JP2008007586A - Boron trifluoride catalyst and room temperature moisture curable resin composition containing the boron trifluoride catalyst - Google Patents

Abstract

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ^１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。
【選択図】なしThe present invention provides a curing catalyst that quickly develops a curable organic polymer that exhibits a very high catalytic activity immediately after addition and has a hydrolyzable silyl group or the like in its molecule, and a method for preparing the same.
The compound (a1) comprising boron trifluoride and / or its complex (0.001 to 10 parts by weight), the compound having an amino group in the molecule (a2) (0.01 to 30 parts by weight), and A compound obtained by heat-treating a mixture of 0.01 to 30 parts by weight of a compound (a3) having a hydrolyzable silyl group represented by the following general formula (1) in the molecule.

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.
[Selection figure] None

Description

  The present invention contains a compound having at least one compound amino group selected from boron trifluoride and derivatives thereof, and a compound having a hydrolyzable silyl group, which catalyses the reaction between moisture and a hydrolyzable silyl group extremely high. The present invention relates to a moisture curable resin composition containing a catalyst compound obtained by subjecting a mixture to heat treatment to an extremely high curing rate and a method for producing the same.

  Conventionally, organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate have been widely used as curing catalysts for curable organic polymers having hydrolyzable silyl groups in the molecule. In particular, when the silylated urethane resin described in Patent Document 1 is used as the curable organic polymer, a curable organic polymer composition having a relatively high curing rate is obtained by blending the organic tin compound. be able to. Moreover, when the specific organotin compound-based curing catalyst described in Patent Documents 2 and 3 is used, a curable organic polymer composition having a higher curing rate can be obtained.

  However, among the curable organic polymers, so-called modified silicone resins, which are conventionally known, have a reactive group that is a methyldimethoxysilyl group, so that even if a large amount of such an organic tin compound is blended, it increases. There is a limit to the curing rate. That is, even if a large amount of an organotin compound is blended as a curing catalyst, the desired curing rate cannot be obtained. If a large amount is blended, a phenomenon that the curing rate is rather slow due to a dilution effect or a plastic effect may occur. . In addition, when the content of the tin compound, which is a heavy metal, increases, another problem arises that the risk and the hazard increase.

Further, when a curable organic polymer composition containing a large amount of an organic tin compound or the like is used as an adhesive or a sealing material for a plastic containing a hydrolyzable group in a molecule such as polyurethane or polyester, for example, The organotin compound in the curable composition sometimes deteriorates these plastics.
In addition to the organic tin compound, organic acid and amine compounds are also known as curing catalysts for the modified silicone resin as those containing no heavy metal. However, even if these are used, a high curing rate cannot be obtained. Rather, these compounds are actually used as cocatalysts in combination with organotin compounds.

Under such circumstances, as a result of intensive studies by the present inventors, a Lewis acid such as boron trifluoride and / or a derivative thereof is extremely useful for a curable organic polymer having a hydrolyzable silyl group or the like in the molecule. Has been found to work as a proper curing catalyst, and has led to the invention of a curable organic polymer composition that is fast curing and excellent in storage stability (Patent Document 4). However, in the preparation method according to the invention of the above-mentioned Patent Document 4, the composition is finally rapidly cured, but the catalytic activity is not sufficient immediately after the incorporation of the Lewis acid and / or its derivative. Therefore, in order to impart fast curability from the initial stage of blending, it is necessary to increase the blending amount of the Lewis acid and / or derivative thereof.
Therefore, the present inventors have further studied earnestly, by mixing a Lewis acid and / or derivative thereof with a curable organic polymer having a hydrolyzable silyl group or the like in the molecule, followed by heat treatment, It discovered that sclerosis | hardenability could be accelerated from the compounding initial stage, and came to invent the curable organic polymer composition excellent in sclerosis | hardenability (patent document 5).

Japanese Patent No. 3030020 JP 2001-139820 A JP 2001-172515 A Japanese Patent Application No. 2004-208672 Japanese Patent Application No. 2005-036719

  However, in the preparation method according to the invention of Patent Document 5, the curable organic polymer which is the main raw material of the curable resin composition is processed, so that the processing amount becomes enormous and sufficient for industrial use. There wasn't. Therefore, further development of a curing catalyst for quickly curing a curable organic polymer having a hydrolyzable silyl group or the like in the molecule immediately after its blending and a method for adjusting the same has been demanded.

  The present inventors have continued research to solve the above problems, and mixed a Lewis acid such as boron trifluoride and / or a derivative thereof with a curable organic polymer having a hydrolyzable silyl group or the like in the molecule. Only a mixture of boron trifluoride and / or a complex thereof, a compound having an amino group in the molecule, and a compound having a hydrolyzable silyl group in the molecule. As a result, it has been found that when a pre-heated product is blended with a curable organic polymer having a hydrolyzable silyl group or the like in its molecule, a very high catalytic activity can be expressed and the present invention is completed. It was. The present invention is composed of the following first to tenth inventions.

