JP4445584B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition containing a hydrolyzable silicon group, which can be cured at room temperature, and more specifically, it is possible to reduce environmental burden and to ensure safety while ensuring safety. The present invention relates to a curable composition having a high curing rate.

  Curable resins having hydrolyzable silicon groups in the molecule are widely used as base polymers for sealants, adhesives, adhesives, paints and the like. This curable resin is also called a moisture curable polymer because the hydrolyzable silicon group is cured by hydrolysis and crosslinking with moisture in the atmosphere. In particular, curable resins whose hydrolyzable silicon groups are alkoxysilanes are widely used because of their safety and low odor. (Patent Document 1 and Patent Document 2)

  However, since a sufficient curing rate cannot be obtained at room temperature only with an alkoxysilyl group, these curable resins are usually used in combination with a curing catalyst in order to obtain a sufficient curing rate. Organotin compounds are widely used as curing catalysts.

  On the other hand, it has been proposed to use an amine compound, a carboxylic acid compound, or a bismuth compound or a titanium compound as a curing catalyst (Patent Document 3 and Patent Document 4). However, these catalyst systems are not practically satisfactory in curing rate.

  Further, as an alkoxysilyl group having sufficient curability even without a catalyst, a heteroatom such as oxygen, nitrogen, or sulfur having an unshared electron pair is bonded to the α-position carbon bonded to the hydrolyzable silicon atom (hereinafter referred to as “α A compound sometimes referred to as “-silane structure” has been proposed (Patent Document 5).

Japanese published patent: JP-A-52-73998 Japanese published patent: Japanese Patent Laid-Open No. 63-112642 Japanese published patent: Japanese Patent No. 3793074 Japanese published patent: Japanese Patent No. 3768072 Japanese published patent: Japanese Patent Publication No. 2005-514504

Some organotin compounds have become problematic in recent years. In particular, among organic tin compounds, those containing highly toxic tributyltin derivatives are desired to be suppressed to 1000 ppm or less with respect to the composition.
In addition, not only tributyltin derivatives but also catalysts with a focus on heavy metals containing tin are of concern for toxicity and environmental impact, so it is needless to say that sufficient handling and usage are required when using them. .
The problem to be solved by the present invention is to obtain a curable composition having a necessary and sufficient curing speed while achieving reduction of environmental burden and ensuring safety.

  In order to solve such a problem, as a result of intensive studies, the present inventors have found that a curable resin containing a hydrolyzable silicon group and a curable resin having an α-silane structure in the molecule within a certain range. It was found that a sufficient curing rate can be obtained at room temperature by mixing at a ratio and further adding an aminosilane compound having no α-silane structure as a catalyst, thereby completing the present invention.

That is, the first invention is
A curable resin (A) having a hydrolyzable silicon group represented by formula (1) in the molecule;
A curable resin (B) having a hydrolyzable silicon group represented by the formula (2) in the molecule;
The compound represented by the formula (3), the condensation reaction product of the compound represented by the formula (3) alone, and the condensation reaction product of the compound represented by the formula (3) and another silane compound are selected. At least one aminosilane compound (C);
A curable resin composition containing
While the curable resin (B) is contained in 15 to 900 parts by mass with respect to 100 parts by mass of the curable resin (A), the total amount of the curable resin (A) and the curable resin (B) is 100 parts by mass. The present invention relates to a curable resin composition containing 0.1 to 20 parts by mass of an aminosilane compound (C).

_{^{-X-SiR 1 a (OR 2}} ) 3-a ··· formula (1)
(However, X represents a hydrocarbon group having 2 or more carbon atoms, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, and a represents 0, 1 or 2, respectively.)

_{^{-A-CH 2 -SiR 3 b (}} OR 4) 3-b ··· formula (2)
(However, A 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 silicon group, and R ³ and R ⁴ are carbon atoms having 1 to 20 carbon atoms. A plurality of alkyl groups, b represents 0, 1 or 2, respectively.)

