JP2009215330A - ONE-PACK CURABLE COMPOSITION CONTAINING POLYMER HAVING SiF GROUP - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pack curable composition having excellent curing property. <P>SOLUTION: The one-pack curable composition includes a polymer (A) having a silicon group expressed by general formula (1):-SiF<SB>a</SB>Z<SB>3-a</SB>and calcium carbonate (B). In the formula, F represents a fluorine atom; Z represents a hydroxyl group or a hydrolyzable group except for fluorine; a represents 1, 2, or 3; and when two of Z are present, they may be identical or different from each other. The present invention also discloses a sealing material and an adhesive using the above curable composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a one-component curable composition containing a polymer having a silicon group having a Si—F bond (sometimes referred to as “SiF group”).

  A polymer containing at least one silicon group having a hydroxyl group or hydrolyzable group bonded to a silicon atom (hereinafter also referred to as “reactive silicon group”) in one molecule is reactive due to moisture or the like even at room temperature. It is known to have a property that a rubber-like cured product can be obtained by crosslinking by forming a siloxane bond accompanied by a hydrolysis reaction of a silicon group.

  Among these polymers having reactive silicon groups, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a polyisobutylene polymer are disclosed in Patent Document 1, Patent Document 2, and the like. Already industrially produced and widely used in applications such as sealing materials, adhesives and paints.

  When these polymers are used in curable compositions used for sealing materials, adhesives, paints, etc., various properties such as curability and adhesiveness and mechanical properties of the cured product are required.

  A curable composition containing a polymer having a reactive silicon group is usually cured using a curing catalyst such as an organic tin compound having a carbon-tin bond, represented by dibutyltin bis (acetylacetonate). . When it is necessary to cure in a short time during use, a method such as increasing the amount of the curing catalyst is common. However, in recent years, the toxicity of organotin compounds has been pointed out, and caution is required for their use from the viewpoint of environmental safety. As curing catalysts other than organic tin compounds, Patent Document 3 and Patent Document 4 disclose carboxylic acid tin salts and other carboxylic acid metal salts, and Patent Document 5 discloses a catalyst system using a combination of carboxylic acid and an amine compound. . However, these catalysts are often inferior in curability as compared with organotin catalysts.

  The inventors disclosed in Patent Document 6 that by using a polymer having a SiF group, very high curability can be obtained without using an organotin catalyst.

In addition, curable compositions used for sealing materials, adhesives, paints and the like and rubber-like cured products obtained by curing include calcium carbonate, silica and the like for the purpose of improving strength, improving workability, and imparting design properties. Various fillers are often used.
JP-A-52-73998 JP-A 63-6041 JP 55-9669 A JP 2003-206410 A JP-A-5-117519 Japanese Patent Application No. 2006-248235

  The present inventors use calcium carbonate as a filler together with a polymer having a SiF group, and in a one-component curable composition prepared by kneading various compounding components under dehydrating conditions, It has been found that a cure delay can occur.

An object of the present invention is to provide a one-component curable composition that exhibits good curability without substantially using an organotin catalyst.

  In view of the above circumstances, as a result of intensive studies by the present inventors, it was found that a novel polymer having a specific terminal structure can solve the above problems, and the present invention has been completed.

That is, the present invention
(1)
General formula (1):
-SiF _a Z _3-a (1)
(In the formula, F is a fluorine atom, Z is a hydroxyl group or a hydrolyzable group other than fluorine. A is either 1, 2, or 3. When two Z are present, the two Z are the same. 1-type curable composition comprising a silicon group-containing polymer (A) and calcium carbonate (B), which may be different from each other.
(2)
The one-component curable composition according to (1) above, wherein the polymer (A) has a number average molecular weight of 3,000 to 100,000.
(3)
1-component curable composition in any one of said (1) or (2) whose a of said general formula (1) is 3,
(4)
The main chain skeleton of the polymer (A) is at least one selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth) acrylic acid ester polymers. The one-component curable composition according to any one of (1) to (3),
(5)
The one-component curable composition according to any one of (1) to (4), wherein the calcium carbonate (B) is precipitated calcium carbonate,
(6)
Furthermore, the following general formula (2):
-SiR ¹ _3-b Y _b (2)
(Wherein R ¹ is each independently a hydrocarbon group having 1 to 20 carbon atoms, or R ² ₃ SiO— (R ² is each independently a hydrocarbon group having 1 to 20 carbon atoms)). And Y is independently a hydroxyl group or a hydrolyzable group other than fluorine, and b is any one of 1, 2, and 3). The one-component curable composition according to any one of the above (1) to (5), comprising a polymer (C) having an average of one or more silicon groups per molecule,
(7)
Furthermore, the one-component curable composition according to any one of the above (1) to (6), which contains an amine compound (D) as a curing catalyst,
(8)
A sealing material comprising the one-component curable composition according to any one of (1) to (7) above,
(9)
An adhesive comprising the one-component curable composition according to any one of (1) to (7),
About.

  The polymer and curable composition of the present invention have excellent curability without using an organotin catalyst. Such a curable composition of the present invention can be suitably used for a sealing material and an adhesive.

  The present invention will be described in detail below. In the present specification, a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond is also referred to as a “reactive silicon group”.

  A curable composition containing a polymer (polymer (A)) containing a silicon group represented by the general formula (1) of the present invention (hereinafter also referred to as “trifunctional fluorosilyl group”) is as follows: Further, the present invention relates to a moisture curable composition that is curable by moisture even at room temperature.

  The polymer (A) of the present invention does not have a Si-F bond, which will be described later, and has a fast curability as compared with a polymer (C) containing a reactive silicon group having a hydrolyzable group other than fluorine. It is characterized by showing. Moreover, the curable composition which shows quick sclerosis | hardenability can also be obtained by using together a polymer (A) and a polymer (C).

In the one-component curable composition of the present invention, the general formula (1):
-SiF _a Z _3-a (1)
(In the formula, F is a fluorine atom, Z is a hydroxyl group or a hydrolyzable group other than fluorine. A is either 1, 2, or 3. When two Z are present, the two Z are the same. Or it may be different.) It is essential to contain a polymer (A) having a silicon group represented by:

  Examples of the hydrolyzable group other than fluorine represented by Z in the general formula (1) include a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, and an acid amide group. Aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  Specific examples of the silicon group represented by the general formula (1) (hereinafter also referred to as “trifunctional fluorosilyl group”) include a trifluorosilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, and a difluorophenoxysilyl group. Group, difluorochlorosilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, fluorodiphenoxysilyl group, fluorodichlorosilyl group and the like. From the viewpoint of ease of synthesis, a trifluorosilyl group, a fluorodimethoxysilyl group, a fluorodiethoxysilyl group, a difluoromethoxysilyl group, and a difluoroethoxysilyl group are more preferable. From the viewpoint of high curability, a difluoromethoxysilyl group and a difluoroethoxy group are preferred. A silicon group in which 2 to 3 fluorine atoms are substituted on a silicon group, such as a silyl group or a trifluorosilyl group, is preferable, and a trifluorosilyl group is most preferable.

  In a curable composition containing a polymer having a fluorosilyl group, when calcium carbonate is used in combination, the curability may be lowered. Furthermore, in a one-component curable composition in which a polymer, a filler, various compounding agents, and a curing catalyst are all mixed, the curability may be lowered during storage for a certain period after the preparation of one component. Need to be improved.

  Therefore, the present inventors use the polymer (A) having a trifunctional fluorosilyl group as an essential component, so that excellent curability can be obtained even in a one-component curable composition using calcium carbonate as a filler. It was found that can be demonstrated.

The cause of the decrease in curability due to calcium carbonate is not clear, but it is assumed that the activity of the fluorosilyl group is reduced by the partial reaction of the fluorosilyl group and calcium carbonate. In the present invention, the use of the polymer (A) having a trifunctional fluorosilyl group can suppress the decrease in the activity of the fluorosilyl group compared to the Si—F bond in the bifunctional fluorosilyl group. This may be because the Si-F bond of the trifunctional fluorosilyl group is more stable.

  Here, the polymer (A) of the present invention is a single polymer in which the trifunctional fluorosilyl group and the main chain skeleton are the same, that is, the number of trifunctional fluorosilyl groups per molecule, The polymer may be a single polymer having the same bonding position, the number of Fs of the fluorosilyl group, and the main chain skeleton, and any or all of these are different. It may be. In any case where the polymer (A) of the present invention is a single polymer or a mixture of a plurality of polymers, the polymer (A) is preferably used as a resin component of a curable composition exhibiting fast curing properties. In order to obtain a rubber-like cured product that exhibits high curability, high strength, high elongation, and low elastic modulus, the trifunctional fluoro contained in the polymer (A) can be used. The average number of silyl groups per molecule of the polymer should be at least 1, preferably 1.1-5, and more preferably 1.2-3. If the number of trifunctional fluorosilyl groups contained in one molecule is less than 1 on average, curability may be insufficient, and good rubber elastic behavior may be difficult to develop. Moreover, when the number of trifunctional fluorosilyl groups contained in one molecule is more than 5 on average, the elongation of the rubber-like cured product may be small. As described above, the trifunctional fluorosilyl group may be present at the end of the main chain or side chain of the polymer molecular chain, and particularly when present at the end of the main chain. Since the effective network length of the organic polymer component contained in the cured product to be formed is increased, it is easy to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus. When two or more trifunctional fluorosilyl groups are present in one molecule, each silicon group may be the same or different.

  In addition, the polymer (A) of the present invention has a trifunctional fluorosilyl group and a fluoro group such as a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group (for example, a methyldimethoxysilyl group). A substituent other than a silyl group may be contained. As such a polymer (A), for example, one main chain end is a trifunctional fluorosilyl group, and the other main chain end has only a hydrolyzable group other than fluorine as a hydrolyzable group. Mention may be made of polymers which are silicon groups.

  Any method may be used for the introduction of the trifunctional fluorosilyl group, but the introduction method (method (i)) by the reaction of a low molecular silicon compound having a fluorosilyl group with a polymer, and addition of fluorine other than fluorine. A method (method (ii)) of modifying a silicon group of a polymer containing a reactive silicon group having a decomposable group (hereinafter sometimes referred to as “polymer (X)”) to a fluorosilyl group. It is done.

