JP6779471B2 - Curing catalyst, curable resin composition and cured product thereof - Google Patents

Description

Cross reference

This application claims priority based on the application of Japanese Patent Application No. 2014-168681 filed in Japan on August 21, 2014, and the contents described in the application are incorporated herein by reference. In addition, the contents described in the patents, patent applications and documents cited in the present application are incorporated herein by reference.

The present invention relates to a curing catalyst, a curable resin composition containing the same, and a cured product obtained by curing the resin composition.

Conventionally, a polyorganosiloxane composition, which is a kind of curable resin composition, has been used as an adhesive or a sealing material because it exhibits excellent weather resistance and durability when cured. In recent years, cured products of polyorganosiloxane compositions tend to be required to have higher strength. In order to meet this demand, for example, a polyorganosiloxane composition in which a filler made of an inorganic or organic compound is mixed is known (see Patent Document 1).

Organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate are widely used as catalysts in the curable resin composition. In recent years, there has been a strong demand for conversion to compounds with a low load in terms of both environment and health, and amine compounds, carboxylic acid compounds (see Patent Document 2), and bismus compounds with relatively high safety (Patent). It has been proposed to use a titanium alkoxide-based catalyst, a guanidine compound as a silanol condensation catalyst (see Patent Document 4), or the like. However, these catalysts have not yet replaced the current organic tin compound-based catalysts.

As a result of searching for a new catalyst that can replace the organic tin compound-based catalyst, the applicant focused on a catalyst containing titanium alkoxide as an essential component and stabilized it with a bidentate chelating agent. For curing resins and polyurethane resins produced from organic polymers having reactive silicon such as reactive silanol group-containing or reactive silyl group-containing polymers by blending a specific ratio of guanidine compound therein. It has been found that a catalyst can be obtained (see Patent Document 5).

Japanese Unexamined Patent Publication No. 9-118827 Japanese Unexamined Patent Publication No. 08-41358 Japanese Unexamined Patent Publication No. 05-39428 International Publication WO2007 / 094272 International Publication WO 2013/153773

However, there is a demand for further improvement in the catalyst developed earlier by the applicant. It is a desire to make the color lighter. When a catalyst containing titanium alkoxide and bidentate chelation is used, the cured product is colored red or yellow, although the curing characteristics when curing the synthetic resin are excellent. Any place where coloring is not a problem is fine, but there is a problem that it is difficult to use in places where coloring is not preferred. For this reason, there is a demand for a catalyst that remains colorless or lightly colored even if it is colored, without deteriorating the curing characteristics.

The present invention has been made in view of the above problems, and is a curable resin composition comprising a curing catalyst having excellent curing characteristics and being difficult to color a cured product of a synthetic resin, and the curing catalyst, and the resin composition. The purpose is to obtain a cured product obtained by curing an object.

In order to achieve the above object, the present inventors have focused on alkoxides of metals other than titanium as a result of intensive studies, and the metal alkoxides and at least one of hydroxycarboxylic acid esters and malonic acid diesters. By adding a catalyst containing one ligand to the polymer, we succeeded in obtaining a cured product having excellent curability and being uncolored or lightly colored.

That is, one embodiment of the present invention is a curing catalyst having a function of curing a synthetic resin, in which at least one of (A) zirconium alkoxide and (B) hydroxycarboxylic acid ester and malonic acid diester is arranged. It is a curing catalyst containing a ligand.

Another embodiment of the present invention is a curing catalyst in which the (A) zirconium alkoxide contains at least one of zirconium propoxide and zirconium butoxide.

Yet another embodiment of the present invention is a curing catalyst in which the ligand (B) contains a citrate ester.

Yet another embodiment of the invention is a curing catalyst in which the ligand (B) comprises at least one of diethyl malate and dibutyl malonate.

Yet another form of the present invention is a curing catalyst further comprising (C) methyltriethoxysilane.

Yet another embodiment of the present invention is also a curing catalyst having an alcohol component of 30 parts by mass or less with respect to 100 parts by mass of the curing catalyst.

Further, one embodiment of the present invention is a curable resin composition containing any of the above-mentioned curing catalysts and (D) a crosslinkable silyl group-containing resin.

Yet another embodiment of the present invention is a curable resin composition in which the curing catalyst is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (D) crosslinkable silyl group-containing resin.

Further, one embodiment of the present invention is a cured product obtained by curing the curable resin composition.

According to the present invention, it is possible to obtain a curable resin composition containing a curable catalyst having excellent curable properties and being difficult to color a cured product of a synthetic resin, and a cured product obtained by curing the resin composition. Can be done.

FIG. 1 shows the results of the absorbance of the cured product cured by using each catalyst in Experiments 1, 5 and 6 in Experimental Example 1. FIG. 2 shows the results of the absorbance of the cured product cured by using each catalyst in Experiments 1, 2, and 3 in Experimental Example 1. FIG. 3 shows the results of the absorbance of the cured product cured by using each catalyst in Experiments 1, 9 and 10 in Experimental Example 1. FIG. 4 shows the results of the absorbance of the cured product cured by using each catalyst in Experiments 4, 7 and 8 in Experimental Example 1. FIG. 5 shows the experimental No. 1 in Experimental Example 1. The appearance of each cured product of 1-3, 5-7, 9 and 10 is shown in the photograph. FIG. 6 shows the infrared absorption spectra of the ZrnP-CAtE catalyst (Experiment No. 17) and the ZrnP-CAtE catalyst (concentration) (Experiment No. 18) in Table 4 as an example.

Next, embodiments of the curing catalyst, curable resin composition, and cured product of the present invention will be described.

I. Curing catalyst The curing catalyst according to this embodiment is a curing catalyst having a function of curing a synthetic resin, and is composed of (A) zirconium alkoxide.
(B) With at least one ligand of hydroxycarboxylic acid ester and malonic acid diester,
including.

Further, the curing catalyst may further contain (C) methyltriethoxysilane. In the present specification, the "contains" or "contains" state is broadly interpreted to include not only a mere mixed state but also a partially reacted state. Hereinafter, (A) zirconium alkoxide, (B) ligand, (C) methyltriethoxysilane which can be optionally added, and (C') other additives which can be optionally added will be described in detail.

