KR20110043590A - Curable resin composition - Google Patents

Abstract

화학식 2

화학식 3

상기 화학식 1, 2 및 3에서,
X는 탄소수 2 이상의 탄화수소기이고,
A는 가수분해성 규소기에 포함되는 규소 원자에 결합하는 메틸렌기에 비공유 전자쌍을 갖는 헤테로 원자가 결합하고 있는 결합 관능기이고,
R¹, R², R³, R⁴, R⁸, R⁹는 탄소수 1 내지 20개의 알킬기이고,
R⁵, R⁶은 유기기 또는 수소 원자이고,
R⁷은 가수분해성 규소 원자에 결합하는 탄소 원자에 헤테로 원자가 결합하지 않은 유기기이고,
a, b, c는 0, 1 또는 2이다.An environmental load is reduced, and it provides a curable resin composition which has a sufficient sufficient curing speed with safety. The composition is a curable resin (A) having a hydrolyzable silicon group (1) in a molecule, a curable resin (B) having a hydrolyzable silicon group (2) in a molecule, a compound (3) or a condensate of (3) alone or At least 1 aminosilane compound (C) of the condensate of (3) and another silane compound is contained at a specific ratio.
Formula 1

Formula 2

Formula 3

In Chemical Formulas 1, 2 and 3,
X is a hydrocarbon group of 2 or more carbon atoms,
A is a bond functional group to which a hetero atom having a non-covalent electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silicon group,
R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ⁹ are alkyl groups having 1 to 20 carbon atoms,
R ⁵ and R ⁶ are an organic group or a hydrogen atom,
R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom,
a, b, c is 0, 1 or 2.

Description

Curable Resin Composition {CURABLE RESIN COMPOSITION}

TECHNICAL FIELD The present invention relates to a curable resin composition containing a hydrolyzable silicon group that can be cured under a room temperature atmosphere. More particularly, the present invention relates to a curable composition having a sufficient and sufficient curing rate while reducing environmental load and ensuring safety. will be.

Curable resin which has a hydrolyzable silicon group in a molecule | numerator is used widely as base polymers, such as a sealant, an adhesive agent, an adhesive, and a coating material. 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 air. Especially curable resin whose hydrolyzable silicon group is an alkoxysilane is widely used by the point which is few in safety and odor (patent document 1 and patent document 2).

However, since a sufficient curing rate cannot be obtained at room temperature only with the alkoxysilyl group, such a curable resin is usually used in combination with a curing catalyst in order to obtain a sufficient curing rate. Organic tin compounds are widely used as curing catalysts.

On the other hand, using an amine compound, a carboxylic acid compound, or a bismuth type compound and a titanium type compound as a curing catalyst is proposed (patent document 3 and patent document 4). However, in such a catalyst system, the curing rate was not practically satisfactory.

Moreover, it is an alkoxysilyl group which has sufficient sclerosis | hardenability even if it is a catalyst, and couple | bonded hetero-atoms, such as oxygen, nitrogen, and sulfur which have a lone pair with the alpha-position carbon couple | bonded with the hydrolyzable silicon atom (it describes as "alpha-silane structure" hereafter). In some cases, a compound has been proposed (Patent Document 5).

Japanese Patent Application Laid-Open No. 52-73998 Japanese Laid-Open Patent Publication No. 63-112642 Japanese Patent Publication No. 3793074 Japanese Patent Publication No. 3768072 Japanese Laid-Open Patent Publication No. 2005-514504

As for organotin compounds, their toxicity has recently become a problem. In particular, among the organotin compounds, in which tributyltin derivatives having high toxicity are contained, it is desired to suppress the content to 1000 ppm or less with respect to the composition.

In addition, not only tributyltin derivatives but also catalysts based on heavy metals containing tin are concerned about toxicity and environmental load.

An object of the present invention is to achieve a reduction in environmental load and to obtain a curable composition having a sufficient and sufficient curing rate while ensuring safety.

In order to solve such a problem, the present inventors, as a result of intensive studies, mix a curable resin containing a hydrolyzable silicon group and a curable resin having an α-silane structure in a molecule in a certain range of ratios, and further use α- as a catalyst. By adding an aminosilane compound having no silane structure, it was found that a sufficient curing rate was obtained at room temperature, thus completing the present invention.

That is, the first invention,

Curable resin (A) which has a hydrolyzable silicon group represented by General formula (1) in a molecule | numerator,

Curable resin (B) which has a hydrolyzable silicon group represented by General formula (2) in a molecule | numerator, and

At least one aminosilane compound (C) selected from a compound represented by the formula (3), a condensation reaction product of the compound represented by the formula (3) alone, and a condensation reaction product of the compound represented by the formula (3) with another silane compound,

As curable resin composition containing

15-900 mass parts of curable resin (B) is contained with respect to 100 mass parts of curable resin (A), and an aminosilane compound (C) with respect to 100 mass parts of total of curable resin (A) and curable resin (B). It relates to curable resin composition contained 0.1-20 mass parts.

