carbon atom having 1 to 20 carbon atoms. A hydrogen group, R ⁴ is one or more groups selected from a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms such as 2- (butoxy) ethyl group. , B represents 0, 1 or 2, respectively.

The hydrolyzable silyl group is a group in which a linking group containing a hetero atom having an unshared electron pair is bonded to a silicon atom via a methylene group. Further, the hydrolyzable silyl group is bonded to the main chain skeleton through this bonding group. As the heteroatom, a nitrogen (N) atom, an oxygen (O) atom, or a sulfur (S) atom is preferable because it is versatile. In addition, as a linking group containing a hetero atom having an unshared electron pair, a urethane linking group, a thiourethane linking group, a urea linking group, a thiourea linking group, a substituted urea linking group, a substituted thiourea linking group, an amide linking group, Bonding groups or functional groups containing oxygen atoms, nitrogen atoms, sulfur atoms such as sulfide bond groups, hydroxyl groups, primary amino groups, secondary amino groups and tertiary amino groups are preferably used. In particular, among these linking groups, those having a nitrogen-containing polar group are preferred, and further, a urethane linking group (—NHCOO—), a urea linking group (—NHCONH—), a substituted urea linking group (—NHCONR—; R = organic Most preferably).
By mix | blending curable resin (B) with curable resin (A), the hardening performance of curable resin (A) is pulled up. That is, it is assumed that the curable resin (B) is a curable resin and also acts as a curing accelerator for the curable resin (A). By this action, a practical curing rate can be obtained using a non-tin curing catalyst (D) which is generally considered to have a low catalytic activity.

In addition to the bond with the methylene group, 1 to 3 alkoxyl groups (OR ⁴ ) are bonded as hydrolyzable groups, and the hydrocarbon group (R ³ ) is 2 to 2 as the remaining bonds. 0 units are connected.
Here, R ^3, R ⁴ is a 1-20C hydrocarbon group having a carbon. The alkoxyl group (OR ⁴ ) is preferably a methoxy group, an ethoxy group, or a propoxy group, and more preferably a methoxy group or an ethoxy group. The hydrocarbon group (R ³ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group.
Further, the hydrolyzable silyl group of the curable resin (B) is an alkyl dialkoxysilyl group (b = 1) or a trialkoxysilyl group (b = 0), the availability, the modulus of the cured product, etc. From the point of view, it is preferable.

In the present application, a chemical structure represented by the above formula (2) may be referred to as an “α-silane structure”. By selecting the α-silane structure, the moisture reactivity is much higher than that of the usual hydrolyzable silyl group, so that the curing rate is sufficient even if a tin-based catalyst is not used or a much smaller amount is used than usual. Can be obtained. Furthermore, as described above, the curable resin having an α-silane structure raises the curing performance of the curable resin having another hydrolyzable silyl group.
As the main chain skeleton of the curable resin (B), polyoxyalkylene, vinyl polymer (eg, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester, polycarbonate, polydimethyl Although those generally used for silicone resins such as siloxane and modified silicone resins are employed, polyoxyalkylene and / or poly (meth) acrylic acid esters can be easily obtained, It is preferable from the viewpoint of film properties. Furthermore, polyoxyalkylene is most preferable because of low viscosity and excellent workability.

In order to obtain the curable resin (B), synthesis may be performed by a conventionally known method. For example, a method of reacting an isocyanate polymer having an hydroxyl group in a molecule such as a polyether compound and / or an acrylic polyol compound with an isocyanate methylalkoxysilane compound is known. More specifically, it can be easily synthesized by the methods described in JP-T-2004-518801, JP-T-2004-536957, JP-T-2005-501146, and the like. The said curable resin (B) can be used individually or in combination of 2 or more types.
As a commercially available product of the curable resin (B), GENIOSIL STP-E10 manufactured by Wacker Chemie AG (molecular weight of about 10,000 converted from methoxy group equivalent, viscosity of about 10,000 mPa · s / 25 ° C. (catalog value)), GENIOSIL STP-E30 (molecular weight about 16,000 converted from methoxy group equivalent, viscosity about 30,000 mPa · s / 25 ° C. (catalog value)) and the like. In these structures, W in the general formula (2) is —O—CO—NH—, R ³ is CH ₃ , and R ⁴ is CH ₃ , and is represented by the following general formula (3).
—O—CO—NH—CH ₂ —SiCH ₃ (OCH ₃ ) ₂ Formula (3)

The main chain skeleton of the curable resin (A) and the curable resin (B) may be the same or different. However, it is preferable that the curable resin (A) and the curable resin (B) are compatible since the effects of the present invention are more easily obtained.
In order to improve the compatibility of the curable resin (A) and the curable resin (B), a conventionally known technique can be used. For example, a compound generally known as a compatibilizing agent can be added. Further, the main chain skeleton of the curable resin (A) and the curable resin (B) can be improved by selecting a combination having good compatibility. Specifically, the compatibility can be improved by using the main chain skeleton having a relatively close polarity. For example, if the same main chain skeleton is selected for both, the compatibility is very good. Even if they are not the same, it is also preferable to select skeletons having relatively similar structures such as polyolefin skeletons or polyether skeletons. Furthermore, it is known that a polyoxyalkylene skeleton and a poly (meth) acrylate skeleton having a specific structure also have good compatibility. Examples of combinations having good compatibility as described above are exemplified, but the present invention is not limited to these.

[About the basic compound (C)]
The basic compound (C) in the present invention affects the electronic state of the non-tin curing catalyst (D) and the hydrolyzable silyl group, and is not particularly limited as long as it is a basic compound. Even a salt with an acid can be used as long as it is basic. For example, primary to tertiary amine compounds or salts thereof, quaternary ammonium salts, organic acid metal salts, and the like can be suitably used. Further, it may be a reaction product of an amine compound and an epoxy compound.

Specific examples of the basic compound (C) include, for example, N-methyl-3,3′-iminobi (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,2-diaminopropane, 1,3-diamino. Propane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5. 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, -Toluylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, di-o-tolylguanidine, acetamidine, bis (aminopropyl) piperazine, N- (3 -Aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether, compounds having a plurality of primary amino groups such as Huntsman's Jeffamine (trade name); piperazine, cis-2,6 -Dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4 -Piperidyl) -propane, 4-aminopropylaniline, homopiperazine, , N′-diphenylthiourea, N, N′-diethylthiourea, N-methyl-1,3-propanediamine and other compounds having a plurality of secondary amino groups; methylaminopropylamine, ethylaminopropylamine, ethyl Aminoethylamine, laurylaminopropylamine, 2-hydroxyethylaminopropylamine, 1- (2-aminoethyl) piperazine, N-aminopropylpiperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamine ethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, formula: H ₂ N (C ₂ H ₄ NH) _n H (n Compound represented by ≒ 5) Compounds having a primary amino group and a secondary amino group such as products (trade name: Polyate, manufactured by Tosoh Corporation); quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; manufactured by Sankyo Air Products DABCO (registered trademark) series, DABCOBL series, 1,8-diazabicyclo [5.4.0] -7-undecene, etc., containing a plurality of nitrogen-containing linear or cyclic tertiary amines and quaternary ammonium salts, etc. Is mentioned.