(A) Zirconium Alkoxide A compound in which the hydrogen of the hydroxy group of an alcohol is replaced with zirconium, which comprises zirconium ethoxydo, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide, and zirconium isobutoxide. Among them, zirconium n-propoxide and zirconium n-butoxide can be more preferably exemplified. In addition to the zirconium alkoxide, a metal alkoxide other than the zirconium alkoxide may be contained, but in order to reduce coloration, it is particularly preferable not to contain the titanium alkoxide.

(B) Ligand The term "ligand" as used herein refers to a compound capable of coordinating a metal of a metal alkoxide. Therefore, it does not matter whether the "ligand" actually coordinates with the metal.

(B1) Hydroxycarboxylic Acid Ester A hydroxycarboxylic acid ester is one or a mixture of two or more products produced by an ester reaction between a hydroxycarboxylic acid having 3 to 6 carbon atoms and an alcohol having 1 to 20 carbon atoms. Examples of the hiroxycarboxylic acid include monocarboxylic acids such as lactic acid and glyceric acid, dicarboxylic acids such as malic acid and tartaric acid, and tricarboxylic acids such as citric acid. Alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, ter-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, Examples thereof include aliphatic saturated alcohols such as decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and stearyl alcohol.

Examples of the hydroxycarboxylic acid ester produced by the ester reaction between the above hydroxycarboxylic acid and the above alcohol include malic acid ester, citric acid ester, lactic acid ester, tartrate acid ester, glycol monoester, glycerin monoester, and glycerin diester. The ricinol acid ester can be mentioned. In particular, citric acid ester is preferable, and triethyl citrate and tributyl citrate are more preferable.

The hydroxycarboxylic acid ester is contained in the curing catalyst, preferably in the range of 0.2 to 4.0 mol, more preferably in the range of 0.2 to 2.0 mol, with respect to 1 mol of the metal alkoxide. .. When zirconium alkoxide is used as the metal alkoxide, the hydroxycarboxylic acid ester is preferably used in the range of 0.2 to 1.6 mol with respect to 1 mol of the zirconium alkoxide.

(B2) Malonic Acid Diester The malonic acid diester includes, for example, a malonic acid alkyl ester represented by a malonic acid dialkyl ester, an alkyl malonic acid dialkyl ester, and the like.
An example of a malonic acid diester is a malonic acid ester represented by the following structural formula (Chemical Formula 1). In the structural formula, R ¹ and R ² are both selected from an alkyl group having 1 or more carbon atoms, an aryl group, an aralkyl group, a triorganosyloxy group, an alkenyl group, a cycloalkyl group and the like, and may be the same or different from each other. Examples of the malonic acid diester include one or more such as dimethyl malonate, diethyl malonate, diisopropyl malate, din-butyl malate, dit-butyl malate, benzylmethyl malonate and diphenyl malonate. It can be preferably used, and in particular, at least one of diethyl malate and dibutyl malate can be more preferably used.

The malonic acid diester is contained in the curing catalyst in a range of preferably 0.2 to 4.0 mol, more preferably 0.2 to 2.0 mol, based on 1 mol of the metal alkoxide. .. When zirconium alkoxide is used as the metal alkoxide, the malonic acid diester is preferably used in the range of 0.2 to 1.6 mol per 1 mol of zirconium alkoxide.

Another example of the malonic acid diester is a malonic acid ester represented by the following structural formula (Chemical Formula 2). In the structural formula, R ¹ , R ² and R ³ are all selected from an alkyl group having one or more carbon atoms, an aryl group, an aralkyl group, a triorganosyloxy group, an alkenyl group or a cycloalkyl group, and are the same or different from each other. But it's okay. Examples of the malonic acid diester include one or more such as dimethyl methylmalate, diethyl methylmalonate, diethyl ethylmalonate, diethyl butylmaronate, diethyl phenylmaronate, dibutyl ethylmalate, and dibutyl butylmaronate. It can be preferably used, and in particular, at least one of diethyl methylmalate, diethyl ethylmalonate and diethyl butylmalonate can be more preferably used.

The malonic acid diester is contained in the curing catalyst in a range of preferably 0.2 to 4.0 mol, more preferably 0.2 to 2.0 mol, with respect to 1 mol of the metal alkoxide. .. When zirconium alkoxide is used as the metal alkoxide, the malonic acid diester is preferably used in the range of 0.2 to 1.6 mol per 1 mol of zirconium alkoxide.

(C) Methyltriethoxysilane Methyltriethoxysilane can be used as an arbitrary additive in order to improve the curing properties of the catalyst. Methyltriethoxysilane is preferably added in a ratio of 0.1 to 0.7, more preferably 0.2 to 0.5, based on the total mass of the metal alkoxide and the ligand.

(C') Other additives (guanidine compound)
Guanidine compounds have the general formula: Any one of the _{^{R 7 N = C (NR 7}} 2) 2 (5 pieces of ^{R 7} is an organic group, the remaining four ^{R 7} are each independently hydrogen Atomic, saturated hydrocarbon group, -C (= NR ⁸ ) -NR ⁸ ₂ (3 R ^8s are each independently hydrogen atom or organic group), or = C (-NR ⁸ ₂ ) ₂ (4) R ⁸ is independently represented by a hydrogen atom or an organic group).