In Chemical Formulas 1, 2 and 3,

X is a hydrocarbon group of 2 or more carbon atoms,

R ¹ , R ² is an alkyl group having 1 to 20 carbon atoms,

a is 0, 1 or 2,

A is a bond functional group to which a hetero atom having a non-covalent electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silicon group,

R ³ , R ⁴ is an alkyl group having 1 to 20 carbon atoms,

b is 0, 1 or 2.

R ⁵ and R ⁶ are an organic group or a hydrogen atom,

R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom,

R ⁸ and R ⁹ are alkyl groups having 1 to 20 carbon atoms,

c is 0, 1 or 2.

Usually, although an aminosilane compound (C) acts as a very weak curing catalyst with respect to curable resin (A), it cannot fully harden curable resin (A) independently. However, since curable resin (B) is interposed here, both curable resin (A) and curable resin (B) are fully hardened by the catalytic effect of an aminosilane compound (C).

Moreover, 2nd invention is related with the curable resin composition which concerns on 1st invention characterized by the principal chain of curable resin (A) being essentially polyoxyalkylene and / or poly (meth) acrylic acid ester.

Moreover, 3rd invention relates to the curable resin composition which concerns on the 1st or 2nd invention characterized by the hydrolyzable silicon group of curable resin (A) being an alkyl dialkoxy silyl group.

Moreover, 4th invention relates to curable resin composition in any one of 1st-3rd term | claim whose curable resin (A) does not contain a urethane bond or a urea bond in the molecule | numerator.

In addition, the fifth invention relates to the curable resin composition according to any one of the first to fourth aspects, wherein the main chain of the curable resin (B) is essentially polyoxyalkylene.

The sixth invention also relates to the curable resin composition according to any one of the first to fifth aspects, wherein the organic tin catalyst is 0 to less than 1000 ppm.

Moreover, 7th invention relates to the sealant composition which makes the curable composition which concerns on any one of 1st-6th invention mainly as a curable component.

Moreover, 8th invention relates to the adhesive composition which uses the curable composition which concerns on any one of 1st-6th invention mainly as a curable component.

Curable resin composition which concerns on this invention exhibits the effect of providing sufficient hardening speed, achieving the reduction of environmental load, and ensuring safety.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, this invention is not limited only to these illustrations, Of course, various changes can be added within the range which does not deviate from the summary of this invention.

[About Curable Resin (A)]

Curable resin (A) in this invention is curable resin which has a hydrolyzable silicon group represented by General formula (1) in a molecule | numerator.

Formula 1

In Chemical Formula 1,

X is a hydrocarbon group of 2 or more carbon atoms,

R ¹ , R ² is an alkyl group having 1 to 20 carbon atoms,

a is 0, 1 or 2.

The hydrocarbon group (X) having 2 or more carbon atoms is bonded to the silicon atom in the hydrolyzable silicon group, which is bonded to the main chain skeleton. In addition, with respect to the silicon atom, in addition to the number of bonds with hydrocarbon group X, one to three alkoxy groups (OR ² ) are bonded as a hydrolyzable group, and two to zero hydrocarbon groups (R ¹ ) are bonded as the remaining number of bonds. I'm doing it.

Here, R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms. An alkoxy group (OR ²⁾ as a methoxy to ethoxy group, a propoxy group, preferably a butoxy group, and more preferably a methoxy group or an ethoxy group. As hydrocarbon group (R <^1> ) couple | bonded with the remaining bond water of a silicon atom, it is preferable that they are a methyl group, an ethyl group, a propyl group, and a butyl group, More preferably, they are a methyl group or an ethyl group.

In addition, when hydrolyzable silicon group of curable resin (A) especially desires the comparatively low modulus and high elongation hardened | cured material represented by the sealing material, it is an alkyl dialkoxy silyl group (a = 1), and the balance of hardening speed and modulus It is preferable at the point which is easy to take.

Although the molecular weight of curable resin (A) is not specifically limited, 1,000-80,000 are preferable, 1,500-60,000 are more preferable, 2,000-40,000 are especially preferable. If the molecular weight is less than 1,000, the physical properties may recede due to the excessively high crosslinking density. If the molecular weight is more than 80,000, the viscosity is increased and the workability is deteriorated. Therefore, a large amount of solvent or a plasticizer is required. It may become.

As the main chain skeleton of the curable resin (A), a main chain skeleton generally used for silicone resins such as polyoxyalkylenes, vinyl polymers, saturated hydrocarbon polymers, unsaturated hydrocarbon polymers, polyesters, polycarbonates, polydimethylsiloxanes and modified silicone resins Although at least 1 sort (s) of frame | skeleton selected from is employ | adopted, it is especially preferable that it is polyoxyalkylene and / or poly (meth) acrylic acid ester from the point of the film physical property of hardened | cured material. Here, "essentially" means that the said structure is a principal element of the repeating unit which is a main chain skeleton of curable resin (A). In addition, the said structure may be contained independently in curable resin (A), and may be contained 2 or more types. In addition, in this application, acrylic acid and methacrylic acid are named generically and described as "(meth) acrylic acid."