Moreover, it is preferable from surfaces, such as sclerosis | hardenability, the physical property of hardened | cured material, and adhesive provision, that a basic compound (C) is an aminosilane compound (C1). The aminosilane compound (C1) in the present invention is a compound having one or more amino groups and a hydrolyzable silyl group in the molecule. The aminosilane compound exemplified by the following formula (4) or the following formula (4) ) And other silane compounds as exemplified by the silane compound represented by the following formula (5). The aminosilane compound is preferably an aminosilane compound in which two or more carbon atoms are bonded between the nitrogen atom of the amino group and the silicon atom of the crosslinkable silyl group.
R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _b (OR ⁹ ) _3-b (4)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms having a molecular weight of 500 or less, and R ⁷ is a molecular weight of 500 or less in which a hetero atom is not bonded to a carbon atom bonded to a silicon atom contained in a hydrolyzable silyl group. An organic group, R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁹ is a phenyl group, an alkyl group having 1 to 20 carbon atoms, and a carbon number 1 typified by 2- (butoxy) ethyl group. One or more groups selected from ˜20 organic groups, b represents 0, 1 or 2, respectively)
Si (R ¹⁰ ) (R ¹¹ ) (R ¹² ) (OR ¹³ ) (5)
(In the formula, R ¹⁰ , R ¹¹ and R ¹² are a phenyl group, an alkyl group having a molecular weight of 500 or less, a mercaptopropyl group, a ureidopropyl group, a phenoxy group, and an alkoxyl group having 1 to 20 carbon atoms, 2- Each represents one or more groups selected from organic groups having a molecular weight of 500 or less typified by (butoxy) ethoxy groups, R ¹³ represents a phenyl group, an alkyl group having 1 to 20 carbon atoms, and a 2- (butoxy) ethyl group. And one or more groups selected from organic groups having 1 to 20 carbon atoms represented by

Here, R ⁵ and R ⁶ in the above formula (4) are an organic group or a hydrogen atom, and the amino group may be any of primary, secondary, and tertiary amines, Primary or secondary amine.
R ⁷ represents an organic group in which a hetero atom is not bonded to a carbon atom bonded to a silicon atom contained in a hydrolyzable silyl group (for example, a hydrocarbon group having 2 or more carbon atoms). Here, as the hetero atom, a nitrogen (N) atom, an oxygen (O) atom, or a sulfur (S) atom is preferable because it is versatile.
In addition to the bond with the organic group R ⁷ , the silicon atom has 1 to 3 alkoxyl groups (OR ⁹ ) as hydrolyzable groups and 2 to 0 hydrocarbon groups (R ⁸ ) as the remaining bonds. It is what is united.

Here, R < ⁸ > is a C1-C20 alkyl group, respectively. The alkoxyl group (OR ⁹ ) is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group. The hydrocarbon group (R ⁸ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group.
The hydrolyzable silyl group of the aminosilane compound (C1) is an alkyl dialkoxysilyl group (c = 1) or a trialkoxysilyl group (c = 0). It is preferable from the point.

Specific examples of the aminosilane compound (C1) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2 -Aminoethyl) -3-propyltrimethoxysilane, N- (2-aminoethyl) -3-propylmethyldimethoxysilane, N- (2-aminoethyl) -3-propyltriethoxysilane, N- (6-amino) (Hexyl) aminomethyltriethoxysilane, N- (2-aminoethyl) -3-propylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, [ 2-Aminoethyl- (2'-aminoethyl)]-3-amino Primary amino group-containing aminosilane compounds such as propyltrimethoxysilane, MS3301 (trade name, manufactured by Chisso Corporation), MS3302 (trade name, manufactured by Chisso Corporation), X-40-2651 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) ) And other compounds obtained by condensing a silyl group of aminosilane alone or with other alkoxysilane compounds, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-butylaminopropyltrimethoxysilane, Secondary amino group-containing aminosilane compounds such as N-ethylaminoisobutyltrimethoxysilane and bis (trimethoxysilylpropyl) amine, and tertiary amino such as imidazolesilane compounds having an imidazole group and a hydrolyzable silyl group in the molecule. Amino acid having a group Emissions, but ketimine silane compound having a functional group which forms a primary amino group reacts with water or aldimine silane compounds and the like, but are not limited to.
What is necessary is just to select an aminosilane compound (C1) suitably, in order to obtain desired performance, and also these may use 1 type (s) or 2 or more types.

[Non-tin curing catalyst (D)]
The non-tin curing catalyst (D) in the present invention is one or more curing catalysts selected from the group consisting of a metal-based curing catalyst (d1) containing no tin compound, boron trifluoride and / or a complex thereof (d2). It is.

[About the metal-based curing catalyst (d1) containing no tin compound]
In the present invention, the metal-based curing catalyst (d1) containing no tin compound is a curable resin by subjecting a hydrolyzable silyl group contained in the curable resin (A) and the curable resin (B) to a condensation reaction. (A) and a catalyst compound for curing the curable resin (B), a compound mainly composed of a group 1 alkali metal metal element, a compound mainly composed of a group 2 alkaline earth metal element, Transition metal group metal elements (for example, Group 3 rare earth group metal elements, Group 4 titanium group metal elements, Group 5 vanadium group metal elements, Group 6 chromium group metal elements, Group 7) A compound mainly composed of a manganese group metal element, a group 8 iron group metal element, a group 9 metal element, a group 10 platinum group metal element, a group 11 copper group metal element), Compounds mainly composed of group 12 zinc group metal elements, group 13 Compounds mainly metalloid based metal elements include compounds mainly comprising nitrogen group metal element of Group 15 is.

  The metal-based curing catalyst (d1) has a structure such as alkoxide, carboxylate, chelate, etc., so that the activity as a catalyst is increased and the compatibility with the curable resin (A) and the curable resin (B) is improved. The catalytic ability is effectively expressed. In the metal-based curing catalyst (d1), one compound may have a structure such as alkoxide, carboxylate, chelate or the like, or a plurality of structures may be mixed. Further, for example, when alkoxide is taken as an example, a plurality of alkoxide structures (for example, a methoxide structure and a butoxide structure) may be mixed, and a structure such as a carboxylate or a chelate may be mixed. Good.

  Examples of the alkoxide structure include, but are not limited to, methoxide, ethoxyside, normal propoxide, isopropoxide, normal butoxide, s-butoxide, isobutoxide, t-butoxide, and the like. Examples of the carboxylate structure include, but are not limited to, naphthenate, octylate, dodecanoate, stearate, isostearate, oleate, and the like. Furthermore, examples of the chelate structure include, but are not limited to, various chelate compounds in addition to an acetylacetonate complex and an ethyl acetoacetate complex.

  Specific examples of the metal-based curing catalyst (d1) include, as a compound mainly composed of a group 1 alkali metal group metal element, lithium naphthenate, sodium stearate, potassium octylate, etc., group 2 alkaline earth. As a compound mainly composed of a metal group metal element, magnesium naphthenate, calcium octylate, barium octylate, etc., as a compound mainly composed of a transition metal group metal element, yttrium octylate, titanium tetrabutoxide, titanium acetylacetone complex, Titanium diisopropoxybis (ethyl acetoacetate), zirconium tetrapropoxide, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), vanadyl acetylacetonate, vana Umum acetylacetonate, chromium acetylacetone complex, manganese acetylacetone complex, iron octylate, cobalt naphthenate, cobalt octylate, nickel acetylacetone complex, copper naphthenate, copper acetylacetone complex, etc. mainly composed of group 12 zinc group metal elements Zinc acetylacetonate monohydrate, zinc naphthenate, zinc octylate, etc. as the compounds to be used are compounds mainly composed of Group 13 earth metal elements, such as aluminum acetylacetone complex, aluminum tributoxide, aluminum ethyl Examples of the acetoacetate complex, indium acetylacetone complex, etc., which are mainly composed of a group 15 nitrogen group metal element, include bismuth naphthenate and bismuth tris (2-ethylhexanoate). But it is not limited to these.