Examples of the guanidine compound include 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,2,3-pentamethylguanidine. , 2-Ethyl-1,1,3,3-tetramethylguanidine, 1-benzylguanidine, 1,3-dibenzylguanidine, 1-benzyl-2,3-dimethylguanidine, 1-phenylguanidine, 1-(o) -Trill) guanidine, 1- (3-methylphenyl) guanidine, 1- (4-methylphenyl) guanidine, 1- (2-chlorophenyl) guanidine, 1- (4-chlorophenyl) guanidine, 1- (2,3-) Xyryl) guanidine, 1- (2,6-xylyl) guanidine, 1- (1-naphthyl) guanidine, 2-phenyl-1,3-dicyclohexylguanidine, 1-phenyl-1-methylguanidine, 1- (4-chlorophenyl) ) -3- (1-Methylethyl) guanidine, 1- (4-methylphenyl) -3-octylguanidine, 1- (4-methoxyphenyl) guanidine, 1,1'-[4- (dodecyloxy) -m -Phenylene] bisguanidine, 1- (4-nitrophenyl) guanidine, 4-guanidinobenzoic acid, 2- (phenylimino) imidazolidine, 2- (5,6,7,8-tetrahydronaphthalene-1-ylamino)- 2-Imidazoline, N- (2-Imidazolin-2-yl) -2,3-xylidine, N- (2-Imidazolin-2-yl) -1-naphthaleneamine, 1,1'-[methylenebis (p-phenylene) )] Bisguanidine, 1,5,7-triazabicyclo [4.4.0] -5-decene, 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decene , 7-n-propyl-1,5,7-triazabicyclo [4.4.0] -5-decene, 7-isopropyl-1,5,7-triazabicyclo [4.4.0] -5 -Decene, 7-n-butyl-1,5,7-triazabicyclo [4.4.0] -5-decene, 7-n-cyclohexyl-1,5,7-triazabicyclo [4.4. 0] guanidine compounds such as -5-decene, 2,3,5,6-tetrahydro-3-phenyl-1H-imidazole [1,2-a] imidazole; 1-methylbiguanide, 1-n-butylbiguanide, 1 -(2-Ethylhexyl) biganide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1 -Diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, 1- (3-methylphenyl) biguanide, 1- (4-methylphenyl) biguanide, 1- (2-Chlorophenyl) biguanide, 1- (4-chlorophenyl) biguanide, 1- (2,3-kisilyl) biguanide, 1- (2,6-kisilyl) biguanide, 1- (1-naphthyl) biguanide, 1,3 −Diphenylbiguanide, 1,5-diphenylbiguanide, 1-phenyl-1-methylbiguanide, 1- (4-chlorophenyl) -5- (1-methylethyl) biguanide, 1- (4-methylphenyl) -5-octyl Biguanide, 1- (4-methoxyphenyl) biguanide, 1- (3,4-dichlorophenyl) -5- (1-methylethyl) biguanide, 1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide] , 2-Guanidino-1H-benzoimidazole, 1- (4-nitrophenyl) biguanide, 1-benzyl biguanide, 1- (2-phenylethyl) biguanide, 3- (2-phenylethyl) biguanide, N, N-di Amidinoaniline, 1,5-ethylenebiguanide, 1-morpholinobiguanide, 3-morpholinobiguanide, 1- (4-chlorobenzyloxy) biguanide, 1-n-butyl-N2-ethylbiguanide, 1,1'-ethylenebisbiguanide , 1- [3- (diethylamino) propyl] biguanide, 1- [3- (dibutylamino) propyl] biguanide, N', N''-dihexyl-3,12-diimino-2,4,11,13-tetra Azatetradecandiamidine, 4- [3- (Amidino) guanidino] benzenesulfonic acid, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidine, 5- [3- (2,4,5-trichloro) Phenoxy) propoxy] -1- Biguanide compounds such as isopropyl biguanide; and the like can be exemplified. Of these guanidine compounds, particularly preferred are 1,1,3,3-tetramethylguanidine and 1-phenylguanidine.

The guanidine compound is preferably added in a molar ratio of 0.1 to 5 and even in a ratio of 0.2 to 3 with respect to the metal alkoxide.

II. Curable Resin Composition The curable resin composition according to this embodiment comprises a curing catalyst and (D) a crosslinkable silyl group-containing resin. The crosslinkable silyl group-containing resin is the main agent of the curable resin composition. In the curable resin composition, the crosslinkable silyl group-containing resin may be simply mixed with the curing catalyst and other additives, or may be partially reacted, and the reaction is completely completed and cured. It is good if it is not in a state. Hereinafter, (D) a crosslinkable silyl group-containing resin will be described in detail.

(D) Crosslinkable Cyril Group-Containing Resin The crosslinkable silyl group-containing resin is a resin having a silicon-containing group having a hydrolyzable functional group bonded to a silicon atom or a silanol group capable of causing a condensation reaction. Here, the hydrolyzable group is not particularly limited, but for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy. The basis etc. can be mentioned. Of these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group such as a methoxy group is preferable. In a typical example, the crosslinkable silyl group-containing resin mainly contains at least one of the following general formulas (“Chemical Formula 3”, “Chemical Formula 4” and “Chemical Formula 5”, respectively). A polymer having one end or both ends of a chain or side chain.

Following general formula ( "Formula 3", "of 4" and "Formula 5") R ^4, R ⁵ and R ⁶ in the functional group of good hydrogen even being the same or different or carbon, It is an alkyl group, an aryl group, an aralkyl group, a triorganosyloxy group, an alkenyl group or a cycloalkyl group of several 1 or more. Specific examples of R ⁴ , R ⁵ and R ^{6 in} the above general formula include hydrogen, methyl group, ethyl group, cyclohexyl group, phenyl group, benzyl group, trimethylsiloxy group, triphenylsiloxy group, methylene group and ethylene group. , Cyclopropyl group. Of these exemplified groups, a methyl group is particularly preferred. Further, X and Y may be the same or different from each other, and are groups other than the alkoxy group such as hydrogen and hydrocarbon groups.

Specific examples of the crosslinkable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. Of these, a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group having high activity are more preferable, and a trimethoxysilyl group is particularly preferable.

The crosslinkable silyl group-containing resin includes a silyl group-containing polyether, a silyl group-containing polyester, a silyl group-containing organic polysiloxane-based polymer, a silyl group-containing vinyl-based polymer, a silyl group-containing polyester-modified vinyl-based polymer, and a silyl group. Examples thereof include a silyl group-containing diallyl phthalate polymer, a silyl group-containing diarylphthalate polymer, a silyl group-containing polyisobutylene, a silyl group-containing ethylene / α-olefin copolymer, and a mixture thereof. For example, when the crosslinkable silyl group-containing resin is a silyl group-containing polyether, a method of cationic polymerization or anionic polymerization is performed using ethylene oxide, propylene oxide, butene oxide, tetrahydrofuran or the like as a main chain polyether. Those produced by using can be preferably exemplified. For example, when the crosslinkable silyl group-containing resin is a silyl group-containing polyester, carboxylic acids such as maleic acid, succinic acid, glutaric acid, adipic acid, and phthalic acid, their anhydrides, esters or halides thereof, and chemicals The main chain is polyester polyols prepared by reacting with a quantitatively excess polyol such as ethylene glycol, propylene glycol, or glycerin, or lactone polyols obtained by ring-opening polymerization of lactones. Can be preferably exemplified. For example, when the crosslinkable silyl group-containing resin is a silyl group-containing organic polysiloxane-based polymer, those having a main chain connected by a siloxane bond (Si—O—Si bond) can be preferably exemplified.