As a commercial item of curable resin (A), it sells many as a silicone resin or a modified silicone resin. For example, Cyril series, MS polymer series, MA series, SA series, OR series, and EPION series by Kaneka Corporation; Asahi Glass Co., Ltd. ES series, ESGX series; Silane-modified polyalphaolefin produced by Degussa Japan, XPR series manufactured by Toagosei Co., Ltd., ARUFON US series; Soken Chemical Co., Ltd. Actflow series etc. are mentioned.

Moreover, as curable resin (A), curable silicone-type resin containing polar groups, such as a urethane bond and a urea bond, can also be used in a molecule | numerator. What is necessary is just to synthesize | combine curable resin (A) containing a polar group in a molecule | numerator by a conventionally well-known method. For example, the method of making an amino group containing alkoxysilane compound (or a mercapto group containing alkoxysilane compound) react with an isocyanate group terminal polymer, the method of making an isocyanate group containing alkoxysilane compound react with a hydroxyl group terminal polyol, etc. are known. More specifically, Japanese Patent No. 3030020, Japanese Patent No. 3343604, Japanese Patent Application Laid-Open No. 2005-54174, US Patent 7208560, US Patent No. 7230064, and Japanese Patent Application Laid-Open No. 8-053528 , And can be easily synthesized by the method described in JP-A-6-211879.

Especially as curable resin (A), when the comparatively low modulus and high stretch hardened | cured material represented by the sealing material are desired, it is preferable that a urethane bond or a urea bond is not contained in the molecule | numerator from the point of being easy to adjust modulus, etc. Do.

[About curable resin (B)]

Curable resin (B) in this invention is curable resin which has a hydrolyzable silicon group represented by General formula (2) in a molecule | numerator.

Formula 2

In Chemical Formula 2,

A is a bond functional group to which a hetero atom having a non-covalent electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silicon group,

R ³ , R ⁴ is an alkyl group having 1 to 20 carbon atoms,

b is 0, 1 or 2.

The said hydrolyzable silicon group couple | bonds with the silicon atom contained in the said hydrolyzable silicon group the bond functional group which the hetero atom which has a lone pair has couple | bonded via the methylene group. A bond functional group is a structure which connects a hydrolyzable silicon group and a main chain, and if a hetero atom which has a non-covalent electron pair couple | bonds with the methylene group couple | bonded with the silicon atom contained in a hydrolyzable silicon group, it will not specifically limit, Specifically, a (thio) urethane bond, (Thio) urea bond, (thio) substituted element bond, (thio) ester bond, (thio) ether bond, etc. are illustrated. Moreover, the said hydrolyzable silicon group is couple | bonded with the main chain skeleton through this coupling | bonding functional group.

In addition, with respect to the silicon atom, in addition to the number of bonds with the methylene group, 1 to 3 alkoxy groups (OR ⁴ ) are bonded as hydrolyzable groups, and 2 to 0 hydrocarbon groups (R ³ ) are bonded as the remaining number of bonds. It is.

Here, R ³ and R ⁴ are each an alkyl group having 1 to 20 carbon atoms. An alkoxy group (OR ⁴⁾ As, the methoxy group, an ethoxy group, a propoxy group, preferably a butoxy group, and more preferably a methoxy group or an ethoxy group. As hydrocarbon group (R <^3> ) couple | bonded with the remaining bond water of a silicon atom, it is preferable that they are a methyl group, an ethyl group, a propyl group, and a butyl group, More preferably, they are a methyl group or an ethyl group.

The hydrolyzable silicon group of the curable resin (B) is preferably an alkyldialkoxysilyl group (b = 1) or a trialkoxysilyl group (b = O) from the viewpoint of availability and modulus of the cured product.

Although the molecular weight of curable resin (B) is not specifically limited, 1,000-80,000 are preferable, 1,500-60,000 are more preferable, 2,000-40,000 are especially preferable. If the molecular weight is less than 1,000, the physical properties may recede due to the excessively high crosslinking density. If the molecular weight is more than 80,000, the viscosity is increased and the workability is deteriorated. Therefore, a large amount of solvent or a plasticizer is required. It may become.

In this application, such chemical structure is described as "(alpha)-silane structure." By selecting the α-silane structure, since the moisture reactivity is much higher than that of a conventional hydrolyzable silicon group, a sufficient curing rate can be obtained even when a tin catalyst is not used or even in a smaller amount than usual.

As the main chain skeleton of the curable resin (B), a main chain skeleton generally used for silicone resins such as polyoxyalkylenes, vinyl polymers, saturated hydrocarbon polymers, unsaturated hydrocarbon polymers, polyesters, polycarbonates, polydimethylsiloxanes, and modified silicone resins Although at least 1 sort (s) of frame | skeleton chosen from is employ | adopted, it is especially preferable that it is polyoxyalkylene essentially from the point of the availability, the film physical properties of hardened | cured material, etc. Here, "essentially" means that the said structure is a principal element of the repeating unit which is a main chain skeleton of curable resin (B). In addition, the said structure may be contained independently in curable resin (B), and may be contained 2 or more types.