R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _c (OR ⁹ ) _3-c (3)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms, R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom, and R ⁸ and R ⁹ are each having 1 carbon atom. -20 alkyl groups, c represents 0, 1 or 2, respectively)

  Usually, the aminosilane compound (C) acts as a very weak curing catalyst for the curable resin (A), but the curable resin (A) cannot be completely cured by itself. However, when the curable resin (B) intervenes here, both the curable resin (A) and the curable resin (B) are completely cured by the catalytic effect of the aminosilane compound (C).

Further, the second invention is characterized in that the main chain of the curable resin (A) is essentially polyoxyalkylene and / or poly (meth) acrylic acid ester, and is curable according to the first invention. The present invention relates to a resin composition.
The third invention relates to the curable resin composition according to the first or second invention, wherein the hydrolyzable silicon group of the curable resin (A) is an alkyl dialkoxysilyl group. It is.

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.
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 essentially polyoxyalkylene. Is.
The sixth invention relates to the curable resin composition according to any one of the first to fifth inventions, wherein the organotin catalyst is 0 to less than 1000 ppm.

Moreover, 7th invention is related with the sealant composition which has the curable composition which concerns on any 1st-6th invention as a main component of a sclerosing | hardenable component.
The eighth invention relates to an adhesive composition mainly comprising a curable composition according to any one of the first to sixth inventions as a curable component.

  The curable resin composition according to the present invention has the effect of achieving a necessary and sufficient curing rate while achieving a reduction in environmental burden and ensuring safety.

  Hereinafter, embodiments of 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 silicon group represented by the formula (1) in the molecule.

_{^{-X-SiR 1 a (OR 2}} ) 3-a ··· formula (1)
(However, X represents a hydrocarbon group having 2 or more carbon atoms, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, and a represents 0, 1 or 2, respectively.)

In the hydrolyzable silicon 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 alkoxy 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 an alkyl 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, and more preferably a methyl group or an ethyl group.
In addition, the hydrolyzable silicon 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 typified by a sealing material is desired. It is preferable that it is easy to balance the curing rate and the modulus.
The molecular weight of the curable resin (A) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the crosslink density becomes too high, which may result in brittle properties. If the molecular weight exceeds 80,000, the viscosity becomes high and the workability deteriorates, so a large amount of solvent or plasticizer is required. In some cases, blending may be limited.

  Examples of the main chain skeleton of the curable resin (A) include polyoxyalkylene, vinyl polymer, saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester resin, polycarbonate, polydimethylsiloxane, and other silicone resins and modified silicone resins. One or more kinds of skeletons selected from generally used main chain skeletons are adopted, and in particular, the polyoxyalkylene and / or the poly (meth) acrylate is essentially a cured product. It is preferable from the viewpoint of film properties. Here, “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (A). Moreover, in the curable resin (A), this structure may be contained independently, and 2 or more types may be contained. In the present application, acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”.

  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 a hydroxyl group-terminated polyol with an isocyanate group-containing alkoxysilane compound, and the like are known. More specifically, Japanese Patent No. 3030020, Japanese Patent No. 3343604, Japanese Patent Laid-Open No. 2005-54174, United States Patent 7208560, United States Patent 7230064, Japanese Patent Laid-Open No. 8-05528, Japanese Patent Laid-Open No. Can be easily synthesized by the method described in Japanese Patent No. 2-11879.
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.

[About curable resin (B)]
The curable resin (B) in the present invention is a curable resin having a hydrolyzable silicon group represented by the formula (2) in the molecule.

^{_{-A-CH 2 -SiR 3 b (}} OR 4) 3-b ··· formula (2)
(However, A 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 silicon group, and R ³ and R ⁴ are carbon atoms having 1 to 20 carbon atoms. A plurality of alkyl groups, b represents 0, 1 or 2, respectively.)

