JP6052061B2 - Curable composition and curing catalyst - Google Patents

Description

  The present invention relates to a liquid tin-based curing catalyst, a method for producing the curing catalyst, a curable composition containing the curing catalyst, and a cured product obtained by curing the curable composition.

  A room temperature curable composition containing a crosslinkable silyl group-containing organic polymer has already been industrially produced and widely used in applications such as sealing materials, adhesives and paints. Usually, these curable compositions are cured using various metal catalysts, and are used for various applications depending on the type and amount of addition.

  As the catalyst, a reaction product of organotin and an ester compound is conventionally known (see, for example, Patent Documents 1 to 4). Among the ester compounds, in particular, a catalyst using a phthalate ester is generally used. This phthalate ester is stipulated as a VOC guideline formulation substance by the Ministry of Health, Labor and Welfare, and its existence has been pointed out. In recent years, catalyst design with non-phthalate esters has been demanded. In order to improve safety, a method using a dioctyltin compound instead of a dibutyltin compound has been proposed, but the dioctyltin compound has a low reactivity, and there is a problem that a curing rate is delayed particularly under low temperature conditions. It was.

Furthermore, the demand for fast-curing type products is high in the market, but as a manufacturer, the fast-curing type has a defect such as curing during the manufacture of the product. For example, Patent Document 4 discloses a curable composition containing a crosslinkable silyl group-containing organic polymer having a crosslinkable silyl group represented by —SiX ₃ and a reaction product of a dialkyltin oxide and an ester compound. However, since the reactivity is high, there is a problem that the product is cured during production, which is a problem. Also, considering the production stability, when using an organotin curing catalyst with relatively low activity, fast curing cannot be obtained. Considering rapid curing, use an organotin curing catalyst with relatively high activity. In such a case, the production stability cannot be obtained in the same manner as the reaction product of the dialkyltin oxide and the ester compound.

  Recently, equipment that can produce catalysts in a completely sealed system has been developed and has been well received by manufacturers of room temperature curing products, but the number of additives is limited and the equipment is very expensive. Therefore, there is a problem to introduce.

Japanese Patent Publication No. 1-58219 Japanese Patent No. 3062625 JP-A-8-337713 JP 2003-138151 A

  The present invention has been made in view of the above-described problems of the prior art, and the present invention can accelerate the curing rate, and is excellent in adhesiveness, storage stability and curability, It aims at providing the manufacturing method of a curable composition, the hardened | cured material which hardens this curable composition, the liquid tin type curing catalyst used for this curable composition, and the manufacturing method of this curing catalyst.

  In order to solve the above problems, the present inventors have conducted intensive research, and as a result, by using a reaction product obtained by reacting a specific tin compound and a specific alkoxysilane compound at a specific molar ratio, It has been found that a curable composition excellent in various physical properties such as adhesiveness, storage stability and curability can be obtained without lowering the curing rate.

That is, the curable composition of the present invention is a curable composition containing (A) a crosslinkable silicon group-containing organic polymer and (B) a liquid tin-based curing catalyst,
The (B) liquid tin-based curing catalyst comprises one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): It is a reaction product obtained by reacting the tin atom of the tin compound in a range of 0.20 to 1.40 mol with respect to 1 mol of OR ³ groups of the silane compound,
The liquid tin-based curing catalyst (B) is contained in an amount of 0.01 to 15 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group or an aminoalkylaminoalkyl group, and a phenyl group , A vinyl group, or an alkyl group having 6 to 20 carbon atoms, and more preferably a phenyl group or a vinyl group. R ² is a methyl group or a phenyl group, a is 0 or 1 (if provided that ^{R 1} is an alkyl group having 6 to 20 carbon atoms and a is 0), ^{R 3} is from 1 to 4 carbon atoms It is a group selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, and a plurality of R ³ may be the same or different.

  The (A) crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer having a crosslinkable silicon group, a (meth) acrylic polymer having a crosslinkable silicon group, and a saturated hydrocarbon having a crosslinkable silicon group. It is preferably at least one selected from the group consisting of polymers based on polyoxyalkylene polymers having a crosslinkable silicon group, polyoxyalkylene polymers having a crosslinkable silicon group, and crosslinkable silicon groups. More preferably, it is a mixture with a (meth) acrylic polymer or a saturated hydrocarbon polymer having a crosslinkable silicon group.

In the present invention, the (A) crosslinkable silicon group-containing organic polymer is selected from the group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic polymer having a crosslinkable silicon group. More preferably, R ^{1 in the} formula (1) is a vinyl group.

In the present invention, the (A) crosslinkable silicon group-containing organic polymer is a saturated hydrocarbon polymer having a crosslinkable silicon group, and R ^{1 in the} formula (1) is a phenyl group. And the alkoxysilane compound represented by the formula (1) is more preferably diphenylalkoxysilane.

The manufacturing method of the curable composition of this invention mix | blends 0.01-15 mass parts of (B) liquid tin-type curing catalysts with respect to 100 mass parts of (A) crosslinkable silicon group containing organic polymer, A) A method for producing a curable composition comprising a step of obtaining a curable composition containing a crosslinkable silicon group-containing organic polymer and the (B) liquid tin-based curing catalyst,
The (B) liquid tin-based curing catalyst comprises one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): It is a reaction product obtained by reacting a tin atom of the tin compound in a range of 0.20 to 1.40 mol with respect to 1 mol of OR ³ groups of the silane compound.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group, and R ² Is a methyl group or a phenyl group, a is 0 or 1 (provided that a is 0 when R ¹ is an alkyl group having 6 to 20 carbon atoms), and R ³ is a monovalent group having 1 to 4 carbon atoms. A group selected from the group consisting of a hydrocarbon group and a monovalent halogenated hydrocarbon group, and a plurality of R ³ may be the same or different.