  As the metal-based curing catalyst (d1), specifically, the following ones including commercially available products can be used. Specific examples of commercially available products include nursem aluminum, nursem chromium, nursem first cobalt, nursem second cobalt, nursem copper, nursem ferric iron, nursem nickel, nursem vanadyl, nursem zinc, nursem indium, nursem magnesium, nurse Sem Manganese, Nasemu Yttrium, Nasemu Cerium, Nasemu Strontium, Nasemu Palladium, Nasemu Barium, Nasemu Molybdenyl, Nasemu Lanthanum, Nasemu Zirconium, Nasemu Titanium, Naphtex Co Series, Nikka Octix Co Series, Naphtex Mn Series, Nikka Octix Mn Series, Naphtex Zn Series, Nikka Octix Zn Series, Naftex Ca Series, Nikka Octics Ca Series, Naphtec K series, Nikka Octix K series, Nikka Octix Bi series, Bidecanoic acid Bi series, Pecat series, PA series, Naftex Zr series, Nikka Octix Zr series, Naftex Fe series, Nikka Octix Fe series, Naphtex Mg series , Naftex Li series, Naphtex Cu series, Naphtex Ba series, Nikka Octix Reals series, Nikka Octix Ni series, etc. (above, product names made by Nippon Chemical Industry Co., Ltd.), Olgaxix ZA-40, Olgaxix ZA-65, ORGATICS ZC-150, ORGATICS ZC-540, ORGATICS ZC-570, ORGATICS ZC-580, ORGATICS ZC-700, ORGATICS B-320, ORGATICS TA-10, ORGATICS TA-25, ORGATICS TA-22, ORGATICS TA-30, ORGATICS TC-100, ORGATICS TC-401, ORGATICS TC-200, ORGATICS TC- 750, Olga Tix TPHS, etc. (above, trade names made by Matsumoto Fine Chemical Co., Ltd.), SNAPCURE 3020, SNAPCURE 3030, VERTEC NPZ, etc. (above, trade names made by Johnson Matthey), Neostan U-600, Neostan U-660, etc. Kasei Co., Ltd. product name), Kenriact NZ01, Kenriact NZ33, Kenriact NZ39, etc. (above, product name produced by Kenrich), Aluminum Etoxide, AIPD, PADM, AMD, ASBD, ALCH, ALC -TR, aluminum chelate M, aluminum chelate D, aluminum chelate A, algomer, algomer 800AF, algomer 1000SF, pre-act ALM, etc. (above, product names manufactured by Kawaken Fine Chemical Co., Ltd.), A-1, B-1, TOT, TOG, T-50, T-60, A-10, B-2, B-4, B-7, B-10, TBSTA, DPSTA-25, S-151, S-152, S-181, etc. Soda Co., Ltd. trade name), Octope series, Kerop series, Olipe series, Acetop series, Chemihope series (trade name made by Hope Pharmaceutical Co., Ltd.) and the like, but are not limited thereto.

  Among these, when it is at least one selected from the group consisting of zirconium compounds, titanium compounds, aluminum compounds, and bismuth compounds, it is possible to reduce the environmental burden, to ensure safety, and to achieve a curing rate that can withstand actual use. Is preferable in that it is easily obtained. When importance is attached to the stability of the metal-based curing catalyst (d1), a structure such as carboxylate or chelate is preferable. When importance is attached to the catalytic activity of the metal-based curing catalyst (d1), alkoxide or carboxylate is preferred. Etc. are preferred. However, the metal-based curing catalyst (d1) may be appropriately selected in order to obtain desired cured film properties and / or curing speed, and these may be used alone or in combination of two or more.

[About boron trifluoride and / or its complex (d2)]
The boron trifluoride and / or its complex (d2) in the present invention is a compound composed of boron trifluoride and a complex of boron trifluoride and a Lewis base. The curable resin (A) and the curable resin ( B) A catalyst compound that cures the curable resin (A) and the curable resin (B) by subjecting the hydrolyzable silyl group contained therein to a condensation reaction. Specific examples of the compound (d2) composed of boron trifluoride and / or its complex include, for example, boron trifluoride amine complex, alcohol complex, ether complex, thiol complex, sulfide complex, carboxylic acid complex, and water complex. Etc. are exemplified. Among the above boron trifluoride complexes, alcohol complexes or amine complexes are preferred from the viewpoint of easy availability and ease of blending, and amine complexes having both stability and catalytic activity are particularly preferred.

Examples of the amine compound used in the amine complex of boron trifluoride include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2, 2,6,6-tetramethylpiperidine, 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 , 8,1 -Tetraoxaspiro [5.5] 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, Huntsman Such as Jeffermine A compound having a primary amino group, piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine, 2-amino Methylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'-diethylthiourea, N -Compounds having a plurality of secondary amino groups such as methyl-1,3-propanediamine, and further methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethylaminopropylamine 1- (2-aminoethyl) piperazine, N-aminopropi Piperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamineethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4- Aminomethylpiperidine, a compound represented by the formula H ₂ N (C ₂ H ₄ NH) _n H (n≈5) (trade name: Polyate, manufactured by Tosoh Corporation), N-alkylmorpholine, 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 In addition to bicyclic tertiary amine compounds such as [4.4.0] dec-5-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene , Γ-aminopropyltriethoxysilane, 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-a Examples include aminosilane compounds such as minoundecyltriethoxysilane, but are not limited thereto. The amine complexes of boron trifluoride are commercially available and can be used in the present invention. Examples of the commercially available products include Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, and BAK 1171 manufactured by Air Products Japan.

[About the amount]
In the present invention, the curable resin (A) and the curable resin (B) are mixed at (A) / (B) = 98/2 to 50/50 (mass ratio), and further cured. The basic compound (C) is 0.001 to 30 parts by mass with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B), and the non-tin curing catalyst (D) is 0.001 to 0.001. 10 parts by mass is contained.
The mixing ratio of the curable resin (A) and the curable resin (B) is preferably (A) / (B) = 98/2 to 55/45, more preferably (A) / (B). = 95 / 5-60 / 40, particularly preferably (A) / (B) = 90 / 10-70 / 30. When the curable resin (B) is less than 2% by mass, the effect of the curable resin (B) to exert the catalytic activity of the non-tin curing catalyst (D) is not sufficient, and the curable resin (B) When it exceeds 50 mass%, storage stability may worsen by the effect of curable resin (B).

Moreover, in this invention, 0.001-30 mass parts of basic compounds (C) are contained with respect to 100 mass parts of total of curable resin (A) and curable resin (B), Preferably it is 0. 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass. If the amount of the basic compound (C) is less than 0.001 part by mass, a problem is likely to occur in terms of curing speed, and if it exceeds 30 parts by mass, it is difficult to adjust the film properties of the cured product. Cheap.
Furthermore, in this invention, 0.001-10 mass parts of said non-tin curing catalysts (D) are contained with respect to 100 mass parts of total of curable resin (A) and curable resin (B), Preferably Is 0.005 to 5 parts by mass, more preferably 0.01 to 1.0 part by mass. If the amount of the non-tin curing catalyst (D) is less than 0.001 part by mass, the curing accelerating effect may not be sufficient, and if it exceeds 10 parts by mass, the adhesiveness and physical properties of the final cured product will be adversely affected. May affect.