A bonding functional group in which a hetero atom having an unshared electron pair is bonded to a silicon atom contained in the hydrolyzable silicon group via a methylene group is bonded to the hydrolyzable silicon group. The bond functional group is a structure that connects the hydrolyzable silicon group and the main chain, especially if a heteroatom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in the hydrolyzable silicon group. Specific examples include (thio) urethane bonds, (thio) urea bonds, (thio) substituted urea bonds, (thio) ester bonds, (thio) ether bonds, and the like. Further, the hydrolyzable silicon group is bonded to the main chain skeleton via this bonding functional group.
In addition to the bond with the methylene group, the silicon atom has 1 to 3 alkoxy groups (OR ⁴ ) as hydrolyzable groups and 2 to 2 hydrocarbon groups (R ³ ) as the remaining bonds. 0 units are connected.
Here, R ³ and R ⁴ are each an alkyl group having 1 to 20 carbon atoms. The alkoxyl group (OR ⁴ ) 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 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.
The hydrolyzable silicon group of the curable resin (B) is easily an alkyldialkoxysilyl group (b = 1) or trialkoxysilyl group (b = 0), the modulus of the cured product, etc. From the point of view, it is preferable.
The molecular weight of the curable resin (B) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the crosslink density becomes too high, which may result in brittle properties. If the molecular weight exceeds 80,000, the viscosity becomes high and the workability deteriorates, so a large amount of solvent or plasticizer is required. In some cases, blending may be limited.

  In the present application, such a chemical structure is referred to as an “α-silane structure”. By selecting an α-silane structure, the moisture reactivity is much higher than that of a normal hydrolyzable silicon group, so that a sufficient curing rate can be obtained even when a tin catalyst is not used or a much smaller amount is used than usual. Obtainable.

  Examples of the main chain skeleton of the curable resin (B) include polyoxyalkylene, vinyl polymer, saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester, polycarbonate, polydimethylsiloxane, and other silicone resins and modified silicone resins. One or more skeletons selected from main chain skeletons that are generally used are employed, and in particular, they are essentially polyoxyalkylenes from the viewpoints of availability, film properties of cured products, and the like. preferable. Here, “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (B). Moreover, this structure may be contained independently in curable resin (B), and 2 or more types may be contained.

  In order to obtain the curable resin (B), synthesis may be performed by a conventionally known method. For example, a method in which an isocyanate methyl alkoxysilane compound is reacted with a polyol compound, a urethane prepolymer is synthesized by reacting a polyol compound with a polyisocyanate compound, and then the urethane prepolymer has an active hydrogen group at the α-position of an aminomethylalkoxysilane compound or the like. A method of reacting a compound having a hetero atom bonded thereto 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.

  Examples of commercially available curable resin (B) include GENIOSIL STP-E10, GENIOSIL STP-E30 manufactured by Wacker Chemie AG.

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 a 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.

[Aminosilane compound (C)]
The aminosilane compound (C) in the present invention is a compound having one or more amino groups and hydrolyzable silicon groups in the molecule, and two or more carbon atoms between the amino group and the hydrolyzable silicon group. It is a bonded aminosilane compound. The aminosilane compound (C) in the present invention is an aminosilane compound having no α-silane structure. A low molecular aminosilane compound having an α-silane structure is not suitable because of its high toxicity.

  Examples of the aminosilane compound (C) include an aminosilane compound (c1) represented by the following general formula (3), a condensation reaction product of the aminosilane compound (c1) alone, or an aminosilane compound (c1) and the following general formula (4). The condensation reaction product with other silane compounds as exemplified by the silane compound (c2) represented by Among these, the aminosilane compound (c1) or the condensation reaction product of the aminosilane compound (c1) alone is more preferable because the effect of the amino group in the aminosilane compound (C) can be expressed more easily.

  The amino group contained in the aminosilane compound (C) may be any of primary, secondary, and tertiary amino groups, but the curable resin composition according to the present invention may be an adhesive, a sealing material, In applications that require adhesiveness such as pressure-sensitive adhesives, primary or secondary amino groups that are more likely to exhibit the adhesion-imparting effect are preferred, and primary amino groups are particularly preferred. Moreover, the amino group contained in the said aminosilane compound (C) may be one, and may be two or more. Moreover, as a hydrolysable silicon group contained in the said aminosilane compound (C), when it illustrates with the aminosilane compound (c1) shown by following General formula (3), it will be an alkyl dialkoxy silyl group (c = 1) or trialkoxy. A silyl group (c = 0) is preferable because it is easily available and the modulus of the cured product can be easily adjusted. The number of hydrolyzable silicon groups contained in the aminosilane compound (C) may be one, or two or more.