Examples of easily available crosslinkable silyl group-containing resins on the market are "Kaneka Cyril EST280" (a crosslinkable silyl group-containing polyether polymer belonging to a modified silicone resin) and "Kaneka MS Polymer" manufactured by Kaneka Co., Ltd. "S303" (silyl terminal-modified polyether), "X-21-5841" (silyl group-modified polydimethylsiloxane) manufactured by Shinetsu Silicone Co., Ltd., "ARUFON" (alkoxysilyl group-containing acrylic polymer) manufactured by Toa Synthetic Co., Ltd. ) Can be mentioned.

The Mw (weight average molecular weight) of the crosslinkable silyl group-containing resin is not particularly limited, but is, for example, 500 to 100,000, preferably 2,000 to 50,000.

The mass ratio of the crosslinkable silyl group-containing resin to the curable catalyst in the curable resin composition is not particularly limited. For example, assuming that the mass of the crosslinkable silyl group-containing resin is X and the mass of the curable catalyst is Y, for example. , X: Y = 100 to 3.3: 1 (the curing catalyst is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the crosslinkable silyl group-containing resin), preferably X: Y = 80 to It is 5: 1 (the curing catalyst is 1.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the crosslinkable silyl group-containing resin), and more preferably X: Y = 50 to 6.6: 1 ( The curing catalyst is 2 parts by mass or more and 15.2 parts by mass or less with respect to 100 parts by mass of the crosslinkable silyl group-containing resin).

The alcohol component in the curing catalyst is preferably 30 parts by mass or less, more preferably 27 parts by mass or less, still more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less in 100 parts by mass of the curing catalyst.

(E) Other Additives (E'1) Coupling Agent A coupling agent may be added to the curable resin composition according to this embodiment. The coupling agent is effective in improving the adhesion between the curable resin composition and the inorganic base material (the object to be adhered or sealed). As the coupling agent, aminosilane-based cups such as aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (aminoethyl) aminoprovirtrimethoxysilane. Ring agent; Epoxysilanes such as glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents; Mercaptosilane-based coupling agents such as mercatopropyltrimethoxysilane and mercatopropyltriethoxysilane; methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, metachlorixpropyltrimethoxysilane, imidazole Silane-based coupling agents such as silane and triazinesilane; hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexametercyclotrisilazane. And other organosilazane compounds can be exemplified.

The amount of the coupling agent added is 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A). It is a mass part.

(E'2) Filler Examples of the filler that can be arbitrarily added include inorganic oxides such as silica, titanium oxide, alumina, and zirconia, carbonates such as calcium carbonate and magnesium carbonate, and barium sulfate, which are in the form of particles. A plate-like or fibrous filler can be exemplified. In particular, silica having a small particle size and good compatibility with the curable resin composition is preferable. The content of the filler is 2 to 99% by mass with respect to the total mass of the curable resin composition including the filler.

(E'3) Light Stabilizer A light stabilizer may be added to the curable resin composition according to this embodiment. The light stabilizer is effective in improving the weather resistance of the resin or imparting thermal stability. As the light stabilizer, it can be used without any particular restrictions, and a hindered amine-based light stabilizer can be particularly preferably used. Examples of the hindered amine-based photostabilizer include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and poly [{6- (1,1). , 3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,3) 2,6,6-Tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine, 2,4-bis [N-butyl-N- (1,2,2,2) 6,6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl)- 4-Hydroxyphenyl} methyl] butylmalonate, N, N', N'', N'''-tetrax- (4,6-bis- (butyl- (N-methyl-2,2,6,6-) Tetramethylpiperidin-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis (2, Examples thereof include a polycondensate of 2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine.

The amount of the light stabilizer added is 0.1 to 7 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A). It is a department.

(E'4) UV Absorbent An UV absorber may be added to the curable resin composition according to this embodiment. The ultraviolet absorber has a function of absorbing ultraviolet rays, and is effective for improving the weather resistance of the resin or imparting thermal stability. The ultraviolet absorber can be used without particular limitation, and for example, benzotriazole-based, salicylic acid-based, benzophenone-based, cyanoacrylate-based, and triazine-based agents can be preferably used. Of these, a benzophenone-based ultraviolet absorber can be preferably used.

Examples of the benzotriazole system include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 2- (2'-hydroxy-). 5'-octylphenyl) -benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylluphenyl) benzotriazole, 2- {2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl} benzo Examples thereof include triazole and 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol}. Examples of the salicylic acid system include phenylsalicylate, p-tert-butylphenylsalicylate, and p-octylphenylsalicylate. Examples of the benzophenone system include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2'-dihydroxy-4-. Examples thereof include methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and bis (2-methoxy-4-hydroxy-5-benzophenone) methane. Examples of the cyanoacrylate system include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate. As a triazine system, 2- {4', 6'-bis (2 ", 4" -dimethylphenyl) -1', 3', 5'-triazine-2'-yl} -5- (octyloxy) phenol , 2- (4', 6'-diphenyl-1', 3', 5'-triazine-2'-yl) -5- (hexyloxy) phenol can be exemplified.

The amount of the ultraviolet absorber added is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A). It is a mass part.
(E'5) Plasticizer A plasticizer may be added to the curable resin composition according to this embodiment. Plasticizers give the material flexibility and help mix and disperse the formulation. Examples of the plasticizing agent include phthalic acid esters such as dioctyl phthalate and diisononyl phthalate, adipic acid esters such as dioctyl adipate and diisononyl adipate, trimellitic acid esters and pyromellitic acid ester citrates. The amount of the plasticizing agent added is 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A).