In order to obtain curable resin (B), it is good to synthesize | combine by a conventionally well-known method. For example, a method of reacting an isocyanate methylalkoxysilane compound with a polyol compound, reacting the polyol compound with a polyisocyanate compound to synthesize a urethane prepolymer, and then applying an active hydrogen group to the urethane prepolymer at an α position such as an aminomethylalkoxysilane compound. The method of making the compound which the hetero atom which has the bond couple, etc. react are known. More specifically, it can be synthesize | combined easily by the method of Unexamined-Japanese-Patent No. 2004-518801, Unexamined-Japanese-Patent No. 2004-536957, Unexamined-Japanese-Patent No. 2005-501146, etc.

As a commercial item of curable resin (B), GENIOSIL STP-E10 by the Wacker Chemie AG, GENIOSIL STP-E30, etc. are mentioned.

Each main chain skeleton of curable resin (A) and curable resin (B) may be same or different. However, the one in which the curable resin (A) and the curable resin (B) are commonly used is preferable because the effect of the present invention is more easily obtained.

In order to improve the compatibility of curable resin (A) and curable resin (B), a conventionally well-known technique can be used. For example, compounds generally known as compatibilizers can be added. Moreover, the main chain skeleton of curable resin (A) and curable resin (B) can also be improved by selecting the combination with favorable compatibility. Specifically, compatibility can be improved by using a thing whose polarity of a principal chain skeleton is comparatively close. For example, when both of the same backbone skeletons are selected, compatibility is very good. Moreover, even if it is not the same, it is also preferable to select the frame | skeleton comparatively similar in structure, such as polyolefin skeletons and polyether skeletons. It is also known that the polyoxyalkylene skeleton and the poly (meth) acrylate skeleton having a specific structure have good compatibility. As mentioned above, although the example of the compatibility with favorable compatibility was illustrated, this invention is not limited to these.

[Aminosilane Compound (C)]

In the present invention, the aminosilane compound (C) is a compound having at least one amino group and a hydrolyzable silicon group in a molecule, and is an aminosilane compound in which two or more carbon atoms are bonded between the amino group and the hydrolyzable silicon group. The aminosilane compound (C) in this invention is an aminosilane compound which does not have an alpha silane structure. Low molecular aminosilane compounds having an α-silane structure are not suitable because of their high toxicity.

As said aminosilane compound (C), the condensation reaction product of the aminosilane compound (c1) represented by the following general formula (3), the aminosilane compound (c1) alone, or the silane represented by the aminosilane compound (c1) and the following general formula (4) And condensation reaction products with other silane compounds exemplified in the compound (c2). In these, the condensation reaction product of an aminosilane compound (c1) or an aminosilane compound (c1) alone is more preferable at the point which is easy to express the effect of the amino group in the said aminosilane compound (C).

As an amino group contained in the said aminosilane compound (C), although the amino group of any of primary, secondary, and tertiary may be sufficient, adhesiveness, such as an adhesive agent, a sealing material, an adhesive, etc. are used for the curable resin composition which concerns on this invention. In the required use, a primary or secondary amino group, in which the adhesion imparting effect is more easily expressed, is preferable, and a primary amino group is particularly preferable. In addition, one or two or more amino groups may be contained in the aminosilane compound (C). In addition, as a hydrolyzable silicon group contained in the said aminosilane compound (C), when illustrated by the aminosilane compound (c1) represented by following formula (3), an alkyl dialkoxy silyl group (c = 1) or a trialkoxy silyl group ( c = 0) is preferable from the point that it is easy to obtain and the modulus preparation of hardened | cured material is easy. The hydrolyzable silicon group contained in the said aminosilane compound (C) may be one, or may be two or more.

Formula 3

In Chemical Formulas 3 and 4,

R ⁵ and R ⁶ are an organic group or a hydrogen atom,

R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom,

R ⁸ and R ⁹ are alkyl groups having 1 to 20 carbon atoms,

c is 0, 1 or 2,

R ¹⁰ , R ¹¹ and R ¹² are selected from a phenyl group, an alkyl group having a molecular weight of 500 or less, a mercaptopropyl group, a ureidepropyl group, a phenoxy group, and an organic group having a molecular weight of 500 or less represented by an alkoxy group having 1 to 6 carbon atoms. It is one or more kinds of groups,

R ¹³ is at least one group 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 Formula (3 ').

[Formula 3 ']

In Chemical Formula 3 ',

R ^{5 '} and R ^6' are an organic group or a hydrogen atom having a molecular weight of 500 or less,

R ^{7 '} is a divalent organic group having a molecular weight of 500 or less, wherein a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom, and may contain a secondary amino group.

