JP4847019B2 - Room temperature moisture curable resin composition and room temperature moisture curable adhesive - Google Patents

Description

  The present invention relates to a curable resin composition having a hydrolyzable silyl group and cured by moisture in the atmosphere at room temperature, and a moisture curable adhesive containing the curable resin composition. The present invention relates to a curable resin composition that is accelerated and can be cured in an extremely short time, and a moisture-curable adhesive containing the same.

  Resins having silicon-containing characteristic groups such as hydrolyzable silyl groups in the molecule have been studied for use as moisture curable resins from the viewpoint of curing by reaction with moisture in the atmosphere.

  For example, Patent Document 1 below discloses that a resin having a hydrolyzable silyl group is used as a curable resin for moisture curable powder coatings. This powder coating contains a heat latent catalyst that promotes a hydrolysis reaction by heating, and a powdery curable resin melts and is cured by heating to form a coating film. Therefore, it does not react at room temperature and is stored stably. Further, a slush molding material using the same mechanism as described above is disclosed in Patent Document 2 below. In this document, a mold obtained by heating a resin composition containing a powdered thermoplastic polyurethane resin whose surface is treated with a hydrolyzable silane compound and a thermal latent catalyst that promotes a hydrolysis reaction of a silyl group at a constant temperature is used. After the molding, the powder is melted and the surface is cross-linked by moisture.

  On the other hand, it is also attempted to use a resin having a hydrolyzable silyl group as a curable resin for an adhesive or a sealing material that cures at room temperature. In this case, the curable resin is liquid at normal temperature, and the hydrolysis reaction due to moisture in the atmosphere is promoted by the catalyst, so that the resin is cured.

  Conventionally, organic tin compounds such as dibutyltin dilaurate and dibutyltin diacetonate have been widely used as curing catalysts in the case of using a curable resin having a silicon-containing characteristic group such as a hydrolyzable silyl group in such room temperature curing type applications. In particular, when a silylated urethane-based resin as described in Patent Document 3 below is used as a curable resin having a silicon-containing characteristic group, the curing rate is relatively high by blending an organic tin compound. A curable resin composition can be obtained.

  In addition to the above organic tin compounds, organic acids and amine compounds are well known as curing catalysts for curable resins having silicon-containing characteristic groups.

Japanese Patent Laid-Open No. 11-1635 Japanese Patent Laid-Open No. 11-228833 Japanese Patent No. 3030020

  Conventional adhesives and sealants using a curable resin having a silicon-containing characteristic group as described above have a low curing rate, and in order to meet market needs where faster curing is desired, the curing rate Improvements have been attempted.

  However, if a large amount of organotin compound, which is a curing catalyst, is added to increase the curing rate, the storage stability will decrease and the content of tin compound, which is a heavy metal, will increase, making the environment more dangerous and harmful. Another problem is that the load increases. In addition, when used as an adhesive or sealing material for a plastic containing a hydrolyzable group such as polyurethane or polyester, the organic tin compound blended in the curable resin may deteriorate the plastic. Mixing a large amount of tin compound or the like becomes a problem.

  Also, when an organic acid or an amine compound is used as a curing catalyst, the curing rate of the curable resin having a silicon-containing characteristic group is slow. For this reason, organic acids and amine compounds are actually used as promoters.

  The present invention solves the above-described problems, and uses a curable resin having a silicon-containing characteristic group to reduce the risk and environmental burden, and to cure the resin very quickly with moisture at room temperature. An object of the present invention is to provide a moisture curable adhesive containing

In order to achieve the above object, as a result of intensive research, the present inventors have found that the object of the present invention is a curable resin composition in which a basic compound and a Lewis acid or a complex thereof are blended with a curable resin. We have found that it can be achieved.
According to one aspect of the present invention, a room temperature moisture curable resin composition comprises a curable resin (A) having a hydrolyzable silyl group in the molecule, and a basic compound having a pK _{BH +} value (MeCN) of 20 or more ( and B), containing a curing catalyst comprising a complex of a metal halide and Lulu chairs acid is selected from the group consisting of boron halides (C), the curable resin (a), a hydrolyzable silyl group It is a polyoxyalkylene having a group obtained by adding a silicon hydride compound having an alkenyl group, and the hydrolyzable group is composed of a dialkoxysilyl group having two identical or different alkoxy groups .

Further, according to one aspect of the present invention, room temperature moisture curable resin composition, the curable resin (A) 100 parts by mass of per the basic compound (B) 0.01 to 10 parts by weight, before Symbol complex of Le chair acid (C) is summarized in that contains 0.001 to 10 parts by weight.

According to the present invention, a room temperature moisture curable adhesive contains the above room temperature moisture curable resin composition.

  According to the present invention, there is provided a curable resin composition that can be cured extremely quickly at room temperature without increasing the environmental load caused by an organic metal using a curable resin having a silicon-containing characteristic group. It can be used in various fields as a curable moisture curable adhesive, and the applicability of adhesives, sealing materials, and the like is enhanced.

  When a curable resin having a silicon-containing characteristic group such as a hydrolyzable silyl group is used as an adhesive or sealing material that cures at room temperature, it can be applied uniformly to the adhesive or sealing surface without using a solvent. For this purpose, a curable resin that is liquid at room temperature, that is, has fluidity or deformability, is used. At this time, in order to increase the curing rate of the curable resin, it is necessary to examine the reactivity of the silicon-containing characteristic group and the catalyst that promotes the hydrolysis reaction of the silicon-containing characteristic group.

 In order to increase the curing rate at room temperature, the inventors of the present application studied the effectiveness of blending various substances as a curing catalyst with a curable resin having a silicon-containing characteristic group at room temperature and under certain conditions. When the above conditions are satisfied, it has been found that a Lewis acid and its complex are effective as a curing catalyst, and act on a liquid curable resin at room temperature to be cured extremely quickly, and proposed in a previous application (PCT / JP2004 / 010549). ing. Lewis acid compounds are well known as curing catalysts for heat-curable epoxy resins (see, for example, JP-A-2-251274 and JP-A-2-228376), but curable resins having hydrolyzable silyl groups. In this case, the results are very different depending on the number of hydrolyzable groups (alkoxy groups or the like) bonded to silicon. That is, when there are three hydrolyzable groups (trifunctional silyl group), the Lewis acid or its complex functions extremely effectively as a curing catalyst, and the liquid curable resin cures in a short time. When the number of decomposable groups is 2 or less (bifunctional or monofunctional silyl group), the reaction by the catalyst is very slow and is extremely difficult to cure. It is known that resins having a trifunctional silyl group tend to cure faster than resins having a bifunctional silyl group, but when a specific Lewis acid or a complex thereof is used as a catalyst Is clearly different from the tendency in the absence of a catalyst, and the difference between a bifunctional silyl group and a trifunctional silyl group is significant. In the previous application, as a technique for improving this, it has been proposed to introduce a polar element into the molecule of the curable resin, but the improvement in the curing rate of the bifunctional silyl group is not so great.