Method for Producing Curable Resin Composition The curable resin composition is basically obtained by mixing a crosslinkable silyl group-containing resin and a curing catalyst. In addition to the metal alkoxides and ligands that are essential components of the curing catalyst, at least one of methyltriethoxysilane, guanidine compounds, coupling agents, fillers, light stabilizers and UV absorbers is further added. In some cases, it is preferable to mix it with a crosslinkable silyl group-containing resin in advance, and then add the metal alkoxide and the ligand. It is better to mix at least one of methyltriethoxysilane, guanidine compound, coupling agent, filler, light stabilizer and UV absorber before the crosslinkable silyl group-containing resin proceeds. This is because more uniform mixing is possible. The mixed environment is preferably an inert gas atmosphere. Further, it is preferable to perform an alcohol component reducing step of reducing the alcohol component in the curing catalyst before mixing the curing catalyst with the crosslinkable silyl group-containing resin. The alcohol component reduction step can be carried out by heating, depressurizing, or a combination thereof. The amount of alcohol is preferably obtained by measuring the infrared absorption spectrum of the curing catalyst before and after the alcohol reduction step and using the ratio of the peak areas of OH, but the calculation method uses a method other than the area ratio of the infrared absorption peaks. It may be something to do.

III. Cured product The cured product according to this embodiment can be obtained by bringing the curable resin composition into contact with air or moisture. The curing conditions of the curable resin composition are not particularly limited, but in an environment of, for example, a temperature of 15 to 45 ° C., preferably 20 to 30 ° C., and a humidity of 30 to 70% RH, preferably 40 to 60% RH. It can be obtained by allowing it to stand.

The color of the cured product is colorless and transparent, pale yellow, pale orange, pale white, etc. The color is lighter than the color of the cured product (yellow, yellow-orange) obtained by using a curing catalyst containing titanium alkoxide or the color of the cured product (white turbidity) obtained by using an organic tin-based curing catalyst.

Hereinafter, examples of the present invention will be described. However, the present invention is not limited to the following examples.

I Material used (A) Crosslinkable silyl group-containing resin Methoxysilyl-terminated PPG polymer (manufactured by Kaneka Corporation, product name: MS polymer S303)
(B) Catalyst 1. Metal alkoxide 1) Zyrosine-n-propoxide (ZrnP, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
2) Zircon-n-butoxide (ZrnB, manufactured by Kanto Chemical Co., Ltd.)
3) Titanium tetraisopropoxide (TTiP, manufactured by Kanto Chemical Co., Inc.) ・ ・ ・ Comparative material 4) Titanium tetraethoxydo (TTE, manufactured by Merck Schuchardt OHG) ・ ・ ・ Comparative material 2. Ligand 1) Triethyl citrate (CAtE, manufactured by Tokyo Chemical Industry Co., Ltd.)
2) Tributyl citrate (CAtB, manufactured by Tokyo Chemical Industry Co., Ltd.)
3) Ethyl acetoacetate (EAcAc, manufactured by Kanto Chemical Co., Inc.)
4) Didiethyl malonate (MdE, manufactured by Nakaraitesk Co., Ltd.)
5) Acetylacetone (AcAc, manufactured by Kanto Chemical Co., Inc.) ... Comparative material 3. Silane compound 1) Methyltriethoxysilane (MTES, manufactured by Shin-Etsu Chemical Co., Ltd.)
2) Methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Silicone Co., Ltd.) ・ ・ ・ Comparative material 4. Tin catalyst (comparative material)
1) Dibutyltin dilaurate (DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.)
2) Dibutyltinbis (acetylacetone) (DBTbis (AcAc), manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-220H)
5. Silane coupling agent (comparative material)
3-Aminopropyltrimethoxysilane (combined with other catalysts, manufactured by Tokyo Chemical Industry Co., Ltd.)
(C) Additive 1-Phenylguanidine (PhG, manufactured by Nippon Carbide Industries, Ltd.)

II Evaluation method (A) Skinning time 1) Initial skinning time The skinning time means the dry time to the touch. Actually, a stainless steel spatula is used, and the time until the cured film stretched on the surface does not transfer to the spatula is defined as the skinning time.
The specific method is as follows. A predetermined amount of modified polyorganosiloxane having an alkoxylyl group terminal and a catalyst are placed in an ointment container (UG ointment jar manufactured by Mano Chemical Container Co., Ltd.), sealed, and then rotated and revolved mixer (manufactured by Shinky Co., Ltd.). ) Was used for 1 minute of stirring and 1 minute of defoaming treatment to obtain a liquid curable composition. After leaving this sealed at room temperature (about 23 ° C) for 30 minutes, it is opened in an environment of 23 ° C and 50% humidity to start curing, and the surface is covered with a stainless steel spatula to stretch the skin. The time until was measured.
2) Skin-covering time delay rate After allowing the sample prepared in the same manner as in (A) above to stand at room temperature (23 ° C), transfer it to a syringe (SH11CPP-B manufactured by Sanei Tech), and keep it in a sealed state at 50 ° C. It was allowed to stand for 7 days. After returning to room temperature, the sample was taken out, and the skinning time was measured in an environment of room temperature (23 ° C.) and humidity of 50%. The ratio to the initial skinning time before storage was calculated as the skinning time delay rate. When the delay rate> 1, it means that the skinning time is extended by storage and the quality is deteriorated.
(B) Color The liquid curable composition obtained in the same manner as in (A) above was allowed to stand at room temperature (about 23 ° C.) for 30 minutes while being sealed, and then in an environment of 23 ° C. and 50% humidity. After being left open for 7 days and cured, the color of the cured product was evaluated visually and using an ultraviolet-visible spectrophotometer (UV-160A, manufactured by Shimadzu Corporation). The wavelength measured by the ultraviolet spectrophotometer is 350 nm to 800 nm, and the absorbance is measured. The value obtained by dividing the obtained absorbance by the thickness of the sample is used as the evaluation value, and it can be said that the larger this value is, the more colored or turbid the sample is.
(C) Viscosity increase rate The viscosity of the liquid curable composition prepared in the same manner as in (A) above was measured, and the viscosity of the composition obtained by static storage in the same manner as in (A) 2) was also measured. , The ratio of the viscosity after storage to that before storage was calculated as the thickening rate. When the thickening rate> 1, it means that the stickiness is increased by storage and the quality is deteriorated.