R ^{8 '} and R ^9' are an alkyl group having 1 to 20 carbon atoms,

c is 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 -Dimethylbutyl triethoxysilane, 4-amino-3-dimethylbutylmethyldiethoxysilane, bis (3-trimethoxypropyl) amine, bis (3-methyldimethoxypropyl) amine, N-phenylaminopropyltrimeth Methoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutylmethyldimeth Aminosilanes such as cysilane, N-butylaminopropyltrimethoxysilane, N-butylaminopropylmethyldimethoxysilane, diethylenetriaminopropyltrimethoxysilane and N- (2-propenyl) aminopropyltrimethoxysilane Although a compound is mentioned, It is not limited to these. In addition, ketiminsilane compounds such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine also have a primary amino group due to moisture, and thus the aminosilane compound (c1). Substantially included). Among these, in using 3-aminopropyl trimethoxysilane or N- (2-aminoethyl) -3-aminopropyl trimethoxysilane in that it is easy to obtain, and it is high in hardening promoting effect. desirable. Moreover, it is known that the hardened | cured material which the aminosilane compound was mix | blended is generally easy to discolor yellow by heat and light. When used for applications in which such yellowing is not preferred, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutelmethyldimethoxysilane, 4-amino-3-dimethylbuteltriethoxysilane, The number of hydrogen atoms bonded to the carbon at the β-position of the nitrogen atom, such as 4-amino-3-dimethylbutylmethyldiethoxysilane, N-ethylaminoisobutyltrimethoxysilane, and N-ethylaminoisobutylmethyldimethoxysilane The use of a few aminosilane compounds is preferable because yellowing is reduced.

About the silane compound (c2)

Specific examples of the silane compound (c2) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Tetraethoxysilane, dimethoxy diethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-uradepropyl trimethoxysilane, etc. are illustrated. Among these, it is preferable to use methyl trimethoxysilane and dimethyldimethoxysilane from a viewpoint of the ease of condensation reaction with an aminosilane compound (c1).

The condensation reaction product of the aminosilane compound (c1) alone or the aminosilane compound (c1) and the silane compound (c2) may be synthesized by a conventionally known method. Specifically, the method of making an aminosilane compound (c1) react with water, or the method of making an aminosilane compound (c1) and a silane compound (c2) react with water is mentioned. Aminosilane compound (c1) alone or the condensation reaction product of an aminosilane compound (c1) and a silane compound (c2) is marketed, These can be used in this invention. As a commercial item, the silyl groups of aminosilanes, such as MS3301 (Chitso Co., Ltd. brand name), MS3302 (Chitso Co., Ltd. brand name), X-40-2651 (Shin-Etsu Chemical Co., Ltd. brand name), are independent or its The compound which some condensed with the other alkoxysilane compound is mentioned.

What is necessary is just to select the said aminosilane compound (C) suitably in order to obtain desired hardened film physical property and / or hardening rate, You may use together 1 type individually or 2 or more types.

[About Blending Amount]

In this invention, 15-900 mass parts of curable resin (B) is contained with respect to 10 mass parts of curable resin (A), Preferably 18-800 mass parts of curable resin (B), More preferably, 20-part 700 mass parts, Especially preferably, it is 30-500 mass parts, Most preferably, it is 50-300 mass parts. When the amount of curable resin (B) is less than 15 mass parts, the effect of hardening promotion by curable resin (B) may not fully be exhibited (that is, hardening rate does not become enough), and when it exceeds 900 mass parts, On the contrary, the relative ratio of the curable resin (A) decreases, making it difficult to balance such as adhesive strength and physical properties after curing (particularly hardened film properties are hard to be obtained).

In addition, in this invention, 0.1-20 mass parts of aminosilane compounds (C) are contained with respect to 100 mass parts of total of curable resin (A) and curable resin (B), Preferably an aminosilane compound (C) It is 0.5-15 mass parts, More preferably, it is 1-10 mass parts. When the quantity of an aminosilane compound (C) is less than 0.1 mass part, hardening promotion may not be enough (it is easy to produce a problem in terms of a curing rate), and when it exceeds 20 mass parts, it is relatively curable resin (A) and Since the ratio of curable resin (B) is reduced, it becomes difficult to adjust the film physical property of hardened | cured material, a large amount of water is required for hardening, and internal troubles worsen easily.

In the present invention, the aminosilane compound (C) mainly acts as a curing catalyst.

Usually, although an aminosilane compound (C) acts as a very weak curing catalyst with respect to curable resin (A), it cannot fully harden curable resin (A) independently. However, since curable resin (B) is interposed here, both curable resin (A) and curable resin (B) are fully hardened by the catalytic effect of an aminosilane compound (C).

Thereby, sufficient hardening speed and hardened film physical property can be obtained, without using the organometallic catalyst which has become an essential component conventionally, especially an organic tin catalyst. Thereby, even if the organic tin-based catalyst is not substantially used or is used, it can be solved with a very small amount of formulation of less than 1000 ppm.

[Other Ingredients]

In the curable resin composition which concerns on this invention, arbitrary conventionally well-known compounds and a substance can be mix | blended as another component. For example, various resins other than curable resin used by this invention, curing catalysts, such as a non-tin metal catalyst other than an aminosilane compound (C), an amine catalyst, an acidic catalyst, a basic catalyst, (gamma) -aminopropyl trimethoxy Silane coupling agents such as silanes, 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 agent, ultraviolet absorber, pigment, titanate coupling agent, aluminum coupling agent, dry oil and the like.