[Other ingredients]
In the curable resin composition according to the present invention, any conventionally known compound or substance can be blended as other components. For example, various resins other than the curable resin used in the present invention, curing catalysts such as basic compounds (C) or acidic catalysts other than the non-tin curing catalyst (D), γ-glycidoxypropyltrimethoxysilane, etc. Silane coupling agent, hydrophilic or hydrophobic silica powder, filler such as calcium carbonate, tackifier such as phenol resin, thixotropic agent such as amide wax, dehydrating agent such as calcium oxide, diluent, plasticizer , Flame retardants, oligomers, anti-aging agents, ultraviolet absorbers, pigments, drying oils, and the like can be blended.

The curable resin composition according to the present invention can be used for all applications to which a conventional curable resin has been applied. For example, it can be used as an adhesive, a sealing material, an adhesive, a paint, a coating material, a sealing material, a casting material, a coating material, and the like.
The curable resin composition according to the present invention is cured by condensation polymerization of hydrolyzable silyl groups in the presence of moisture. Therefore, when used as a one-component composition, it is handled in an airtightly sealed state so as not to come into contact with air (water in the air) during storage or transportation. And if it opens and uses it in arbitrary places at the time of use, it will contact with the water | moisture content in air and a curable resin will harden | cure. When used as a two-component curable composition, the effect of the present invention is obtained when the above-mentioned curable resin, the above-mentioned basic compound (C) and the above-mentioned non-tin curing catalyst (D) are mixed. To express.

Moreover, when using as an adhesive precursor composition, if necessary, with respect to said curable resin composition, a tackifier resin is mix | blended and mixed uniformly, and an adhesive precursor composition is obtained. Here, the pressure-sensitive adhesive precursor composition refers to a liquid resin composition that becomes a pressure-sensitive adhesive composition by being cured. In addition, when mixing curable resin composition and tackifying resin uniformly, for example, when compatibility of both is inadequate, you may use an organic solvent. As the organic solvent, alcohols such as ethanol, ethyl acetate, toluene, methylcyclohexane and the like are used. Further, when the compatibility between the curable resin composition and the tackifier resin is good or when the organic solvent is not preferred, the organic solvent may not be used.
A pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive precursor composition thus obtained to the surface (one side or both sides) of a conventionally known tape base or sheet base and curing it. And an adhesive tape or an adhesive sheet is obtained.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
[Preparation of curable resin (A)]
(Preparation of curable resins A-1 to A-3)
As curable resin A-1, Exester S2410 (Asahi Glass Co., Ltd. product name, polyether having a methyldimethoxysilyl group) was prepared.
As curable resin A-2, Silyl MA440 (trade name, manufactured by Kaneka Corporation, polyether having acrylic-modified methyldimethoxysilyl group) was prepared.
As curable resin A-3, Exester G3440ST (trade name, manufactured by Asahi Glass Co., Ltd., a polyether having a trimethoxysilyl group) was prepared.

(Synthesis of curable resin A-4)
In a reaction vessel, while stirring N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (206.4 parts by mass) at room temperature under a nitrogen atmosphere, methyl acrylate (172.2 parts by mass, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane) is added dropwise over 1 hour, and further reacted at 50 ° C. for 7 days. Silane compound SE-1 having a secondary amino group was obtained.
In another reaction vessel, Actol P-28 (trade name, manufactured by Mitsui Chemicals Polyurethanes, polyoxypropylene polyol, average molecular weight 4,000, 90 parts by mass), PR-3007 (trade name, manufactured by ADEKA, polyoxypropylene) / Polyoxyethylene polyol, 10 parts by mass), isophorone diisocyanate (12.4 parts by mass) and dioctyltin diversate (50 ppm relative to the sum of P-28 and PR-3007) are stirred under a nitrogen atmosphere. While mixing, the reaction was carried out at 80 ° C. for 3 hours to obtain a urethane resin U-1 having a main chain of an oxyalkylene polymer and an isocyanate group in the molecule.
Further, the above-mentioned silane compound SE-1 (24.9 parts by mass) was added, and the mixture was allowed to react at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere. In addition, a curable resin A-4A having a bonding group containing a hetero atom through three methylene groups from a silicon atom and having a methyldimethoxysilyl group was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

  The curable resin A-4A (100 parts by mass) was placed in a reaction vessel, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. There, 37.5 parts by mass of methyl methacrylate, 25 parts by mass of butyl acrylate, 3.0 parts by mass of 3-acryloxypropylmethyldimethoxysilane, 7.0 parts by mass of 3-mercaptopropylmethyldimethoxysilane, and 2,2 A monomer mixed solution in which 0.48 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was mixed was dropped over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.16 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts by mass of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.02 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts by mass of methyl ethyl ketone was dropped to conduct a polymerization reaction. Furthermore, after reacting at 80 ° C. for 3 hours, the unreacted components are distilled off under reduced pressure, whereby a curable resin having a curable resin A-4A and a vinyl polymer having a methyldimethoxysilyl group in the molecule. Curable resin A-4 which is a mixture of resin A-4B was obtained.