The liquid tin-based curing catalyst of the present invention comprises one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): wherein the tin atoms of the tin compound are reacted in a range of 0.20 to 1.40 mole with respect to OR ³ group 1 mole of compound characterized by comprising the reaction product formed by.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group, and R ² Is a methyl group or a phenyl group, a is 0 or 1 (provided that a is 0 when R ¹ is an alkyl group having 6 to 20 carbon atoms), and R ³ is a monovalent group having 1 to 4 carbon atoms. A group selected from the group consisting of a hydrocarbon group and a monovalent halogenated hydrocarbon group, and a plurality of R ³ may be the same or different.

The method for producing a liquid tin-based curing catalyst of the present invention comprises at least one tin compound selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): The method includes a step of reacting a tin atom of the tin compound in an amount of 0.20 to 1.40 mol with respect to 1 mol of OR ³ groups of the alkoxysilane compound to obtain a reaction product.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group, and R ² Is a methyl group or a phenyl group, a is 0 or 1 (provided that a is 0 when R ¹ is an alkyl group having 6 to 20 carbon atoms), and R ³ is a monovalent group having 1 to 4 carbon atoms. A group selected from the group consisting of a hydrocarbon group and a monovalent halogenated hydrocarbon group, and a plurality of R ³ may be the same or different.

  In the present invention, the (B) liquid tin-based curing catalyst preferably further contains (C) a diluent.

  The cured product of the present invention is obtained by curing the curable composition of the present invention.

  According to the present invention, the curing rate can be accelerated, and the curable composition excellent in adhesiveness, storage stability and curability, the method for producing the curable composition, and curing the curable composition. The cured product, the liquid tin-based curing catalyst used in the curable composition, and a method for producing the curing catalyst can be provided. Moreover, according to this invention, the curable composition whose physical property of hardened | cured material is a low modulus can also be obtained.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

The (B) liquid tin-based curing catalyst of the present invention comprises at least one tin compound selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): It is a reaction product obtained by reacting a tin atom of the tin compound in a range of 0.20 to 1.40 mol with respect to 1 mol of OR ³ groups of the alkoxysilane compound.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group or an aminoalkylaminoalkyl group, and a liquid tin From the viewpoint of improving the stability of the system curing catalyst, a phenyl group, a vinyl group, or an alkyl group having 6 to 20 carbon atoms is preferable, and a phenyl group or a vinyl group is more preferable. R ² is a methyl group or a phenyl group, and a is 0 or 1 (provided that a is 0 when R ¹ is an alkyl group having 6 to 20 carbon atoms). R ³ is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 4 carbon atoms and a monovalent halogenated hydrocarbon group, preferably a methyl group or an ethyl group, and a plurality of R ³ are the same. It can be different.

  Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, Amino group-containing silanes such as N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane Epoxy group containing γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Silanes; vinyltrimethoxy Vinyl group-containing silanes such as lan, vinyltriethoxysilane, vinyltripropoxysilane, vinylisopropoxysilane; having an alkyl group having 6 to 20 carbon atoms such as hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane Alkylsilanes; phenyl group-containing silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like, Vinyl group-containing silanes and alkyl silanes having an alkyl group having 6 to 20 carbon atoms are preferred, and phenyl group-containing silanes and vinyl group-containing silanes are more preferred.

As the dioctyl tin carboxylate, a known dioctyl tin carboxylate can be used, and there is no particular limitation, but a dioctyl tin carboxylate having a structure represented by the following formula (2) is preferable.

In the formula (2), n is 1 to 4, and R ¹¹ and R ¹² are each a monovalent organic group. For example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, a cyclo An alkynyl group, an aryl group, an aralkyl group, etc. are mentioned, An alkyl group or an alkenyl group is preferable. The carbon number of R ¹¹ and R ¹² is not particularly limited, but is preferably 1 to 21, more preferably 1 to 17, and still more preferably 1 to 11.

  The dioctyltin carboxylate may be a commercially available dioctyltin carboxylate, or obtained by reacting dioctyltin oxide with at least one organic acid selected from the group consisting of monocarboxylic acids and monocarboxylic anhydrides. The reaction product obtained may be used. Alternatively, dioctyl tin oxide, an organic acid, and an alkoxysilane compound represented by the formula (1) may be added simultaneously to obtain a reaction product that is a liquid tin-based curing catalyst of the present invention.

  As the monocarboxylic acid, a saturated carboxylic acid and / or an unsaturated carboxylic acid can be used, but a saturated fatty acid having 2 to 22 carbon atoms, an unsaturated fatty acid having 2 to 22 carbon atoms, and an aroma having 7 to 22 carbon atoms. A group carboxylic acid or naphthenic acid is preferable, and a saturated fatty acid having 2 to 22 carbon atoms is particularly preferable. Similarly, as the monocarboxylic acid anhydride, a saturated carboxylic acid anhydride and / or an unsaturated carboxylic acid anhydride can be used, but a saturated fatty acid anhydride having 2 to 22 carbon atoms and an unsaturated carbon having 2 to 22 carbon atoms can be used. Saturated fatty acid anhydrides and aromatic carboxylic acid anhydrides having 7 to 22 carbon atoms are preferred.