Curable resin composition concerning this invention hardens | cures by hydrocondensation of hydrolyzable silicon groups in presence of water. Therefore, when used as a one-component composition, it is handled in a hermetically sealed state so as not to contact with air (moisture in the air) during storage or conveyance. In addition, when it is used, the curable resin is cured in contact with moisture in the air when it is opened and applied at an arbitrary location. When using as a two-component curable composition, when mixing said curable resin and said aminosilane compound (C), the effect which concerns on this invention is expressed.

Curable resin composition which concerns on this invention can be used for all the uses to which the conventional curable resin was applied. For example, it can use as an adhesive agent, a sealant, an adhesive, a coating material, a coating material, a wood filler material, a casting material, a coating material, etc. In particular, since the composition having the curable resin composition according to the present invention as a main component can provide a composition having a low environmental load, high safety, and a high curing rate, the use of a sealant or an adhesive composition requiring a shortening of the working time. It can be used suitably. In addition, a "main body" means that the crosslinked network structure by condensation of the hydrolyzable silicon group of the said curable resin composition becomes a main structural component in the crosslinked network structure when the said composition hardens.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

Synthesis Example 1 Synthesis of Curable Resin A-1

In the reaction vessel, methyl acrylate (172.2 g, 2.0 mol) was stirred for 1 hour while N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (222.4 g, 1.0 mol) was stirred at room temperature under a nitrogen atmosphere. Was added dropwise over and reacted at 80 ° C. for 10 hours to obtain a silane compound SE-1 having a trimethoxysilyl group and a secondary amino group in the molecule.

In a reaction vessel, "PML S 4012" (made by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, average molecular weight 10,000, 950 g), "PR-3007" (made by Asahi Denka Kogyo Co., Ltd., propylene oxide and ethylene Copolymerized polyol of oxide, average molecular weight 3,000, 50g), isophorone diisocyanate (53.3g) and dibutyltin dilaurate (50mg) was injected and reacted for 3 hours at 80 ℃ while stirring and mixing in a nitrogen atmosphere, the main chain Urethane resin U-1 which is an oxyalkylene polymer and has an isocyanate group in the molecule | numerator was obtained.

Further, by adding the silane compound SE-1 (105.6 g) and reacting under a nitrogen atmosphere with stirring and mixing at 80 ° C. for 1 hour, the main chain is an oxyalkylene polymer, and a urethane bond, a substituted element bond, and a tree in the molecule thereof. A crosslinkable reactive silicon group containing oxyalkylene polymer SU-1 with methoxysilyl group was obtained. The generation of SU-1 was confirmed by the IR analysis that the peak (2265 cm ^-1 ) of the isocyanate group was not observed.

Into the reaction vessel, 200 g of the crosslinkable reactive silicon group-containing oxyalkylene polymer SU-1 was placed and heated to 80 ° C under a nitrogen atmosphere. Here, 75 g of methyl methacrylate, 50 g of lauryl methacrylate, 14 g of 3-acryloxypropyl trimethoxysilane, 14 g of 3-mercaptopropyl trimethoxysilane, and 2,2'- azobis (2,4- The monomer mixture which mixed 1.53 g of dimethylvaleronitrile) was added dropwise over 90 minutes, and polymerization reaction was performed. In addition, the polymerization reaction was carried out at 80 ° C. for 120 minutes. The hydrolyzable silicon group which consists of a crosslinkable reactive silicon group containing oxyalkylene polymer SU-1 and a crosslinkable reactive silicon group containing (meth) acrylic acid ester polymer by depressurizingly distilling an unreacted agent after that, Containing curable resin A-1 was obtained.

(Examples 1 to 4 / Comparative Examples 1 and 2)

[Review of Appropriate Compounding Amount]

As curable resin (A), the modified silicone resin "Excestar S2420" (refer to Asahi Glass Co., Ltd.) which has a polyoxypropylene main chain and has a methyldimethoxysilyl group as a crosslinkable group at the terminal as curable resin (B) "GENIOSIL STP-E30" (Wacker Chemie AG, manufactured by Wacker Chemie AG., Having a molecular weight of approximately 16000 and a viscosity of about 30000 mPas / s) having a main chain of polyoxypropylene and having a methyl-disilylsilyl-type α-silyl structure at its terminal. 25 degreeC) is used as 3-aminopropyl trimethoxysilane as an aminosilane compound (C), and it mixes rapidly for 1 minute by the compounding ratio (the number shows a mass part) shown in Table 1, and prepares curable resin composition. And the film formation time was measured.

The film formation time left the curable resin composition in an atmosphere of 23 ± 1 ° C. and a relative humidity of 50 ± 5%, and gently touched the surface with a fingertip degreased with ethanol, and the surface curable resin composition adhered to the fingertip. It was calculated as time until we disappeared (based on JIS A 1439).

(Comparative Examples 3 and 4)

[Effect of Aminosilane Compound (C)]

Modified silicone resin "Excestar S2420" (reference: manufactured by Asahi Glass Co., Ltd.) (curable resin (A)), "GENIOSIL STP-E30" [Reference: Wacker Chemie AG. Manufacture] (curable resin (B)) is rapidly mixed for 1 minute at the blending ratio shown in Table 1 without using an aminosilane compound (C), to prepare a curable resin composition, as in Examples 1 to 4 The film formation time was measured.