  The first invention comprises 0.001 to 10 parts by weight of a compound (a1) composed of boron trifluoride and / or a complex thereof, 0.01 to 30 parts by weight of a compound (a2) having an amino group in the molecule, and The compound obtained by heat-treating a mixture of 0.01 to 30 parts by weight of the compound (a3) having a hydrolyzable silyl group represented by the following general formula (1) in the molecule thereof: Compound.

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。
第２の発明は、第１の発明の化合物であり、下記一般式（１）で表される加水分解性シリル基を有する硬化性有機重合体（Ａ）に配合したときに常温で湿気硬化触媒として作用することを特徴とする触媒化合物である。

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.
2nd invention is a compound of 1st invention, and when it mix | blends with the curable organic polymer (A) which has a hydrolyzable silyl group represented by following General formula (1), a moisture hardening catalyst at normal temperature It is a catalyst compound characterized by acting as.

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。
第３の発明は、三フッ化ホウ素及び／又はその錯体からなる化合物（ａ１）が、三フッ
化ホウ素及び／又はそのアミン錯体であることを特徴とする第２の発明に記載の触媒化合物である。

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.
A third invention is a catalyst compound according to the second invention, wherein the compound (a1) comprising boron trifluoride and / or its complex is boron trifluoride and / or its amine complex. is there.

A fourth invention is characterized in that the hydrolyzable silyl group of the compound (a3) having a hydrolyzable silyl group represented by the general formula (1) in the molecule is a dialkoxysilyl compound. 2 or the catalyst compound according to any one of the third inventions.

5th invention contains the curable organic polymer (A) which has a hydrolyzable silyl group represented by following General formula (1), and the catalyst compound in any one of 2nd-4th invention. It is a room temperature moisture-curable resin composition.

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。
第６の発明は、三フッ化ホウ素及び／又はその錯体からなる化合物（ａ１）０．００１〜１０重量部、及び、その分子中にアミノ基及び下記一般式（１）で表される加水分解性シリル基を有する化合物（ａ４）０．０１〜３０重量部との混合物を加熱処理することにより得られることを特徴とする化合物である。

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.
The sixth invention relates to 0.001 to 10 parts by weight of a compound (a1) composed of boron trifluoride and / or a complex thereof, and a hydrolysis represented by an amino group and the following general formula (1) in the molecule It is obtained by heat-treating a mixture of 0.01 to 30 parts by weight of the compound (a4) having a functional silyl group.

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。
第７の発明は、第６の発明の化合物であり、下記一般式（１）で表される加水分解性シリル基を有する硬化性有機重合体（Ａ）に配合したときに常温で湿気硬化触媒として作用することを特徴とする触媒化合物である。

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.
7th invention is a compound of 6th invention, and when it mix | blends with the curable organic polymer (A) which has a hydrolyzable silyl group represented by following General formula (1), a moisture hardening catalyst at normal temperature It is a catalyst compound characterized by acting as.

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。
第８の発明は、三フッ化ホウ素及び／又はその錯体からなる化合物（ａ１）が、三フッ化ホウ素及び／又はそのアミン錯体であることを特徴とする第７の発明に記載の触媒化合物である。

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.
An eighth invention is the catalyst compound according to the seventh invention, wherein the compound (a1) comprising boron trifluoride and / or its complex is boron trifluoride and / or its amine complex. is there.

The ninth invention is characterized in that the hydrolyzable silyl group of the compound (a4) having an amino group and a hydrolyzable silyl group represented by the following general formula (1) in the molecule is a dialkoxysilyl compound. The catalyst compound according to any one of the seventh and eighth invention items.
The tenth invention comprises a curable organic polymer (A) having a hydrolyzable silyl group represented by the following general formula (1), and the catalyst compound according to any of the seventh to ninth inventions. It is a room temperature moisture-curable resin composition characterized by containing.

但し、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.

  By using the catalyst compound according to the present invention, very high catalytic activity can be expressed immediately after the catalyst component is blended. Due to this effect, even a two-component curable composition that has so far required a large amount of the catalyst component can be sufficiently cured from the beginning.

  The curable organic polymer (A) in the present invention is a curable organic polymer containing a hydrolyzable silyl group represented by the following general formula (1) in the molecule.

上記一般式（１）において、Ｘはヒドロキシル基又はアルコキシル基等の加水分解性基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは０、１又は２を、それぞれ示す。

In the above general formula (1), X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.