In the present invention, the reaction of one or more tin compounds selected from the group consisting of the dioctyltin oxide and the dioctyltin carboxylate with the alkoxysilane compound represented by the following formula (1) is performed by OR of the alkoxysilane compound. from 0.20 to 1.40 mole of tin atoms of the tin compound with respect to ³ group 1 mol, preferably reacted in a range of 0.25 to 1.10. If it is less than 0.20 mol, there is a possibility that a sufficient curing rate cannot be obtained under room temperature conditions and low temperature conditions. Further, sufficient deep part curability may not be obtained. Furthermore, when a curing catalyst is used for the curable composition, the rubber hardness of the resulting cured product tends to increase, and the elongation of the film of the cured product tends to decrease, such being undesirable. When it exceeds 1.40 mol, it becomes difficult to dissolve the dioctyltin oxide and the alkoxysilane compound, and even if dissolved, the stability of the liquid tin-based curing catalyst tends to decrease. In addition, when this curing catalyst is used in a curable composition, the compatibility with the polymer (A) tends to decrease particularly under low temperature conditions, and a sufficient curing rate may not be obtained under low temperature conditions. Therefore, it is not preferable.

  The temperature condition of the reaction is not particularly limited, but it is preferably heated at 70 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The reaction rate can be increased by setting the reaction temperature to 70 ° C. or higher. Moreover, by making reaction temperature 140 degrees C or less, side reactions, such as thermal decomposition and gelatinization, can be prevented. The reaction time is not particularly limited, but is preferably 1 hour to 5 hours, and more preferably 1 hour to 3 hours. By this reaction, the liquid tin-based curing catalyst of the present invention that is liquid at normal temperature (for example, 23 ° C.) is obtained.

  The reaction between the tin compound and the alkoxysilane compound may be performed by reacting one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate with an alkoxysilane compound, and dioctyltin. An oxide, an organic acid, and an alkoxysilane compound may be reacted. The carboxylic acid ester by-produced in the reaction between dioctyltin carboxylate and the alkoxysilane compound may or may not be removed, but is preferably used after being removed. By removing the by-produced carboxylic acid ester, the curing rate of the curable composition using the liquid tin-based curing catalyst of the present invention can be further increased.

  The (B) liquid tin-based curing catalyst of the present invention may further contain (C) another compounding material such as a diluent or a plasticizer, and it is particularly preferable that the (B) diluent is contained. (C) There is no restriction | limiting in particular in the time of adding other compounding substances, such as a diluent, and it may be before and after the reaction with the said tin compound and an alkoxysilane compound, but the said (C) diluent is used before or during the reaction. It is preferable to add. By blending the (C) diluent, the stability of the (B) liquid tin-based curing catalyst can be improved. As the diluent (C), a diluent described later is preferably used. In the reaction, the alkoxysilane compound may be used alone or in combination of two or more.

  The curable composition of the present invention is a curable composition containing (A) a crosslinkable silicon group-containing organic polymer and the above-described (B) liquid tin-based curing catalyst of the present invention.

  As the (A) crosslinkable silicon group-containing organic polymer, those having various main chain skeletons can be used, but on average, one molecule has 0.8 or more crosslinkable silicon groups. An organic polymer whose main chain is not polysiloxane is preferred.

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability when made into one-component compositions.

In the present invention, the (A) crosslinkable silicon group-containing organic polymer is selected from the group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic polymer having a crosslinkable silicon group. In the case of using one or more of the above, (B) the liquid tin-based curing catalyst is a liquid tin-based curing catalyst using an alkoxysilane compound in which R ^{1 in the} formula (1) is a vinyl group, to accelerate the curing rate. This is more preferable.

Moreover, in this invention, when using the saturated hydrocarbon type polymer which has a crosslinkable silicon group as said (A) crosslinkable silicon group containing organic polymer, from the point of acceleration of a cure rate, (B) liquid tin type As the curing catalyst, a liquid tin-based curing catalyst using an alkoxysilane compound in which R ^{1 in the} formula (1) is a phenyl group is preferable, and a liquid tin-based curing catalyst using diphenylalkoxysilane is more preferable.

  The crosslinkable silicon group of the (A) organic polymer used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (3) is preferable.

In the formula (3), R ²¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ^21. ₃ represents a triorganosiloxy group represented by SiO— (R ²¹ is the same as above), and when two or more R ²¹ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. d represents 0, 1, 2, or 3, and e represents 0, 1, or 2, respectively. Moreover, p in the following general formula (4) need not be the same. p shows the integer of 0-19. However, d + (sum of e) ≧ 1 is satisfied.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and d + (sum of e) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (5) is preferable because it is easily available.

In the formula (5), R ²¹ and X are the same as those described above, and d is an integer of 1, 2 or 3. In view of curability, in order to obtain a curable composition having a sufficient curing rate, in the above formula (5), d is preferably 2 or more, more preferably 3.

Specific examples of R ²¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ²¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl 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 group. Among these, a hydrogen atom, an alkoxyl 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 alkoxyl group, an amide group, and an aminooxy group are more preferable. An alkoxyl group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among alkoxyl groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. And a silyl group [—SiR ²¹ (OR) ₂ ]. Here, R is an alkyl group such as a methyl group or an ethyl group.

  Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

  The number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inconvenient in terms of elongation characteristics.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more in one molecule of the polymer. 1.1 to 5 may be present. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to develop good rubber elastic behavior. The crosslinkable silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (6).
-R ²² -O- (6)
In the general formula (6), R ²² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. .

Specific examples of the repeating unit represented by the general formula (6) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used as a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.

  As a method for synthesizing a polyoxyalkylene polymer, for example, polymerization using an alkali catalyst such as KOH, for example, organic aluminum as disclosed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623 A polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting a compound with a porphyrin, such as a polymerization method using a double metal cyanide complex catalyst described in JP-B-46-27250 and JP-B-59-15336, etc. However, it is not particularly limited. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; The thing obtained from reaction with coalescence can be mention | raise | lifted.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has this can be mention | raise | lifted. An unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene-based polymer having can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal. Examples thereof include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, JP-B No. 3-2450, JP-A No. 2005-213446, No. 2005-306891, International Publication No. WO2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.