 In the present application, as a technique capable of sufficiently improving the curing rate in the case of a bifunctional silyl group, it is proposed to blend a basic compound into the curable resin composition.

 In the present invention, the curable resin composition is selected from the group consisting of a curable resin (A) having a hydrolyzable silyl group in the molecule, a basic compound (B), a metal halide and a boron halide. And a Lewis acid complex (C). Lewis acid or its complex (C) is a curing catalyst and acts on the hydrolyzable group of the hydrolyzable silyl group to hydrolyze the hydrolyzable group and enhance its detachability to couple the silyl groups together. By allowing the reaction to proceed, the curability is increased. In this case, when the basic compound (B) is blended with the resin, the curing rate is remarkably improved, and hydrolysis and coupling proceed rapidly even with a bifunctional silyl group having low reactivity. When the basicity or the blending amount of the basic compound (B) to be blended is high, there is a tendency that curing is markedly accelerated. Therefore, the basic compound (B) is an electron of the curing catalyst and the hydrolyzable group. The Lewis acid is activated by hydrolyzing the state by facilitating the movement and localization of electrons by affecting the state and facilitating coordination with the Lewis acid and ligand exchange of the Lewis acid complex. It is considered that the reactivity of the decomposable group is increased.

 Hereinafter, each component which comprises the curable resin composition and moisture hardening type adhesive agent of this invention is demonstrated in detail.

 The present invention is basically applicable to the curable resin described in the prior application (PCT / JP2004 / 010549) by the applicant of the present application, and is therefore the main component of the curable resin composition of the present invention. The curable resin (A) contains at least one hydrolyzable silyl group (that is, a group in which 1 to 3 hydrolyzable groups are bonded to silicon) in the molecule, which is described in detail in the prior application. Since the present invention can improve the curing rate to the extent comparable to that of trifunctional resin even in the case of a resin having low reactivity with a hydrolyzable silyl group being bifunctional, This is particularly useful when using a curable resin having a bifunctional hydrolyzable silyl group. Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, oxime groups and alkenyloxy groups, as well as hydrogen atoms and halogen atoms. Among them, preferred are a hydrogen 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, an oxime group, and an alkenyloxy group, particularly high reactivity and low odor. From this point, an alkoxy group is preferable. As an alkoxy group, a C1-C12 thing is preferable and a methoxy group and an ethoxy group are especially preferable. The hydrolyzable groups in the bifunctional and trifunctional hydrolyzable silyl groups may be the same or different from each other, and the hydrolyzable silyl groups contained in the curable resin (A) are also the same. However, different types of groups may be included. Different types of curable resins may be used in combination, such as a combination of a bifunctional resin and a trifunctional resin.

 The curable resin (A) is not particularly limited as to the structure of the portion other than the hydrolyzable silyl group, and usable resins include, for example, organopolysiloxane, modified silicone (for example, trade name: S manufactured by Kaneka Corporation). Series, SAT series, MA series, MAX series, EST series, ESX series, SAX series, etc.) Product name: ES-S series, ES-GX3440ST, etc., Japanese Patent Publication No. 4-69659, 7-108928 No. 25,468, JP-A 64-22904, JP 2539445, etc., hydrolyzable silyl group-containing saturated hydrocarbon polymers, trade names manufactured by Kaneka Corporation: Epion series, hydrolyzable Silyl group-containing vinyl polymer (for example, trade name: SA100S, OR100S, S manufactured by Kaneka Corporation) 300S, SA110S, etc.), silicone alkoxy oligomers (for example, trade names: KC-89S, KR series, X-40 series, X-41 series, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), silicones whose molecular ends are alkoxysilyl groups Examples of the resin include silicone alkoxy oligomers and silane coupling agents.

  JP-A Nos. 11-100197, 2000-143757, 2000-169544, 2002-212415, 2004-123900, 2004-123901, Patent No. 3030020, No. 3295663, The silylated urethane-based resin proposed in JP-A-3313360, JP-A-3317353, JP-A-3335001, etc., the curable resin described in Japanese Patent Application No. 2004-208672, and the epoxy resin A curable resin carbonated by the action of carbon and then silylated with an aminosilane compound, as proposed in JP-A-63-83131, JP-A-63-83160, JP-A-2-238045, etc. Aromatic dithiol compounds and / or aromatics on the terminal epoxy group polymer Family-based diimino curable resin compounds obtained by adding an epoxy silane compound was terminated thiolated by the action of the like can be used.

  Examples of the resin exemplified above as the curable resin (A) whose main chain skeleton is an oxyalkylene polymer include JP-B Nos. 45-36319, 46-12154, 49-32673, and JP-A-50-50. 156599, 51-73561, 54-6096, 55-82123, 55-123620, 55-125121, 55-13122, 55-135135, 55-137129 Resins generally referred to as modified silicones proposed in each publication are included, and are suitably used in the present invention.

  As a method for producing an oxyalkylene polymer, a method in which a silicon hydride compound having a hydrolyzable silyl group in the molecule is added to an alkenyl group of a polyoxyalkylene having an alkenyl group, and a polyalkylene having an alkenyl group A method of radical addition reaction of a mercapto group of a mercaptosilane compound having a mercapto group and the hydrolyzable silyl group in the molecule to an alkenyl group of oxyalkylene is well known, and the main chain skeleton is utilized by using these. A resin which is an oxyalkylene polymer can be obtained. In addition, WO 2004/073330, WO 2004/108774, and Japanese Patent Application No. 2004-208672 also have descriptions regarding curable resins that can be suitably used in the present invention, and these can be referred to.

JP-A-9-272715, 9-272714, 11-080249, 11-080250, 11-005815, 11-116617, 11-116606, 11-080571. 11-080570, 11-130931, 11-100433, 11-116763, JP-A-2003-82192, 2003-119339, 2003-171416, 2003-246661, Reactive silyl group-containing vinyl polymers described in JP-A Nos. 2003-327852, 2003-327620, 2004-002835, etc., trade names: XPR-15, XPR-22, etc. manufactured by Toagosei Co., Ltd. Reactive plasticizer XPR series, product name made by Soken Chemical Co., Ltd .: Actflow series etc. are also curable It can be used as fat (A).
The curable resin (A) is prepared by selecting one or a plurality of polymerizable compounds containing at least one hydrolyzable silyl group and appropriately polymerizing or copolymerizing the selected one, as necessary. May be. The polymerizable compound containing at least one hydrolyzable silyl group is a monomer having at least one hydrolyzable silyl group in the molecule and having a carbon-carbon double bond polymerizable by radical polymerization, This can be produced by reacting an aminosilane compound having a hydrolyzable silyl group as a silylating agent with a compound having a radical-polymerizable carbon-carbon double bond as a polymerization element. Alternatively, the curable resin (A) can also be prepared by reacting the silylating agent with an appropriately selected or synthesized resin.