  The main chain skeleton of the curable organic polymer (A) is not particularly limited, and can be appropriately selected according to required performance and use. Examples of the main chain skeleton include polyoxyalkylene, saturated hydrocarbon polymer, vinyl polymer (for example, (meth) acrylic acid ester monomer copolymer), polythiol, polyester, organopolysiloxane, and polycarbonate. is there. Of these, polyoxyalkylene, saturated hydrocarbon polymer and vinyl polymer are preferable, and polyoxyalkylene and vinyl polymer are more preferable. The molecular weight of the curable organic polymer (A) is not particularly limited, but the number average molecular weight is preferably 500 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 2,000 to 20,000.

Known methods for introducing hydrolyzable silyl groups into these main chain skeletons include hydrosilylation reactions using hydrosilane compounds and radical addition reactions using mercaptosilane compounds. Furthermore, you may copolymerize a (meth) acrylic acid monomer, a (meth) acrylic acid ester monomer, etc. in presence of these curable organic polymer (A) and / or another curable compound.
The curable organic polymer (A) is commercially available and can be used in the present invention. Examples of commercially available products include trade names of Kaneka Corporation; S203, S303, SAT200, SAT070, MA440, MA447, Epion series, SA series, OR series, etc.
Asahi Glass Co., Ltd. product names; ES-S2410, ES-S2420, ES-S3430, ES-S3460, and the like.

  Examples of the curable organic polymer (A) preferably used in the present invention include Japanese Patent Publication Nos. 45-36319, 46-12154, 49-32673, Japanese Patent Laid-Open Nos. 50-156599 and 51-73561. 54-6096, 55-82123, 55-123620, 55-125121, 55-131022, 55-135135, 55-137129, etc. Included are curable organic polymers commonly referred to as modified silicone resins.

  Moreover, in this invention, the curable organic polymer (A) which contains a polar group in a molecule | numerator can be used suitably. Here, the polar group is a urethane bond group, a thiourethane bond group, a urea bond group, a thiourea bond group, a substituted urea bond group, a substituted thiourea bond group, an amide bond group, a sulfide bond group, a hydroxyl group, a first group A linking group or functional group containing an oxygen atom, a nitrogen atom, or a sulfur atom, such as a secondary amino group, secondary amino group, and tertiary amino group. It is preferable to introduce such a polar group in the vicinity of the hydrolyzable silyl group because the curing of the curable organic polymer is further promoted.

  In particular, among these polar groups, urethane bond groups, thiourethane bond groups, urea bond groups, thiourea bond groups, substituted urea bond groups, substituted thiourea bond groups, amide bond groups, primary amino groups, primary amino groups, Those having a nitrogen-containing polar group such as a secondary amino group and a tertiary amino group are preferred for further promoting curing, and a urethane bond group (—NHCOO—) is most preferred because it significantly promotes curing. . The reason for the acceleration of curing is that the nitrogen-containing polar group present in the molecule of the curable organic polymer is a domain having good molecular compatibility with the complex that is the curing catalyst according to the present invention. Conceivable. As a result, the complex according to the present invention is likely to gather in the vicinity of the hydrolyzable silyl group of the curable organic polymer and easily interact with each other, and the ability of the hydrolyzable group to be further eliminated further increases the hydrolyzable silyl group. This is probably because the coupling reaction between the two is further promoted.

  In the curable organic polymer (A) containing a polar group in the molecule, each polar group may be introduced into the main chain by a conventionally known method. For example, it is proposed in Japanese Patent No. 3030020, Japanese Patent No. 3313360, Japanese Patent No. 3317353, Japanese Patent No. 3350011, Japanese Patent No. 3415091, Japanese Patent No. 3471667, Japanese Patent No. 3462139, Japanese Patent No. 3462139, Japanese Patent No. 3499828, etc. In general, curable organic polymers called silylated urethane resins are included.

  The compound (a1) comprising boron trifluoride and / or a complex thereof in the present invention is a compound comprising boron trifluoride and a complex of boron trifluoride and a Lewis base. The compound (a1) is a Lewis acid and / or a derivative thereof and is useful as a curing catalyst for the curable organic polymer (A), the compound (a2) having an amino group in the molecule, and the above By adding the compound (a3) having a hydrolyzable silyl group represented by the general formula (1) in the molecule as a curing catalyst after heat treatment, the curable organic polymer (A ) Is cured. Specific examples of the compound (a1) composed of boron trifluoride and / or its complex include, for example, boron trifluoride amine complex, alcohol complex, ether complex, thiol complex, sulfide complex, carboxylic acid complex, and water complex. Etc. are exemplified. Among the boron trifluoride complexes, an amine complex having both stability and catalytic activity is particularly preferable.