  The above polyoxyalkylene polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) A diene compound such as butadiene or isoprene is homopolymerized, or a copolymer with the olefin compound is copolymerized. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.

  As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but in particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843) It is known that it can be easily produced by using it, can be polymerized with a molecular weight of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and can introduce various functional groups at the molecular ends.

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 63-254149, Japanese Patent Publication No. 64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

  The above saturated hydrocarbon polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. For example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester monomers such as 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; (meth) Cyclohexyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl ) Acrylate, dicyclopentanyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylic acid ester monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylic acid ester monomers such as ethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenylthioethyl (meth) acrylate; 2-methoxy (meth) acrylate, (meth) acrylic acid (Meth) acrylate esters such as 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate Monomer: γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxy Silyl group-containing (meth) acrylic acid ester monomers such as tildimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; (meth) acrylic acid derivatives such as ethylene oxide adducts of (meth) acrylic acid; (meth) acrylic Trifluoromethyl methyl acid, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, (meth ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) 2-perfluorohexylethyl acrylate , Fluorine-containing (meth) acrylate monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl Maleimide monomers such as maleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferably, it is a (meth) acrylic acid ester-based polymer using one or two or more (meth) acrylic acid alkyl ester monomers and optionally using other (meth) acrylic acid monomers, By using the group-containing (meth) acrylic acid ester monomer together, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled. A methacrylic acid ester polymer composed of a methacrylic acid ester monomer is particularly preferred because of its good adhesiveness. Moreover, when performing viscosity reduction, a softness | flexibility provision, and tackiness provision, it is suitable to use an acrylate ester monomer timely. In the present specification, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In the present invention, the method for obtaining the (meth) acrylic acid ester polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). And a radical polymerization method using a radical polymerization reaction is preferable. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. A reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

  The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto.
Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (7):
—CH ₂ —C (R ²⁵ ) (COOR ²⁶ ) — (7)
(Wherein R ²⁵ represents a hydrogen atom or a methyl group, R ²⁶ represents an alkyl group having 1 to 5 carbon atoms), and a (meth) acrylate monomer unit represented by the following general formula (8):
^{_{-CH 2 -C (R 25) (}} COOR 27) - ··· (8)
(Wherein R ²⁵ is the same as described above, and R ²⁷ represents an alkyl group having 6 or more carbon atoms). A copolymer comprising a (meth) acrylate monomer unit is represented by a crosslinkable silicon group. It is a method of blending and producing a polyoxyalkylene polymer.

As R < ²⁶ > of the said General formula (7), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group etc., Preferably it is 1-4, More preferably, it is 1-. 2 alkyl groups. The alkyl group of R ²⁶ may alone, or may be a mixture of two or more.

R ^{27 in the} general formula (8) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7 to 30, preferably 8 to 20 Long chain alkyl groups. The alkyl group of R ²⁷ is same as in the case of R ^26, alone may be, or may be a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units represented by the formulas (7) and (8). The term “substantially” as used herein refers to the copolymer. It means that the sum of the monomer units of the formula (7) and the formula (8) present therein exceeds 50% by mass. The sum of the monomer units of the formulas (7) and (8) is preferably 70% by mass or more.
The abundance ratio of the monomer unit of the formula (7) and the monomer unit of the formula (8) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40, by mass ratio.

  Examples of monomer units other than the formulas (7) and (8) that may be contained in the copolymer (hereinafter also referred to as other monomer units) include α such as acrylic acid and methacrylic acid. , Β-unsaturated carboxylic acids; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc. And other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  Having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (meta ) As the acrylate polymer, for example, it has a crosslinkable silicon group described in JP-A-63-112642, and the molecular chain has substantially (1) an alkyl group having 1 to 8 carbon atoms (meta (Meth) acrylic acid ester-based copolymers containing an acrylic acid alkyl ester monomer unit and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms These (meth) acrylic acid ester copolymers can also be used.

The number average molecular weight of the (meth) acrylic acid ester polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and still more preferably 1,000 to 4,500. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved. The (meth) acrylic acid ester polymer may be used alone or in combination of two or more.
The compounding ratio of the polyoxyalkylene polymer having the crosslinkable silicon group and the (meth) acrylic acid ester polymer having the crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester The total amount of the polymer and the polyoxyalkylene polymer is preferably 100 parts by mass, and the (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, more preferably 20 to 20 parts by mass. It is in the range of 50 parts by mass, more preferably in the range of 25 to 45 parts by mass. If the amount of the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable.

  Organic polymers formed by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group are disclosed in JP-A-1-168774 and JP-A-2000-. Although it is proposed in Japanese Patent No. 186176, etc., it is not particularly limited thereto.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in the presence of an organic polymer having a crosslinkable silicon group ( A method of polymerizing a meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslink with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10-200 mass parts of the (meth) acrylic acid ester-type polymer which has a crystalline silicon group, and it is more preferable to use 20-80 mass parts.

  In the curable composition of the present invention, the blending ratio of each compounding substance is not particularly limited. It is preferable to mix | blend 0.01-20 mass parts, 0.1-20 mass parts is more preferable, 0.5-15 mass parts is further more preferable.

The curable composition of the present invention preferably further contains (C) a diluent. (C) Physical properties, such as a viscosity, can be adjusted by mix | blending a diluent.
(C) As a diluent, a well-known diluent can be widely used and there is no restriction | limiting in particular, For example, saturated hydrocarbon solvents, such as normal paraffin and an isoparaffin, a linearlen dimer (Idemitsu Kosan Co., Ltd. brand name) Α-olefin derivatives such as toluene, xylene and other aromatic hydrocarbon solvents, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, diacetone alcohol and other alcohol solvents, ethyl acetate, butyl acetate, acetic acid Various solvents such as ester solvents such as amyl and cellosolve acetate, citrate solvents such as acetyltriethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are listed.