Even if it does not mix | blend another hardening catalyst by using together "Excestar S2420" which is curable resin (A), and "GENIOSIL STP-E30" which is curable resin (B), from the result of Examples 1-4 and Comparative Examples 1 and 2. It can be seen that sufficient curing rate is obtained only with 3-aminopropyltrimethoxysilane, which is the aminosilane compound (C).

In addition, it is understood from the results of Examples 1 to 4 and Comparative Examples 3 and 4 that the curing rate is not sufficient when the aminosilane compound (C) is not used.

(Examples 5 to 10)

The film formation time when 70 mass parts of various curable resins (A) and 30 mass parts of curable resins (B) were used together was measured. Only 3 parts by mass of the aminosilane compound (C) was used as the catalyst.

As curable resin (B) "GENIOSIL STP-E30" [Refer to Wacker Chemie AG. Manufacture] was used as the aminosilane compound (C) 3-aminopropyltrimethoxysilane. Various curable resin (A), curable resin (B), and aminosilane compound (C) are rapidly mixed for 1 minute by the mixing | blending ratio (number shows a mass part) shown in Table 2, and it is like Examples 1-4. The film formation time was measured.

(Comparative Examples 5 to 9)

The film formation time at the time of mix | blending 3 mass parts of aminosilane compounds (C) with 100 mass parts of various curable resin (A) was measured.

Various curable resins (A) and aminosilane compound (C) were quickly mixed for 1 minute by the mixing | blending ratio (number is a mass part) shown in Table 3, and the film formation time was measured like Examples 1-4.

In addition, the used raw material is as follows.

EXCESTAR G3440ST (* 1)

Modified silicone resin whose main chain is a polyoxypropylene polymer and has a trimethoxysilyl group as a crosslinkable group (manufactured by Asahi Glass Co., Ltd.)

MA440 (* 2)

A mixture of a modified silicone resin whose main chain is a polyoxypropylene polymer and has a methyldimethoxysilyl group as a crosslinkable group, and a poly (meth) acrylic polymer having an alkoxysilyl group in its molecule (manufactured by Kaneka Co., Ltd.)

SAT400 (* 3)

Modified silicone resin whose main chain is a polyoxypropylene polymer and has a methyldimethoxysilyl group as a crosslinkable group (manufactured by Kaneka Co., Ltd.)

ARUFON US-6110 (* 4)

Alkoxy silyl group-containing vinyl polymer [Reference: manufactured by Toagosei Co., Ltd.]

Act flow AS-301 (* 5)

Alkoxy silyl group-containing vinyl polymer [see: Soken Chemical Co., Ltd.]

From the result of Examples 5-10, by using various curable resin (A) and curable resin (B) together, even if it does not mix | blend another curing catalyst, only the aminosilane compound (C) 3-aminopropyl trimethoxysilane is sufficient hardening. It can be seen that the speed is obtained.

On the other hand, it can be seen from the results of Comparative Examples 5 to 9 that only the addition of the aminosilane compound (C) to various curable resins (A) results in a film formation time of two days or more, and very slow curing. have.

(Examples 11-15, Comparative Examples 10-14)

As curable resin (A), the modified silicone resin "Kaneka MS polymer-S203" [reference: Kaneka Corporation make] which has a principal chain polyoxypropylene and has a methyldimethoxysilyl group as a crosslinkable group at the terminal is made into curable resin ( As B), "GENIOSIL STP-E10" having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type? -Silyl structure at its terminal (manufactured by Wacker Chemie AG., Equivalent weight of methoxy group, about 10000, viscosity of about 10000 mPa) S / 25 ° C), as the aminosilane compound (C), using N- (2-aminoethyl) -3-aminopropyltrimethoxysilane as shown in Tables 4 and 5 (parts by mass) The mixture was rapidly stirred for 1 minute to prepare a curable resin composition, and the film formation time was measured.

Film formation time left curable resin composition in the atmosphere of 23 +/- 1 degreeC and 50 +/- 5% of relative humidity, and lightly touches the surface with the fingertip degreased with ethanol, and the surface curable resin composition adheres to the fingertip. It was calculated as time until we disappeared (based on JIS A 1439).

From the result of Table 4 and Table 5, by using curable resin (A) and curable resin (B) together, N- (2-aminoethyl) -3-amino which is an aminosilane compound (C) without mix | blending another hardening catalyst It can be seen that a sufficient curing rate is obtained only with propyltrimethoxysilane. On the other hand, when N- (2-aminoethyl) -3-aminopropyl trimethoxysilane is not used, it turns out that film formation time becomes 2 days or more, and hardening is very slow.