  Specific examples of the method (i) include the following methods. (A) A method of reacting a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule with a compound having a functional group reactive to the functional group and a trifunctional fluorosilyl group . Examples thereof include a method of reacting a polymer having a hydroxyl group at the terminal with isocyanate propyl trifluorosilane, and a method of reacting a polymer having a SiOH group at the terminal and difluorodiethoxysilane. (B) A method of hydrosilylating a polymer containing an unsaturated group in a molecule with a hydrosilane having a trifunctional fluorosilyl group. For example, a method of reacting a polymer having an allyl group at a terminal with difluoromethoxyhydrosilane can be mentioned. (C) A method of reacting a polymer containing an unsaturated group with a compound having a mercapto group and a trifunctional fluorosilyl group. For example, a method in which a polymer having an allyl group at a terminal is reacted with mercaptopropyl trifluorosilane can be mentioned.

In the method (ii), a known method can be used as a method for converting a reactive silicon group having a hydrolyzable group other than fluorine into a fluorosilyl group. Specific examples include a method of converting an alkoxysilyl group, a chlorosilyl group, and a hydrosilyl group into a fluorosilyl group, and various fluorinating agents can be used for fluorination. Specific examples of the fluorinating agent include NH ₄ F, Bu ₄ NF (Bu is a butyl group), HF, BF ₃ , Et ₂ NSF ₃ (Et is an ethyl group) for fluorination of alkoxysilane. ), HSO ₃ F, SbF ₅ , VOF ₃ , CF ₃ CHFCF ₂ NEt _2, etc., fluorination of chlorosilane includes AgBF ₄ , SbF ₃ , ZnF ₂ , NaF, KF, CsF, NH ₄ F, CuF ₂ , _{NaSiF 6, NaPF 6, NaSbF 6} , NaBF 4, Me 3 SnF (Me is a methyl _group.), KF (HF), such as _{1.5 to 5 1.5 to 5,} in the fluorination of hydrosilane, AgF, Examples include, but are not limited to, PF ₅ , Ph ₃ CBF ₄ , SbF ₃ , NOBF ₄ , and NO ₂ BF ₄ . The above fluorination is introduced in Organometallics 1996, 15, 2478 (Ishikawa et al.). From the viewpoint of simplicity of reaction, efficiency, safety, etc., fluorination of an alkoxysilyl group using BF ₃ and fluorination of a chlorosilyl group using CuF ₂ or ZnF ₂ are preferred. BF ₃ includes BF ₃ gas, BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ piperidine complex, BF ₃ alcohol complex, BF ₃ phenol complex, BF ₃ carboxylic acid complex, and BF ₃ dihydrate. Products, BF ₃ phosphate complexes, etc., but from the viewpoint of ease of handling, BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex, BF ₃ dihydrate Things are preferred. Among them, BF ₃ ether complex, BF ₃ alcohol complex, and BF ₃ dihydrate have high activity, and fluorination proceeds efficiently, and further, by-products are not generated, and the post-treatment is easy. Preferably, BF ₃ ether complex is particularly preferable. Furthermore, in the fluorination with a BF ₃ ether complex, the reaction proceeds without heating, but heating is preferable for more efficient fluorination. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 60 ° C. or higher and 130 ° C. If it is 50 ° C. or lower, the reaction does not proceed efficiently, and it may take time for fluorination. There exists a possibility that a polymer (A) may decompose | disassemble that it is 150 degreeC or more.

In the fluorination with the BF ₃ complex, coloring may occur depending on the type of the polymer (X) to be used. From the viewpoint of suppression of coloring, it is preferable to use a BF ₃ alcohol complex or BF ₃ dihydrate.

The fluorinating agent used in the production of the polymer (A) may also act as a curing catalyst for the polymer (A), and the polymer (A) is produced using the method (ii). If water is present at times, the silanol condensation reaction proceeds and the viscosity of the resulting polymer (A) may increase. For this reason, the production of the polymer (A) is preferably performed in an environment free from moisture as much as possible. Before the fluorination, the polymer (X) to be fluorinated is azeotroped using toluene, hexane or the like. It is preferable to perform a dehydration operation such as subjecting to dehydration. However, when a BF ₃ amine complex is used, fluorination hardly progresses after the dehydration operation, and the reactivity tends to be improved by adding a small amount of water. Is preferably added. Further, from the viewpoint of the stability of the polymer (A), it is preferable to remove the fluorinating agent and by-product fluorinating agent-derived components after fluorination by filtration, decantation, liquid separation, vacuum devolatilization and the like. When the polymer (A) is produced using the BF ₃ -based fluorinating agent, the BF ₃ remaining in the produced polymer (A) and the BF ₃ -derived component produced by the reaction are B The amount is preferably less than 500 ppm, more preferably less than 100 ppm, and particularly preferably less than 50 ppm. By removing the components derived from BF ₃ and BF _3, it is possible to suppress an increase in viscosity of the obtained polymer (A) itself and a mixture of the polymer (A) and the polymer (X). In view of this point, the fluorination method using a BF ₃ ether complex or a BF ₃ alcohol complex is preferable because the boron component can be removed relatively easily by vacuum devolatilization, and the method using a BF ₃ ether complex is particularly preferable. .

  Here, when the polymer (X) has two or more hydrolyzable groups other than fluorine, all hydrolyzable groups may be fluorinated, or the amount of the fluorinating agent is reduced. May be partially fluorinated by adjusting the fluorination conditions. For example, in the method (ii), when the polymer (A) is produced using the polymer (X), the amount of the fluorinating agent is not particularly limited, and the fluorine atom in the fluorinating agent is not limited. It is sufficient that the molar amount is equal to or greater than the molar amount of the polymer (X). When all the hydrolyzable groups contained in the polymer (X) are to be fluorinated by the method (ii), the molar amount of fluorine atoms in the fluorinating agent is contained in the polymer (X). It is preferable to use the fluorinating agent in such an amount that it is equimolar or more with respect to the total molar amount of the hydrolyzable group in the reactive silicon group. Here, the “fluorine atom in the fluorinating agent” means a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in the reactive silicon group of the polymer (X). A fluorine atom that can be substituted.

  The low molecular compound having a fluorosilyl group in the method (i) can also be synthesized from a general-purpose reactive silicon group-containing low molecular compound by using the fluorination method.

  In the method (i), since there is a reactive group for reacting the polymer and the silicon-containing low molecular weight compound together with the fluorosilyl group, when the reaction becomes complicated, the polymer (A) is prepared by the method (ii). It is preferable to obtain

  In addition, the manufacturing method of the polymer (polymer (X)) containing the reactive silicon group which has hydrolyzable groups other than a fluorine used by the said method (ii) is mentioned later.

  The glass transition temperature of the polymer (A) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably −20 ° C. or lower. When the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and handling may be difficult, and the flexibility of the cured product obtained when used as a curable composition is reduced and elongation is increased. May decrease. The glass transition temperature can be determined by DSC measurement.

  The polymer (A) may be linear or branched. The number average molecular weight of the polymer (A) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC. is there. If the number average molecular weight is less than 3,000, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  Next, the main chain skeleton of the polymer (A) of the present invention will be described in detail. Also introduced is a method for producing a polymer (polymer (X)) containing a reactive silicon group having a hydrolyzable group other than fluorine for synthesizing the polymer (A) by the method (ii). To do.

  The main chain skeleton of the polymer (A) of the present invention is not particularly limited, and those having various main chain skeletons can be used.

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 Copolymers of acrylonitrile and styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols A polyester polymer obtained by condensation of lactones or ring-opening polymerization of lactones; a (meth) acrylic acid ester polymer 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 polymers; polysulfides Polymer: Polyamide 6 by ring-opening polymerization of ε-caprolactam, Polyamide 6 · 6 by condensation polymerization of hexamethylenediamine and adipic acid, Polyamide 6 · 10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Polyamide 11, ε-aminolauro by condensation polymerization Polyamide-based polymer by ring-opening polymerization of cutam, a polyamide-based polymer such as a copolyamide having two or more components among the above-mentioned polyamides; for example, a polycarbonate-based polymer produced by condensation polymerization from bisphenol A and carbonyl chloride, Examples include organic polymers such as diallyl phthalate polymers. Further, polysiloxane inorganic polymers such as polydiorganosiloxane can also be used. Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, polyoxyalkylene polymers, (meth) acrylic acid ester polymers, polysiloxane polymers are A cured product obtained when the glass transition temperature is relatively low and used as a curable composition is more preferable because of its excellent cold resistance.

  Organic polymers such as saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylic ester polymers are used as adhesive groups for low molecular weight components when used as a base polymer for adhesives and sealants. It is preferable because there is little contamination due to transfer to materials.

  In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep-part curability when made into a one-component composition, and also excellent in adhesiveness. The polyoxyalkylene polymer is most preferable.

The polyoxyalkylene polymer essentially has the general formula (3):
—R ³ —O— (3)
(Wherein R ³ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ³ in the general formula (3) is the number of carbon atoms. A linear or branched alkylene group having 1 to 14 is preferable, and a linear or branched alkylene group having 2 to 4 carbon atoms is more preferable. Specific examples of the repeating unit represented by the general formula (3) include

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 the polymer (A) is used for a sealant or the like, a polymer composed mainly of a propylene oxide polymer is preferable because it is amorphous and has a relatively low viscosity.

  Examples of the method for synthesizing a polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent 3,278,457, US Patent 3,278,458, US Patent 3,278,459, US Patent 3,427,256, US Patent 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Uses a compound catalyst That polymerization method, including but not limited in particular.

  A method for producing a polyoxyalkylene polymer (X) containing a reactive silicon group having a hydrolyzable group other than fluorine used for the production of the polymer (A) is disclosed in Japanese Patent Publication Nos. 45-36319 and 46. -12154, JP-A-50-156599, 54-6096, 55-13767, 55-13468, 57-164123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. , U.S. Pat. No. 4,366,307, U.S. Pat. No. 4,960,844, etc., and JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632. No. 72527, JP-A-3-47825, JP-A-8-231707, number average molecular weight 6, 00 Although Mw / Mn can be exemplified manufacturing method of the molecular weight distribution is narrow polyoxyalkylene polymer with a high molecular weight of 1.6 or less, but it is not particularly limited thereto.