(Synthesis of curable resin A-5)
In the reaction vessel, PMLS4012 (trade name, manufactured by Asahi Glass Co., Ltd., polyoxypropylene polyol, average molecular weight 10,000, 100 parts by mass), isophorone diisocyanate (4.71 parts by mass) and dioctyltin diversate (50 ppm with respect to PMLS4012) ) And stirring and mixing under a nitrogen atmosphere, the mixture was reacted at 80 ° C. for 3 hours to obtain a urethane resin U-2 having a main chain of an oxyalkylene polymer and an isocyanate group in the molecule.
Further, the silane compound SE-1 (7.55 parts by mass) was added, and the mixture was allowed to react at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere, whereby the main chain was an oxyalkylene polymer, and silicon atoms Thus, a curable resin A-5 having a bonding group containing a hetero atom via three methylene groups and having a methyldimethoxysilyl group was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin A-6)
In a reaction vessel, while stirring N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (222.4 parts by mass) at room temperature under a nitrogen atmosphere, methyl acrylate (172.2 parts by mass, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane) is added dropwise over 1 hour, and further reacted at 50 ° C. for 7 days. Silane compound SE-2 having a secondary amino group was obtained.
In another reaction vessel, the silane compound SE-2 (7.86 parts by mass) was added to the urethane resin U-2 (104.7 parts by mass), and the mixture was stirred and mixed in a nitrogen atmosphere at 80 ° C. The curable resin A-6 having a trimethoxysilyl group, the main chain of which is an oxyalkylene polymer, having a bonding group containing a heteroatom through three methylene groups from a silicon atom. Got. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin A-7)
While stirring 3-aminopropyltrimethoxysilane (179.3 parts by mass) at room temperature under a nitrogen atmosphere in a reaction vessel, lauryl acrylate (240.4 parts by mass, 1 to 3-aminopropyltrimethoxysilane) The silane compound SE-3 having a trimethoxysilyl group and a secondary amino group in the molecule was obtained by dropwise addition over 1 hour and further reacting at 50 ° C. for 7 days.
In another reaction vessel, PMLS4012 (trade name, manufactured by Asahi Glass Co., Ltd., polyoxypropylene polyol, average molecular weight 10,000, 100 parts by mass), isophorone diisocyanate (4.63 parts by mass) and Nikka Octix Zr 12% (T) (Trade name, manufactured by Nippon Kagaku Sangyo Co., Ltd., zirconyl octylate, Zr content ≈12% by mass, 200 ppm with respect to PMLS 4012), and stirred at 80 ° C. for 3 hours while stirring and mixing in a nitrogen atmosphere. A urethane resin U-3 having a chain of an oxyalkylene polymer and an isocyanate group in the molecule was obtained.
Further, the above silane compound SE-3 (8.63 parts by mass) was added and reacted at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere, whereby the main chain was an oxyalkylene polymer, and silicon A curable resin A-7 having a bonding group containing a hetero atom through three methylene groups from the atom and having a trimethoxysilyl group was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin A-8)
While stirring 3-aminopropyltrimethoxysilane (179.3 parts by mass) at room temperature under a nitrogen atmosphere in a reaction vessel, NK ester S-1800A (trade name, manufactured by Shin-Nakamura Kogyo Co., Ltd., isostearyl acrylate, 324. 5 parts by mass, 1 molar equivalent to 3-aminopropyltrimethoxysilane) was added dropwise over 1 hour, and further reacted at 50 ° C. for 7 days to give a trimethoxysilyl group and a secondary amino group in the molecule. Silane compound SE-4 was obtained.
In another reaction vessel, ARUFON UH-2000 (trade name, manufactured by Toa Gosei Co., Ltd., acrylic polyol, average molecular weight 11,000, 100 parts by mass), isophorone diisocyanate (7.53 parts by mass) and Nikka Octix Zr 12% (T ) (Nippon Kagaku Sangyo Co., Ltd., trade name, zirconyl octylate, Zr content ≈ 12% by mass, 200 ppm with respect to ARUFON UH-2000) and reaction at 80 ° C. for 3 hours while stirring and mixing in a nitrogen atmosphere Then, the reaction was further carried out at 100 ° C. for 12 hours to obtain a urethane-based resin U-4 whose main chain is an acrylic polymer and has an isocyanate group in the molecule.
Further, the above silane compound SE-4 (16.03 parts by mass) was added and reacted at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere, so that the main chain was an acrylic polymer and from silicon atoms. Curable resin A-8 which has a bonding group containing a hetero atom through three methylene groups and has a trimethoxysilyl group was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin A-9)
While stirring 3-aminopropyltriethoxysilane (264.4 parts by mass) at room temperature under a nitrogen atmosphere in the reaction vessel, methyl acrylate (102.8 parts by mass, 1 to 3-aminopropyltriethoxysilane) The silane compound SE-5 having a triethoxysilyl group and a secondary amino group in the molecule was obtained by adding dropwise a molar equivalent) over 1 hour and further reacting at 50 ° C. for 7 days.
In another reaction vessel, silane compound SE-5 (6.91 parts by mass) was added to urethane resin U-2 (104.7 parts by mass), and the mixture was stirred at 80 ° C. in a nitrogen atmosphere. And curable resin A-9 having a triethoxysilyl group, the main chain of which is an oxyalkylene polymer, has a bonding group containing a heteroatom through three methylene groups from a silicon atom. Got. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin A-10)
While stirring N- (2-aminoethyl) -3-aminopropyltriethoxysilane (264.4 parts by mass) at room temperature in a nitrogen atmosphere in a reaction vessel, methyl acrylate (172.2 parts by mass, N- (2-aminoethyl) -3-aminopropyltriethoxysilane) is added dropwise over 1 hour, and further reacted at 50 ° C. for 7 days. Silane compound SE-6 having a secondary amino group was obtained.
In another reaction vessel, the silane compound SE-6 (9.75 parts by mass) was added to the urethane resin U-2 (104.7 parts by mass), and the mixture was stirred at 80 ° C. in a nitrogen atmosphere. And curable resin A-10 having a triethoxysilyl group, the main chain of which is an oxyalkylene polymer, a bonding group containing a heteroatom through three methylene groups from a silicon atom. Got. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

[Preparation of curable resin (B)]
(Preparation of curable resin B-1)
As curable resin B-1, GENIOSIL STP-E10 (trade name, manufactured by Wacher Chemie), having an α-silane structure represented by formula (2) at the molecular end, and a hydrolyzable silyl group is a methyldimethoxysilyl group A polyether having a molecular weight of about 10,000 converted from the methoxy group equivalent was prepared.
(Preparation of curable resin B-2)
As curable resin B-2, GENIOSIL STP-E30 (trade name, manufactured by Wacher Chemie) has an α-silane structure represented by the formula (2) at the molecular end, and the hydrolyzable silyl group is a methyldimethoxysilyl group. A polyether having a molecular weight of about 16,000 converted from methoxy group equivalent was prepared.

(Synthesis of curable resin B-3)
In the reaction vessel, (cyclohexylaminomethyl) triethoxysilane (5.69 parts by mass) was added to U-3 (104.6 parts by mass), and the mixture was stirred and mixed in a nitrogen atmosphere at 80 ° C. By allowing the reaction for a period of time, a curable resin B-3 having an α-silane structure at the molecular end and the hydrolyzable silyl group being a triethoxy group was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin B-4)
In a reaction vessel, while stirring N- (6-aminohexyl) aminomethyltriethoxysilane (292.4 parts by mass) at room temperature under a nitrogen atmosphere, methyl acrylate (172.2 parts by mass, N- (6- Aminohexyl) 2.3 molar equivalents) based on aminomethyltriethoxysilane) and further reacted at 50 ° C. for 7 days to have an α-silane structure represented by formula (2) in the molecule A silane compound SE-7 in which the hydrolyzable silyl group was a triethoxysilyl group was obtained.
In another reaction vessel, silane compound SE-7 (11.97 parts by mass) was added to U-3 (104.6 parts by mass), and the mixture was stirred and mixed in a nitrogen atmosphere at 80 ° C. for 1 hour. By reacting, a curable resin B-4 having an α-silane structure at the molecular end and having a hydrolyzable silyl group as a triethoxy group was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

[Preparation of Basic Compound (C)]
(Preparation of basic compound C-1)
As basic compound C-1, Farmin 08D (manufactured by Kao Corporation, octylamine) was prepared.
(Preparation of basic compound C-2)
As basic compound C-2, DBU (manufactured by San Apro, 1,8-diazabicyclo [5.4.0] undec-7-ene) was prepared.
(Preparation of basic compound C-3)
Triethylamine was prepared as the basic compound C-3.
(Preparation of aminosilane compound C-4)
As the aminosilane compound C-4, KBM-603 (trade name, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared.
(Preparation of aminosilane compound C-5)
As the aminosilane compound C-5, KBM-903 (trade name, 3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared.

[Preparation of metal-based curing catalyst (d1) as non-tin curing catalyst (D)]
(Preparation of curing catalysts D-1 to D-15)
As the curing catalyst D-1, ZA-65 (trade name, manufactured by Matsumoto Fine Chemical Co., Ltd., 1-butanol solution of zirconium tetranormal butoxide, Zr content ≈ 20.7% by mass) was prepared.
As the curing catalyst D-2, ZC-570 (trade name, manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium monobutoxyacetylacetonate bis (ethylacetoacetate)) was prepared.
ZC-580 (trade name, zirconium dibutoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.) was prepared as the curing catalyst D-3.
As the curing catalyst D-4, VERTEC NPZ (trade name, product of Johnson Matthey, zirconium tetranormal propoxide: 1-propanol≈75: 25 (mass%)) was prepared.