III Experimental Example (A) Experimental Example 1
1. 1. Preparation conditions (Experiment 1) ZrnP-CAtE-based catalyst A 70% propanol solution of ZrnP is prepared, and CAtE is added thereto so that ZrnP: CAtE = 1: 1 in molar ratio to prepare a ZrnP-CAtE-based catalyst. did. Next, in a predetermined container, 0.118 g (amount of metal alkoxide of 0.73 mol per 1 mol of polymer. Hereinafter, the same applies to Experiment 8) and 5 g of MS polymer S303 are added to the ZrnP-CAtE catalyst. Was mixed by the method of II (A) to obtain a liquid curable composition, and then the initial skinning time (minutes), color, absorbance (at 400 nm), delay rate of skinning time and thickening rate were evaluated. ..
(Experiment 2) ZrnB-CAtB-based catalyst A 90% butanol solution of ZrnB was prepared, and CAtB was added thereto so that the molar ratio was ZrnB: CAtB = 1: 1 to prepare a ZrnB-CAtB-based catalyst. Next, 0.125 g of the ZrnB-CAtB-based catalyst and 5 g of the MS polymer S303 were mixed in the same manner as in (Experiment 1) to obtain a liquid curable composition, which was then evaluated in the same manner as in Experiment 1. went.
(Experiment 3) ZrnB-MdE-based catalyst A 90% butanol solution of ZrnB was prepared, and MdE was added thereto so that the molar ratio was ZrnB: MdE = 1: 1 to prepare a ZrnB-MdE-based catalyst. Next, 0.093 g of ZrnB-MdE-based catalyst and 5 g of MS polymer S303 were mixed in the same manner as in (Experiment 1) to obtain a liquid curable composition, which was then evaluated in the same manner as in Experiment 1. went.
(Experiment 4) (ZrnB-2EAcAc) + PhG-based catalyst A 90% butanol solution of ZrnB was prepared, and EAcAc was added to the solution so that ZrnB: EAcAc = 1: 2 in terms of molar ratio to obtain a ZrnB-2EAcAc-based catalyst. Made. Next, PhG was added so that the molar ratio of ZrnB: EAcAc: PhG was 1: 2: 1 to obtain a (ZrnB-2EAcAc) + PhG-based catalyst. 0.130 g (ZrnB-2EAcAc) + PhG-based catalyst and 5 g of MS polymer S303 were mixed in a predetermined container in the same manner as in Experiment (1) to obtain a liquid curable composition, and then the same as in Experiment 1. Evaluation was performed.
(Experiment 5) TTE-CAtB catalyst (comparative catalyst)
A TTE-CAtB catalyst was prepared by adding CAtB to TTE so that TTE: CAtB = 1: 1 in molar ratio. Next, 0.093 g of TTE-CAtB-based catalyst and 5 g of MS polymer S303 were mixed in a predetermined container in the same manner as in (Experiment 1) to obtain a liquid curable composition, and then Experiment 1 The same evaluation was made.
(Experiment 6) Titanium chelate catalyst (comparative catalyst)
A titanium chelate (TTiP-2EAcAc) -based catalyst was prepared by adding EAcAc to TTiP so that TTiP: EAcAc = 1: 2 in molar ratio. Next, 5 g of MS polymer S303 and 0.086 g of a titanium chelate catalyst were mixed in the same manner as in (Experiment 1) to obtain a liquid curable composition, and then the same evaluation as in Experiment 1 was performed. ..
(Experiment 7) ZrnB-2EAcAc-based catalyst (comparative catalyst)
A 90% butanol solution of ZrnB was prepared, and EAcAc was added thereto so that the molar ratio was ZrnB: EAcAc = 1: 2 to prepare a ZrnB-2EAcAc-based catalyst. Next, 0.109 g of ZrnB-2EAcAc-based catalyst and 5 g of MS polymer S303 were mixed in the same manner as in (Experiment 1) to obtain a liquid curable composition, which was then evaluated in the same manner as in Experiment 1. went.
(Experiment 8) ZrnB (comparative catalyst)
0.068 g of a 90% butanol solution of ZrnB and 5 g of MS polymer S303 were mixed in the same manner as in (Experiment 1) to obtain a curable composition in a liquid laboratory, and then the same evaluation as in Experiment 1 was performed.
(Experiment 9) DBTDL + 3-aminopropyltrimethoxysilane (comparative catalyst)
0.1 g of DBTDL, 0.1 g of 3-aminopropyltrimethoxysilane, and 5 g of MS polymer S303 were mixed in the same manner as in (Experiment 1) to obtain a liquid curable composition. The same evaluation as in Experiment 1 was performed.
(Experiment 10) DBTbis (AcAc) + 3-aminopropyltrimethoxysilane (comparative catalyst)
0.068 g of DBTbis (AcAc), 0.1 g of 3-aminopropyltrimethoxysilane, and 5 g of MS polymer S303 were mixed in the same manner as in (Experiment 1) to obtain a liquid curable composition. After that, the same evaluation as in Experiment 1 was performed.

2. Evaluation Results Table 1 shows the evaluation results of the cured product cured using each catalyst. Figures 1 to 4 show the results of the absorbance of the cured product cured using each catalyst. Further, FIG. 5 shows the experimental No. The appearance of each cured product of 1-3, 5-7, 9 and 10 is shown in the photograph.