Examples of the amine compound used in the amine complex of boron trifluoride include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2, 2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N-methyl-3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1 , 2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2,4 , 8,1 -Tetraoxaspiro [5.5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenyl ether, 3 , 3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, m-toluylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, di-o -Tolylguanidine, 1,1,3,3-tetramethylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether, sun technochemical Jefami A compound having a plurality of primary amino groups such as piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N′-di-t-butylethylenediamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'-diethylthio Compounds having a plurality of secondary amino groups such as urea and N-methyl-1,3-propanediamine, and further methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethyl Aminopropylamine, 1- (2-aminoethyl) piperazine, N-amino Propylpiperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamineethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4 -Aminomethylpiperidine, a compound represented by the formula H2N (C2H4NH) nH (n≈5) (trade name: Polyate, manufactured by Tosoh Corporation), N-alkylmorpholine, 1,8-diazabicyclo [5.4. 0] undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5, 1,4-diazabicyclo [2] 2.2] Octane, pyridine, N-alkylpiperidine, 1,5,7-triazabici (B) Bicyclic tertiary amine compounds such as [4.4.0] dec-5-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene; Other, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (Aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) ) Aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -11- An aminosilane compound such as aminoundecyltriethoxysilane may be mentioned, but is not limited thereto.

The amine complexes of boron trifluoride are commercially available and can be used in the present invention. Examples of the commercially available products include Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, and BAK 1171 manufactured by Air Products Japan.
The compound (a2) having an amino group in the molecule in the present invention is a compound having an amino group such as a primary amino group, a secondary amino group, or a tertiary amino group in the molecule. Specific examples of the compound (a2) include monoalkylamine compounds such as butylamine, octylamine, dodecylamine and aniline, dialkylamine compounds such as dibutylamine, dioctylamine and piperidine, triethylamine, trioctylamine, 1,4- Trialkylamine compounds such as diazabicyclo [2.2.2] octane, nitrogen-containing heterocyclic compounds such as pyridine and 1,8-diazabicyclo [5.4.0] undecene-7, guanidine, 1,1,3, Although guanidine compounds, such as 3-tetramethyl guanidine, etc. are mentioned, it is not limited to these.

  The compound (a3) having a hydrolyzable silyl group in the molecule in the present invention is a compound having a hydrolyzable silyl group represented by the general formula (1) in the molecule. Specific examples of the compound (a3) include epoxy silane compounds such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, or 3-mercaptopropylmethyldimethoxy. Mercaptosilane compounds such as silane, thioester silane compounds such as 3-octanoylthiopropyltrimethoxysilane, ketimine silane compounds such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and 3-ureidopropyl Ureidosilane such as triethoxysilane, (meth) acrylsilane compound such as 3-acryloxypropyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane Isocyanate silane compounds such as run, vinyl silane compounds such as vinyl trimethoxy silane, alkyl silane compounds such as hexyl trimethoxy silane, decyl trimethoxy silane or cyclohexyl methyl dimethoxy silane, alkyl silicate compounds such as methyl silicate, ethyl silicate or propyl silicate, Or, oligomer compounds thereof may be mentioned, but the invention is not limited to these. As those oligomer compounds, Shin-Etsu Chemical Co., Ltd. KC-89S, KR-500, KR-217, X-41-1053, X-41-1805, X-40-2308, X-40-9238, etc. Although it is mentioned, it is not limited to these. Among the compounds (a3), a compound in which the hydrolyzable silyl group is a dialkoxysilyl group is particularly preferable because of its high catalytic effect.

  The said compound (a1), the said compound (a2), and the said compound (a3) will turn into a compound with very high catalyst activity by mixing them and heat-processing. The reason for the compounds having very high catalytic activity is that the compounds (a1) and (a3) react with each other to form a compound having very high catalytic activity by heat treatment. Inferred. The compound (a2) is considered to have an effect of efficiently promoting the chemical reaction between the compound (a1) and the compound (a3) due to the basicity of the amino group present in the molecule. The compound (a1) alone has catalytic activity, but the compound produced by the chemical reaction between the compound (a1) and the compound (a3) has a very high catalytic activity, so that it can be quickly cured immediately after compounding. It is considered possible.

  The compounding ratio (parts by weight) of the compound (a1), the compound (a2), and the compound (a3) mixed and heat-treated is preferably the compound (a1): the compound (a2): The compound (a3) is 0.001 to 10: 0.01 to 30: 0.01 to 30, more preferably 0.01 to 5.0: 0.1 to 20: 0.1 to 20. Especially preferably, it is 0.1-2.0: 0.1-10: 0.1-10. Furthermore, the compounding ratio of the compound (a1), the compound (a2), and the catalyst compound obtained by mixing and heating the compound (a3) is 100 parts by weight of the curable organic polymer (A). The amount is preferably 0.001 to 30 parts by weight, more preferably 0.01 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight.