R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _c (OR ⁹ ) _3-c (3)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms, R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom, and R ⁸ and R ⁹ are each having 1 carbon atom. -20 alkyl groups, c represents 0, 1 or 2, respectively)

Si (R ¹⁰ ) (R ¹¹ ) (R ¹² ) (OR ¹³ ) (4)
(However, in the formula, R ¹⁰ , R ¹¹ and R ¹² are represented by 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 alkoxy group having 1 to 6 carbon atoms. Each represents one or more groups selected from organic groups having a molecular weight of 500 or less, and R ¹³ represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.)

  Formula (3) is preferably an aminosilane compound represented by the following general formula (3 ').

^{R 5 'R 6' N-} R 7 '-SiR 8' c (OR 9 ') 3-c ··· formula (3')
(However, R ⁵ ′ and R ⁶ ′ are organic groups or hydrogen atoms having a molecular weight of 500 or less, R ⁷ ′ is a hetero atom not bonded to a carbon atom bonded to a hydrolyzable silicon atom, A divalent organic group having a molecular weight of 500 or less which may contain an amino group, R ⁸ ′ and R ⁹ ′ each represent an alkyl group having 1 to 20 carbon atoms, and c represents 0, 1 or 2. )

[Aminosilane compound (c1)]
Specific examples of the aminosilane compound (c1) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldie Xysilane, bis (3-trimethoxypropyl) amine, bis (3-methyldimethoxypropyl) amine, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N -Aminosilane compounds such as ethylaminoisobutylmethyldimethoxysilane, N-butylaminopropyltrimethoxysilane, N-butylaminopropylmethyldimethoxysilane, diethylenetriaminopropyltrimethoxysilane, N- (2-propenyl) aminopropyltrimethoxysilane For example, but not limited to. Further, a ketimine silane compound such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine is also substantially included in the aminosilane compound (c1) because a primary amino group is generated by moisture. include. Among them, the use of 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is easy to obtain and has a high curing acceleration effect. To preferred. Further, it is known that a cured product in which an aminosilane compound is blended is generally easily yellowed by heat or light. When used in applications where yellowing is not preferred, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane Aminosilanes with a small number of hydrogen atoms bonded to the β-position carbon of nitrogen atoms, such as 4-amino-3-dimethylbutylmethyldiethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutylmethyldimethoxysilane, etc. Use of a compound is preferable because yellowing is reduced.

[Silane Compound (c2)]
Specific examples of the silane compound (c2) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, Examples include dimethoxydiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-ureidopropyltrimethoxysilane. Of these, methyltrimethoxysilane and dimethyldimethoxysilane are preferably used from the viewpoint of easy condensation reaction with the aminosilane compound (c1).

  The aminosilane compound (c1) alone or the condensation reaction product of the aminosilane compound (c1) and the silane compound (c2) may be synthesized by a conventionally known method. Specifically, a method of reacting the aminosilane compound (c1) with water or a method of reacting the aminosilane compound (c1) and the silane compound (c2) with water can be mentioned. The aminosilane compound (c1) alone or the condensation reaction product of the aminosilane compound (c1) and the silane compound (c2) is commercially available, and these can be used in the present invention. Examples of commercially available products include aminosilane silyl groups such as 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.) or the like. Examples thereof include compounds partially condensed with other alkoxysilane compounds.

  The aminosilane compound (C) may be appropriately selected in order to obtain desired cured film properties and / or curing speed, and may be used alone or in combination of two or more.