As a curing catalyst D-5, SNAPCURE3030 (trade name, manufactured by Johnson Matthey, zirconium-based compound) was prepared.
As a curing catalyst D-6, SNAPCURE 3020 (trade name, zirconium-based compound manufactured by Johnson Matthey) was prepared.
As the curing catalyst D-7, Nikka Octix Zr 12% (T) (trade name, manufactured by Nippon Chemical Industry Co., Ltd., zirconyl octylate, Zr content ≈ 12% by mass) was prepared.
As a curing catalyst D-8, Kenriact NZ01 (trade name, manufactured by Kenrich, neopentyl (diallyl) oxytrineodecanoyl zirconate) was prepared.
As the curing catalyst D-9, Nikka Octix Bi 25% (trade name, bismuth octylate, Bi content ≈ 25% by mass, manufactured by Nippon Chemical Industry Co., Ltd.) was prepared.
As the curing catalyst D-10, PACCAT 25 (trade name, bismuth compound, Bi content ≈ 25% by mass, manufactured by Nippon Chemical Industry Co., Ltd.) was prepared.

As the curing catalyst D-11, Neostan U-600 (trade name, bismuth tris (2-ethylhexanoate) manufactured by Nitto Kasei Co., Ltd.) was prepared.
As a curing catalyst D-12, ORGATIX TA-25 (trade name, titanium tetranormal butoxide manufactured by Matsumoto Fine Chemical Co., Ltd.) was prepared.
As the curing catalyst D-13, Preneact ALM (trade name, manufactured by Kawaken Fine Chemical Co., Ltd., acetoalkoxyaluminum diisopropylate) was prepared.
As the curing catalyst D-14, Nikka Octix K10% (HG) (trade name, potassium octylate, K content ≈ 10% by mass, manufactured by Nippon Chemical Industry Co., Ltd.) was prepared.
As the curing catalyst D-15, Nikka Octix Ca 5% (T) (trade name, calcium octylate, Ca content ≈ 5% by mass, manufactured by Nippon Chemical Industry Co., Ltd.) was prepared.
As the curing catalyst D-16, nursem zinc (trade name, manufactured by Nippon Chemical Industry Co., Ltd., zinc acetylacetonate monohydrate) was prepared.

[Preparation of Boron Trifluoride and / or Complex (d2) as Non-Tin Curing Catalyst (D)]
(Preparation of curing catalyst D-17 which is a boron trifluoride complex)
A boron trifluoride monoethylamine complex was prepared as a curing catalyst D-17, which is a boron trifluoride complex.
(Preparation of curing catalyst D-18, which is a boron trifluoride complex)
As a curing catalyst D-18, which is a boron trifluoride complex, a boron trifluoride methanol complex methanol solution (a boron trifluoride methanol complex was 21.3% by mass) was prepared.

(Preparation of curing catalyst D-19 which is a boron trifluoride complex)
In a reaction vessel, DBU (manufactured by San Apro, 1,8-diazabicyclo [5.4.0] undec-7-ene, 152.2 parts by mass) is dissolved in diethyl ether (dehydrated) (304.5 parts by mass). While stirring at room temperature, boron trifluoride diethyl ether complex (141.9 parts by mass) was added dropwise over 10 minutes, and the mixture was further stirred for 3 hours to be reacted. Thereafter, the pressure was reduced in a 90 ° C. water bath, and the obtained solid was recrystallized from tetrahydrofuran and diethyl ether (mass ratio 2 to 1) to obtain boron trifluoride DBU complex D-19.

(Preparation of curing catalyst D-20 which is a boron trifluoride complex)
In a reaction container, Jeffamine M-600 (trade name, monoamine compound, average molecular weight of about 600, 600 parts by mass, manufactured by Huntsman) was dissolved in diethyl ether (dehydrated) (900 parts by mass) and stirred at room temperature. Boron fluoride diethyl ether complex (141.9 parts by mass) was added dropwise over 10 minutes, and the mixture was further reacted by stirring for 3 hours. Thereafter, the pressure was reduced in a 90 ° C. water bath to obtain boron trifluoride complex D-20.

[Comparison of curing speed]
The comparison of the curing rate was performed using the skinning time. The skinning time was defined as the time until a cured film was formed on the surface in air under the condition of 23 ± 2 ° C. and relative humidity of 50 ± 5%. The time when the cured film was formed was the time when the surface of each curable resin composition exposed with a metal spatula was touched and each curable resin composition was not attached to the spatula.

[Verification using metal-based curing catalyst (d1) containing no tin compound]
(Examples 1 to 10)
Curable resin A-1 (90 parts by mass), curable resin B-1 (10 parts by mass), basic compound C-1 (2.0 parts by mass), and curing catalysts D-1 to D-5, D-9 to D-13 (2.0 parts by mass) were mixed for 30 seconds under the condition of 23 ± 2 ° C. and relative humidity of 50 ± 5% to obtain each curable resin composition. Immediately after mixing, the starting time was taken, and the skinning time of the obtained curable resin composition was measured. Table 1 shows the measurement results. In addition, (circle) notation of a table | surface shows having mix | blended.
(Comparative Examples 1-10)
A curable resin composition was prepared in the same manner as in Examples 1 to 10 except that the curable resin B-1 was changed to the curable resin A-5 in Examples 1 to 10, and the skinning time was measured. Table 1 shows the measurement results.

  As shown in Table 1, since the curable resin composition (Examples 1 to 10) according to the present invention contains the curable resin (B) having an α-silane structure, the non-tin metal compound having low catalytic activity. It can be seen that even when a zirconium compound, a bismuth compound, a titanium compound, and an aluminum compound are used as a curing catalyst, curing is very fast. On the other hand, the curable resin compositions of Comparative Examples 1 to 10 contain a curable resin that does not have an α-silane structure but has a bonding group containing a hetero atom having an unshared electron pair in the molecule. Nevertheless, curing is very slow. From this, it can be said that the curable resin composition concerning this invention has expressed the activity of the non-tin metal type compound effectively, and is very useful industrially. Furthermore, since the curable resin composition concerning this invention has curable resin (A) as a main component, compared with the case where it hardens | cures with an organotin catalyst etc. without using curable resin (B). This has a very useful result that the curing is fast without significant difference in physical properties.

(Examples 11 to 16)
Curable resin A-1 (90 parts by mass), curable resin B-1 (10 parts by mass), basic compound C-2 (2.0 parts by mass), and curing catalysts D-2 to D-6, D-13 (2.0 parts by mass) was mixed for 30 seconds under conditions of 23 ± 2 ° C. and relative humidity of 50 ± 5% to obtain each curable resin composition. Immediately after mixing, the starting time was taken, and the skinning time of the obtained curable resin composition was measured. Table 2 shows the measurement results.

(Comparative Examples 11-16)
A curable resin composition was prepared in the same manner as in Examples 11 to 16 except that the curable resin B-1 was changed to the curable resin A-5 in Examples 11 to 16, and the skinning time was measured. Table 2 shows the measurement results.