  In consideration of both safety and dilution effect of the curable composition of the present invention, as the diluent (C), a saturated hydrocarbon solvent is preferable, and normal paraffin and isoparaffin are more preferable. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number 11, flash point 68 ° C), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number) 12, flash point 85 ° C.), IP solvent 2028 (isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C.) and the like.

  The blending ratio of the (C) diluent is not particularly limited, but it is preferable to blend 0 to 50 parts by mass of the (C) diluent with respect to 100 parts by mass of the (A) organic polymer. It is more preferable to mix 1 to 30 parts by mass, and further preferable to mix 0.1 to 15 parts by mass. The said (C) diluent may be used by 1 type, and may be used in combination of 2 or more type.

  In addition to the above-described components, the curable composition of the present invention, if necessary, other curing catalyst, filler, ultraviolet absorber, antioxidant, anti-aging agent, adhesion imparting agent, physical property modifier, Substances such as plasticizers, thixotropic agents, dehydrating agents (storage stability improvers), flame retardants, tackifiers, sag-preventing agents, colorants, radical polymerization initiators, etc. may be added and are compatible. These polymers may be blended.

  As the other curing catalyst, known curing catalysts can be widely used as long as they do not affect the performance of the curable composition, and are not particularly limited. For example, organometallic compounds and amines can be mentioned. In particular, it is preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; dibutyltin diacetyl Chelate compounds such as acetonate, dibutyltin diethyl acetoacetate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmer Rate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin Dialkyltin dicarboxylates such as ridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate; Reaction products of dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide and ester compounds such as dioctyl phthalate, diisodecyl phthalate and methyl maleate; and tetravalent compounds such as oxy derivatives (stannoxane compounds) of these dialkyl tin compounds Tin compounds; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate and tin ferzatic acid; or reaction products and mixtures of these with amine compounds such as laurylamine Monoalkyltin compounds such as monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide and monooctyltin compounds; lead organic acids such as lead octylate and lead naphthenate; bismuth octylate, neodecanoic acid Examples include bismuth organic acids such as bismuth and bismuth rosinate; other acidic catalysts and basic catalysts known as silanol condensation catalysts.

  Examples of the filler include reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide. Further, fillers such as calcium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon, organic balloon, organic fiber and inorganic fiber can be used.

  When it is desired to obtain a cured product having high strength by using these fillers, mainly fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and When a filler selected from activated zinc white is used in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silicon group, preferable results are obtained. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used. If it is used in the range of 5 to 500 parts by weight per 100 parts by weight of the same polymer, preferable results can be obtained. These fillers may be used alone or in combination of two or more.

  The antioxidant is used to prevent oxidation of the curable composition to improve weather resistance and heat resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. It is done.

  The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the curable composition, for example, ultraviolet absorption of benzotriazole, triazine, benzophenone, benzoate, etc. Agents and the like.

  The anti-aging agent is used to prevent heat deterioration of the curable composition and improve heat resistance. For example, an anti-aging agent such as an amine-ketone type and an aromatic secondary amine type are used. Antiaging agents, benzimidazole type antiaging agents, thiourea type antiaging agents, phosphorous acid type antiaging agents and the like can be mentioned.

  The plasticizer is added for the purpose of improving elongation properties after curing or adjusting the hardness to reduce the modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate Aliphatic esters such as butyl oleate; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives Polyoxyethylene alkyl ethers such as tetraethylene glycol diethyl ether; polystyrene oligomers such as poly-α-methylstyrene; hydrocarbon oligomers such as polybutadiene; chlorinated paraffins; UP-1080 ( Acrylic plasticizers such as Toagosei Co., Ltd., UP-1110 (Toagosei Co., Ltd.), UP-1061 (Toagosei Co., Ltd.); UP-2000 (Toagosei Co., Ltd.) ), UHE-2012 (manufactured by Toagosei Co., Ltd.) and the like; hydroxyl group-containing acrylic plasticizers such as UC-3510 (manufactured by Toagosei Co., Ltd.); carboxyl group-containing acrylic polymers such as UG-4000 (Toagosei) Epoxy group-containing acrylic polymers such as Synthetic Co., Ltd .; less than 0.8, such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.), preferably Examples include acrylic polymers having less than 0.4 silyl groups; oxyalkylene resins having less than 0.8, preferably less than 0.4 silyl groups.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include zeolite, calcium oxide, magnesium oxide, and zinc oxide.

  Examples of the flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; phosphorus flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide flame retardants such as antimony trioxide; Flame retardants; chlorine flame retardants and the like.

  Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldi Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product is increased, and if it is too small, the adhesiveness is lowered. Therefore, 0.1 to 15 masses per 100 mass parts of the crosslinkable silicon group-containing organic polymer. It is preferable to add part, more preferably 0.5 to 10 parts by weight.

  The tackifier is preferable for improving the wettability to the adherend and increasing the peel strength. Examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something.

  The curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type. The curable composition of the present invention can be cured at normal temperature by moisture in the atmosphere, and is suitably used as a normal temperature moisture-curable curable composition, but if necessary, curing is accelerated by heating as appropriate. You may let them.

  The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. Since the curable composition of the present invention is excellent in adhesiveness, storage stability, and curability, it is particularly preferable to use it as an adhesive, but for various other buildings, automobiles, civil engineering, electric / electronics. It can be used for fields.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Production Examples 1-27)
Dictyl tin oxide, alkoxysilane compound, and (C) diluent were added in predetermined amounts to a flask equipped with a cooling tube at a mixing ratio shown in Tables 1 to 3, and the mixture was stirred in nitrogen atmosphere at 100 ° C. for 2 hours. Thus, tin-based curing catalysts B1 to B27 that are liquid at 23 ° C. were obtained.