  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 having such a skeleton is (1) ethylene, propylene, 1-butene. , An olefinic compound having 2 to 6 carbon atoms such as isobutylene is polymerized as a main monomer, (2) a diene compound such as butadiene or isoprene is homopolymerized, or the diene compound and It can be obtained by a method such as hydrogenation after copolymerization with the olefin compound. Among these, isobutylene polymers and hydrogenated polybutadiene polymers are preferable because it is easy to introduce a functional group at a terminal, easily control the molecular weight, and increase the number of terminal functional groups. A polymer is particularly preferred.

  The polymer (A) whose main chain skeleton is a saturated hydrocarbon polymer and a cured product thereof 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 in terms of rubber properties, repeating units derived from isobutylene are used. Those containing 50% by weight or more are preferred, those containing 80% by weight or more are more preferred, and those containing 90 to 99% by weight are particularly preferred.

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

  Examples of a method for producing a saturated hydrocarbon polymer (X) containing a reactive silicon group having a hydrolyzable group other than fluorine used for the production of the polymer (A) include Japanese Patent Publication No. 4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-1-197509, JP-A-2539445, JP-A-2873395, JP-A-7-53882 Although described in the specification and the like, it is not particularly limited thereto.

  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. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethylethyl, 2- (perfluoroethyl) -2- (perfluorobutylethyl) (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (meth) acrylate (tri) Fluoromethyl) methyl, ( T) 2-trifluoromethyl-2-perfluoroethylethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate Examples include (meth) acrylic acid monomers such as hexadecylethyl.

  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, Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclamate Maleimide monomers such as hexylmaleimide; 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, Examples include vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

These vinyl monomers may be used alone or a plurality of them may be copolymerized. Especially, the copolymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property etc. of the polymer obtained is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. When the polymer (A) is used for general architectural purposes, a butyl acrylate monomer is required from the viewpoint of physical properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance, and heat resistance. Is more preferable. On the other hand, in applications requiring oil resistance such as automobile applications, a copolymer mainly composed of ethyl acrylate is more preferable. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low-temperature characteristics (cold resistance). Therefore, in order to improve the low-temperature characteristics, a part of ethyl acrylate is butyl acrylate. It is also possible to replace with. However, as the ratio of butyl acrylate is increased, the good oil resistance is impaired. Therefore, for applications that require oil resistance, the ratio is preferably 40 mol% or less, and more preferably 30 mol. % Or less is more preferable. In order to improve low temperature characteristics without impairing oil resistance, it is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, the ratio is preferably 40 mol% or less when heat resistance is required. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40 to 50/20 in molar ratio). To 30/30 to 20). In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  It does not specifically limit as a synthesis method of a (meth) acrylic acid ester type polymer, What is necessary is just to carry out by a well-known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity becomes high. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high rate It is preferable to use a living radical polymerization method.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing a (meth) acrylate monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, In addition to the characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction at the end, and has a large degree of freedom in designing initiators and catalysts. The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of this atom transfer radical polymerization method include Matjajszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  As a method for producing a (meth) acrylic acid ester polymer (X) containing a reactive silicon group having a hydrolyzable group other than fluorine, which is used for the production of the polymer (A), for example, JP 3-B No. 14068, Japanese Patent Publication No. 4-55444, Japanese Patent Laid-Open No. Hei 6-221922, etc. disclose production methods using a free radical polymerization method using a chain transfer agent. Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.

As described above, the polymer (A) of the present invention is any one of the various main chain skeletons described above.
It may have a main chain skeleton of a seed or a mixture of polymers having different main chain skeletons. Specifically, a group consisting of a polyoxyalkylene polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, and a (meth) acrylic acid ester polymer having a reactive silicon group A polymer obtained by blending two or more selected from the above also belongs to the polymer (A) of the present invention.

A polyoxyalkylene polymer containing a reactive silicon group having a hydrolyzable group other than fluorine, and a (meth) acrylic acid ester polymer containing a reactive silicon group having a hydrolyzable group other than fluorine, and Have been proposed in JP 59-122541, JP 63-112642, JP 6-172631, JP 11-116763, etc. In particular, it is not limited to these. A preferred specific example has a reactive silicon group, and the molecular chain is substantially the following general formula (4):
—CH ₂ —C (R ⁴ ) (COOR ⁵ ) — (4)
(Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkyl group having 1 to 8 carbon atoms) and a (meth) acrylic acid ester having an alkyl group having 1 to 8 carbon atoms A monomer unit and the following general formula (5):
^{_{-CH 2 -C (R 4) (}} COOR 6) - (5)
(Wherein, R ⁴ is the same as above, and R ⁶ represents an alkyl group having 10 or more carbon atoms) represented by a (meth) acrylate monomer unit having an alkyl group having 10 or more carbon atoms And a copolymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group.

R ^{5 in the} general formula (4) is, for example, 1 to 8, preferably 1 to 4, carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, and 2-ethylhexyl group. More preferred are 1 or 2 alkyl groups. The alkyl group of R ⁵ may alone, or may be a mixture of two or more.

R ^{6 in the} general formula (5) is, for example, a long chain having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10 to 30, preferably 10 to 20 An alkyl group is mentioned. The alkyl group of R ⁶ may alone, or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based copolymer is substantially composed of monomer units of the general formula (4) and the general formula (5). It means that the total of the monomer units of general formula (4) and general formula (5) present in the copolymer exceeds 50% by weight. The total of the monomer units of the general formula (4) and the general formula (5) is preferably 70% by weight or more.

  In addition, the abundance ratio of the monomer unit of the general formula (4) and the monomer unit of the general formula (5) is preferably 95: 5 to 40:60, and 90:10 to 60:40 in weight ratio. Further preferred.

  Examples of monomer units other than the general formula (4) and general formula (5) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; N-methylolacrylamide, N- Monomers containing nitrogen-containing groups such as amide groups such as methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, Examples thereof include monomer units derived from vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

A saturated hydrocarbon polymer containing a reactive silicon group having a hydrolyzable group other than fluorine, and a (meth) acrylic acid ester copolymer containing a reactive silicon group having a hydrolyzable group other than fluorine. Polymers obtained by blending these are proposed in JP-A-1-168774, JP-A-2000-186176, etc., but are not particularly limited thereto.

  Furthermore, as a method for producing a polymer obtained by blending a (meth) acrylic acid ester-based copolymer containing a reactive silicon functional group having a hydrolyzable group other than fluorine, there are other hydrous methods other than fluorine. A method of polymerizing a (meth) acrylate monomer in the presence of a polymer containing a reactive silicon group having a decomposable group 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.

  Here, the main chain skeleton of the polymer (A) of the present invention may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

  Although it does not specifically limit as said urethane bond component, The group (henceforth an amide segment) produced | generated by reaction of an isocyanate group and an active hydrogen group can be mentioned.

The amide segment has the following general formula (6):
—NR ⁷ C (═O) — (6)
(R ⁷ represents a hydrogen atom or a substituted or unsubstituted organic group).

  Specifically, the amide segment includes a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between the isocyanate group and an amino group; a thiol formed by a reaction between the isocyanate group and a mercapto group. A urethane group etc. can be mentioned. In the present invention, the group generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group is also included in the group of the general formula (6).

When an industrially easy production method of the polymer (X) containing a reactive silicon group having a hydrolyzable group other than amide segment and fluorine is exemplified, an excessive amount of polymer having an active hydrogen-containing group at the terminal is excessive. After reacting the polyisocyanate compound to form a polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or part of the isocyanate group is represented by the following general formula (7)
U-R ⁸ -SiR ¹ _3-b Y _b (7)
(However, in the formula, R ¹ , Y and b are the same as those in the general formula (2). R ⁸ is a divalent organic group, more preferably substituted or unsubstituted 2 having 1 to 20 carbon atoms. U is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, an unsubstituted or monosubstituted amino group, and the U group of a silicon compound represented by The thing manufactured by the method can be mentioned. Examples of known production methods for polymers relating to this production method include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557), Japanese Patent Application Laid-Open No. 58-109529 (US Pat. No. 4,374,237), Japanese Patent Application Laid-Open No. Sho 62- 13430 (US Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-T 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-21879 (US Pat. No. 5364955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-11-100197, JP-A-2000-169544, JP-A-2000-169545, JP-A-2002-212415, JP-A-3313360, US Pat. No. 4,067,844, US Pat. No. 3711 No. 45, JP 2001-323040, and the like.

Further, the polymer having an active hydrogen-containing group at the terminal is represented by the following general formula (8).
_{^{O = C = N-R 8}} -SiR 1 3-b Y b (8)
(Wherein R ¹ , R ⁸ , Y and b are the same as those in the general formulas (2) and (7)) and a reactive silicon group-containing isocyanate compound having a hydrolyzable group other than fluorine, What is manufactured by making this react is mentioned. Examples of known production methods for polymers relating to this production method include JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6,046,270), JP-A 58-29818. (US Pat. No. 4,345,053), JP-A-3-47825 (US Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981, etc. Is mentioned.

  Examples of the polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydrocarbon polymer having a hydroxyl group at the terminal (polyolefin polyol). , Polythiol compound, polyamine compound, polyalkyleneimine, polysiloxane and the like. Among these, polyether polyol, polyacryl polyol, polyolefin polyol, and polysiloxane are preferable because the obtained polymer has a relatively low glass transition temperature and the obtained cured product has excellent cold resistance. In particular, the polyether polyol is particularly preferable because the resulting polymer has a low viscosity, good workability, and good deep part curability. Polyacryl polyols and saturated hydrocarbon polymers are more preferred because the cured products of the resulting polymers have good weather resistance and heat resistance.

  As the polyether polyol, those produced by any production method can be used, but those having at least 0.7 hydroxyl groups per molecular terminal in terms of the total molecular average are preferable. Specifically, an oxyalkylene polymer produced using a conventional alkali metal catalyst, a polyhydroxy compound having at least two hydroxyl groups in the presence of a double metal cyanide complex or cesium, and the like are used as an initiator. Examples include oxyalkylene polymers produced by reacting oxides.