[About the amount]
In this invention, 15-900 mass parts of curable resin (B) are contained with respect to 100 mass parts of curable resin (A), Preferably curable resin (B) is 18-800 mass parts, More preferably It is 20 to 700 parts by mass, particularly preferably 30 to 500 parts by mass, and most preferably 50 to 300 parts by mass. If the amount of the curable resin (B) is less than 15 parts by mass, the effect of accelerating the curing by the curable resin (B) may not be sufficiently exhibited (that is, the curing rate is not sufficient), and 900 parts by mass is reduced. On the contrary, the relative proportion of the curable resin (A) decreases, making it difficult to achieve a balance such as adhesion strength and physical properties after curing (especially hardened film properties are difficult to obtain).
Furthermore, in this invention, 0.1-20 mass parts of aminosilane compounds (C) are contained with respect to the total 100 mass parts of curable resin (A) and curable resin (B), and preferably aminosilane. A compound (C) is 0.5-15 mass parts, More preferably, it is 1-10 mass parts. If the amount of the aminosilane compound (C) is less than 0.1 parts by mass, curing-accelerated curing may not be sufficient (prone to cause problems in terms of curing speed), and if it exceeds 20 parts by mass, it is relatively curable. Since the ratio of the resin (A) and the curable resin (B) is reduced, it is difficult to adjust the film properties of the cured product, or a large amount of moisture is required for curing, resulting in poor internal curability. Prone to occur.

In the present invention, the aminosilane compound (C) mainly functions as a curing catalyst.
Usually, the aminosilane compound (C) acts as a very weak curing catalyst for the curable resin (A), but the curable resin (A) cannot be completely cured by itself. However, when the curable resin (B) intervenes here, both the curable resin (A) and the curable resin (B) are completely cured by the catalytic effect of the aminosilane compound (C).
As a result, a sufficient curing rate and cured film physical properties can be obtained without using an organometallic catalyst, particularly an organotin catalyst, which has conventionally been regarded as an essential component. As a result, the organotin-based catalyst is substantially not used, or even if it is used, it can be formulated with a very small amount of less than 1000 ppm.

[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, non-tin-based metal catalysts other than aminosilane compounds (C), amine-based catalysts, acidic catalysts, curing catalysts such as basic catalysts, γ-aminopropyltrimethoxy Silane coupling agents such as silane, fillers such as hydrophilic or hydrophobic silica powders, tackifiers such as phenol resins, thixotropic agents such as anhydrous silica, dehydrating agents such as calcium oxide, diluents, plasticizers , Flame retardants, oligomers, anti-aging agents, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents, drying oils, and the like can be blended.

  The curable resin composition according to the present invention is cured by condensation polymerization of hydrolyzable silicon 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 effects of the present invention are manifested when the above-described curable resin and the above-described aminosilane compound (C) are mixed.

  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, sealant, pressure-sensitive adhesive, paint, coating material, sealing material, casting material, coating material, and the like. In particular, by using the curable resin composition according to the present invention as a main component, it is possible to provide a composition having a low environmental load, high safety, and a high curing rate, so that the working time can be shortened. It can be suitably used for applications such as sealants or adhesive compositions as required. The “main body” means that in the crosslinked network structure when the composition is cured, the crosslinked network structure formed by condensation of hydrolyzable silicon groups of the curable resin composition is a main component.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not necessarily limited to an Example.

Synthesis Example 1 Synthesis of Curable Resin A-1 In a reaction vessel, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (222.4 g, 1.0 mol) was stirred at room temperature in a nitrogen atmosphere. While adding methyl acrylate (172.2 g, 2.0 mol) dropwise over 1 hour and further reacting at 80 ° C. for 10 hours, a silane having a trimethoxysilyl group and a secondary amino group in the molecule Compound SE-1 was obtained.
In the reaction vessel, “PML S 4012” (Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, average molecular weight 10,000, 950 g), “PR-3007” (Asahi Denka Kogyo Co., Ltd., propylene oxide and ethylene oxide Copolymerized polyol, average molecular weight 3,000, 50 g), isophorone diisocyanate (53.3 g) and dibutyltin dilaurate (50 mg) were charged and reacted at 80 ° C. for 3 hours with stirring and mixing in a nitrogen atmosphere. Urethane resin U-1 which is an oxyalkylene polymer and has an isocyanate group in its molecule was obtained.
Furthermore, by adding the silane compound SE-1 (105.6 g) and reacting at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere, the main chain is an oxyalkylene polymer, and in the molecule A crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 having a urethane bond, a substituted urea bond and a trimethoxysilyl group was obtained. The formation of SU-1 was confirmed by the fact that an isocyanate group peak (2265 cm ⁻¹ ) was not observed by IR analysis.
200 g of the crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 was put in a reaction vessel, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. There, methyl methacrylate 75g, lauryl methacrylate 50g, 3-acryloxypropyltrimethoxysilane 14g, 3-mercaptopropyltrimethoxysilane 14g, and 2,2'-azobis (2,4-dimethylvaleronitrile) 1. A monomer mixed solution in which 53 g was mixed was dropped over 90 minutes to carry out a polymerization reaction. Furthermore, a polymerization reaction was performed at 80 ° C. for 120 minutes. Thereafter, the unreacted components are distilled off under reduced pressure, whereby the crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 and the crosslinkable reactive silicon group-containing (meth) acrylic acid ester polymer are used. A hydrolyzable silicon group-containing curable resin A-1 was obtained.