In Tables 1-3, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are as follows.
U-800P: dioctyl tin oxide, trade name: Neostan U-800P, manufactured by Nitto Kasei Co., Ltd.
KBM-1003: Vinyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-202SS: diphenyldimethoxysilane, trade name: Shin-Etsu Silicone KBM-202SS, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-103: Phenyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-3103C: Decyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM-3103C, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-403: 3-glycidoxypropyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-903: 3-aminopropyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.
KBE-1003: Vinyltriethoxysilane, trade name: Shin-Etsu Silicone KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.
N-11: Paraffin-based diluent, trade name: Cactus normal paraffin N-11, manufactured by Japan Energy Co., Ltd.

The appearance and stability of the obtained tin-based curing catalyst were evaluated by the following methods. The results are shown in Tables 1-3.
1) Appearance test Each tin-based curing catalyst was placed in a transparent glass bottle, and turbidity was visually confirmed at room temperature (23 ° C). The evaluation criteria are as follows.
○: Transparent, Δ: Slightly turbid, X: Turbid or separated.

2) Stability test Each tin-based curing catalyst was placed in a transparent glass bottle and allowed to stand for 1 month at 50 ° C, and then the change in appearance was visually confirmed. The evaluation criteria are as follows.
○: No change, Δ: Partial precipitation, ×: Solidification.

(Production Example 28)
A four-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 30.0 g (0.08 mol) of dioctyltin oxide (U-800P), 4.1 g (0.04 mol) of acetic anhydride and 200 g of toluene. After reacting at 0 ° C. for 2 hours to obtain dioctyltin carboxylate, toluene was distilled off under reduced pressure. Next, 10.0 g (0.07 mol) of vinyltrimethoxysilane (KBM-1003) was added and stirred and reacted at 120 ° C. for 3 hours. Then, the produced methyl acetate was distilled off and cooled to room temperature. Was added to obtain a tin-based curing catalyst B28 which was yellow transparent and Sn / OR ³ = 0.41.
When the appearance test and the stability test were performed on the obtained tin-based curing catalyst B28, both the appearance and the stability were evaluated as “good”.

(Comparative Production Examples 1-12)
As shown in Table 4, tin-based curing catalysts X1 to X12 were obtained by the same method as in Production Example 1 except that each material was changed. The appearance and stability of the obtained tin-based curing catalyst were evaluated by the same method as in Production Example 1. The results are shown in Table 4.

In Table 4, the compounding quantity of each compounding substance is shown by g. Details of the compounding substances are the same as in Table 1, and details of the remaining compounding substances are as follows.
Ethyl silicate 28: Ethyl silicate, trade name of Colcoat Co., Ltd.

  As shown in Tables 1 to 4, the tin-based curing catalysts obtained in Production Examples 1 to 28, which are liquid tin-based curing catalysts of the present invention, were excellent in appearance and stability. In particular, when a vinyl group-containing alkoxysilane compound or a phenyl group-containing alkoxysilane compound was used, the stability was further improved. Moreover, stability was able to be improved by mix | blending an appropriate quantity of (C) diluent.

(Synthesis Example 1)
In a flask, 40 parts by mass of ethyl acetate as a solvent, 59 parts by mass of methyl methacrylate, 25 parts by mass of 2-ethylhexyl methacrylate, 22 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by mass of ruthenocene dichloride as a metal catalyst were added. The mixture was charged and heated to 80 ° C. while introducing nitrogen gas. Next, 8 parts by mass of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by mass of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. Distilling off the solvent and unreacted material, an acrylic ester system having a trimethoxysilyl group having a polystyrene-reduced mass average molecular weight of about 6000, Mw / Mn of 1.6, and Tg of 61.2 ° C. A polymer A1 was obtained.

(Examples 1-20)
As shown in Tables 5 and 6, (A) the crosslinkable silicon group-containing organic polymer and the filler were charged in predetermined amounts and mixed and stirred. The mixture was heated to 100 ° C. and kneaded and dehydrated by mixing under reduced pressure for 2 hours. After cooling to room temperature, (B) a liquid tin-based curing catalyst, (C) a diluent, an adhesion-imparting agent, and a dehydrating agent were respectively charged in predetermined amounts, and a curable composition was prepared by mixing and stirring. The following measurement was performed with respect to the obtained curable composition. The results are shown in Tables 5-8.

1) Viscosity The viscosity of the curable composition immediately after blending the curable composition was measured using a BH type rotational viscometer according to JIS K6833.

2) Tack free time (TFT)
The touch drying time of the curable composition immediately after blending the curable composition was measured according to JIS A1439 5.19 (measurement conditions: 5 ° C. or 23 ° C. 50% RH).

3) Storage stability test Each curable composition was filled in a glass bottle and allowed to stand in a hot-air circulating dryer adjusted to 50 ° C. After a predetermined time (1, 2, or 4 weeks) at 50 ° C., the mixture was cooled to room temperature, and the viscosity and tack-free time (measurement condition: 23 ° C., 50% RH) were measured in the same manner as described above. Moreover, the rate of thickening was calculated from the viscosity after storage and the viscosity immediately after blending the curable composition.

4) Deep Curability Test Each curable composition was filled in a polyethylene container having a diameter of 40 mm and a depth of 20 mm, and the surface was smoothed, and then placed in an environment of 23 ° C. and 50% relative humidity for 24 hours. . After 24 hours, the cured part was taken out and the thickness from the surface was measured with a micro gauge.