  Further, the curable resin (A) has a urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group in the molecule. One or more bonds and / or groups (polar elements) selected from the group consisting of a group and a tertiary amino group may be included, whereby the reactivity of the hydrolyzable silyl group is improved. Among these elements, those having a urethane bond are preferable because the synthesis conditions of the resin are simple. The method for introducing the polar element is not particularly limited. The linking group generated when linking a plurality of raw materials by a chemical reaction may be the polar element, or the compound containing the polar element may be linked by a chemical reaction from the beginning. The number of the polar elements contained in the curable resin (A) is not particularly limited.

 The curable resin (A) is preferably a resin having a number average molecular weight of about 500 to 30,000, particularly 2,000 to 20,000, from the viewpoint of preparing a curable resin composition having fluidity at room temperature. .

  The details of the preparation method and modifications other than the above regarding the curable resin (A) can be referred to the description of the prior application (PCT / JP2004 / 010549).

 The basic compound (B) in the present invention affects the electronic state of the Lewis acid or its complex (C), which is a curing catalyst, and the hydrolyzable silyl group, and is particularly limited as long as it is a basic compound. In addition, salts with acids such as carboxylic acids can be used as long as they are basic. For example, primary to tertiary amine compounds and salts thereof, quaternary ammonium salts, organic acid metal salts and the like can be suitably used. A reaction product of an amine compound and an epoxy compound may be used.

Specific examples of the basic compound (B) include, for example, N-methyl-3,3′-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,2-diaminopropane, 1,3-diamino. Propane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5. 5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenyl ether, 3,3'-dimethyl-4 , 4'-diaminodiphenylmethane, tolidine base, m- Louylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, di-o-tolylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) Compounds having a plurality of primary amino groups such as 1,3-propanediamine, bis (3-aminopropyl) ether, and Jeffamine (trade name) manufactured by Sun Techno Chemical Co .; 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'-diphe Compounds having a plurality of secondary amino groups such as ruthiourea, N, N′-diethylthiourea, N-methyl-1,3-propanediamine; methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylamino Propylamine, 2-hydroxyethylaminopropylamine, 1- (2-aminoethyl) piperazine, N-aminopropylpiperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline , Ethylamine ethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, represented by the formula: H ₂ N (C ₂ H ₄ NH) _n H (n≈5) Compound (trade name: Polye A compound having a primary amino group and a secondary amino group such as Tosoh Corporation; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; DABCO (registered trademark) manufactured by Sankyo Air Products ) Series, DABCO BL series, 1,8-diazabicyclo [5.4.0] -7-undecene and other linear nitrogen-containing or cyclic tertiary amines and quaternary ammonium salts.

 Γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, N-β (Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (amino Ethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl) amino Propyltrimethoxysilane, N-phenyl γ- aminopropyltrimethoxysilane, N- (2- aminoethyl) -11-Amino aminosilane compounds such as undecyl trimethoxysilane may be mentioned.

  Commercial products of the above compounds can also be used. Commercially available products manufactured by Shin-Etsu Chemical Co., Ltd., trade name, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBM-902, KBE-902, KBE-9103, KBM-573, KBM -575, KBM-576, KBM-6123, KBE-585, X-12-806, X-12-666, X-12-896, X-12-5263, X-12-580, X-12-575 , X-12-577, X-12-563B, X-12-565, X-12-562, X-12-817H, KBM-6063, manufactured by Nihon Unicar Co., Ltd., trade names: A-1100, A-1102 , A-1110, A-1120, A-1122, A-9669, A-1160, A-1170, A-1ink15, Y-11637, GE Toshiba Silicone , Product name: TSL8331, TSL8340, TSL8345, TSL8802, Chisso Corporation, trade name: S360, S320, S310, S311, S321, S330, Degussa Japan Co., Ltd., trade name: Dynasylan (DYNASYLAN) 1189, and the like.

  Further, organic acid salts showing basicity such as ammonium acetate, cobalt acetate, and aluminum laurate can also be used.

 The said basic compound (B) can be used individually or in combination of 2 or more types.

The basic compound (B) preferably has a higher basicity. Particularly, a compound having a pK _{BH +} value (MeCN) of 20 or more is a low-reactivity curing in which the hydrolyzable silyl group is bifunctional. Even in the case of the curable resin, it is possible to realize fast curability comparable to that when a trifunctional curable resin is used. The difference in basicity of the basic compound (B) has a greater effect on the curing rate than the difference in the ligand of the Lewis acid that is the curing catalyst, and the change on the curing catalyst and the silicon group is greater. It is considered important in improving the curing rate. Particularly effective are 1,8-diazabicyclo [5,4,0] -7-undecene (DBU, pKBH ₊ = 24.3), 1,5-diazabicyclo [4,3,0] -5-nonene ( DBN, pK _{BH +} = 23.9), 1,1,3,3-tetramethylguanidine (TMG, pK _{BH +} = 23.3), 1,5,7-triazabicyclo [4.4.0] -5 -Decene (TBD, pKBH ₊ = 26.0) and 7-methyl-1,5,7-triazabicyclo [44.0] -5-decene (MTBD, pKBH ₊ = 25.4) It is done.

  The compounding quantity of the said basic compound (B) is 0.01-10 mass parts with respect to 100 mass parts of said curable resins (A), Preferably it is 0.1-5 mass parts.

  In the curable resin composition of this invention, a Lewis acid or its complex (C) is mix | blended as a curing catalyst. Lewis acids include titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, antimony chloride and other metal halides, and boron trifluoride and boron tribromide halogens. Examples thereof include boron halides. The effect on the curable resin (A) is considered to be influenced by the acid strength of the Lewis acid. As the Lewis acid complex, amine complexes, alcohol complexes, ether complexes, organic acid complexes and the like of the above Lewis acid can be used. Examples of the amine compound constituting the amine complex include ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine and the like, and the basic compound (B). The compounds exemplified in are included. Examples of the alcohol compound constituting the alcohol complex include primary alcohols such as methanol, ethanol, n-propanol and n-butanol, secondary alcohols such as isopropanol and 2-butanol, and aromatic alcohols such as phenol. Examples of the ether compound constituting the ether complex include linear or cyclic ethers such as dimethyl ether, diethyl ether, di-n-butyl ether, and tetrahydrofuran. Examples of the organic acid constituting the organic acid complex include carboxylic acid compounds such as acetic acid.