Examples 1 to 4 / Comparative Examples 1 and 2
[Examination of appropriate amount]
As the curable resin (A), a modified silicone resin “Excestar S2420” (manufactured by Asahi Glass Co., Ltd.) having a main chain of polyoxypropylene and having a methyldimethoxysilyl group as a crosslinkable group at the terminal is used as the curable resin (B). "GENIOSIL STP-E30" having a main chain of polyoxypropylene and having an α-silyl structure of a methyldimethoxysilyl group type at the end (manufactured by Wacker Chemie AG., Molecular weight of about 16000 converted from equivalent amount of methoxy group, viscosity of about 30000 mPa S / 25 ° C.), using 3-aminopropyltrimethoxysilane as the aminosilane compound (C), and rapidly mixing for 1 minute at the blending ratios shown in Table 1 (numbers represent parts by mass). A composition was prepared and its skinning time was measured.
For the skinning time, the curable resin composition is left in an atmosphere of 23 ± 1 ° C. and a relative humidity of 50 ± 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated | required as time until it stops adhering to a fingertip (based on JISA1439).

(Comparative Examples 3 and 4)
[Effect of aminosilane compound (C)]
Modified silicone resin “Excestar S2420” (manufactured by Asahi Glass Co., Ltd.) (curable resin (A)), “GENIOSIL STP-E30” (manufactured by Wacker Chemie AG.) (Curable resin (B)) was converted into aminosilane compound (C) The curable resin composition was prepared by quickly mixing for 1 minute at the blending ratio shown in Table 1, and the skinning time was measured in the same manner as in Examples 1 to 4.

From the results of Examples 1 to 4 and Comparative Examples 1 and 2, by using “Excestar S2420” which is a curable resin (A) and “GENIOSIL STP-E30” which is a curable resin (B), It can be seen that a sufficient curing rate can be obtained only with 3-aminopropyltrimethoxysilane, which is the aminosilane compound (C), without the addition of the curing catalyst.
Moreover, from the results of Examples 1 to 4 and Comparative Examples 3 and 4, it can be seen that the curing rate is not sufficient when the aminosilane compound (C) is not used.

(Examples 5 to 10)
The skinning time was measured when 70 parts by mass of various curable resins (A) and 30 parts by mass of curable resin (B) were used in combination. As a catalyst, only 3 parts by mass of the aminosilane compound (C) was used.
“GENIOSIL STP-E30” (manufactured by Wacker Chemie AG.) Was used as the curable resin (B), and 3-aminopropyltrimethoxysilane was used as the aminosilane compound (C). Various curable resins (A), curable resins (B), and aminosilane compounds (C) were rapidly mixed for 1 minute at the blending ratios shown in Table 2 (numbers represent parts by mass), and Examples 1-4 Similarly, the skinning time was measured.

(Comparative Examples 5-9)
The skinning time was measured when 3 parts by mass of the aminosilane compound (C) was blended with 100 parts by mass of various curable resins (A).
Various curable resins (A) and aminosilane compounds (C) were rapidly mixed for 1 minute at a blending ratio (numbers are parts by mass) shown in Table 3, and the skinning time was measured in the same manner as in Examples 1 to 4.