(Examples 16 to 21, Comparative Examples 15 to 20)

As curable resin (A), the modified silicone resin "Kaneka MS polymer-S203" [reference: Kaneka Corporation make] which has a principal chain polyoxypropylene and has a methyldimethoxysilyl group as a crosslinkable group at the terminal is made into curable resin ( As B), "GENIOSIL STP-E10" having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type? -Silyl structure at its terminal (manufactured by Wacker Chemie AG., Equivalent weight of methoxy group, about 10000, viscosity of about 10000 mPa) S / 25 ° C) using N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane as the aminosilane compound (C), the blending ratios shown in Tables 6 and 7 (mass parts) The mixture was rapidly stirred for 1 minute to prepare a curable resin composition, and the film formation time was measured.

Film formation time left curable resin composition in the atmosphere of 23 +/- 1 degreeC and 50 +/- 5% of relative humidity, and lightly touches the surface with the fingertip degreased with ethanol, and the surface curable resin composition adheres to the fingertip. It was calculated as time until we disappeared (based on JIS A 1439).

From the results of Tables 6 and 7, by using the curable resin (A) and the curable resin (B) in combination, N- (2-aminoethyl) -3-amino which is an aminosilane compound (C) even if no other curing catalyst is added It can be seen that a sufficient curing rate is obtained only with propylmethyldimethoxysilane. On the other hand, when N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane is not used, it turns out that film formation time becomes 2 days or more and hardening is very slow.

(Examples 22 to 24, Comparative Examples 21 to 23)

As curable resin (A), the modified silicone resin "Kaneka MS polymer-S203" [reference: Kaneka Corporation make] which has a principal chain polyoxypropylene and has a methyldimethoxysilyl group as a crosslinkable group at the terminal is made into curable resin ( As B), "GENIOSIL STP-E10" having a main chain of polyoxypropylene and having a methyldimethoxysilyl group-type? -Silyl structure at its terminal (manufactured by Wacker Chemie AG., Equivalent weight of methoxy group, about 10000, viscosity of about 10000 mPa) S / 25 ° C) as an aminosilane compound (C) at a compounding ratio (mass part) shown in Table 8 using MS3301 (an oligomeric compound having a Chisoso trade name, an amino group and a hydrolyzable silicon group) It mixed rapidly for 1 minute, prepared curable resin composition, and measured the film formation time.

Film formation time left curable resin composition in the atmosphere of 23 +/- 1 degreeC and 50 +/- 5% of relative humidity, and lightly touches the surface with the fingertip degreased with ethanol, and the surface curable resin composition adheres to the fingertip. It was calculated as time until we disappeared (based on JIS A 1439).

From the results of Table 8, it is understood that by using the curable resin (A) and the curable resin (B) together, a sufficient curing rate is obtained only with MS3301, which is an aminosilane compound (C), even when no other curing catalyst is added. On the other hand, when MS3301 is not used, it turns out that film formation time becomes two days or more and hardening is very slow.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

In addition, this application is based on the JP Patent application (Japanese Patent Application No. 2008-187669) of an application on July 18, 2008, The whole content is integrated by reference. In addition, all references cited herein are incorporated in their entirety.

Industrial availability

Curable resin composition which concerns on 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 agent, a sealant, an adhesive, a coating material, a coating material, a wood filler material, a casting material, a coating material, and the like.

Claims (8)

Curable resin (A) which has a hydrolyzable silicon group represented by General formula (1) in a molecule | numerator,
Curable resin (B) which has a hydrolyzable silicon group represented by General formula (2) in a molecule | numerator, and
At least one aminosilane compound (C) selected from a compound represented by the formula (3), a condensation reaction product of the compound represented by the formula (3) alone, and a condensation reaction product of the compound represented by the formula (3) with another silane compound
As curable resin composition containing
15-900 mass parts of curable resin (B) is contained with respect to 100 mass parts of curable resin (A), and an aminosilane compound (C) with respect to 100 mass parts of total of curable resin (A) and curable resin (B). Curable resin composition contained 0.1-20 mass parts of this.
Formula 1

Formula 2

Formula 3

In Chemical Formulas 1, 2 and 3,
X is a hydrocarbon group of 2 or more carbon atoms,
R ¹ , R ² is an alkyl group having 1 to 20 carbon atoms,
a is 0, 1 or 2,
A is a bond functional group to which a hetero atom having a non-covalent electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silicon group,
R ³ , R ⁴ is an alkyl group having 1 to 20 carbon atoms,
b is 0, 1 or 2.
R ⁵ and R ⁶ are an organic group or a hydrogen atom,
R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a hydrolyzable silicon atom,
R ⁸ and R ⁹ are alkyl groups having 1 to 20 carbon atoms,
c is 0, 1 or 2. The curable resin composition according to claim 1, wherein the main chain of the curable resin (A) is essentially polyoxyalkylene and / or poly (meth) acrylic acid ester. The curable resin composition according to claim 1 or 2, wherein the hydrolyzable silicon group of the curable resin (A) is an alkyldialkoxysilyl 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 the molecule thereof. 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 organic tin catalyst is 0 to less than 1000 ppm. The sealant composition comprising the curable composition according to any one of claims 1 to 6 as a main component of the curable component. The adhesive composition which uses the curable composition in any one of Claims 1-6 as a main agent of a curable component.