Among the above Lewis acids, titanium chloride (IV), tin chloride (IV), zirconium chloride (IV), aluminum chloride (III) and boron trifluoride (BF ₃ ) are preferable, and zirconium chloride (IV) is preferred from the viewpoint of stability. ) And boron trifluoride are more preferable, and boron trifluoride is particularly preferable from the viewpoint of catalytic activity. Among the Lewis acid complexes, a boron trifluoride complex is particularly preferable in terms of easy handling. Among the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferable. As the Lewis acid and its complex, commercially available products containing the above compounds as components can be used. Examples of commercially available products include Air Products Japan, trade names: Anchors 1040, 1115, 1170, 1222, BAK1171, and the like. It is done.

  A Lewis acid or its complex (C) is not restricted to 1 type, It can use in combination of 2 or more type. The amount of the Lewis acid or its complex (C) is preferably 0.001 to 10 parts by mass, particularly preferably 0.01 to 5 parts by mass, per 100 parts by mass of the curable resin (A).

  In the curable resin (A) having a hydrolyzable silyl group, one type or two or more types of acrylic or methacrylic (hereinafter abbreviated as “(meth) acrylic”) monomers or styrene monomers are homopolymerized or When copolymerized, the curable resin (A) contains a polymer whose main chain skeleton is a vinyl polymer, and when this is used in the preparation of the curable resin composition of the present invention, the adhesiveness and toughness of the resin are improved. Can be improved. Of the above monomers, (meth) acrylic monomers are particularly preferred.

  As the (meth) acrylic monomer, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Nonyl acrylate, decyl (meth) acrylate, pentadecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, (meth) acrylic acid-2-hydroxypropyl, (meth) Glycidyl acrylic acid, (meth) -2-aminoethyl acrylate, .gamma. (methacryloyloxy) methyldimethoxysilane, .gamma. (methacryloyloxy) methyl diethoxy silane, and the like. Examples of the styrenic monomer include styrene, α-methylstyrene, divinylstyrene, and the like.

  The (co) polymerization of the monomers may be performed in the absence of a solvent or in a solvent. Solvents include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cycloheptane, ester compounds such as ethyl acetate and butyl acetate, acetone, Ketone compounds such as methyl ethyl ketone, ether compounds such as diethyl ether and tetrahydrofuran, alcohol compounds such as methanol, ethanol, propanol and butanol, amide compounds such as dimethylformamide and diethylformamide, amide compounds such as dimethylformamide and diethylformamide, dimethyl sulfoxide, Examples thereof include sulfoxide compounds such as diethyl sulfoxide. The (co) polymerization of the monomer is performed in a temperature range of 0 to 200 ° C, preferably room temperature to 150 ° C.

  The curable resin composition of the present invention is prepared by mixing the curable resin (A), the basic compound (B), and a Lewis acid or complex (C) thereof. In addition to these components, fillers, plasticizers, various additives, diluents, dehydrating agents, and the like can be appropriately blended according to the performance required for the application to be applied. Adhesives, sealants, paints, coating agents, sealants (for example, sealants that cover cracks to prevent injection from leaking during concrete crack repair), casting agents It can be used effectively as a coating agent.

  Examples of the filler include calcium carbonate, various kinds of treated calcium carbonate, silica-based powder, organic polymer powder, clay, talc, glass balloon, and plastic balloon. The silica-based powder and the organic polymer powder preferably have a particle size of 10 nm to 300 μm, more preferably 100 nm to 100 μm, and particularly preferably 1 to 30 μm.

  Examples of the silica-based powder include hydrophilic silica-based powder, hydrophobic silica-based powder, and fused silica glass powder. Of these, hydrophobic silica-based powder is preferable. Examples of the hydrophobic silica-based powder include silica-based powders such as fumed silica (fumed silica) and silica airgel, which are often used as thixotropic agents in adhesives and the like, and organic silicon compounds such as dimethyldichlorochloride. Hydrophobic materials that have been hydrophobized with silane, hexamethyldisilazane, dimethylsiloxane, trimethoxyoctylsilane, etc. can be used. Particularly, fumed silica treated with hexamethyldisilazane and silica airgel with dimethylsiloxane and / or Or what was processed with hexamethyldisilazane is preferable.

  The hydrophobizing treatment is performed by stirring the silica-based powder and the organosilicon compound at a high speed at a temperature of about 100 to 400 ° C. In order to make both contact uniformly, it is desirable to carry out in a medium such as an organic solvent. The mixing ratio of the silica-based powder and the organosilicon compound is usually 3 to 40 parts by mass of the organosilicon compound per 100 parts by mass of the silica-based powder.

  Organic polymer powders include urethane resin powders, polyester powders, acrylic resin powders, styrene resin powders, vinyl resin powders such as polyvinyl chloride, and polyolefin powders such as polyethylene and polypropylene. Body, silicone powder and the like.

Fused quartz glass powder can be used as well. As the fused silica glass powder, those having a SiO ₂ content of 99.8% by mass or more and extremely low impurities such as alkali metals are preferable. The fused silica glass fine powder may be used as it is, or may be used after surface treatment with a surface treatment agent. Examples of the surface treatment agent include organic titanate compounds, organic aluminum compounds, organic zirconium compounds, and alkoxysilanes. Examples of organic titanate compounds include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium, dipropoxy bis (acetylacetonato) titanium, titanium propoxyoctylene glycolate, titanium stearate, isopropyl Triisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridodecylphosphite) titanate, tetra (2,2-diallyloxy) Methyl-1-butyl) bis (ditridodecyl) phosphite titanate, bis (dioctylpyro) Sufeto) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate, and the like. Examples of the organic aluminum compound include acetoalkoxyaluminum diisopropylate, and examples of the organic zirconium compound include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, and zirconium stearate butyrate. Alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, bistris (β-methoxyethoxy) silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl). ) -Γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (γ , Δ-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethosylsilane, hexamethyldisilazane And the like.

  As the plasticizer, phthalic acid esters such as dioctyl phthalate and dibutyl phthalate; fatty acid carboxylic acid esters such as dioctyl adipate and dibutyl sebacate can be used.

  Examples of the various additives include anti-aging agents, ultraviolet absorbers, pigments, tackifiers, titanate coupling agents, aluminum coupling agents, epoxy resins, and flame retardants.

  Anti-aging agent is a compound having a secondary amino group, a tertiary amino group, a hydroxyl group, a carboxyl group, a mercapto group and / or a primary amino group in the molecule, and an anti-aging agent for various resins. Are widely used.