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex has a lower degree of unsaturation, a smaller Mw / Mn, a lower viscosity, a high acid resistance, and a high weather resistance oxyalkylene heavy. It is preferable because a coalescence can be obtained.

  Examples of the polyacrylic polyol include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure. Specific examples include UH-2000 manufactured by Toagosei Co., Ltd.

  Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. .

Although there is no limitation in particular as a silicon compound of the said General formula (7), when it illustrates concretely, (gamma) -aminopropyltrimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyltrimethoxysilane, (N -Phenyl) -γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethoxysilane, N-phenylaminomethyltrimethoxysilane, etc. Amino group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; and the like. JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), JP-A 2000-169544, JP-A 2000-169545. As described in the above, Michael addition reaction product of various α, β-unsaturated carbonyl compounds and amino group-containing silanes, or Michael of various (meth) acryloyl group-containing silanes and amino group-containing compounds. Addition reactants can also be used as silicon compounds of general formula (7).

  The reactive silicon group-containing isocyanate compound of the general formula (8) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methoxydiethoxysilyl. Examples thereof include propyl isocyanate and trimethoxysilylmethyl isocyanate. Further, as described in JP-A-2000-119365 (US Pat. No. 6,046,270), a compound obtained by reacting a silicon compound of the general formula (7) with an excess of the polyisocyanate compound is also represented by the general formula: It can be used as the reactive silicon group-containing isocyanate compound (8).

  When there are many amide segments in the main chain skeleton of the polymer (A) of the present invention, the viscosity of the polymer tends to increase. Moreover, a viscosity may rise after storage and workability | operativity of the composition obtained may fall. Therefore, in order to obtain a composition having excellent storage stability and workability, it is preferable that the amide segment is not substantially contained. On the other hand, curability tends to be improved by the amide segment in the main chain skeleton of the polymer (A). Therefore, when the main chain skeleton of the polymer (A) contains an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 5, and 2 to 3 Particularly preferred. When the number is less than 1, the curability may not be sufficient, and when the number is more than 10, the polymer may become highly viscous and difficult to handle.

Further, among the polymers produced by the above method using the compound of the general formula (7) or the general formula (8), a polymer comprising a compound in which R ⁸ is —CH ₂ — is particularly excellent. The curability tends to be obtained.

  Moreover, in this invention, if the polymer (A) which has a trifunctional fluorosilyl group is contained as an essential component, you may use together the polymer which has a fluorosilyl group which is not trifunctional.

The non-trifunctional fluorosilyl group may be in any position in the polymer molecule, and if it is at the end of the main chain or side chain, —SiR ′ ₂ F, —SiR′F ₂ , —SiR′FZ -SiR'F-, -SiF ₂ -or ≡SiF (wherein R 'is independently any hydrocarbon group, Z is a hydroxyl group or a hydrolysis other than fluorine, if incorporated in the main chain of the polymer) Sex group).

Specific examples of fluorosilyl groups that are not trifunctional are shown below. As silicon groups having no hydrolyzable group other than fluorine (—SiR ′ ₂ F, —SiR′F ₂ ), fluorodimethylsilyl group, fluorodiethylsilyl group, fluorodipropylsilyl group, fluorodiphenylsilyl group, fluorodiethyl Examples include benzylsilyl group, difluoromethylsilyl group, difluoroethylsilyl group, difluorophenylsilyl group, difluorobenzylsilyl group and the like. As a silicon group (-SiR'FZ) having both fluorine and other hydrolyzable groups,
Examples thereof include a fluoromethoxymethylsilyl group, a fluoroethoxymethylsilyl group, a fluoromethoxyethylsilyl group, and a fluoromethoxyphenylsilyl group. Examples of silicon groups (—SiR′F—, —SiF ₂ —, ≡SiF) incorporated into the main chain of the polymer include —Si (CH ₃ ) F—, —Si (C ₆ H ₅ ) F -, - SiF ₂ -, and the like ≡SiF.

  The main chain skeleton of a polymer having a fluorosilyl group that is not trifunctional and the method for synthesizing the main chain skeleton can be explained in the same manner as for the polymer (A). The main chain skeleton is preferably a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylic acid ester polymer because of excellent compatibility with the polymer (A). The polymer having a non-trifunctional fluorosilyl group may be linear or branched, and the number average molecular weight is preferably about 3,000 to 100,000 in terms of polystyrene in GPC.

  In the present invention, the resin component having a reactive silicon group may contain only the polymer (A), or together with the polymer (A), other than fluorine as the hydrolyzable group shown below. The polymer (C) which is a polymer containing a reactive silicon group having only the hydrolyzable group may be contained. In the curable composition of the present invention, the polymer (A) comprises a polymer (A) as a resin component having a silicon-containing group (reactive silicon group) that can be crosslinked by forming a siloxane bond in the curable composition. ) Only when it contains not only the function of improving the curability of the curable composition, but also when the curable composition contains both the polymer (A) and the polymer (C), It also has a function of improving the curability of the entire curable composition.

Here, the polymer (C) is the following general formula (2):
-SiR ¹ _3-b Y _b (2)
(Wherein R ¹ is each independently a hydrocarbon group having 1 to 20 carbon atoms, or R ² ₃ SiO— (R ² is each independently a hydrocarbon group having 1 to 20 carbon atoms)). And Y is independently a hydroxyl group or a hydrolyzable group other than fluorine, and b is any one of 1, 2, and 3). It is a polymer having on average one or more silicon groups per molecule.

  It does not specifically limit as a hydrolysable group of a polymer (C), What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  When two or more hydrolyzable groups or hydroxyl groups are present in one reactive silicon group, they may be the same or different.

Specific examples of R ¹ include, for example, alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, R ² is methyl group, Examples include a triorganosiloxy group represented by R ² ₃ SiO— which is a phenyl group and the like. Of these, a methyl group is particularly preferred.

More specific examples of the reactive silicon group of the polymer (C) include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethyl. Silyl group, methoxydimethylsilyl group,
An ethoxydimethylsilyl group is mentioned. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group is particularly preferable because of high activity and good curability. In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability. The triethoxysilyl group is particularly preferred because the alcohol produced in the hydrolysis reaction of the reactive silicon group is ethanol, which has higher safety.

  In addition, a polymer having a reactive silicon group having three hydrolyzable groups on one silicon atom can provide high curability, and can also have good restorability, durability, and creep resistance. There is a tendency to give a product, which is preferable.

  Introduction of the reactive silicon group of the polymer (C) may be performed by a known method. That is, for example, the following method can be mentioned.

  (D) A polymer having a functional group such as a hydroxyl group in a molecule is reacted with an organic compound having an active group and an unsaturated group which are reactive with the functional group, and a polymer containing an unsaturated group is obtained. obtain. Alternatively, an unsaturated group-containing polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Subsequently, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

  (E) A compound having an unsaturated group obtained in the same manner as in the method (d) is reacted with a compound having a mercapto group and a reactive silicon group.

  (F) The polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

  Among the above methods, among the methods (d) and (f), the method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is a relatively short reaction. It is preferable because a high conversion rate can be obtained over time. Furthermore, the polymer having a reactive silicon group obtained by the method (d) becomes a curable composition having a lower viscosity and better workability than the polymer obtained by the method (f), Since the polymer obtained by the method (e) has a strong odor based on mercaptosilane, the method (d) is particularly preferred.

  Specific examples of the hydrosilane compound used in the method (d) include, for example, chlorosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, and dichlorophenylsilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxy Alkoxysilanes such as methylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane; acyloxysilanes such as diacetoxymethylsilane, diacetoxyphenylsilane; bis (dimethylketoximate) methylsilane And ketoximate silanes such as bis (cyclohexyl ketoximate) methylsilane, but are not limited thereto. Of these, chlorosilanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable since the hydrolyzability of the resulting curable composition is gentle and easy to handle. Among the alkoxysilanes, dimethoxymethylsilane is particularly preferable because it is easily available and the curable composition containing the resulting polymer has high curability, storage stability, elongation characteristics, and tensile strength.

Among the hydrosilane compounds, the following general formula (9):
H-SiY ₃ (9)
(In the formula, Y is the same as in the general formula (2).) The curable composition containing the polymer (C) obtained by the addition reaction of the hydrosilane compound is excellent in the curable composition. This is preferable. Of the hydrosilane compounds represented by the general formula (9), trialkoxysilanes such as trimethoxysilane, triethoxysilane, and triisopropoxysilane are more preferable.

Among the trialkoxysilanes, a trialkoxysilane having an alkoxy group having 1 carbon atom (methoxy group) such as trimethoxysilane may proceed rapidly, and the disproportionation reaction proceeds. Then, a highly reactive compound such as dimethoxysilane is produced. From the viewpoint of safety in handling, the general formula (10):
H-Si (OR ⁹ ) ₃ (10)
It is preferable to use a trialkoxysilane having an alkoxy group having 2 or more carbon atoms represented by the formula (3 R ⁹ are each independently an organic group having 2 to 20 carbon atoms). From the viewpoint of availability and safety in handling, triethoxysilane is most preferable.

  As a synthesis method of (e), for example, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of a polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. However, it is not particularly limited. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyldiethoxymethyl. Examples thereof include, but are not limited to, silane and mercaptomethyltriethoxysilane.

  As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (f), for example, a method disclosed in JP-A-3-47825, etc. Although it is mentioned, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyldimethoxymethylsilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyldiethoxymethyl. Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  As described above, a disproportionation reaction may proceed in a silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane. As the disproportionation reaction proceeds, a rather dangerous compound such as dimethoxysilane is formed. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when using a group in which three hydrolyzable groups such as a trimethoxysilyl group are bonded to one silicon atom as the silicon-containing group, use the synthesis method (e) or (f). Is preferred.

In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, the average number of reactive silicon groups contained in the polymer (C) is preferably at least one per polymer molecule. 1.1 to 5 may be present. When the number of reactive silicon groups contained in one molecule is less than 1 on average, it may be difficult to develop good rubber elastic behavior. In addition, when the number of reactive silicon groups contained in one molecule is more than 5 on average, the elongation of the rubber-like cured product may be small. The reactive silicon group may be present at the end of the main chain or side chain of the polymer molecular chain, or may be incorporated in the main chain, but is particularly present at the end of the main chain. When it does, since the effective network length of the organic polymer component contained in the finally formed cured product becomes long, it becomes easy to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus. When two or more reactive silicon groups are present in one molecule, each reactive silicon group may be the same or different.