5) Adhesiveness Each curable composition was applied to each substrate degreased with IPA and MEK so as to be 100 μm on one side using a glass rod, and allowed to stand at 23 ° C. and 50% RH for 2 minutes. They were bonded together with a 1 inch wrap, pressed with two pinches, and cured for 7 days at 23 ° C. and 50% RH. It was measured at a test speed of 50 mm / min in accordance with the tensile shear bond strength test method for rigid adherends. Further, the fracture state of the adhesive surface was evaluated according to the following evaluation criteria.
CF: cohesive failure, AF: adhesive failure, C10A90 to C90A10: The area of the fractured state of CF and AF is expressed as an approximate percentage. CnA (100-n) is CFn%, AF (100-n)% It means the destruction state.

6) Physical properties of film Each curable composition was stretched using a spacer having a thickness of 2 mm, and cured for 7 days at 23 ° C. and 50% RH. No. 2 dumbbell was punched out of the cured film, JIS K6251 vulcanized rubber and thermoplastic rubber-Stress at 50% elongation (50% modulus, indicated as 50% Mo in the table), break strength, The film properties of elongation at break were measured. The test speed was 200 mm / min.
The hardness was measured using a Shore A hardness meter according to JIS K6253 vulcanized rubber and thermoplastic rubber—how to obtain the hardness.

In Table 5 and 6, the compounding quantity of each compounding substance is shown by g. Tin-based curing catalysts B1, 2, 4-13, 15-19, 21, 23 and 25 are tin-based curing catalysts obtained in Production Examples 1, 2, 4-13, 15-19, 21, 23 and 25, respectively. B1, 2, 4-13, 15-19, 21, 23 and 25, the details of the compounding substances are the same as those in Table 1, and the details of the remaining compounding substances are as follows.
MA440: A mixture of a polymer having a main chain of polyoxypropylene and having a dimethoxysilyl group at the molecular end and a polymer having a main chain of a polymethacrylate ester and having a dimethoxysilyl group in the molecule, manufactured by Kaneka Corporation Product name Cyrillic MA440.
Ryton A-5: Heavy calcium carbonate, trade name manufactured by Bihoku Powder Chemical Co., Ltd.
Calfine 500: Surface fatty acid-treated colloidal calcium carbonate, trade name of Maruo Calcium Co., Ltd.
KBM-603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Shin-Etsu Silicone KBM-603.

(Comparative Examples 1 to 13)
A curable composition was obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 9. Each measurement was performed by the method similar to Example 1 with respect to the obtained curable composition. The results are shown in Tables 9-11.

In Table 9, the compounding quantity of each compounding substance is shown by g. Tin-based curing catalysts X1 to 12 are tin-based curing catalysts X1 to 12 obtained in Comparative Production Examples 1 to 12, respectively. Details of each compounding substance are the same as those in Table 4, and details of the remaining compounding substances are as follows. It is as follows.
Neostan U-220H: Dibutyltin diacetylacetonate, trade name of Nitto Kasei Co., Ltd.

  As shown in Tables 5 to 11, in Examples 1 to 20, the low temperature curability is improved, the curability is excellent in adhesion, storage stability and curability, and the physical properties of the cured product are low modulus. A composition was obtained.

(Examples 21 and 22 and Comparative Examples 14 and 15)
A curable composition was obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 12. Each measurement was performed by the method similar to Example 1 with respect to the obtained curable composition. The results are shown in Table 13. In Examples 21 and 22 and Comparative Examples 14 and 15, in addition to the stress at 50% elongation, the stress at 100% elongation (100% modulus, indicated as 100% Mo in the table) was also measured.

In Table 12, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are the same as described above, and details of the remaining compounding substances are as follows.
S303H: Polyoxyalkylene polymer having a methyldimethoxysilyl group, trade name MS polymer S303H manufactured by Kaneka Corporation.

  As shown in Table 13, in Examples 21 and 22, the low temperature curability is improved, the adhesive properties, the storage stability and the curability are excellent, and the physical properties of the cured product are low modulus. was gotten.

(Examples 23 and 24 and Comparative Examples 16 and 17)
A curable composition was obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 14. Each measurement was performed by the method similar to Example 1 with respect to the obtained curable composition. The results are shown in Table 15.

In Table 14, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are the same as described above, and details of the remaining compounding substances are as follows.
SA120S: (meth) acrylic acid ester copolymer having a methyldimethoxysilyl group, trade name XMAP SA120S manufactured by Kaneka Corporation.

  As shown in Table 15, in Examples 23 and 24, low temperature curability was improved, and a curable composition excellent in adhesiveness, storage stability and curability was obtained.

(Examples 25-27)
A curable composition was obtained in the same manner as in Example 1 except that the compounding materials were changed as shown in Table 16. Each measurement was performed by the method similar to Example 1 with respect to the obtained curable composition. The results are shown in Tables 16-18.

  In Table 16, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are the same as described above, and tin-based curing catalysts B26 to 28 are tin-based curing catalysts B26 to 28 obtained in Production Examples 26 to 28, respectively.

  As shown in Tables 16 to 18, in Examples 25 to 27, the low temperature curability is improved, and the curability is excellent in adhesion, storage stability and curability, and the physical properties of the cured product are low modulus. A composition was obtained.

(Examples 28-30 and Comparative Examples 18-20)
A curable composition was obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 19. Each measurement was performed by the method similar to Example 1 with respect to the obtained curable composition. The results are shown in Tables 19 and 20.