From Table 1 and FIGS. 1 to 5, the following was found. When the titanium catalyst system (Experiments Nos. 5 and 6) and the tin catalyst system (Experiments Nos. 9 and 10) were used, the result was that the cured product was deeply colored. However, when a zirconium catalyst system (Experiments Nos. 1-3, 7 and 8) was used, a colorless or lightly colored cured product was obtained, and the absorbance was also low. However, Experiment No. No. 7 has an extremely long skin-covering time of 150 minutes. In No. 8, the delay rate of the skinning time is as large as 30 or more. It did not reach that of 1-3. When a catalyst system in which triethyl citrate or tributyl citrate and diethyl malonate were added to zirconium alkoxide (Experiments Nos. 1, 2 and 3) was used, a catalytic system in which ethyl acetoacetate was added to zirconium alkoxide (experiment No. 1, 2 and 3). Compared with Experiment No. 7), the skinning time was shorter and the catalytic ability was excellent. In addition, Experiment No. The catalyst system in which PhG was added to No. 7 (Experiment No. 4) had a long skin-covering time, and Experiment No. 4 was used. The absorbance at a wavelength of 350 nm was higher than that of 1-3, and a light yellow coloration was observed. Further, as is clear from FIG. 1, when the titanium catalyst system (Experiments No. 5 and 6) is used, it can be seen from the numerical values that the light absorption at the wavelength of 400 to 450 nm is large and the color is colored yellow. Further, from FIG. 3, when the tin catalyst system (Experiments No. 9 and 10) is used, the absorbance is high in the entire visible light range of 400 to 800 nm. The sample is cloudy, indicating that light scattering is strong. From these results, it was found that after curing, it was colorless or almost colorless, had low absorbance, short skinning time, low delay rate of skinning time, and low thickening rate of 1.2 or less. Nos. 1 to 3 are Experiment Nos. It can be evaluated that it has excellent performance as compared with 4 to 10.

(B) Experimental Example 2
1. 1. Preparation Conditions (Experiment 11) ZrnP-CAtE-based catalyst 5 g of MS polymer S303 was mixed and stirred with 0.3 g of the ZrnP-CAtE-based catalyst prepared in the same manner as in Experiment 1 to obtain a liquid curable composition. The composition was transferred to a predetermined container and allowed to stand in an environment of 50 ° C. for 7 days in a sealed state, and then the skinning time and viscosity were measured at room temperature to calculate the change before and after the standing.
(Experiment 12) ZrnB-CAtB-based catalyst 5 g of MS polymer S303 was mixed and stirred with 0.3 g of the ZrnB-CAtB-based catalyst prepared in the same manner as in Experiment 2 to obtain a liquid curable composition. The composition was transferred to a predetermined container and allowed to stand in a closed state in an environment of 50 ° C. for 7 days, and then the skinning time and viscosity were measured at room temperature to calculate the change before and after standing.
(Experiment 13) ZrnB-based catalyst 0.3 g of a 90% butanol solution of ZrnB and 5 g of MS polymer S303 were mixed and stirred to obtain a liquid curable composition. The composition was transferred to a predetermined container and allowed to stand in an environment of 50 ° C. for 7 days in a sealed state, and then the skinning time and viscosity were measured at room temperature to calculate the change before and after the standing.

2. Evaluation Results As shown in Table 2, in the ZrnB-based catalyst without a ligand (Experiment No. 13), the initial skinning time is short, but the delay rate is large. On the other hand, in the catalyst system having a ligand (Experiments Nos. 11 and 12), the delay rate was small, and the superior effect of the ligand on the storage stability of the catalyst was clarified.

(C) Experimental Example 3
1. 1. Production conditions (Experiment 14) ZrnB-CAtB catalyst + MTES
A ZrnB-CAtB-based catalyst prepared in the same manner as in Experiment 2 was prepared. Next, 0.1 g of MTES and 5 g of MS polymer S303 were mixed, 0.3 g of a ZrnB-CAtB-based catalyst was added thereto, and the mixture was stirred to obtain a liquid curable composition. Subsequent processing and evaluation are the same as in Experimental Example 2.
(Experiment 15) ZrnP-CAtE catalyst + MTES
A ZrnP-CAtE-based catalyst prepared in the same manner as in Experiment 1 was prepared. Next, 0.1 g of MTES and 5 g of MS polymer S303 were mixed, 0.3 g of a ZrnP-CAtE-based catalyst was added thereto, and the mixture was stirred to obtain a liquid curable composition. Subsequent processing and evaluation are the same as in Experimental Example 2.
(Experiment 16) ZrnP-CAtE catalyst + MTMS (comparative catalyst)
Other than changing MTES to MTMS, the same treatment and evaluation as with ZrnP-CAtE catalyst + MTES was performed.

2. Evaluation Results Table 3 shows the cured products cured using each catalyst in comparison with the cured products obtained in Experimental Example 2 in which no silane compound was added.

As is clear from Table 3, in the catalyst system to which methyltriethoxysilane was added (Experiment Nos. 14 and 15), the skin-covering time was longer than that in the catalyst system to which methyltrimethoxysilane was added (Experiment No. 16). It was short and had excellent catalytic ability. However, the addition of methyltriethoxysilane did not reduce the skinning time. On the other hand, the effect of adding methyltriethoxysilane was observed in terms of lowering the thickening rate.