The raw materials used are as follows.
・ EXCESTAR G3440ST (* 1)
Modified silicone resin whose main chain is a polyoxypropylene polymer and has a trimethoxysilyl group as a crosslinkable group (Asahi Glass Co., Ltd.)
・ MA440 (* 2)
A mixture of a modified silicone resin whose main chain is a polyoxypropylene polymer having a methyldimethoxysilyl group as a crosslinkable group and a poly (meth) acrylic polymer having an alkoxysilyl group in the molecule (manufactured by Kaneka Corporation)
・ SAT400 (* 3)
Modified silicone resin whose main chain is a polyoxypropylene polymer and has a methyldimethoxysilyl group as a crosslinkable group (manufactured by Kaneka Corporation)
・ ARUFON US-6110 (* 4)
Alkoxysilyl group-containing vinyl polymer (Toagosei Co., Ltd.)
・ ACT FLOW AS-301 (* 5)
Alkoxysilyl group-containing vinyl polymer (manufactured by Soken Chemical Co., Ltd.)

From the results of Examples 5 to 10, by using various curable resins (A) and curable resins (B) in combination, 3-aminopropyl, which is an aminosilane compound (C), without adding another curing catalyst. It can be seen that a sufficient curing rate can be obtained with only trimethoxysilane.
On the other hand, from the results of Comparative Examples 5 to 9, it can be seen that the addition of the aminosilane compound (C) to various curable resins (A) results in a skinning time of 2 days or longer and the curing is very slow.

(Examples 11-15, Comparative Examples 10-14)
As the curable resin (A), a modified silicone resin “Kaneka MS Polymer S203” (manufactured by Kaneka Corporation) having a polyoxypropylene main chain and a methyldimethoxysilyl group as a crosslinkable group at the end is used as a curable resin (B ) "GENIOSIL STP-E10" (manufactured by Wacker Chemie AG., Having a main chain of polyoxypropylene and having a methyldimethoxysilyl group type α-silyl structure at the end, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity About 10,000 mPa · s / 25 ° C.) using N- (2-aminoethyl) -3-aminopropyltrimethoxysilane as the aminosilane compound (C), with the blending ratio (parts by mass) shown in Table 4 and Table 5. The mixture was rapidly mixed for 1 minute to prepare a curable resin composition, and the skinning time was measured.
For the skinning time, the curable resin composition is left in an atmosphere of 23 ± 1 ° C. and a relative humidity of 50 ± 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated | required as time until it stops adhering to a fingertip (based on JISA1439).

  From the results of Tables 4 and 5, N- (2-amino), which is an aminosilane compound (C), can be used by combining the curable resin (A) and the curable resin (B) without adding another curing catalyst. It can be seen that a sufficient curing rate can be obtained with only ethyl) -3-aminopropyltrimethoxysilane. On the other hand, when N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is not used, it can be seen that the skinning time is 2 days or more and the curing is very slow.

(Examples 16 to 21, Comparative Examples 15 to 20)
As the curable resin (A), a modified silicone resin “Kaneka MS Polymer S203” (manufactured by Kaneka Corporation) having a polyoxypropylene main chain and a methyldimethoxysilyl group as a crosslinkable group at the end is used as a curable resin (B ) "GENIOSIL STP-E10" (manufactured by Wacker Chemie AG., Having a main chain of polyoxypropylene and having a methyldimethoxysilyl group type α-silyl structure at the end, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity About 10,000 mPa · s / 25 ° C.) using N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane as the aminosilane compound (C), and in the blending ratio (parts by mass) shown in Table 6 and Table 7. The mixture was rapidly mixed for 1 minute to prepare a curable resin composition, and the skinning time was measured.
For the skinning time, the curable resin composition is left in an atmosphere of 23 ± 1 ° C. and a relative humidity of 50 ± 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated | required as time until it stops adhering to a fingertip (based on JISA1439).