In Table 19, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are the same as described above, and the polymer A1 is an acrylate polymer A1 having a trimethoxysilyl group obtained in Synthesis Example 1, and details of the remaining compounding substances are as follows. .
EPION EP-505S: a polymer containing 33% by weight of process oil, having a main chain of polyisobutylene and having a methyldimethoxysilyl group at the molecular end, a trade name manufactured by Kaneka Corporation.
Topsizer No. 3: N-ethyl-o / p-toluenesulfonamide, trade name manufactured by Fujiamide Chemical Co., Ltd.

  As shown in Tables 19 and 20, in Examples 28 to 30, curable compositions having excellent storage stability and curability and having a cured product with low modulus were obtained.

Claims (16)

(A) A curable composition containing a crosslinkable silicon group-containing organic polymer and (B) a liquid tin-based curing catalyst,
The (B) liquid tin-based curing catalyst comprises one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): It is a reaction product obtained by reacting the tin atom of the tin compound in a range of 0.20 to 1.40 mol with respect to 1 mol of OR ³ groups of the silane compound,
A curable composition comprising 0.01 to 15 parts by mass of the (B) liquid tin-based curing catalyst with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer.
R ¹ R ² _a Si (OR ³ ) _3-a (1)
(In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group; ² is a methyl group or a phenyl group, a is 0 or 1 (if provided that ^{R 1} is an alkyl group having 6 to 20 carbon atoms and a is 0), ^{R 3} is 1 of 1 to 4 carbon atoms A group selected from the group consisting of a valent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the plurality of R ³ may be the same or different.)   The (A) crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer having a crosslinkable silicon group, a (meth) acrylic polymer having a crosslinkable silicon group, and a saturated carbonization having a crosslinkable silicon group. The curable composition according to claim 1, wherein the curable composition is at least one selected from the group consisting of hydrogen polymers. The curable composition according to claim 1 or 2, wherein R ^{1 in the} formula (1) is a phenyl group, a vinyl group, or an alkyl group having 6 to 20 carbon atoms. The curable composition according to claim 1 or 2, wherein R ^{1 in the} formula (1) is a phenyl group or a vinyl group. The (A) crosslinkable silicon group-containing organic polymer is one or more selected from the group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic polymer having a crosslinkable silicon group. The curable composition according to claim 1, wherein R ^{1 in the} formula (1) is a vinyl group.   The (A) crosslinkable silicon group-containing organic polymer has a polyoxyalkylene polymer having a crosslinkable silicon group, or a polyoxyalkylene polymer having a crosslinkable silicon group and a crosslinkable silicon group (meth). The curable composition according to claim 1, which is a mixture with an acrylic polymer. The (A) crosslinkable silicon group-containing organic polymer is a saturated hydrocarbon polymer having a crosslinkable silicon group, and R ^{1 in the} formula (1) is a phenyl group. The curable composition of any one of 1-4.   The curable composition according to claim 7, wherein the alkoxysilane compound represented by the formula (1) is diphenylalkoxysilane.   The curable composition according to any one of claims 1 to 8, wherein the (B) liquid tin-based curing catalyst further contains (C) a diluent. (A) 0.01-15 parts by mass of (B) liquid tin-based curing catalyst is added to 100 parts by mass of the crosslinkable silicon group-containing organic polymer, and (A) the crosslinkable silicon group-containing organic polymer and (B) A method for producing a curable composition comprising a step of obtaining a curable composition containing a liquid tin-based curing catalyst,
The (B) liquid tin-based curing catalyst comprises one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1): A method for producing a curable composition, which is a reaction product obtained by reacting a tin atom of the tin compound in an amount of 0.20 to 1.40 mol with respect to 1 mol of OR ³ groups of the silane compound. .
R ¹ R ² _a Si (OR ³ ) _3-a (1)
(In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group; ² is a methyl group or a phenyl group, a is 0 or 1 (if provided that ^{R 1} is an alkyl group having 6 to 20 carbon atoms and a is 0), ^{R 3} is 1 of 1 to 4 carbon atoms A group selected from the group consisting of a valent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the plurality of R ³ may be the same or different.)     The method for producing a curable composition according to claim 10, wherein the (B) liquid tin-based curing catalyst further contains (C) a diluent. One or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1) are added to 1 mol of OR ³ group of the alkoxysilane compound. A liquid tin-based curing catalyst comprising a reaction product obtained by reacting tin atoms of the tin compound in a range of 0.20 to 1.40 mol.
R ¹ R ² _a Si (OR ³ ) _3-a (1)
(In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group; ² is a methyl group or a phenyl group, a is 0 or 1 (if provided that ^{R 1} is an alkyl group having 6 to 20 carbon atoms and a is 0), ^{R 3} is 1 of 1 to 4 carbon atoms A group selected from the group consisting of a valent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the plurality of R ³ may be the same or different.)   The liquid tin-based curing catalyst according to claim 12, further comprising (C) a diluent. One or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the following formula (1) are added to 1 mol of OR ³ group of the alkoxysilane compound. The manufacturing method of the liquid tin type curing catalyst characterized by including the process of making the tin atom of the said tin compound react in 0.20-1.40 mol, and obtaining the reaction product.
R ¹ R ² _a Si (OR ³ ) _3-a (1)
(In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, an epoxycycloalkyl group, an aminoalkyl group, or an aminoalkylaminoalkyl group; ² is a methyl group or a phenyl group, a is 0 or 1 (if provided that ^{R 1} is an alkyl group having 6 to 20 carbon atoms and a is 0), ^{R 3} is 1 of 1 to 4 carbon atoms A group selected from the group consisting of a valent hydrocarbon group and a monovalent halogenated hydrocarbon group, and the plurality of R ³ may be the same or different.)   The method for producing a liquid tin-based curing catalyst according to claim 14, wherein the liquid tin-based curing catalyst further contains (C) a diluent.   A cured product obtained by curing the curable composition according to claim 1.