The compound (a4) having an amino group and a hydrolyzable silyl group in the molecule of the present invention has an amino group such as a primary amino group, a secondary amino group, or a tertiary amino group in the molecule. And a compound having a hydrolyzable silyl group represented by the general formula (1). Specific examples of the compound (a4) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino). Ethyl) -3-aminopropylmethyldimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, a product name of Nikko Materials Corp .; aminosilane compounds such as IM-1000, Silicone alkoxy oligomers having an amino group and an alkoxysilyl group in the molecule such as X-40-2651 manufactured by Shin-Etsu Chemical Co., Ltd. are exemplified, but not limited thereto. Among the compounds (a4), a compound in which the hydrolyzable silyl group is a dialkoxysilyl group is particularly preferable because of its high catalytic effect.

  The action mechanism of the compound (a4) is the same as that when the compound (a1), the compound (a2), and the compound (a3) are mixed and heat-treated, and an amino group present in the molecule Is presumed that the hydrolyzable silyl group present in the molecule plays the role of the compound (a3). Furthermore, by having an amino group and a hydrolyzable silyl group in the same molecule, it is possible to further increase the activity of the resulting catalyst component.

  The compounding ratio (parts by weight) when mixing and heat-treating the compound (a1) and the compound (a4) is preferably the compound (a1): the compound (a4) = 0.001 to 10: It is 0.01-30, More preferably, it is 0.01-5.0: 0.1-20, Most preferably, it is 0.1-2.0: 0.1-10. Furthermore, the compounding ratio of the catalyst compound obtained by mixing and heat-treating the compound (a1) and the compound (a4) is preferably 0.001 to 30 with respect to 100 parts by weight of the curable organic polymer (A). Parts by weight, more preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight.

The temperature of the heat treatment step necessary for obtaining the effects of the present invention is preferably 30 ° C to 180 ° C, more preferably 40 ° C to 100 ° C, and particularly preferably 50 ° C to 70 ° C. When the heat treatment temperature is lower than 30 ° C., a very long heat treatment time is required to obtain the effect of the present invention. When the heat treatment temperature is higher than 180 ° C., the decomposition reaction of the catalyst component itself may occur, Is not useful in the industry. About 30 degreeC, about heat processing time, Preferably it is 10 minutes-1 month, More preferably, it is 1 day-2 weeks, Most preferably, it is 2 days-1 week. In the case of 180 degreeC, Preferably it is 5 minutes-1 month, More preferably, it is 10 minutes-1 week, Most preferably, it is 15 minutes-1 day. The upper limit of the heat treatment time at 30 ° C. and 180 ° C. is one month in consideration of industrial economics, that is, cost, and even if the heat treatment is further performed, the catalyst activity is lowered. is not.
In addition to the curable organic polymer and the curing catalyst component, any conventionally known arbitrary compound can be blended in the curable resin composition according to the present invention. For example, various resins other than the curable organic polymer (A) according to the present invention, a tin-based or amine-based curing catalyst other than the curing catalyst component according to the present invention, a silane coupling agent, a titanate coupling agent, Aluminum coupling agents, fillers, tackifiers, thixotropic agents, dehydrating agents, diluents, plasticizers, flame retardants, oligomers, anti-aging agents, UV absorbers, pigments, drying oils, etc. can be blended. .

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example. The viscosity in the examples of the present invention is a value measured using a BH viscometer (No. 7 rotor, 10 rotations).
<Synthesis example regarding manufacturing method of curable organic polymer (A)>
(Preparation of curable organic polymer A-1)
While stirring 206.4 g of N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane at 50 ° C. in a nitrogen atmosphere in the reaction vessel, 210.3 g of ethyl acrylate was added dropwise over 1 hour, After reacting at 50 ° C. for 5 hours, reaction was performed at 50 ° C. for 7 days to obtain a reactant SA-1 having a methyldimethoxysilyl group and a secondary amino group in the molecule.

  In a separate reaction vessel, 3000 g of PMLS4012 (polyoxypropylene polyol, number average molecular weight 10,000, OH value = 12.0) manufactured by Asahi Glass Urethane Co., Ltd., 142.6 g of isophorone diisocyanate, and 0.20 g of dibutyltin dilaurate The mixture was allowed to react at 80 ° C. for 3 hours while stirring and mixing in a nitrogen atmosphere to obtain a polyoxyalkylene resin PA-1 having an isocyanate group in the molecule. Thereafter, 296.4 g of the above reactant SA-1 was added thereto, and the mixture was reacted at 90 ° C. for 2 hours with stirring and mixing in a nitrogen atmosphere, whereby the main chain was polyoxyalkylene and methyldimethoxy was present in the molecule. A curable organic polymer A-1 having a silyl group was obtained. The obtained curable organic polymer A-1 was analyzed by FT-IR to confirm that the NCO group had disappeared. The viscosity of the curable organic polymer A-1 at 23 ° C. was 50,000 mPa · s.