  Specific examples of the antioxidant include triacetonediamine, poly [(6-morpholino-s-triazine-2,4-diyl) {2,2,6,6-tetramethyl-4-piperidyl} imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino}], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-1 3-dimethylbutyl-N'-phenyl-p-phenylenediamine, mixed N, N'-diallyl-p-phenylenediamine, alkylated diphenylamine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl -1,3,8-triazaspiro [4.5] decane-2,4-dione, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-diyl} {2,2,6,6-tetramethyl-4-piperidyl} imino] hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], N, N′-bis (3-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5- Triazine condensation , Diphenylguanidine, di-o-tolylguanidine, N-cyclohexylbenzothiazyl-sulfenamide, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone trihydrate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate trihydrate, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2 -Hide Loxy-4-octoxybenzophenone, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'- Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzo Triazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzene Zotriazole, 5-chloro-2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl)- 5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) ) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -Tetrahydrophthalimido-methyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, -(2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, n-hexadecyl- 3,5-di-tert-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2 ', 4'-di-tert-butylphenyl-3,5 -Di-t-butyl-4-hydroxybenzoate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, tris (3,5-di-t- Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, ethylene glycol Bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane N-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) ) Propionate], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propiate Onate], 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 2,2'-butylidene- Bis (4-ethyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-) Butylphenol), 2,2'-methylene-bis (4-methyl-t-butylphenol), 2,2'-methylene-bis (4-ethyl-t-butylphenol), 6- (2-benzotriazolyl)- 4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol, 2,4-dimethyl -6- (1-methylcyclohexyl) phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2 , 6-di-tert-butyl-4-ethylphenol, 2- (2H-benzotriazol-2-yl) -4-menthyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,5-di-t-butylhydroquinone, poly (2,2,4 -Trimethyl-1,2-dihydroquinone), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone, 2,5-di-t-amylhydroquinone, 4,4'-butylidene-bis ( 6 t-butyl-m-cresol), 2,2'-methylene-bis [6- (1-methylcyclohexyl) -p-cresol], 1- [2- {3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, S -(3,5-di-t-butyl-4-hydroxybenzyl) -2-ethyl-n-hexyl-thioglycolate, 4,4'-thiobis (6-t-butyl-m-cresol), p- Benzoquinonedioxime, 1,6-bis (4-benzoyl-3-hydroxyphenoxy) -hexane, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, phenyl salicylate, 4- t-butylphenyl salicylate, 1,1,3-tris (2-methyl-t-butyl-4-hydroxy-5-t-butylphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 3, 9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 , 5] undecane, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, dimethyl succinate 1- (2-hydroxyethyl) ) -4-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4- Droxyphenyl] propionate and polyethylene glycol condensate, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6 All (Irganox E201), a mixture of Irganox E201, glycerin and low density polyethylene, a mixture of Irganox E201 and stearic acid, ethyl bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) A mixture of calcium and polyethylene wax, 2,4-bis [(octylthio) methyl] -o-cresol, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl Steal, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2- (3,5-di-t-butyl-4- Hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,3-bis [{3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyl}] propionohydrazide, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2, -Hydroxy-4-methoxy-2'-carboxybenzophenone, mercaptobenzothiazole, 2-mercaptobenzimidazole, manufactured by Sankyo Lifetech Co., Ltd., trade name: SANOL LS-765, SANOL LS-292, Sanol LS-944, Sanol LS-440, Sanol LS-770, Sanol LS-744, manufactured by Ciba Specialty Chemicals, Inc., trade names: Tinuvin 123, Tinuvin 292, Tinuvin 144, and the like.

  An anti-aging agent comprises the above anti-aging agent, a silicon compound having an organic group (I) having an isocyanate group in the group, and a hydrolyzable group selected from an alkoxy group and an acetoxy group directly bonded to a silicon atom. What was obtained by making it react can also be used. When such a thing is used, the effect of anti-aging can be improved more.

  The silicon compound has an organic group (II) having at least one group selected from a primary amino group, a secondary amino group, and a (meth) acryloyl group in the group, and a water selected from an alkoxy group and an acetoxy group. One or more compounds having a decomposable group directly bonded to 1 to 10 silicon atoms, and an organic compound capable of reacting with an organic group (II) to form a compound having a secondary amino group In the compound obtained by reacting the compound with less than 2 active hydrogens belonging to the secondary amino group in the molecule, the hydrolyzable group is directly bonded to 1 to 10 silicon atoms, or the group A silicon compound having an organic group (III) having one mercapto group or secondary amino group, wherein a hydrolyzable group selected from an alkoxy group and an acetoxy group is directly bonded to 1 to 3 silicon atoms; Two or more isoforms in the molecule Preferably, a compound having Aneto group is a compound obtained by reacting.

  Examples of tackifiers (tackifiers) include rosin and its hydrogenated rosin, (hydrogenated) polymerized rosin, (hydrogenated) rosin glycerin ester, (hydrogenated) rosin pentaerythritol ester, and disproportionation. Rosin glycerin ester and disproportionated rosin pentaerythritol ester, (hydrogenated) terpene phenol resin, ketone resin, petroleum resin (aliphatic, aromatic, aliphatic-aromatic copolymer, alicyclic and their (Hydrogenated product), (hydrogenated) terpene resin, coumarone-indene resin, phenol resin, xylene resin and the like.

  As titanate coupling agents, isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tri (N-amino) And ethyl-aminoethyl) titanate.

  Examples of aluminum coupling agents include (methylacetoacetoxy) aluminum diisopropylate, (ethylacetoacetoxy) aluminum diisopropylate, (isopropylacetoacetoxy) aluminum diisopropylate, (alkylacetoacetate) aluminum diisopropylate, and the like. Can be mentioned.

  Flame retardants include tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexabromocyclododecane, isopropyltris (2,3-dibromopropyl) isocyanurate, tribromophenol , Tetrabromodiphenyl oxide, halogen-containing polyphosphate, halogenated flame retardants such as ethylenebis (pentabromobenzene), ethylenebistetrabromophthalimide, ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) phosphate , Trischloroethyl phosphate, tris (dichloroethylpropyl) phosphate, cresyl phenyl phosphate, xylenyl diphenyl phosphate, acidic phosphate, nitrogen-containing phosphorus Phosphorus-based flame retardant such as compounds, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide and inorganic flame retardants such as magnesium hydroxide.

  The diluent is not particularly limited as long as it is compatible with the curable resin (A) and has a water content of 500 ppm or less. A specific example of the diluent is an alkoxypolysiloxane having an alkoxysilyl group. As the alkoxy group of the alkoxypolysiloxane, those having 1 to 6 carbon atoms are used, preferably a methoxy group, an ethoxy group, and a propoxy group, and particularly preferably a methoxy group and an ethoxy group. Use of a material having 7 or more carbon atoms is not preferable because the curing rate of the resulting composition is extremely slow and the physical properties after curing become soft. Examples of the alkoxypolysiloxane include those having a methyl group as a substituent and those having a methyl group and a phenyl group as substituents.