  From the results of Tables 6 and 7, N- (2-amino), which is an aminosilane compound (C), can be used without using any other curing catalyst by using the curable resin (A) and the curable resin (B) in combination. It can be seen that a sufficient curing rate can be obtained with only ethyl) -3-aminopropylmethyldimethoxysilane. On the other hand, when N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane is not used, it can be seen that the skinning time is 2 days or longer and the curing is very slow.

(Examples 22-24, Comparative Examples 21-23)
As the curable resin (A), a modified silicone resin “Kaneka MS Polymer S203” (manufactured by Kaneka Corporation) having a polyoxypropylene main chain and a methyldimethoxysilyl group as a crosslinkable group at the end is used as a curable resin (B ) "GENIOSIL STP-E10" (manufactured by Wacker Chemie AG., Having a main chain of polyoxypropylene and having a methyldimethoxysilyl group type α-silyl structure at the end, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity About 10000 mPa · s / 25 ° C.), using MS3301 (an oligomer compound having an amino group and a hydrolyzable silicon group, manufactured by Chisso Corporation) as an aminosilane compound (C), the blending ratios shown in Table 8 Prepare a curable resin composition by quickly mixing (parts by weight) for 1 minute. And measured the skinning time.
For the skinning time, the curable resin composition is left in an atmosphere of 23 ± 1 ° C. and a relative humidity of 50 ± 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated | required as time until it stops adhering to a fingertip (based on JISA1439).

  From the results of Table 8, by using the curable resin (A) and the curable resin (B) in combination, a sufficient curing rate can be obtained with only the MS3301 which is the aminosilane compound (C) without blending other curing catalyst. I understand that On the other hand, when MS3301 is not used, it can be seen that the skinning time is 2 days or longer and the curing is very slow.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2008-187669) for which it applied on July 18, 2008, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

  The curable resin composition concerning this invention can be used for all the uses to which the conventional curable resin was applied. For example, it can be used as an adhesive, sealant, adhesive, paint, coating material, sealing material, casting material, coating material, etc.

Claims (8)

A curable resin (A) having a hydrolyzable silicon group represented by formula (1) in the molecule;
A curable resin (B) having a hydrolyzable silicon group represented by the formula (2) in the molecule;
The compound represented by the formula (3), the condensation reaction product of the compound represented by the formula (3) alone, and the condensation reaction product of the compound represented by the formula (3) and another silane compound are selected. At least one aminosilane compound (C);
A curable resin composition containing
While the curable resin (B) is contained in 15 to 900 parts by mass with respect to 100 parts by mass of the curable resin (A), the total amount of the curable resin (A) and the curable resin (B) is 100 parts by mass. A curable resin composition containing 0.1 to 20 parts by mass of an aminosilane compound (C).

_{^{-X-SiR 1 a (OR 2}} ) 3-a ··· formula (1)
(However, X represents a hydrocarbon group having 2 or more carbon atoms, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, and a represents 0, 1 or 2, respectively.)

_{^{-A-CH 2 -SiR 3 b (}} OR 4) 3-b ··· formula (2)
(However, A 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 silicon group, and R ³ and R ⁴ are carbon atoms having 1 to 20 carbon atoms. A plurality of alkyl groups, b represents 0, 1 or 2, respectively.)

R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _c (OR ⁹ ) _3-c (3)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms, R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom, and R ⁸ and R ⁹ are each having 1 carbon atom. -20 alkyl groups, c represents 0, 1 or 2, respectively)   The curable resin composition according to claim 1, wherein the main chain of the curable resin (A) is essentially polyoxyalkylene and / or poly (meth) acrylate.   The curable resin composition according to claim 1 or 2, wherein the hydrolyzable silicon group of the curable resin (A) is an alkyl 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 essentially polyoxyalkylene.   The curable resin composition according to any one of claims 1 to 5, wherein the organotin catalyst is 0 to less than 1000 ppm.   A sealant composition comprising the curable composition according to any one of claims 1 to 6 as a main component of a curable component.   The adhesive composition which has the curable composition as described in any one of Claims 1-6 as a main component of a sclerosing | hardenable component.