(Preparation of curable organic polymer A-2)
1000g of the said curable organic polymer A-1 was put into reaction container, and it heated up to 90 degreeC under nitrogen atmosphere. There, 400 g of methyl methacrylate, 300 g of lauryl methacrylate, 30 g of 3-acryloxypropyltrimethoxysilane, 80 g of 3-mercaptopropyltrimethoxysilane and 7.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) A monomer mixed solution in which was added dropwise over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 90 ° C. for 30 minutes, a mixed solution of 2.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Next, after reacting at 90 ° C. for 30 minutes, a mixed solution of 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 5.0 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after reacting at 90 ° C. for 30 minutes, unreacted components were distilled off under reduced pressure to obtain a curable organic polymer A-2 having a methyldimethoxysilyl group and a trimethoxysilyl group in the molecule. The viscosity of the curable organic polymer A-2 at 23 ° C. was 140,000 mPa · s.

(Preparation of curable organic polymer A-3)
While stirring 222.4 g of N- (2-aminoethyl) 3-aminopropyltrimethoxysilane at 50 ° C. in a nitrogen atmosphere in a reaction vessel, 210.3 g of ethyl acrylate was added dropwise over 1 hour, After reacting at 50 ° C. for 5 hours, reaction was performed at 50 ° C. for 7 days to obtain a reactant SA-3 having a trimethoxysilyl group and a secondary amino group in the molecule.
In another reaction vessel, 3000 g of PMLS4012 (polyoxypropylene polyol, number average molecular weight 10,000, OH value = 12.0) manufactured by Asahi Glass Urethane Co., Ltd., 142.6 g of isophorone diisocyanate, and 0.20 g of dibutyltin dilaurate The mixture was allowed to react at 80 ° C. for 3 hours while stirring and mixing in a nitrogen atmosphere to obtain polyoxyalkylene resin PA-3 having an isocyanate group in the molecule. Thereafter, 308.9 g of the above-mentioned reactant SA-3 was added thereto, and the mixture was reacted at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, whereby the main chain was polyoxyalkylene and trimethoxy in the molecule. A curable organic polymer A-3 having a silyl group was obtained. By analyzing the obtained curable organic polymer A-3 by FT-IR, it was confirmed that the NCO group had disappeared. The viscosity of the curable organic polymer A-3 at 23 ° C. was 58,000 mPa · s.

(Preparation of curable organic polymer A-4)
1000g of the said curable organic polymer A-3 was put into reaction container, and it heated up to 90 degreeC under nitrogen atmosphere. There, 400 g of methyl methacrylate, 300 g of lauryl methacrylate, 30 g of 3-acryloxypropyltrimethoxysilane, 80 g of 3-mercaptopropyltrimethoxysilane and 7.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) A monomer mixed solution in which was added dropwise over 30 minutes to carry out a polymerization reaction. Furthermore, at 90 ° C., 3
After reacting for 0 minutes, a mixed solution of 2.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Next, after reacting at 90 ° C. for 30 minutes, a mixed solution of 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 5.0 g of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after reacting at 90 ° C. for 30 minutes, unreacted components were distilled off under reduced pressure to obtain a curable organic polymer A-4 having a trimethoxysilyl group in the molecule. The viscosity of the curable organic polymer A-4 at 23 ° C. was 156,000 mPa · s.

(Curable silicone resin A-5)
A commercially available modified silicone resin (“MA440” manufactured by Kaneka Corporation, a bifunctional modified silicone resin whose main chain is polyoxyalkylene) was prepared.
(Curable silicone resin A-6)
A commercially available modified silicone resin ("Exstar G3440ST" manufactured by Asahi Glass Co., Ltd., a trifunctional modified silicone resin whose main chain is polyoxyalkylene) was prepared.

<Preparation of curing catalyst>
(Preparation of boron trifluoride DBU complex)
In a reaction vessel, DBU (1,8-diazabicyclo [5.4.0] undec-7-ene, 30.5 g, 0.20 mol) dissolved in diethyl ether (300 g) was stirred under a nitrogen atmosphere. Then, after adding boron trifluoride diethyl ether complex (28.4 g, 0.20 mol), the mixture was reacted at room temperature for 1 hour. Thereafter, diethyl ether was distilled off under reduced pressure to obtain a boron trifluoride DBU complex which was a brown solid at room temperature.
(Preparation of boron trifluoride Jeffamine D2000 complex)
In a reaction vessel, Jeffamine D2000 dissolved in diethyl ether (300 g) (trade name, manufactured by Sun Techno Japan Co., Ltd., a polyether polyol having primary amino groups at both ends, number average molecular weight 2,000, 300.0 g, 0 Boron trifluoride diethyl ether complex (42.6 g, 0.30 mol) was added while stirring under a nitrogen atmosphere, followed by reaction at room temperature for 1 hour. Thereafter, diethyl ether was distilled off under reduced pressure to obtain a boron trifluoride Jeffamine D2000 complex which was a brown liquid at room temperature.