  Alkoxypolysiloxanes having alkoxysilyl groups are commercially available and can be used. As specific examples, trade names: KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-217, KR-9218, KR-, manufactured by Shin-Etsu Chemical Co., Ltd. 213, KR-510, X-40-9227, X-40-9247, X-41-1053, X-41-1056, X-41-1805, X-41-1810, X-41-2651, X- 40-2308, X-40-9238, manufactured by Mitsubishi Chemical Corporation, trade name: MS51 and the like. In addition to these, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanurate silane, 1,3, Isocyanurate silane compounds such as 5-N-tris (3-triethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldiethoxysilylpropyl) isocyanurate silane, and JP2003-221514A The compound etc. which are indicated by gazette are also mentioned. Further, those having an amino group, mercapto group, epoxy group or the like as a substituent can also be used. The alkoxypolysiloxane is preferably blended in an amount of 1 to 70 parts by weight, more preferably 15 to 50 parts by weight, and most preferably 20 to 40 parts by weight per 100 parts by weight of the curable resin (A).

  The dehydrating agent can be used without particular limitation as long as it is compatible with the curable resin (A) and has a water content of 500 ppm or less. Specific examples thereof include calcium oxide, magnesium oxide, orthosilicate ester, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, vinyl alkoxy silane, alkyl alkoxy silane and the like.

  Further, the curable resin composition of the present invention may be an epoxy silane coupling agent, an isocyanate silane coupling agent, a mercapto silane coupling agent, or a urethanization catalyst, depending on the intended performance and application. Manufactured and trade name: desmorapit PA, desmorapit SO, etc. can be added.

  Furthermore, you may mix | blend bismuth type compounds, such as bismuth (2-ethylhexanoate), as a hardening co-catalyst of curable resin (A). Examples of commercially available products that can be used include products manufactured by Nitto Kasei Co., Ltd. (trade names: U-600, U-660) and the like that mainly contain bismuth (2-ethylhexanoate).

  A metal complex can also be used as a cocatalyst. Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, aluminum acetylacetonate, Examples thereof include metal acetylacetonate complexes such as vanadium acetylacetonate, and these are not limited to one type, and two or more types can be used.

  Hereinafter, the present invention will be described in detail with reference to examples.

<Synthesis of silylated urethane resin>
Each compound was mixed under a nitrogen atmosphere in accordance with the blending ratio in Table 1 and reacted at 40 ° C. for 7 days, and then hydrolyzable alkoxysilane having NH groups (reactants 1-A to 1-C) by Michael addition reaction. Got.

次に、表２に示す割合で、ポリオール化合物及びイソシアネート化合物を、３０ｐｐｍのジブチル錫ジアセトナート（商品名：ネオスタンＵ−２２０、日東化成社製）存在下、窒素雰囲気中で攪拌混合しながら９０℃で３時間反応させた。得られた反応物に、表２の割合でシリル化剤として上記反応物１−Ａ〜１−Ｃを窒素雰囲気中で攪拌混合しながら９０℃で1 時間反応させて、液状のシリル化ウレタン樹脂（合成物２−Ａ〜２−Ｄ）を得た。

Next, at a ratio shown in Table 2, the polyol compound and the isocyanate compound were mixed at 90 ° C. with stirring and mixing in a nitrogen atmosphere in the presence of 30 ppm of dibutyltin diacetonate (trade name: Neostan U-220, manufactured by Nitto Kasei Co., Ltd.). The reaction was performed for 3 hours. The obtained reactants were reacted at 90 ° C. for 1 hour while stirring and mixing the above reactants 1-A to 1-C as silylating agents in the proportions shown in Table 2 to obtain a liquid silylated urethane resin. (Compounds 2-A to 2-D) were obtained.

他方、ポリプロピレングリコール（商品名：ＰＭＬ−４０１０、旭硝子ウレタン社製）１００ｇ及びイソシアネートシラン化合物（商品名：ＫＢＥ９００７、信越化学工業社製）４．６ｇを、３０ｐｐｍのジブチル錫ジアセトナート（商品名：ネオスタンＵ−２２０、日東化成社製）存在下、窒素雰囲気中で攪拌混合しながら９０℃で５時間反応させて合成物３を得た。

On the other hand, 100 g of polypropylene glycol (trade name: PML-4010, manufactured by Asahi Glass Urethane Co., Ltd.) and 4.6 g of an isocyanate silane compound (trade name: KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to 30 ppm of dibutyltin diacetate (trade name: Neostan U). -220, manufactured by Nitto Kasei Co., Ltd.) was reacted for 5 hours at 90 ° C. with stirring and mixing in a nitrogen atmosphere to obtain a compound 3.

<Preparation of hardening resin composition>
Example 1
100 g of a curable resin having a dimethoxysilyl group and a main chain skeleton of an oxyalkylene polymer (trade name: S203, manufactured by Kaneka Chemical Co., Ltd.) is placed in a reaction vessel, and the inside of the vessel is kept at 100 ° C. under vacuum. Dehydration was performed for 1 hour. Thereafter, the temperature is returned to room temperature, 3 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) and 0.1 g of boron trifluoride monoethylamine complex are put into a container, and a curable resin composition is obtained. Was prepared and stored in a sealed container.

(Comparative Example 1)
A curable resin composition was prepared in the same manner as in Example 1 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Comparative Example 2)
A curable resin composition was prepared in the same manner as in Example 1 except that 1,8-diazabicyclo [5.4.0] -7-undecene was not blended, and stored in a sealed container.

(Example 2)
100 g of a curable resin having a dimethoxysilyl group and a main chain skeleton of an oxyalkylene polymer (trade name: S203, manufactured by Kaneka Chemical Co., Ltd.) is placed in a reaction vessel, and the inside of the vessel is kept at 100 ° C. under vacuum. Dehydration was performed for 1 hour. Thereafter, the temperature is returned to room temperature, and 3 g of 1,8-diazabicyclo [5.4.0] -7-undecene and 1.0 g of boron trifluoride diethyl ether complex are put into a container to prepare a curable resin composition. And stored in a sealed container.

(Comparative Example 3)
A curable resin composition was prepared in the same manner as in Example 2 except that 1,8-diazabicyclo [5.4.0] -7-undecene was not blended, and stored in a sealed container.

( Reference Example 1 )
70 g of a curable resin having a dimethoxysilyl group and a main chain skeleton of an oxyalkylene polymer (trade name: S303, manufactured by Kaneka Chemical Co., Ltd.) and 30 g of the synthetic product 2-A are placed in a reaction vessel. Dehydration was performed at 100 ° C. for 1 hour while maintaining a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of hexamethylenediamine and 0.1 g of boron trifluoride piperidine complex were charged into the container to prepare a curable resin composition, which was stored in a sealed container.

(Comparative Example 4)
A curable resin composition was prepared in the same manner as in Reference Example 1 except that the boron trifluoride piperidine complex was not blended, and stored in a sealed container.

(Comparative Example 5)
A curable resin composition was prepared in the same manner as in Reference Example 1 except that hexamethylenediamine was not blended, and stored in a sealed container.