  The main chain skeleton of the polymer (C) and the synthesis method thereof can be explained in the same manner as the polymer (A). Moreover, about the manufacturing method of a polymer (C), manufacture of "the polymer (X) containing the reactive silicon group which has hydrolyzable groups other than a fluorine" in description of the above-mentioned polymer (A). This is the same as the method described as the method.

  The polymer (C) may be linear or branched, and its number average molecular weight is preferably about 3,000 to 100,000, more preferably 3,000 to 50,000, in terms of polystyrene in GPC. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 3,000, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  In the curable composition of the present invention, when the polymer (A) and the polymer (C) are contained, the content of the polymer (C) is a weight ratio of the polymer (C) / the polymer (A). The upper limit is preferably 99/1 or less, more preferably 95/5 or less, and still more preferably 90/10 or less. On the other hand, the lower limit of polymer (C) / polymer (A) is preferably greater than 0/100 by weight. If the ratio of the polymer (C) is smaller than this, a sufficient curing rate acceleration effect may not be obtained.

  When the curable composition of the present invention contains both the polymer (A) and the polymer (C), the main chain skeletons of the polymer (A) and the polymer (C) are the same or different. In addition, each of them may be a single main chain skeleton or a mixture of two or more main chain skeletons, but they are preferably compatible with each other.

  A part of the hydrolyzable group (F, Z, Y) of the polymer (A) and the polymer (C) was transesterified by mixing the polymer (C) with the polymer (A). A reactant may be formed. The polymer (A) and polymer (C) of the present invention are meant to include such reactants derived from the polymer (A) and the polymer (C).

  In the present invention, calcium carbonate (B) is used as an essential component. Calcium carbonate (B) is used as a filler capable of adjusting various work properties such as adjusting the workability of the curable composition, adjusting the strength of the cured product, improving adhesion, and imparting chemical resistance. .

Calcium carbonate is large and is divided into heavy calcium carbonate obtained by pulverizing and classifying natural raw materials and precipitated calcium carbonate that is chemically produced (fine calcium carbonate). Precipitated calcium carbonate generally has a larger primary particle size. It is small and preferable. Most of the precipitated calcium carbonate is surface-treated with organic substances such as fatty acids. Among precipitated calcium carbonates, those having a particle size of 0.1 μm or less are called colloidal calcium carbonate. Most of the fine calcium carbonate is surface-treated with organic substances such as fatty acids and fatty acid esters. Examples of the surface treatment agent include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and other esters and salts thereof; polyoxyethylene Sulfate ester type anionic surfactants such as alkyl ether sulfates and long chain alcohol sulfates, and sodium salts and potassium salts thereof; alkylbenzene sulfonic acids, alkyl naphthalene sulfonic acids, paraffin sulfonic acids, α-olefin sulfones Examples thereof include acids, alkylsulfosuccinic acids and the like, and sulfonic acid type anionic surfactants such as sodium salts and potassium salts thereof. The use of fine calcium carbonate as a filler is advantageous for the purpose of obtaining a cured product having high strength, and it is more preferable to use colloidal calcium carbonate.

  The amount of calcium carbonate (B) used is 100 parts by weight of the polymer (A), and when the polymer (C) is contained, the total amount of the polymer (A) and the polymer (C) is 100 parts by weight, 5 to 500 parts by weight, preferably 10 to 200 parts by weight. If the amount of calcium carbonate (B) is less than this, it is difficult to obtain sufficient cured product strength, which may be disadvantageous in terms of the composition cost of the composition. When there is more calcium carbonate (B) than this, a viscosity is too high and workability | operativity may fall or the sclerosis | hardenability of a curable composition may fall.

  In the present invention, fillers other than calcium carbonate (B) can also be used. Fillers other than calcium carbonate (B) include magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc Hana, Shirasu balloon, glass microballoon, organic microballoon of phenol resin or vinylidene chloride resin, filler such as resin powder such as PVC powder, PMMA powder; fibrous filler such as asbestos, glass fiber and filament; fume silica, sedimentation Reinforcing silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, and reinforcing fillers such as carbon black. When it contains 100 parts by weight of the polymer (A) and the polymer (C), it is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the polymer (C). 10 to 200 parts by weight is more preferable.

  As described in JP-A No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, sealed in a bag made of an airtight material, and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved particularly when a one-component composition is used.

  Further, when obtaining a highly transparent composition, as described in JP-A-11-302527, polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as fillers. Further, as described in JP-A-2000-38560, a composition having high transparency can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler. Obtainable. The surface of silicon dioxide fine powder is generally a silanol group (-SiOH), and (-SiO-hydrophobic group) is generated by reacting organosilanide or alcohol with this silanol group. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane and the like are reactively bonded to the silanol group present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.

  When it is desired to obtain a cured product with higher strength, together with calcium carbonate (B), fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid and carbon black, calcined clay, It is preferable to use a filler selected from clay and activated zinc white. If you want to obtain a cured product with a large elongation at break, select mainly from calcium carbonate such as heavy calcium carbonate, magnesium carbonate, titanium oxide, talc, ferric oxide, zinc oxide, and Shirasu balloon. Favorable results can be obtained if a filler is used. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. When using calcium carbonate, it is desirable to use calcium carbonate having a large particle size such as colloidal calcium carbonate and heavy calcium carbonate in combination.

  In order to improve the workability (such as sharpness) of the curable composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon as a filler. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  The curable composition of the present invention is a sizing board, particularly a ceramic sizing board, such as a joint of an outer wall of a house, an adhesive for an outer wall tile, and an outer wall tile, because the cured product obtained has good chemical resistance. However, it is desirable that the design of the outer wall and the design of the sealing material are harmonized with each other. In particular, a high-quality outer wall is used as the outer wall by mixing sputter coating, colored aggregates, and the like. When a flaky or granular material having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm is blended with the curable composition of the present invention, the resulting cured product has such a high-class feeling. In harmony with a certain outer wall and excellent chemical resistance, the appearance of the cured product is an excellent curable composition that lasts for a long time. At this time, when a granular material is used, the surface has a rough feeling of sanding or sandstone, and when a scaly material is used, an uneven surface due to the scaly shape is obtained.

  As described in JP-A-9-53063, preferable diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows.

  In the case of a granular substance, the diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and a substance having an appropriate size is used according to the material and pattern of the outer wall. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.

  The scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

  As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall. A preferable finishing method and the like are described in JP-A-9-53063.

  Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. As described in JP-A-10-251618, preferred diameters, blending amounts, materials, and the like of the balloon are as follows.

The balloon is a spherical filler with a hollow inside. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. In addition, an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface treated with a silane coupling agent.

  The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface with a sandy or sandstone texture. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired. The volume concentration with a particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

  When using a balloon, the anti-slip agent as described in JP-A-2000-154368 and the surface of a cured product as described in JP-A-2001-164237 are matted to give an uneven state. An amine compound for obtaining a state, particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.

  Specific examples of balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073, JP-A-9-53063, JP-A-10-10. -251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.

  Moreover, the thermally expandable fine particle hollow body described in JP-A No. 2004-51701 or JP-A No. 2004-66749 can be used as a balloon. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the bonding part using this curable composition, the gas pressure in the shell of the thermally expandable fine hollow body increases, and the polymer outer shell material softens, so the volume expands dramatically and adhesion It plays the role of peeling the interface. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

  Also when the curable composition of this invention contains sealing material hardened | cured material particle | grains, the hardened | cured material obtained can form an unevenness | corrugation in the surface and can improve the designability. The preferable diameter, blending amount, material and the like of the cured sealant particles are as follows as described in JP-A-2001-115142. The diameter is preferably 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. 5-100 weight% is preferable in a curable composition, Furthermore, 20-50 weight% is more preferable. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber, and the like. The material is not limited as long as it is used for a sealing material, but a modified silicone-based sealing material is preferable.

  The curable composition of the present invention may further contain a curing catalyst. The curing catalyst has a role of promoting a reaction in which the reactive silicon groups of the polymer (A) and the polymer (C) are hydrolyzed and condensed to be crosslinked.

  As the curing catalyst, various known ones such as an organic tin compound, a carboxylic acid metal salt, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid can be used. However, as described above, since the organotin compound has a concern about the influence on the environment, it is preferable to use a non-organotin compound as the curing catalyst. In particular, the amine compound (D) is preferably used as a curing catalyst because the curable composition of the present invention can be rapidly cured while being a non-organotin catalyst.

  The amine compound (D) that can be used as the curing catalyst of the present invention includes nitrogen-containing cyclic compounds such as pyridine. Specific examples of the amine compound include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine. Aliphatic primary amines such as cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, Aliphatic secondary amines such as dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; Aliphatic tertiary amines such as amylamine, trihexylamine and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Aromatic amines such as aniline, laurylaniline, stearylaniline and triphenylamine Pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylamino) pyridine, 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2 -Piperidinemethanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) , 6- (Dibutylamino) -1,8- Azabicyclo [5,4,0] undecene-7 (DBA-DBU), 1,5-diazabicyclo [4,3,0] nonene-5 (DBN), 1,4-diazabicyclo [2,2,2] octane ( DABCO), heterocyclic compounds such as aziridines, and other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1, 3-propanediamine, N, N′-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropyl Amine, 3-dimethylaminop Amines such as propylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- (1-piperazinyl) ethylamine, xylylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol Guanidines such as guanidine and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide, and the like, but are not limited thereto.

  Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU, DBN; guanidines such as guanidine, 1-phenylguanidine, diphenylguanidine; butylbiguanide, 1- Biguanides such as o-tolyl biguanide and 1-phenyl biguanide are preferred because of their high activity. In addition, aryl-substituted biguanides such as 1-o-tolylbiguanide and 1-phenylbiguanide are preferable because they exhibit high adhesiveness.