<Preparation of catalyst solution>
(Solution B-1 and catalyst solution C-1)
In a sample tube, 5.0 g of KBM902 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropylmethyldimethoxysilane) is added, 0.05 g of boron trifluoride monoethylamine complex (BFM) is added thereto, and Solution B -1 was prepared. Then, the catalyst solution C-1 was obtained by curing the solution B-1 at 50 ° C. for 3 days.
(Solution B-2 and catalyst solution C-2)
Similarly, 5.0 g of KBM903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane) is added, 0.05 g of boron trifluoride monoethylamine complex (BFM) is added thereto, and Solution B- 2 was prepared. Then, catalyst solution C-2 was obtained by curing solution B-2 at 50 ° C. for 3 days.

(Solution B-3 and catalyst solution C-3)
Similarly, 5.0 g of KBM903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane) is added, 0.05 g of boron trifluoride piperidine complex (BFP) is added thereto, and Solution B-3 Was prepared. Thereafter, the solution B-3 was cured at 50 ° C. for 3 days to obtain a catalyst solution C-3.
(Solution B-4 and catalyst solution C-4)
Similarly, 5.0 g of KBM903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane) is added, and 0.05 g of boron trifluoride DBU complex is added thereto, and Solution B-4
Was prepared. Then, catalyst solution C-4 was obtained by curing the solution B-4 at 50 ° C. for 3 days.

(Solution B-5 and catalyst solution C-5)
Similarly, 5.0 g of KBM903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane) is added, and 0.05 g of boron trifluoride Jeffamine D2000 complex is added to prepare Solution B-5. did. Then, catalyst solution C-5 was obtained by curing the solution B-5 at 50 ° C. for 3 days.
(Solution B-6 and catalyst solution C-6)
Similarly, 5.0 g of KBE903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltriethoxysilane) is added, and 0.05 g of boron trifluoride monoethylamine complex (BFM) is added thereto, and Solution B- 6 was prepared. Then, the catalyst solution C-6 was obtained by curing the solution B-6 at 50 ° C. for 3 days.

(Solution B-7 and catalyst solution C-7)
Similarly, 5.0 g of KBM 3063 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., hexyltrimethoxysilane) is added, and 0.05 g of boron trifluoride monoethylamine complex (BFM) is added thereto, and 0.5 g of octylamine is added. Solution B-7 was prepared. Then, catalyst solution C-7 was obtained by curing the solution B-7 at 50 ° C. for 3 days.
(Solution B-8 and catalyst solution C-8)
Similarly, 5.0 g of KBM3063 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., hexyltrimethoxysilane) is added, and 0.05 g of boron trifluoride monoethylamine complex (BFM) is added thereto, and 0.5 g of dibutylamine is added. Solution B-8 was prepared. Thereafter, the catalyst solution C-8 was obtained by curing the solution B-8 at 50 ° C. for 3 days.

(Solution B-9 and catalyst solution C-9)
Similarly, 5.0 g of KBM 3063 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., hexyltrimethoxysilane) is added, and 0.05 g of boron trifluoride monoethylamine complex (BFM) is added thereto, and 0.5 g of tributylamine is added. Solution B-9 was prepared. Then, catalyst solution C-9 was obtained by curing the solution B-9 at 50 ° C. for 3 days.
(Solution B-10 and catalyst solution C-10)
Similarly, 5.0 g of KC-89S (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., a silicone alkoxy oligomer in which the organic substituent is a methyl group and the alkoxy group is a methoxy group) is added to boron trifluoride monoethylamine. 0.05 g of complex (BFM) and 0.5 g of octylamine were added to prepare Solution B-10. Then, catalyst solution C-10 was obtained by curing the solution B-10 at 50 ° C. for 3 days.
Table 1 shows the compositions of the solutions B-1 to B-10.

(Examples 1 to 15)
In order to compare the curing speed, the obtained curable organic polymers A-1 to A-6 and the catalyst solutions C-1 to C-10 were rapidly mixed for 1 minute at the blending ratio shown in Table 2, The tension time was measured. For the skinning time, the curable resin composition is left in an atmosphere of 23 ° C. and a relative humidity of 45 to 55%, and the surface is lightly touched with a glass rod. It was calculated as the time until it no longer adheres to the tip.