( Reference Example 2 )
70 g of a curable resin (trade name: S203, manufactured by Kaneka Chemical Co., Ltd.) having a dimethoxysilyl group and a main chain skeleton being an oxyalkylene polymer and 30 g of the synthetic 2-B are placed in a reaction vessel. Dehydration was performed at 100 ° C. for 1 hour while maintaining a vacuum. Thereafter, the temperature is returned to room temperature, 3 g of γ-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.1 g of boron trifluoride monoethylamine complex are put into a container to obtain a curable resin composition. Prepared and stored in sealed container.

(Comparative Example 6)
A curable resin composition was prepared in the same manner as in Reference Example 2 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Comparative Example 7)
A curable resin composition was prepared in the same manner as in Reference Example 2 except that γ-aminopropyltrimethoxysilane was not blended, and stored in a sealed container.

( Reference Example 3 )
A curable resin composition was prepared in the same manner as in Reference Example 2 except that the composite 2-C was used instead of the composite 2-B in Reference Example 2, and stored in a sealed container.

(Comparative Example 8)
A curable resin composition was prepared in the same manner as in Reference Example 3 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Comparative Example 9)
A curable resin composition was prepared in the same manner as in Reference Example 3 except that γ-aminopropyltrimethoxysilane was not blended, and stored in a sealed container.

( Reference Example 4 )
A curable resin composition was prepared in the same manner as in Reference Example 2 except that Compound 2-D was used instead of Compound 2-B in Reference Example 2, and stored in a sealed container.

(Comparative Example 10)
A curable resin composition was prepared in the same manner as in Reference Example 4 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Comparative Example 11)
A curable resin composition was prepared in the same manner as in Reference Example 4 except that γ-aminopropyltrimethoxysilane was not blended, and stored in a sealed container.

( Reference Example 5 )
A curable resin composition was prepared in the same manner as in Reference Example 2 except that Compound 3 was used instead of Compound 2-B in Reference Example 2, and stored in a sealed container.

(Comparative Example 12)
A curable resin composition was prepared in the same manner as in Reference Example 5 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Comparative Example 13)
A curable resin composition was prepared in the same manner as in Reference Example 5 except that γ-aminopropyltrimethoxysilane was not blended, and stored in a sealed container.

<Measurement of skinning time>
Each curable resin composition in the sealed container obtained in Examples 1-2, Reference Examples 1-5 and Comparative Examples 1-13 was stored for 7 days at 23 ° C., and then the skinning time was measured. . The skinning time is measured by leaving the curable resin composition in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and touching the surface of the curable resin composition with a finger. The time required for the formation and no transfer to the finger was defined as the skinning time. Table 3 shows the measurement results.

表３の実施例１、２及び比較例１〜３から、加水分解性シリル基が２官能である硬化性樹脂の硬化において、塩基性化合物であるＤＢＵが硬化触媒の作用を強力に促進して硬化速度を速めることが理解され、硬化触媒がアミン錯体及びエーテル錯体の何れであっても有効であることが明らかである。又、参考例１〜５及び比較例４〜１３は、塩基性化合物による硬化促進が、２官能型及び３官能型の加水分解性シリル基が混在する硬化性樹脂に対しても発揮されることを示し、又、様々な塩基性化合物が有効であることが判る。

From Examples 1 and 2 and Comparative Examples 1 to 3 in Table 3, in the curing of a curable resin having a bifunctional hydrolyzable silyl group, the basic compound DBU strongly promotes the action of the curing catalyst. It is understood that the curing rate is increased, and it is clear that the curing catalyst is effective regardless of whether it is an amine complex or an ether complex. In addition, in Reference Examples 1 to 5 and Comparative Examples 4 to 13, acceleration of curing by a basic compound is exhibited even for curable resins in which bifunctional and trifunctional hydrolyzable silyl groups are mixed. It can also be seen that various basic compounds are effective.

<Preparation of silylated urethane resin>
179.3 g of γ-aminopropyltrimethoxysilane (trade name: KBM903,) and 86.1 g of methyl acrylate were mixed in a nitrogen atmosphere, heated to 40 ° C. and reacted for 7 days to obtain reactant 1-D. It was.

  Polypropylene glycol (trade name: PML-SX4015, manufactured by Asahi Glass Urethane Co., Ltd.) 500 g and isophorone diisocyanate (trade name: Desmodur I, manufactured by Sumika Bayer Co., Ltd.) 15 g were mixed with 30 ppm of dibutyltin diacetonate (trade name: Neostan U-220, Nitto Kasei Co., Ltd.) was allowed to react at 90 ° C. for 3 hours with stirring and mixing in a nitrogen atmosphere. 18 g of the above-mentioned composite 1-D was added to the obtained reaction product and reacted at 90 ° C. for 1 hour with stirring and mixing in a nitrogen atmosphere to obtain a liquid silylated urethane resin (composite 4-A). .

<Preparation of curable resin composition>
( Reference Example 6 )
The reaction vessel was charged with 100 g of the synthetic 4-A, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of triethylamine and 1.0 g of boron trifluoride monoethylamine complex were added to prepare a curable resin composition.

( Reference Example 7 )
100 g of the reactant 4-A was put in a reaction vessel, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of ammonium acetate and 1.0 g of boron trifluoride monoethylamine complex were added to prepare a curable resin composition.

( Reference Example 8 )
100 g of the reactant 4-A was put in a reaction vessel, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of cobalt acetate and 1.0 g of boron trifluoride monoethylamine complex were added to prepare a curable resin composition.

( Reference Example 9 )
100 g of the reactant 4-A was put in a reaction vessel, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of aluminum laurate and 1.0 g of boron trifluoride monoethylamine complex were added to prepare a curable resin composition.

(Comparative Example 14)
100 g of the reactant 4-A was put in a reaction vessel, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 1.0 g of boron trifluoride monoethylamine complex was added to prepare a curable resin composition.

<Measurement of skinning time>
Each curable resin composition obtained in Reference Examples 6 to 9 and Comparative Example 14 was measured for skinning time immediately after preparation. The skinning time is measured by standing the curable resin composition in an atmosphere of a temperature of 23 ° C. and a relative humidity of 30% and touching the surface of the curable resin composition with a finger. The time required for the formation and no transfer to the finger was defined as the skinning time. Table 4 shows the measurement results.

参考例６〜９及び比較例１４は、硬化性樹脂の加水分解性シリル基が３官能型である例である。全体的に皮張り時間が長めであるのは、皮張り時間の測定雰囲気の湿度が低いことによるが、３官能型の加水分解性シリル基の場合においても塩基性化合物によって触媒の硬化作用が促進されることが明らかである。
（参考例１０）
反応容器に、合成物４−Ａを１００ｇ入れ、容器内を真空に保って１００℃で１時間脱水を行った。その後、室温に戻し、塩化ジルコニウムを３ｇ、１，８−ジアザビシクロ［５．４．０］−７−ウンデセンを２．５ｇを投入して硬化性樹脂組成物を調製し、密封容器に保存した。

Reference Examples 6 to 9 and Comparative Example 14 are examples in which the hydrolyzable silyl group of the curable resin is trifunctional. The overall skinning time is longer because the humidity of the atmosphere for measuring the skinning time is low, but even in the case of trifunctional hydrolyzable silyl groups, the basic compound accelerates the curing action of the catalyst. It is clear that
( Reference Example 10 )
The reaction vessel was charged with 100 g of the synthetic 4-A, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of zirconium chloride and 2.5 g of 1,8-diazabicyclo [5.4.0] -7-undecene were added to prepare a curable resin composition, which was stored in a sealed container.