(D) Experimental Example 4
1. 1. Preparation conditions (Experiment 17) ZrnP-CAtE-based catalyst The ZrnP-CAtE-based catalyst prepared in Experiment 1 was mixed with MS polymer S303 (100 parts by mass) so as to be 6 parts by mass, and a liquid curable composition was prepared. After obtaining the results, the initial skinning time (minutes), the delay rate of the skinning time, and the thickening rate were evaluated. The delay rate of the skinning time and the thickening rate are both values evaluated after standing at 50 ° C. for 7 days.
(Experiment 18) ZrnP-CAtE-based catalyst (concentration)
6 parts by mass of the ZrnP-CAtE-based catalyst prepared in Experiment 1 was prepared with respect to MS polymer S303 (100 parts by mass), and a part of the alcohol component was volatilized in a dry nitrogen flow atmosphere while heating, and then MS. It was mixed with polymer S303 (100 mass) to obtain a liquid curable composition. After that, the same evaluation as in Experiment 17 was performed.
(Experiment 19) ZrnB-CAtB-based catalyst A liquid curable composition was obtained under the same conditions as in Experiment 17, except that the ZrnP-CAtE-based catalyst in Experiment 17 was changed to the ZrnB-CAtB-based catalyst prepared in Experiment 2. , The same evaluation as in Experiment 17 was performed.
(Experiment 20) ZrnB-CAtB catalyst (concentration)
A liquid curable composition was obtained under the same conditions as in Experiment 18 except that the ZrnP-CAtE catalyst in Experiment 18 was changed to the ZrnB-CAtB catalyst prepared in Experiment 2, and the same evaluation as in Experiment 17 was performed. ..
(Experiment 21) ZrnB-2EAcAc-based catalyst The ZrnB-2EAcAc-based catalyst prepared in Experiment 7 was mixed with MS polymer S303 (100 parts by mass) so as to be 6 parts by mass to obtain a liquid curable composition. Later, the same evaluation as in Experiment 17 was performed.
(Experiment 22) ZrnB-2EAcAc-based catalyst (concentration 1)
6 parts by mass of the ZrnB-2EAcAc-based catalyst prepared in Experiment 7 was prepared with respect to MS polymer S303 (100 parts by mass), and a part of the alcohol component was volatilized in a dry nitrogen flow atmosphere while heating, and then MS. It was mixed with polymer S303 (100% by mass) to obtain a liquid curable composition. After that, the same evaluation as in Experiment 17 was performed.
(Experiment 23) ZrnB-2EAcAc-based catalyst (concentration 2)
In Experiment 22, the volatilization of the alcohol component was promoted by heating for a long time, and the mixture was mixed with MS polymer S303 (100 parts by mass) to obtain a liquid curable composition. After that, the same evaluation as in Experiment 17 was performed.

2. Evaluation Results Table 4 shows the evaluation results of the cured product cured using each catalyst. Further, FIG. 6 shows a method of calculating the alcohol component from the peak area of OH in the infrared absorption spectrum. FIG. 6 shows the infrared absorption spectra of the ZrnP-CAtE-based catalyst (Experiment No. 17) and the ZrnP-CAtE-based catalyst (concentration) (Experiment No. 18) in Table 4 as an example. The lower spectrum in FIG. 6 is an enlargement of a part of the upper spectrum.

The alcohol amount (%) in Table 4 is a value calculated from the ratio of the alcohol amount (known) before concentration and the OH peak area before and after concentration. In any of the catalyst systems, when the alcohol component was volatilized, the skinning time was short and the thickening rate tended to decrease. However, Experiment No. In 18 and 20, the skinning time was significantly shorter than that in the samples before concentration (Experiment Nos. 17 and 19), respectively (up to 50% reduction), whereas in Experiment Nos. In 22 and 23, the reduction rate of the skinning time was smaller than that in the sample before concentration (Experiment No. 21) (22% reduction at the maximum). From these results, the zirconium alkoxide-hydroxycarboxylic acid ester-based catalyst can be expected to significantly reduce the skinning time by reducing the alcohol component.

(E) Experimental Example 5
1. 1. Preparation conditions (Experiment 24) ZrnB-CAtB-based catalyst The ZrnB-CAtB-based catalyst prepared in Experiment 2 is mixed with MS polymer S303 (100 parts by mass) so as to be 15 parts by mass to prepare a liquid curable composition. After obtaining, the initial skinning time (minutes), the skinning time after storage (minutes), the color, the delay rate of the skinning time (at 400 nm), and the thickening rate were evaluated.
(Experiment 25) ZrnB-CAtB-based catalyst Under the same conditions as in Experiment 24, except that the ZrnB-CAtB-based catalyst prepared in Experiment 2 was mixed with MS polymer S303 (100 parts by mass) so as to be 30 parts by mass. A liquid curable composition was obtained and evaluated in the same manner as in Experiment 24.
(Experiment 26) ZrnB-based catalyst Liquid curing under the same conditions as in Experiment 24, except that the ZrnB-based catalyst prepared in Experiment 8 was mixed with MS polymer S303 (100 parts by mass) so as to be 15 parts by mass. A sex composition was obtained and evaluated in the same manner as in Experiment 24.
(Experiment 27) ZrnB-based catalyst Liquid curing under the same conditions as in Experiment 24, except that the ZrnB-based catalyst prepared in Experiment 8 was mixed with MS polymer S303 (100 parts by mass) so as to be 30 parts by mass. A sex composition was obtained and evaluated in the same manner as in Experiment 24.

2. Evaluation Results Table 5 shows the evaluation results of the cured product cured using each catalyst. Experiments 2, 8, 12, and 13 were evaluated in the same manner as in Experiment 24 and are shown in Table 5.

As is clear from Table 5, all four types of samples using the ZrnB-CAtB-based catalyst were colorless and had a short skinning time. When the amount of catalyst is up to 20 parts by mass with respect to 100 parts by mass of the polymer, the skinning time after storage is within 1 hour, so that better performance can be exhibited as compared with the case where the amount of catalyst is 30 parts by mass. I understood. On the other hand, in Experiment 13 in which the skinning time after storage of all four ZrnB catalysts was 1 hour or more and the skinning time after storage was 1 hour, the skin was more skinned than in Experiment 25 of the ZrnB-CAtB catalyst. Due to the large time delay rate, it is considered to be inferior overall.

The present invention can be used, for example, as an adhesive, a sealing material, or the like.

Claims (8)

A curing catalyst that has the function of curing synthetic resin.
(A) Zirconium alkoxide and
(B) With at least one of the ligands of the citric acid ester and the malonic acid diester,
(C) A curing catalyst further containing methyltriethoxysilane. The curing catalyst according to claim 1, wherein the zirconium alkoxide (A) contains at least one of zirconium propoxide and zirconium butoxide. The curing catalyst according to claim 1 or 2, wherein the ligand (B) contains a citrate ester. The curing catalyst according to any one of claims 1 to 3, wherein the ligand (B) contains at least one of diethyl malonate and dibutyl malonate. The curing catalyst according to any one of claims 1 to 4, wherein the alcohol component is 30 parts by mass or less with respect to 100 parts by mass of the curing catalyst. A curable resin composition comprising the curing catalyst according to any one of claims 1 to 5 and (D) a crosslinkable silyl group-containing resin. The curable resin composition according to claim 6, wherein the curing catalyst is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (D) crosslinkable silyl group-containing resin. A cured product obtained by curing the curable resin composition according to claim 6 or 7.