  As shown in Table 2, the curable resin composition (Examples 11 to 16) according to the present invention uses a highly basic DBU as the basic compound (C), so that the amount of the basic compound (C) is high. Can be cured very quickly using a non-tin metal compound having low catalytic activity. Although the curable resin compositions of Comparative Examples 11 to 16 do not have an α-silane structure, they contain a curable resin in which a bonding group containing a hetero atom having an unshared electron pair is present in the molecule. And curing is slow. This shows that the curable resin composition can be cured very quickly by containing the curable resin (B) having an α-silane structure. In particular, since the curing rate of the curable resin is relatively increased by containing the curable resin (B), it can be cured extremely quickly depending on the curing catalyst selected as in Example 14, and It is also possible to achieve an industrially required curing rate with a small curing catalyst.

(Examples 17 to 28)
Curable resin A-1 (90 parts by mass), curable resin B-1 (10 parts by mass), aminosilane compound C-4 (2.0 parts by mass), and curing catalysts D-1 to D-12 (2 0.0 part by mass) was mixed for 30 seconds under the condition of 23 ± 2 ° C. and relative humidity of 50 ± 5% to obtain each curable resin composition. Immediately after mixing, the starting time was taken, and the skinning time of the obtained curable resin composition was measured. Table 3 shows the measurement results.

(Comparative Examples 17-28)
A curable resin composition was prepared in the same manner as in Examples 17 to 28 except that the curable resin B-1 was changed to the curable resin A-6 in Examples 17 to 28, and the skinning time was measured. Table 3 shows the measurement results.

  As shown in Table 3, since the curable resin composition (Examples 17 to 28) according to the present invention contains the curable resin (B) having an α-silane structure, the non-tin metal compound having low catalytic activity. It can be seen that curing is very fast even when used as a curing catalyst. On the other hand, although the curable resin compositions of Comparative Examples 17 to 28 do not have an α-silane structure, a linking group containing a hetero atom having an unshared electron pair is present in the molecule, and more generally a fast curing is achieved. Despite the inclusion of an alkoxysilyl type curable resin, curing is very slow. From this, it can be said that the curable resin composition concerning this invention has expressed the activity of the non-tin metal type compound effectively, and is very useful industrially.

(Example 29)
Curable resin A-2 (90 parts by mass), curable resin B-1 (10 parts by mass), aminosilane compound C-4 (2.0 parts by mass), and curing catalyst D-4 (2.0 parts by mass) ) Was mixed for 30 seconds under conditions of 23 ± 2 ° C. and relative humidity of 50 ± 5% to obtain each curable resin composition. Immediately after mixing, the starting time was taken, and the skinning time of the obtained curable resin composition was measured. Table 4 shows the measurement results.
(Comparative Example 29)
A curable resin composition was prepared in the same manner as in Example 29 except that the curable resin B-1 was changed to the curable resin A-6 in Example 29, and the skinning time was measured. Table 4 shows the measurement results.

(Example 30)
A curable resin composition was prepared in the same manner as in Example 29 except that the curable resin A-2 was changed to the curable resin A-4, and the skinning time was measured. Table 4 shows the measurement results.
(Comparative Example 30)
A curable resin composition was prepared in the same manner as in Example 30 except that the curable resin B-1 was changed to the curable resin A-6 in Example 30, and the skinning time was measured. Table 4 shows the measurement results.

  As shown in Table 4, the curable resin composition according to the present invention (Examples 29 and 30) contains the curable resin (B) having an α-silane structure, and thus has a low catalytic activity. It can be seen that curing is very fast even when a zirconium-based compound, which is a system compound, is used as a curing catalyst. Moreover, the organotin compound used in the synthesis | combination of curable resin A-4 in Example 30 is less than 100 ppm. Therefore, the content of the organic tin compound contained in the curable resin composition is less than 100 ppm, and the environmental load is very small.

(Example 31)
Curable resin A-1 (95 parts by mass), curable resin B-1 (5 parts by mass), aminosilane compound C-4 (2.0 parts by mass), and curing catalyst D-4 (2.0 parts by mass) ) Was mixed for 30 seconds under conditions of 23 ± 2 ° C. and relative humidity of 50 ± 5% to obtain each curable resin composition. Immediately after mixing, the starting time was taken, and the skinning time of the obtained curable resin composition was measured. Table 5 shows the measurement results.
(Comparative Example 31)
A curable resin composition was prepared in the same manner as in Example 31 except that the curable resin B-1 was changed to the curable resin A-6 in Example 31, and the skinning time was measured. Table 5 shows the measurement results.

  As shown in Table 5, since the curable resin composition (Example 31) according to the present invention contains the curable resin (B) having an α-silane structure, the non-tin metal compound having low catalytic activity. Even when a zirconium-based compound is used as a curing catalyst, it can be seen that curing is very fast.

(Examples 32-35)
Curable resin A-1 (70 parts by mass), curable resin B-1 (30 parts by mass), aminosilane compound C-4 (2.0 parts by mass), and curing catalysts D-13 to D-16 (2 0.0 part by mass) was mixed for 30 seconds under the condition of 23 ± 2 ° C. and relative humidity of 50 ± 5% to obtain each curable resin composition. Immediately after mixing, the starting time was taken, and the skinning time of the obtained curable resin composition was measured. Table 6 shows the measurement results.
(Comparative Examples 32-35)
A curable resin composition was prepared in the same manner as in Examples 32-35 except that the curable resin B-1 was changed to the curable resin A-6 in Examples 32-35, and the skinning time was measured. Table 6 shows the measurement results.

  As shown in Table 6, the curable resin composition according to the present invention (Examples 32 to 35) contains a curable resin (B) having an α-silane structure, and therefore has a low catalytic activity. It can be seen that curing is very fast even when a potassium compound, a calcium compound, a zinc compound, or an aluminum compound, which is a series compound, is used as a curing catalyst.

[Verification using boron trifluoride and / or its complex (d2)]
(Examples 36 to 39, Comparative Examples 36 to 41)
In the reaction vessel, the curable resin (A), the curable resin (B), the basic compound (C), and the curing catalyst (D) were stirred and mixed under dehydrating conditions as shown in Table 7, and the mixture was mixed at 50 ° C. 3 The curable resin composition was obtained by allowing to stand for days. The skinning time of the obtained curable resin composition was measured. Table 7 shows the measurement results.

  In Table 7, the skinning time is measured using a dialkoxysilyl type curable resin as a main component. The dialkoxysilyl-type curable resin is a boron trifluoride complex even if it contains a small amount of a curable resin having a bonding group containing a heteroatom having an unshared electron pair in the molecule, although it does not have an α-silane structure. When it is cured using this curing catalyst, curing is slow (Comparative Examples 36 to 40). However, surprisingly, when a small amount of the curable resin (B) having an α-silane structure is contained, curing is extremely accelerated (Examples 36 to 39). In addition, there is a bonding group containing a heteroatom having an unshared electron pair in the molecule, and more generally, compared with a trialkoxysilyl-type curable resin that is rapidly cured (Comparative Example 41), the same amount. It is quicker to contain the curable resin (B) (Example 38). From these, it can be seen that the α-silane structure in which a hetero atom exists from a silicon atom through one methylene group plays an important role in rapid curing.

(Examples 40 and 41, Comparative Examples 42 and 43)
In the reaction vessel, the curable resin (A), the curable resin (B), the basic compound (C), and the curing catalyst (D) are stirred and mixed under dehydrating conditions as shown in Table 8 and mixed at 50 ° C. for 3 hours. The curable resin composition was obtained by allowing to stand for days. The skinning time of the obtained curable resin composition was measured. Table 8 shows the measurement results.