(Comparative Example 15)
The reaction vessel was charged with 100 g of the synthetic 4-A, and dehydration was performed at 100 ° C. for 1 hour while keeping the inside of the vessel in a vacuum. Thereafter, the temperature was returned to room temperature, and 3 g of zirconium chloride was added to prepare a curable resin composition, which was stored in a sealed container.

<Measurement of skinning time>
Each curable resin composition obtained in Reference Example 10 and Comparative Example 15 was measured for skinning time immediately after preparation. The skinning time is measured by leaving the curable resin composition in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and touching the surface of the curable resin composition with a finger. The time required for the formation and no transfer to the finger was defined as the skinning time. As a result of the measurement, the skinning time of Reference Example 10 was 4 minutes, and the skinning time of Comparative Example 15 was 30 minutes.

The results of Reference Example 10 and Comparative Example 15 indicate that the addition of a basic compound is effective in promoting curing even when the curing catalyst is a metal halide.
(Example 3 )
100 g of a curable resin having a dimethoxysilyl group and a main chain skeleton of an oxyalkylene polymer (trade name: S303, manufactured by Kaneka Chemical Co., Ltd.) is placed in a reaction vessel, and the inside of the vessel is kept at 100 ° C. under vacuum. Dehydration was performed for 1 hour. Thereafter, the temperature is returned to room temperature, 3 g of 1,5-diazabicyclo [4.3.0] -5-nonene and 1.0 g of boron trifluoride monoethylamine complex are put into a container to prepare a curable resin composition. And stored in a sealed container.

(Comparative Example 16)
A curable resin composition was prepared in the same manner as in Example 3 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Example 4 )
100 g of a curable resin having a dimethoxysilyl group and a main chain skeleton of an oxyalkylene polymer (trade name: S303, manufactured by Kaneka Chemical Co., Ltd.) is placed in a reaction vessel, and the inside of the vessel is kept at 100 ° C. under vacuum. Dehydration was performed for 1 hour. Thereafter, the temperature is returned to room temperature, 3 g of 1,1,3,3-tetramethylguanidine and 1.0 g of boron trifluoride monoethylamine complex are put into a container to prepare a curable resin composition and stored in a sealed container. did.

(Comparative Example 17)
A curable resin composition was prepared in the same manner as in Example 4 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

(Example 5 )
100 g of a curable resin having a dimethoxysilyl group and a main chain skeleton of an oxyalkylene polymer (trade name: S303, manufactured by Kaneka Chemical Co., Ltd.) is placed in a reaction vessel, and the inside of the vessel is kept at 100 ° C. under vacuum. Dehydration was performed for 1 hour. Thereafter, the temperature was returned to room temperature, 3 g of 1,5,7-triazabicyclo [4.4.0] -5-decene and 1.0 g of boron trifluoride monoethylamine complex were put into a container, and a curable resin composition was obtained. The product was prepared and stored in a sealed container.

(Comparative Example 18)
A curable resin composition was prepared in the same manner as in Example 5 except that the boron trifluoride monoethylamine complex was not blended, and stored in a sealed container.

<Measurement of skinning time>
Each curable resin composition in the sealed containers obtained in Examples 3 to 5 and Comparative Examples 16 to 18 was stored at 23 ° C. for 7 days, and then the skinning time was measured. The skinning time is measured by leaving the curable resin composition in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and touching the surface of the curable resin composition with a finger. The time required for the formation and no transfer to the finger was defined as the skinning time. Table 5 shows the measurement results.

実施例３〜５で用いた塩基性化合物は、何れも、実施例１及び２と同様に、３官能型の加水分解性シリル基よりかなり反応性が低い２官能型の加水分解性シリル基を有する硬化性樹脂の硬化を好適に促進する。これらの塩基性化合物は、ｐＫ_ＢＨ＋値（ＭｅＣＮ）が約２３〜２６の範囲にあり、トリエチルアミンなどと比べてかなり塩基性度が強い。表３及び４の結果を考え合わせると、硬化促進効果は、添加する塩基性化合物の塩基性が高い方が大きく、ｐＫ_ＢＨ＋値が２０を超えると、反応性の低い２官能型の加水分解性シリル基を有する樹脂についても実用的な速硬化性を実現可能になる。

As in Examples 1 and 2, the basic compounds used in Examples 3 to 5 are bifunctional hydrolyzable silyl groups, which are considerably less reactive than trifunctional hydrolyzable silyl groups. The curing of the curable resin is suitably accelerated. These basic compounds have a pKBH ₊ value (MeCN) in the range of about 23 to 26, and are considerably more basic than triethylamine and the like. Considering the results shown in Tables 3 and 4, the curing acceleration effect is larger when the basic compound to be added has a higher basicity. When the pKBH ₊ value exceeds 20, the bifunctional hydrolyzability is low. Practical fast curability can be realized for a resin having a silyl group.

Claims (6)

A curable resin having a hydrolyzable silyl group in the molecule (A), pK BH ₊ value (MeCN) over 20 basic compound (B), and Ru is selected from the group consisting of metal halides and boron halides It contains a curing catalyst comprising a complex of Le chair acid (C), the curable resin (a), a polyoxyalkylene having a group obtained by adding the alkenyl silicon hydride compounds having a hydrolyzable silyl group The hydrolyzable silyl group comprises a dialkoxysilyl group having two identical or different alkoxy groups, and is a room temperature moisture curable resin composition. The curable resin (A) 100 parts by mass of per the basic compound (B) 0.01 to 10 parts by weight, the claims complex prior kill chair acid (C) containing 0.001 to 10 parts by weight 1. A room temperature moisture curable resin composition according to 1. Before complexes kill chair acid (C) is cold moisture-curable resin composition according to claim 1 or 2 comprising a boron trifluoride complex. The room temperature moisture- curable resin composition according to any one of claims 1 to 3, wherein the basic compound (B) is an amine compound. The amine compound is 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,1,3,3-tetramethylguanidine. 1,5,7-triazabicyclo [4.4.0] -5-decene and 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decene. The room temperature moisture- curable resin composition according to claim 4, which is at least one compound selected. A room temperature moisture curable adhesive containing the room temperature moisture curable resin composition according to any one of claims 1 to 5.