Moreover, although an amine compound shows basicity, the amine compound in which the pKa value of the conjugate acid shows a value of 11 or more is preferable because of high catalytic activity. In particular, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN, and the like are preferable because the conjugate acid has a pKa value of 12 or more and exhibits high catalytic activity.

  From the viewpoint of ease of handling and safety, it is preferable to use an alkylamine having 5 to 20 carbon atoms, more preferably an alkylamine having 6 to 15 carbon atoms. When the number of carbon atoms is smaller than this range, it tends to volatilize and the odor tends to increase. When the number of carbon atoms is larger than this range, it tends to become solid at room temperature and may be difficult to be compatible with the polymer (A) and / or the polymer (C). From the viewpoint of availability, octylamine, 2-ethylhexylamine, laurylamine, and 3-diethylaminopropylamine are more preferable.

  In the present invention, an amino group-containing silane coupling agent (hereinafter referred to as aminosilane) can also be used as the amine compound (D) of the curing catalyst. Aminosilane is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and a substituted or unsubstituted amino group. Examples of the substituent of the substituted amino group include an alkyl group, an aralkyl group, and an aryl group. Examples of the hydrolyzable silicon group include those in which Y is a hydrolyzable group among the groups represented by the general formula (2). Specific examples of the hydrolyzable group include the groups already exemplified, and a methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups bonded to one silicon atom is preferably 2 or more, particularly 3 or more. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- ( 2-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -γ-aminopropyltriisopropoxysilane, N- (2- (2-aminoethyl) aminoethyl) -γ Aminopropyltrimethoxysilane, N- (6-aminohexyl) -γ-aminop Pyrtrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltri Examples include methoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.

The aminosilane of the curing catalyst is preferably an aminosilane having an amino group (—NH ₂ ) from the viewpoint of curability, and from the viewpoint of availability, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyl. Methyldimethoxysilane and N- (2-aminoethyl) -γ-aminopropyltrimethoxysilane are preferred, and γ-aminopropyltrimethoxysilane is particularly preferred.

  A ketimine compound that generates the above amine compound by hydrolysis can also be used as the curing catalyst of the present invention.

Specific examples of the curing catalyst other than the amine compound (D) include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, etc. Carboxylic acid; derivatives of the above carboxylic acids (carboxylic anhydride, ester, amide, nitrile, acyl chloride); tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, carboxyl Titanium oxide, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, carboxylic acid Metal salts of carboxylic acids such as Ngan, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonato), bis (acetylacetonato) diisopropoxytitanium , Titanium compounds such as diisopropoxy titanium bis (ethyl acetocetate); dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin phthalate, dibutyl tin dioctanoate, dibutyl tin bis (2-ethylhexanoate), dibutyl tin bis (methyl maleate) Acid), dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyltin bis (benzine) Maleate), dibutyltin diacetate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis Organotin compounds such as (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester; aluminum tris (acetylacetonate) ), Aluminum compounds such as aluminum tris (ethyl acetoacetate), diisopropoxy aluminum ethyl acetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate) Various metal alkoxides such as tetrabutoxyhafnium; organic acidic phosphates; organic sulfonic acids such as trifluoromethanesulfonic acid; and inorganic acids such as hydrochloric acid, phosphoric acid, and boronic acid. However, for the reasons described above, the amount of the organic tin compound used is 100 parts by weight of the polymer (A), and when the polymer (C) is contained, the total amount of the polymer (A) and the polymer (C). 5 parts by weight or less is preferable, 100 parts by weight or less is more preferable, 0.5 parts by weight or less is more preferable, 0.05 parts by weight or less is further preferable, and it is particularly preferable that no content is contained.

  In the curable composition of the present invention, two or more curing catalysts may be used in combination.

  The amount of the curing catalyst used is 100 parts by weight of the polymer (A). When the polymer (C) is contained, the amount of the curing catalyst is 0. The amount is preferably 001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight. If the blending amount of the curing catalyst is below this range, it may be difficult to obtain a sufficient curing rate, and the catalytic activity may decrease after storage. On the other hand, if the blending amount of the curing catalyst exceeds this range, the pot life may become too short and workability may be deteriorated.

  The curable composition of the present invention contains a polymer (A) and calcium carbonate (B) as essential components, and a polymer (C) and an amine compound (D) as optional components, but these components are not necessarily cured. It does not need to exist as a simple substance in the composition, and may exist as a reaction product generated by mixing with other components. Moreover, in this invention, these components mean containing the compound derived from these components.

The curable composition of the present invention may contain a silane coupling agent as an adhesiveness imparting agent. The silane coupling agent here is a compound having a hydrolyzable silicon group and other functional groups in the molecule, such as various adherends, that is, glass, aluminum, stainless steel, zinc, copper, mortar, etc. When used for an inorganic base material or an organic base material such as polyvinyl chloride, polyacryl, polyester, polyethylene, polypropylene, polycarbonate, etc., it shows a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Such a silane coupling agent can function as a physical property modifier, an inorganic filler dispersibility improving agent, and the like.

  Examples of the hydrolyzable silicon group of the silane coupling agent include those in which Y is a hydrolyzable group among the groups represented by the general formula (2). Specific examples of the hydrolyzable group include the groups already exemplified, and a methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups bonded to one silicon atom is preferably 2 or more, particularly 3 or more.

  Examples of functional groups other than hydrolyzable silicon groups include substituted or unsubstituted amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. Of these, a substituted or unsubstituted amino group, epoxy group, isocyanate group, isocyanurate and the like are preferable because of their high effect of improving adhesiveness, and an amino group is particularly preferable.

  A silane coupling agent having both a hydrolyzable silicon group and an amino group is generally called aminosilane. In the present invention, aminosilane also exhibits a function as a curing catalyst as described above. Accordingly, in the present specification, specific examples of aminosilane are described in the description of the curing catalyst. In addition, when it is desired to further exhibit the function as an adhesiveness imparting agent, aminosilane may be used in an amount more than the necessary amount as a curing catalyst.

  Specific examples of silane coupling agents other than aminosilane include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanate methyl) Isocyanate silanes such as trimethoxysilane and (isocyanatemethyl) dimethoxymethylsilane; Ketimine silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrieth Mercaptosilanes such as xysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy silanes such as silane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxy Carboxysilanes such as methyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxy Examples thereof include vinyl type unsaturated group-containing silanes such as silane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate; The reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, the reaction product of aminosilane and (meth) acryloyloxy group-containing silane, and the like can also be used. Condensates obtained by partially condensing the silanes can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives of these, can also be used as silane coupling agents. .

  The said silane coupling agent may be used only by 1 type, and may mix and use 2 or more types.

  The amount of the silane coupling agent used in the present invention is 100 parts by weight of the polymer (A). When the polymer (C) is contained, the total amount of the polymer (A) and the polymer (C) is 100. 0.01-20 weight part is preferable with respect to a weight part, 0.1-10 weight part is more preferable, and 1-7 weight part is especially preferable. If the blending amount is below this range, sufficient adhesion may not be obtained. If the blending amount exceeds this range, a practical curing rate may not be obtained, or conversely, the curing rate may be too high to make adjustment difficult.

  In addition to the silane coupling agent described above, the adhesiveness-imparting agent is not particularly limited. For example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like can be used. The adhesiveness-imparting agent may be used alone or in combination of two or more.

  Moreover, a silicate can be used for the curable composition of this invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product obtained from the curable composition of the present invention. It also has the effect of further improving curability. Furthermore, it also has the effect of improving adhesion and water-resistant adhesion and adhesion durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When the silicate is used, the amount used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C ) To 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight in total.

  Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

  A partially hydrolyzed condensate of tetraalkoxysilane is more preferable because the effect of improving the restorability, durability, and creep resistance of the cured product obtained from the curable composition is greater than that of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis using a conventional method. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

Moreover, a plasticizer can be added to the curable composition of the present invention. By adding the plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the curable composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can also be used as a plasticizer. When a high-molecular plasticizer is used, the initial physical properties can be maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer not containing a polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) can be improved when an alkyd paint is applied to a cured product obtained by curing the curable composition. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

  Among these polymer plasticizers, when the polymer (A) and the curable composition contain the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) Those that are compatible are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferable, and acrylic polymers such as polyacrylic acid alkyl esters are more preferable. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000 to 1,000. 5,000. Most preferably, it is 1,000-3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, cause contamination due to dust adhesion, etc., and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a terminal group analysis method in the case of a polyether polymer, and by the GPC method in the case of other polymers. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. When it has a reactive silicon group, it is preferably 1 or less on average per molecule, and more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight is the polymer (A), and the curable composition is the polymer (A) and the polymer ( When it contains C), it is preferable that it is lower than a polymer (A) and a polymer (C). Otherwise, the plasticizing effect may not be obtained.

  A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

  The amount of the plasticizer used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) 5-150 weight part is preferable with respect to 100 weight part of total amounts, 10-120 weight part is more preferable, and 20-100 weight part is further more preferable. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

  A tackifier can be added to the curable composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenol resins, modified phenol resins (for example, cashew oil-modified phenol resin, tall oil-modified phenol resin, etc.), terpene phenol resins, xylene-phenol resins, cyclohexane. Pentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9) Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin and the like. These may be used alone or in combination of two or more. Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifying resins may be used alone or in combination of two or more.

  The tackifying resin is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the total amount of the polymer (A) and the polymer (C). Preferably it is 5-1,000 weight part with respect to 100 weight part, More preferably, 10-100 weight part is used.

  A solvent or a diluent can be added to the curable composition of the present invention. The solvent and diluent are not particularly limited, and aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property adjuster, For example, Alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; Dimethyldiisopropenoxysilane, Methyltriisopropenoxy Examples thereof include alkoxysilanes having an unsaturated group such as alkylisopropenoxysilane such as silane, vinyltrimethoxysilane, vinyldimethylmethoxysilane; silicone varnishes; polysiloxanes. By using the physical property adjusting agent, it is possible to increase the hardness when the curable composition of the present invention is cured, and conversely to decrease the hardness and to give an elongation at break. The said physical property modifier may be used independently and may be used together 2 or more types.

In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mentioned. In addition, derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, which generate a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029 Mention may be made, for example, of a compound of a polyhydric alcohol having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol or sorbitol, which generates a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis.