  From the examples in Table 8, it can be seen that the curing rate of the curable resin composition can be further increased by increasing the ratio of the curable resin (B) having an α-silane structure. On the other hand, in the comparative example, even if 30 to 50 parts by mass of a curable resin having a bonding group containing a heteroatom having an unshared electron pair in the molecule, although not an α-silane structure, is cured very much. slow.

(Examples 42 to 44, Comparative Examples 44 to 49)
In the reaction vessel, the curable resin (A), the curable resin (B), the basic compound (C), and the curing catalyst (D) were stirred and mixed under dehydrating conditions as shown in Table 9, and the mixture was mixed at 50 ° C. The curable resin composition was obtained by allowing to stand for days. The skinning time of the obtained curable resin composition was measured. Table 9 shows the measurement results.

  From Table 9, even if various boron trifluoride complexes (D) are used for the curing catalyst, a small amount of the curable resin (B) having an α-silane structure can be used to obtain a dialkoxysilyl type curable resin. It turns out that the curable resin composition which has a main component can be hardened very rapidly. In particular, by using a boron trifluoride DBU complex having a high catalytic activity, it is possible to make the curing rate very fast even if the amount of catalyst is extremely small (Example 43), and this effect is a trialkoxysilyl type. It is obvious that it is not sufficient to contain only the curable resin (Comparative Example 47).

(Example 45, Comparative Examples 50 and 51)
In the reaction vessel, the curable resin (A), the curable resin (B), the basic compound (C), and the curing catalyst (D) were stirred and mixed under dehydrating conditions as shown in Table 10, and the mixture was mixed at 50 ° C. 3 The curable resin composition was obtained by allowing to stand for days. The skinning time of the obtained curable resin composition was measured. Table 10 shows the measurement results.

  In Table 10, when a trialkoxysilyl type curable resin is used as a main component, the curable resin cures quickly even with a small amount of the curing catalyst (D). Even in that case, it can be seen that the curable resin (B) having an α-silane structure has an effect of greatly increasing the curing rate of the curable resin composition.

(Examples 46 to 48, Comparative Examples 52 to 56)
Aminosilane compound C-4 and curing catalyst D-17 were mixed in a sealed container at a mass ratio shown in Table 11, and allowed to stand at 50 ° C. for 3 days to obtain a catalyst solution.
Further, the curable resin (A), the curable resin B-1, and the catalyst solution were mixed for 30 seconds as shown in Table 11 under the condition of 23 ± 2 ° C. and relative humidity of 50 ± 5%, thereby being curable. A resin composition was obtained. The skinning time of the obtained curable resin composition was measured. Table 11 shows the measurement results.

  The curable resin composition according to the present invention may be a curable resin in which the curable resin (A) has a bonding group containing a hetero atom having an unshared electron pair in the molecule, or a basic compound ( C) and the curing catalyst (D) may be added later. At that time, it is clear from Table 11 that the curing rate is dramatically improved by the presence of the curable resin (B) having an α-silane structure.

(Examples 49 and 50, Comparative Examples 57 to 60)
Aminosilane compound C-4 and curing catalyst D-17 or D-19 were mixed in a sealed container at a mass ratio shown in Table 12, and allowed to stand at 50 ° C. for 3 days to obtain a catalyst solution.
Further, the curable resin (A), the curable resin (B), and the catalyst solution were mixed for 30 seconds as shown in Table 12 under the condition of 23 ± 2 ° C. and relative humidity of 50 ± 5%, thereby being curable. A resin composition was obtained. The skinning time of the obtained curable resin composition was measured. Table 12 shows the measurement results.

  The hydrolyzable silyl group having an α-silane structure may be terminated with a triethoxysilyl group, and different side chains are bonded to a hetero atom having an unshared electron pair via a methylene group to a silicon atom. May be. It is clear from Table 12 that even with a curable resin having these structures, the curing rate is dramatically improved by having an α-silane structure. In Examples 49 and 50, no organic tin compound was used for the synthesis of the curable resin (B), and thus the curable resin composition did not contain an organic tin compound. Therefore, the environmental load is very small.

  The curable resin composition according to the present invention can be used for all applications in which a one-component or multi-component curable resin composition has been used. For example, it can be used as an adhesive, an adhesive, a sealing material, a paint, a coating material, a sealing material, a casting material, a coating material, and the like.

Claims (12)

A curable resin (A) having a hydrolyzable silyl group represented by formula (1) in the molecule, a curable resin (B) having a hydrolyzable silyl group represented by formula (2) in the molecule, Contains a basic compound (C) and at least one non-tin curing catalyst (D) selected from the group consisting of a non-tin metal-based curing catalyst (d1), boron trifluoride and / or a complex (d2) thereof A curable resin composition in which the curable resin (A) and the curable resin (B) are mixed at (A) / (B) = 98/2 to 50/50 (mass ratio). Yes, 0.001 to 30 parts by mass of the basic compound (C) and 0 to the non-tin curing catalyst (D) with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). A curable resin composition containing 0.001 to 10 parts by mass.
-X-SiR ¹ _a (OR ² ) _3-a Formula (1)
(However, X is a hydrocarbon group having 2 or more carbon atoms, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a phenyl group, an alkyl group having 1 to 20 carbon atoms, and 2- ( (Butoxy) One or more groups selected from organic groups having 1 to 20 carbon atoms, such as an ethyl group, a represents 0, 1 or 2, respectively.
—W—CH ₂ —SiR ³ _b (OR ⁴ ) _3-b (2)
(W is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silyl group, and R ³ is a carbon atom having 1 to 20 carbon atoms. A hydrogen group, R ⁴ is one or more groups selected from a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms such as 2- (butoxy) ethyl group. , B represents 0, 1 or 2, respectively.   The curable resin composition according to claim 1, wherein the main chain of the curable resin (A) is polyoxyalkylene and / or poly (meth) acrylate.   The curable resin composition according to claim 1 or 2, wherein the hydrolyzable silyl group of the curable resin (A) is a dialkoxysilyl group.   The curable resin composition according to any one of claims 1 to 3, wherein the curable resin (A) does not contain a urethane bond or a urea bond in its molecule.   The curable resin composition according to any one of claims 1 to 4, wherein the main chain of the curable resin (B) is polyoxyalkylene.   The curable resin composition according to any one of claims 1 to 5, wherein the basic compound (C) is an aminosilane compound (C1) having an amino group and a hydrolyzable silyl group in the molecule. object.   The curable resin composition according to any one of claims 1 to 6, wherein the content of the organotin catalyst is 0 to less than 100 ppm.   Furthermore, a halogen-containing compound is not included, The curable resin composition as described in any one of Claims 1-7 characterized by the above-mentioned.   The curing according to any one of claims 1 to 8, wherein the non-tin curing catalyst (D) is at least one selected from the group consisting of a zirconium compound, a titanium compound, an aluminum compound, and a bismuth compound. Resin composition.   The sealing material composition which has the curable resin composition as described in any one of Claims 1-9 as a main component of a sclerosing | hardenable component.   The adhesive composition which has the curable resin composition as described in any one of Claims 1-9 as a main component of a sclerosing | hardenable component.   The adhesive precursor composition which uses the curable resin composition as described in any one of Claims 1-9 as a main component of a sclerosing | hardenable component.