(Comparative Examples 1-15)
Similarly, the obtained curable organic polymers A-1 to A-6 and solutions B-1 to B-10 were rapidly mixed for 1 minute at the blending ratio shown in Table 3, and the skinning time was measured. . For the skinning time, the curable resin composition is left in an atmosphere of 23 ° C. and a relative humidity of 45 to 55%, and the surface is lightly touched with a glass rod. It was calculated as the time until it no longer adheres to the tip.

From the results of Examples 1 to 15 and Comparative Examples 1 to 15, a mixture of a compound comprising a boron trifluoride complex, a compound having an amino group, and a compound having a hydrolyzable silyl group is heat-treated. Thus, it was found that a catalyst capable of imparting fast curability can be synthesized immediately after mixing with the curable organic polymer.
<Preparation of catalyst solution>
(Catalyst solutions E-1 to E-35)
80.0 g of KBM902 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropylmethyldimethoxysilane) is put into a sample tube, and boron trifluoride monoethylamine complex (B
FM), 0.80 g was added to obtain a solution D-1.
2 g of each solution D-1 was taken out into a sample bottle, and after curing at the temperature and period shown in Table 4, catalyst solutions E-1 to E-35 were prepared by allowing to stand at 23 ° C. for 2 hours.

(Examples 16 to 50)
In order to compare the curing speed, the obtained curable organic polymer A-1 and the catalyst solutions E-1 to E-35 were rapidly mixed for 1 minute at the blending ratios shown in Tables 5 to 9, and the skinning time Was measured. For the skinning time, the curable resin composition is left in an atmosphere of 23 ° C. and a relative humidity of 45 to 55%, and the surface is lightly touched with a glass rod. It was calculated as the time until it no longer adheres to the tip.

  From the results of Examples 16 to 50 and Comparative Example 1, it was found that, by curing at a higher temperature, the catalytic activity was exhibited earlier even if the curing period was short.

The curable resin composition according to the present invention can be suitably used for applications such as adhesives, sealants, paints, coating agents, sealants, casting materials, and coating materials. In particular, when used as an adhesive, it can be used for general households, building interiors, industrial lines such as automobiles, audio equipment, and electronic equipment, and civil engineering work such as adhesion of water-stopping materials in tunnel shield construction. Can be used for various purposes. In addition, since a very high catalytic activity can be expressed immediately after the catalyst component is blended, it can be used not only for a one-component type but also for a two-component type adhesive or a two-component type sealant.

Claims (10)

0.001 to 10 parts by weight of the compound (a1) composed of boron trifluoride and / or its complex, 0.01 to 30 parts by weight of the compound (a2) having an amino group in the molecule, and the following in the molecule A compound obtained by heat-treating a mixture of 0.01 to 30 parts by weight of a compound (a3) having a hydrolyzable silyl group represented by the general formula (1).

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2. It is a compound according to claim 1 and acts as a moisture curing catalyst at room temperature when blended with a curable organic polymer (A) having a hydrolyzable silyl group represented by the following general formula (1). Characteristic catalyst compound.

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.   The catalyst compound according to claim 2, wherein the compound (a1) comprising boron trifluoride and / or a complex thereof is boron trifluoride and / or an amine complex thereof.   The hydrolyzable silyl group of the compound (a3) having a hydrolyzable silyl group represented by the general formula (1) in the molecule is a dialkoxysilyl compound. A catalyst compound according to claim 1.
It contains a curable organic polymer (A) having a hydrolyzable silyl group represented by the following general formula (1) and the catalyst compound according to any one of claims 2 to 4. Moisture curable resin composition.

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2. Compound (a1) composed of boron trifluoride and / or its complex (0.001 to 10 parts by weight) and a compound having an amino group and a hydrolyzable silyl group represented by the following general formula (1) in the molecule (A4) A compound obtained by heat-treating a mixture with 0.01 to 30 parts by weight.

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2. It is a compound according to claim 6 and acts as a moisture curing catalyst at room temperature when blended with a curable organic polymer (A) having a hydrolyzable silyl group represented by the following general formula (1). Characteristic catalyst compound.

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.   The catalyst compound according to claim 7, wherein the compound (a1) comprising boron trifluoride and / or a complex thereof is boron trifluoride and / or an amine complex thereof.   The hydrolyzable silyl group of the compound (a4) having an amino group and a hydrolyzable silyl group represented by the general formula (1) in the molecule is a dialkoxysilyl compound, 9. The catalyst compound according to any one of 8. It contains a curable organic polymer (A) having a hydrolyzable silyl group represented by the following general formula (1) and the catalyst compound according to any one of claims 7 to 9. Moisture curable resin composition.

X represents a hydrolyzable group such as a hydroxyl group or an alkoxyl group, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents 0, 1 or 2.