The can also include compounds that produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol a derivative of oxypropylene polymer as described in JP-A-7-258534 by hydrolyzing. Furthermore, a polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis as described in JP-A-6-279893 can also be used.

  The physical property modifier is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the total amount of the polymer (A) and the polymer (C). Preferably it is 0.1-20 weight part with respect to 100 weight part, More preferably, 0.5-10 weight part can be used.

  A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as needed to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the total amount of the polymer (A) and the polymer (C). Preferably 0.1-20 weight part can be used with respect to 100 weight part.

  Moreover, in the curable composition of this invention, you may add the compound containing an epoxy group in 1 molecule. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, An epoxy butyl stearate etc. are mentioned. Of these, E-PS is particularly preferred. The epoxy compound is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the total amount of the polymer (A) and the polymer (C) is 100 weights. It is preferable to use in the range of 0.5 to 50 parts by weight with respect to parts.

  You may add a photocurable substance to the curable composition of this invention. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. A photocurable substance is a substance that undergoes a chemical change in its molecular structure in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl glycol Examples thereof include monomers such as di (meth) acrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, bifunctional Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325 and polyfunctional Aronix M-400 (all Aronix is a product of Toa Gosei Chemical Co., Ltd.) In particular, compounds containing an acrylic functional group are preferable, and compounds containing three or more same functional groups on average in one molecule are preferable.

  Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in publishing, publishing society of printing society publication, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added if necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect. The amount of the photocurable substance used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) 0.1 to 20 parts by weight is preferable with respect to the total amount of 100 parts by weight, and more preferably 0.5 to 10 parts by weight. If the amount of the photo-curing substance used is less than 0.1 parts by weight, the effect of improving the weather resistance may not be obtained. If it exceeds 20 parts by weight, the cured product tends to be too hard and cracks tend to occur.

An oxygen curable substance can be added to the curable composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers modified with drying oils, epoxy resins , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. In addition, the effect may be enhanced when a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.
The amount of the oxygen curable substance used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) Is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight based on the total amount of 100 parts by weight. When the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and when it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

  An antioxidant (anti-aging agent) can be added to the curable composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (All are manufactured by ADEKA Corporation); shown in SANOL LS-770, SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114, SANOL LS-744 (all above are manufactured by Sankyo Corporation). Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) The range of 0.1 to 10 parts by weight is preferable with respect to the total amount of 100 parts by weight, more preferably 0.2 to 5 parts by weight.

  A light stabilizer can be added to the curable composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The amount of the light stabilizer used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) The range of 0.1 to 10 parts by weight is preferable with respect to the total amount of 100 parts by weight, more preferably 0.2 to 5 parts by weight. Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When the photocurable material is used in combination with the curable composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary as a hindered amine light stabilizer as described in JP-A-5-70531. Use of an amine-containing hindered amine light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, LA-62, LA-67, LA-63 ( As mentioned above, light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Corporation) can be exemplified.

An ultraviolet absorber can be added to the curable composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred. The amount of the ultraviolet absorber used is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the polymer (A) and the polymer (C) The range of 0.1 to 10 parts by weight is preferable with respect to 100 parts by weight of the total amount, and more preferably 0.2 to 5 parts by weight. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  An epoxy resin can be added to the curable composition of the present invention. The curable composition to which an epoxy resin is added is particularly preferable as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies Resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferable examples include bisphenol A type epoxy resins or novolac type epoxy resins. When these epoxy resins, the polymer (A), or the curable composition contains the polymer (A) and the polymer (C), the total amount of the polymer (A) and the polymer (C) Is preferably ((A) or (A) + (C)) / epoxy resin = 100/1 to 1/100 by weight. When the ratio of ((A) or (A) + (C)) / epoxy resin is less than 1/100, it is difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and ((A) Or when the ratio of (A) + (C)) / epoxy resin exceeds 100/1, the strength of the organic polymer cured product tends to be insufficient. The preferred use ratio varies depending on the use of the curable composition, etc., and thus cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, When the polymer (A) or the curable composition contains the polymer (A) and the polymer (C) with respect to 100 parts by weight of the epoxy resin, the polymer (A) and the polymer (C) The total amount is preferably 1 to 100 parts by weight, more preferably 5 to 100 parts by weight. On the other hand, when improving the intensity | strength of the hardened | cured material of a polymer (A) component, a polymer (A) 100 weight part or a curable composition contains a polymer (A) and a polymer (C). In this case, the epoxy resin is preferably used in an amount of 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the total amount of the polymer (A) and the polymer (C).

  When adding an epoxy resin, it is natural that the curable composition of the present invention can be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Phenol compounds; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Moreover, a hardening | curing agent may be used independently and may be used together 2 or more types.

  When the epoxy resin curing agent is used, the amount used is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Ketimine can be used as a curing agent for the epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such ketimines can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. Examples of amine compounds include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, and 2,3-diaminobutane. , Such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2- Polyamino amines such as aminoethyl) amine and tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropi Triethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, N-(beta-aminoethyl) aminosilane such-.gamma.-aminopropyl methyl dimethoxy silane; and it may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; Aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, malonic acid Β-dicarbonyl compounds such as dimethyl, diethyl malonate, methyl ethyl malonate, dibenzoylmethane ; And the like can be used.

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. These ketimines may be used alone or in combination of two or more, and can be used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin. The amount used is the kind of epoxy resin and ketimine Can be set as appropriate.

  To the curable composition of the present invention, a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added. The said flame retardant may be used independently and may be used together 2 or more types.

  The flame retardant is 100 parts by weight of the polymer (A), and when the curable composition contains the polymer (A) and the polymer (C), the total amount of the polymer (A) and the polymer (C) is 100%. The amount is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to parts.

Various additives other than the above may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the obtained cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

  The one-component curable composition of the present invention is prepared as a one-component type in which all the blended components are preliminarily blended and sealed and cured by moisture in the air after construction. Since all the blending components are blended in advance, it is preferable that the blending component containing moisture is used after being dehydrated and dried in advance, or dehydrated by decompression during blending and kneading. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercapto By adding an alkoxysilane compound such as propylmethyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane, the storage stability is further improved.

  The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 100 parts by weight of the polymer (A), and the curable composition contains the polymer (A) and the polymer (C). In a case, 0.1-20 weight part is preferable with respect to 100 weight part of total amounts of a polymer (A) and a polymer (C), and 0.5-10 weight part is more preferable.

  The method for preparing the one-component curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, a roll, a kneader, or the like at room temperature or under heating, or a suitable solvent is used. Ordinary methods such as using a small amount to dissolve and mixing the components may be employed.

  When exposed to the atmosphere, the one-component curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

  The one-component curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, and a paint Can be used for spraying materials. Since the hardened | cured material obtained by hardening | curing the curable composition of this invention is excellent in a softness | flexibility and adhesiveness, it is more preferable to use as a sealing material or an adhesive agent among these.

Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or with the help of a primer, it can also be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, Can also be used.

  Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.

(Synthesis Example 1)
Polymerization of propylene oxide using a polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 14,500 having a hydroxyl group at the end (manufactured by Tosoh as a liquid feeding system) HLC-8120GPC was used, TOS-GEL H type manufactured by Tosoh Corporation was used as a column, and a polypropylene oxide having a polystyrene equivalent molecular weight measured using THF as a solvent was obtained. Subsequently, a methanol solution of 1.2 times equivalent NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was Furthermore, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. As a result, a bifunctional polypropylene oxide (P-1) having a number average molecular weight of about 14,500 having an allyl group at the end was obtained.

For 100 parts by weight of the allyl-terminated polypropylene oxide (P-1), 2.8 parts by weight of triethoxysilane and 90 ° C. for 2 hours using 150 ppm of an isopropyl alcohol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. Reaction was performed to obtain a triethoxysilyl group-terminated polypropylene oxide (C-1). ^Further, (using JEOL JNM-LA400, measured in CDCl ₃ solvent) 1 H-NMR was measured silyl group introduction rate in the following manner by. Peak of the terminal proton of the allyl group with respect to the integrated value (M) of the peak of the methyl group in the main chain of the allyl-terminated polypropylene oxide (P-1) before the hydrosilylation reaction (-CH ₃ : around 1.2 ppm) ( _{-O-CH 2 -CH = CH 2} : integral value of 5.1ppm near) the relative value of (T) and (C = T / M), in the main chain of the triethoxysilyl group-terminated polypropylene oxide (C-1) The peak of the methylene proton bonded to the silicon atom of the terminal silyl group (—O—CH ₂ —CH ₂ —CH ₂ —) relative to the integrated value (M ′) of the peak of the methyl group (—CH ₃ : around 1.2 ppm) of From the relative value (C ′ = T ′ / M ′) of the integral value (T ′) of Si (OC ₂ H ₅ ) ₃ : around 0.6 ppm, the silyl group introduction rate (C ′ / C) is about 77%. Met. Since the polymer (C-1) is bifunctional, the terminal triethoxysilyl group can be calculated as an average of about 1.5 per molecule.

(Synthesis Example 2)
To 100 parts by weight of the polymer (C-1) obtained in Synthesis Example 1, 20 parts by weight of methanol was added using 12 ppm of 1 mol / L diethyl ether hydrochloric acid solution as a catalyst and reacted at 70 ° C. for 5 hours, followed by vacuum devolatilization. As a result, trimethoxysilyl group-terminated polypropylene oxide (C-2) was obtained. Converting triethoxysilyl group to trimethoxysilyl groups ^by 1 H-NMR spectrum, a peak of methyl protons of the ethoxy group: and the disappearance of _(-O-CH 2 -CH 3 1.2ppm vicinity).

(Synthesis Example 3)
After 100 parts by weight of the polymer (C-2) obtained in Synthesis Example 2 was azeotropically dehydrated with toluene, 2 parts by weight of methanol was added and BF ₃ diethyl ether at 50 ° C. with good stirring under a nitrogen stream. A mixture of 2.4 parts by weight of the complex and 1.2 parts by weight of dehydrated methanol was slowly added dropwise and mixed. Subsequently, the reaction temperature was raised to 120 ° C. and reacted for 30 minutes. The reaction product was collected and measured for ¹ H-NMR spectrum (measured in a CDCl ₃ solvent using AMX400 manufactured by BRUKER). As a result, silylmethylene (—CH ₂ ) of the polymer (C-1) as a raw material was measured. The peak (m, 0.63 ppm) corresponding to -Si) disappeared, and a broad peak appeared on the low magnetic field side (0.7 ppm-). Further, ¹⁹ FNMR (measured in CDCl ₃ solvent using hexafluorobenzene as an internal standard (−150 ppm) using AMX400 manufactured by BRUKER) showed a peak in the vicinity of −124 ppm. Compared to the peak of the low molecular model compound, this peak was assigned to the ¹⁹ F peak of the trifluorosilyl group. The reaction product was vacuum devolatilized at 120 ° C. for 2 hours to obtain polypropylene oxide (A-1) having a trifluorosilyl group.

(Synthesis Example 4)
After 100 parts by weight of the polymer (C-1) obtained in Synthesis Example 1 was azeotropically dehydrated with toluene, 2.4 parts by weight was added, and BF ₃ diethyl ether was added at 50 ° C. while stirring well under a nitrogen stream. A mixture of 2.5 parts by weight of the complex and 1.2 parts by weight of dehydrated methanol was slowly added dropwise and mixed. Subsequently, the reaction temperature was raised to 120 ° C. and reacted for 30 minutes. The reaction product was collected and measured for ¹ H-NMR spectrum (measured in a CDCl ₃ solvent using AMX400 manufactured by BRUKER). As a result, silylmethylene (—CH ₂ ) of the polymer (C-1) as a raw material was measured. The peak (m, 0.63 ppm) corresponding to -Si) disappeared, and a broad peak appeared on the low magnetic field side (0.8 ppm to). Further, ¹⁹ FNMR (measured in CDCl ₃ solvent using hexafluorobenzene as an internal standard (−150 ppm) using AMX400 manufactured by BRUKER) showed a peak in the vicinity of −124 ppm. Compared to the peak of the low molecular model compound, this peak was assigned to the ¹⁹ F peak of the trifluorosilyl group. The reaction product was vacuum devolatilized at 120 ° C. for 2 hours to obtain polypropylene oxide (A-2) having a trifluorosilyl group.

(Synthesis Example 5)
A dimethoxymethylsilyl group-terminated polypropylene oxide (C-3) was obtained in the same manner as in Synthesis Example 1, except that 1.8 parts by weight of dimethoxymethylsilane was used instead of triethoxysilane in Synthesis Example 1. The average number of terminal dimethoxymethylsilyl groups was calculated to be about 1.6 per molecule.

(Synthesis Example 6)
After 100 parts by weight of the dimethoxymethylsilyl group-terminated polypropylene oxide (C-3) obtained in Synthesis Example 5 was azeotropically dehydrated with toluene, 2 parts by weight of methanol was added while stirring well under a nitrogen stream, and 50 ° C. Then, a mixture of 1.6 parts by weight of BF ₃ diethyl ether complex and 0.77 parts by weight of dehydrated methanol was slowly added dropwise and mixed. Subsequently, the reaction temperature was raised to 90 ° C. and reacted for 30 minutes. When the reaction product was collected and measured for ¹ H-NMR spectrum, the peak (s, 0.1 ppm) corresponding to Si—CH ₃ of the dimethoxymethylsilyl group of the polymer (C-3) as a raw material disappeared. , A peak (t, 0.3 ppm) indicating Si—CH ₃ of a difluoromethylsilyl group appeared. This confirmed that the dimethoxymethylsilyl group in the polymer (C-3) was quantitatively converted to a difluoromethylsilyl group. Using a vacuum pump, vacuum devolatilization was performed at 120 ° C. for 2 hours to remove diethyl ether and BF ₃ -derived components to obtain difluoromethylsilyl group-terminated polypropylene oxide (P-2). The average number of difluoromethyl groups of the polymer (P-2) was about 1.6 per molecule.

(Synthesis Example 7)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of polyoxypropylene diol having a molecular weight of about 2,000 and polyoxypropylene triol having a molecular weight of about 3,000 as an initiator. A polypropylene oxide having a number average molecular weight of about 19,000 (polystyrene equivalent molecular weight measured using Tosoh's HLC-8120GPC as the liquid feeding system, TOS-GEL H type as the column, and THF as the solvent). It was. Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. As a result, a polypropylene oxide having a number average molecular weight of about 19,000 having an allyl group at the end was obtained.

After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain a purified allyl group-terminated polypropylene oxide (hereinafter, allyl polymer). 100 parts by weight of the obtained allyl polymer was reacted with 1.35 parts by weight of methyldimethoxysilane for 5 hours at 90 ° C. using 150 ppm of a 2-propanol solution of platinum vinylsiloxane complex having a platinum content of 3 wt% as a catalyst. Base terminal polypropylene oxide (C-4) was obtained. ^{As a} result of measurement by ¹ H-NMR (measured in CDCl ₃ solvent using JNM-LA400 manufactured by JEOL Ltd.), the number of terminal methyldimethoxysilyl groups was about 1.7 on average per molecule.

(Synthesis Example 8)
Polyoxypropylene diol having a molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 28,500 having a terminal hydroxyl group (manufactured by Tosoh as a liquid feeding system) HLC-8120GPC was used, TOS-GEL H type manufactured by Tosoh Corporation was used as a column, and a polypropylene oxide having a polystyrene equivalent molecular weight measured using THF as a solvent was obtained. Subsequently, it converted into the allyl terminal polypropylene oxide (P-3) by the same operation as the synthesis example 1. In the same manner as in Synthesis Example 1, 1.45 parts by weight of triethoxysilane was reacted with 100 parts by weight of the polymer (P-3) to obtain triethoxysilyl-terminated propylene oxide (C-5). Furthermore, by the same operation as in Synthesis Example 2, trimethoxysilyl-terminated propylene oxide (C-6) having a number average molecular weight of about 28,500 was obtained. The average number of trimethoxysilyl groups at the end of the polymer (C-6) was about 1.6 per molecule.

(Example 1, Comparative Examples 1-5)
Using a Dalton 5L planetary mixer, a one-component curable composition was prepared according to the formulation in Table 1. First, calcium carbonate (B) and a pigment were weighed and vacuum-dried at 120 ° C. for 2 hours. Next, the polymer (A) and the polymer (C), a plasticizer, a thixotropic agent, an ultraviolet absorber, and a light stabilizer were respectively added to a mixer and kneaded. The mixture was uniformly dispersed using three rolls, the mixture was again put into the mixer, and dried under reduced pressure at 120 ° C. for 2 hours. After the mixture was cooled, a silane compound and an amine compound (or organotin compound) were sequentially added and kneaded well. After devolatilization under reduced pressure for 10 minutes, the mixture was quickly enclosed in an aluminum cartridge to prepare a one-component curable composition.

  After preparing a one-pack type curable composition and curing for one week in a 23 ° C. thermostatic chamber, the composition was extruded from the cartridge and evaluated for curability. In a constant temperature and humidity room at 23 ° C., the time when the ointment can was filled with the curable composition and the surface was smoothed was set as the curing start time, and the surface of the cured product was lightly touched with the tip of the spatula every 5 minutes. The time at which the composition no longer adhered to was used as the skinning time, and the curing time was measured. The results are shown in Table 1.

  The one-component curable composition containing the polymer (A-1) having a trifluorosilyl group that is a trifunctional fluorosilyl group showed good curability. This is a curability equivalent to that of the curable composition using the organotin catalyst of Comparative Example 5. On the other hand, the one-component curable composition containing the polymer (A-3) having a bifunctional fluorosilyl group took time to cure.

(Examples 2 and 3, Comparative Examples 6 to 8)
Using a 5L biaxial planetary mixer manufactured by Inoue Seisakusho, a one-component curable composition was prepared in the same procedure as described above according to the formulation in Table 2.

  After preparing a one-pack type curable composition and curing for one week in a 23 ° C. thermostatic chamber, the composition was extruded from the cartridge and evaluated for curability. Skinning time was measured in the same operation as above in a constant temperature and humidity chamber at 23 ° C. and 35%. The results are shown in Table 2.

  The one-component curable composition containing the polymer (A-2) having a trifluorosilyl group showed good curability. In addition, the one-component curable composition of Comparative Example 7 to which 3-methacryloxypropyltrimethoxysilane was added as a low molecular compound having a trifluorosilyl group required more time for curing than the Examples. From this, it can be said that higher curability can be obtained by using a polymer having a trifluorosilyl group at the terminal than by using a low molecular weight compound containing a trifluorosilyl group.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Claims (9)

General formula (1):
-SiF _a Z _3-a (1)
(In the formula, F is a fluorine atom, Z is a hydroxyl group or a hydrolyzable group other than fluorine. A is either 1, 2, or 3. When two Z are present, the two Z are the same. 1-type curable composition characterized by containing the polymer (A) containing the silicon group represented by this, and calcium carbonate (B).   The one-component curable composition according to claim 1, wherein the number average molecular weight of the polymer (A) is 3,000 to 100,000.   The one-component curable composition according to claim 1 or 2, wherein a in the general formula (1) is 3.   The main chain skeleton of the polymer (A) is at least one selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth) acrylic acid ester polymers. The one-component curable composition according to any one of claims 1 to 3.   The one-component curable composition according to any one of claims 1 to 4, wherein the calcium carbonate (B) is precipitated calcium carbonate. Furthermore, the following general formula (2):
-SiR ¹ _3-b Y _b (2)
(Wherein R ¹ is each independently a hydrocarbon group having 1 to 20 carbon atoms, or R ² ₃ SiO— (R ² is each independently a hydrocarbon group having 1 to 20 carbon atoms)). And Y is independently a hydroxyl group or a hydrolyzable group other than fluorine, and b is any one of 1, 2, and 3). The one-component curable composition according to any one of claims 1 to 5, comprising a polymer (C) having an average of at least one silicon group per molecule.   Furthermore, the 1-component curable composition in any one of Claims 1-6 containing an amine compound (D) as a curing catalyst.   A sealing material comprising the one-component curable composition according to claim 1.   An adhesive comprising the one-component curable composition according to any one of claims 1 to 7.