JP2006052353A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain good curability of a curable composition containing an organic polymer having a silicon-containing group curable by forming a siloxane bond by using a non-organotin curing catalyst. <P>SOLUTION: The curable composition comprises (A) the organic polymer having the silicon-containing group curable by forming the siloxane bond, (B) a carboxylic acid and/or a metal carboxylate and (C) a germanium compound having a reactive group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic polymer having a silicon-containing group (hereinafter also referred to as “reactive silicon group”) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. It relates to the curable composition containing this.

  The organic polymer containing at least one reactive silicon group in the molecule is crosslinked at the room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have the property of being obtained.

Among these polymers having reactive silicon groups, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or an isobutylene polymer have already been industrially produced, such as sealing materials, adhesives, paints, etc. It is widely used for applications. (Patent Document 1), (Patent Document 2)
These curable compositions containing an organic polymer having a reactive silicon group are cured using a silanol condensation catalyst and usually have a carbon-tin bond, such as dibutyltin bis (acetylacetonate). Organotin catalysts are widely used. However, in recent years, toxicity of organotin compounds has been pointed out, and development of non-organotin catalysts has been demanded.

As such non-organotin catalysts, various carboxylic acid metal salts and catalyst systems using carboxylic acids and amine compounds in combination have been proposed. (Patent Literature 3), (Patent Literature 4), (Patent Literature 5), (Patent Literature 6)
JP-A-52-73998 JP-A 63-6041 JP 55-9669 A Japanese Patent No. 3062626 JP-A-6-322251 JP-A-5-117519

  However, when a catalyst using a carboxylic acid metal salt or a carboxylic acid described in the above patent is used, there is a problem in that the curability tends to be inferior compared with the case where an organic tin catalyst is used.

  The present invention provides a curable composition containing, as a component, an organic polymer having a reactive silicon group, and a curable composition having practical curability using a non-tin curing catalyst. Objective.

  As a result of intensive investigations to solve such problems, the present inventors have used a carboxylic acid and / or a carboxylic acid metal salt as a curing catalyst, and added a reactive group-containing germanium compound to the catalyst. It was found that the activity was improved and a curable composition having practical curability was obtained using a non-tin curing catalyst, and the present invention was completed.

That is, the present invention
Contains (A) an organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, (B) a carboxylic acid and / or carboxylic acid metal salt, and (C) a germanium compound having a reactive group. The present invention relates to a curable composition.

  As the preferred main chain skeleton of the organic polymer of component (A), at least one selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth) acrylic acid ester polymers. More preferred polyoxyalkylene polymers are polyoxypropylene polymers.

  In addition, since the activation effect by the component (C) is great, the component (B) is preferably a carboxylic acid, and among them, a more preferable carboxylic acid is a carboxylic acid having a quaternary carbon atom adjacent to the carbonyl group. .

The germanium compound of component (C) has the general formula (1):
Ge (OR ¹ ) ₄ (1)
In the formula, each R ¹ is preferably an alkoxygerman represented by a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

  Furthermore, it is preferable to contain an amine compound as component (D).

  As a preferable embodiment of the curable composition according to the present invention, a sealing material or an adhesive using any one of the curable compositions described above can be mentioned.

  The curable composition of the present invention is excellent in curability while using a non-organotin catalyst.

  The present invention will be described in detail below.

  The main chain skeleton of the organic polymer having a reactive silicon group used in 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 Copolymer 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 Polyester polymer obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; Vinyl polymers obtained by radical polymerization of monomers such as (meth) acrylic acid ester monomers, vinyl acetate, acrylonitrile, styrene; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfide heavy polymers Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, condensation of ε-aminoundecanoic acid Nylon 11, ε-aminolaurolactam by polymerization Polyamide polymer such as nylon 12 by ring-opening polymerization and copolymer nylon having two or more components among the above nylons; for example, polycarbonate polymer produced by condensation polymerization from bisphenol A and carbonyl chloride, diallyl phthalate Examples thereof include system polymers.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature. The cured product is more preferable because it is excellent in cold resistance.

  Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their excellent adhesiveness, and polyoxyalkylene polymers are most preferred.

  The glass transition temperature of the organic polymer as component (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. . If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease. The glass transition temperature is a value obtained by DSC measurement.

  Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability when made into one-component compositions. Most preferred.

The reactive silicon group contained in the organic polymer of the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by a reaction accelerated by a curing catalyst. As the reactive silicon group, the general formula (2):
-(SiR ³ _2-b X _b O) _m -SiR ² _3-a X _a (2)
Wherein R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ Represents any of the triorganosiloxy groups represented by SiO—, and when two or more R ² or R ³ are present, they may be the same or different, where R ′ is a carbon atom; The hydrocarbon groups of 1 to 20 and three R's may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, May be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m (SiR ³ _2-b X _b O ) For b in the group, they may be the same or different. .m is an integer of 0 to 19. However, a group represented by shall satisfy a + Σb ≧ 1) and the like.

  It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy 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.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

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

In particular, the general formula (3):
-SiR ² _3-c X _c (3)
A reactive silicon group represented by the formula (wherein R ² and X are the same as described above, c is an integer of 1 to 3) is preferable because it is easily available.

Specific examples of R ² and R ³ in the general formulas (2) and (3) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, benzyl And an aralkyl group such as a group, and a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group, or the like. Of these, a methyl group is particularly preferred.

  More specific examples of the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. 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. Further, triethoxysilyl group and diethoxymethylsilyl group are particularly preferable because the alcohol produced by the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

  The introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method can be mentioned.

  (B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Alternatively, an unsaturated group-containing organic 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.

  (B) An organic polymer containing an unsaturated group obtained in the same manner as in the method (a) is reacted with a compound having a mercapto group and a reactive silicon group.

  (C) An organic 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, the method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is high in a relatively short reaction time. It is preferable because a conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c). The organic polymer obtained by the method (b) has a strong odor based on mercaptosilane, and therefore the method (a) is particularly preferred.

  Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. Alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane Examples thereof include, but are not limited to, ketoximate silanes. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the hydrolyzability of the resulting curable composition is gentle and easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the resulting organic polymer has high curability, storage stability, elongation characteristics, and tensile strength.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical source. Although the method of introduce | transducing etc. is mentioned, it does not specifically limit. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxy. Silane, mercaptomethyltriethoxysilane and the like can be mentioned, but are not limited thereto.

  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 (c), for example, the method described in JP-A-3-47825 can be mentioned. However, 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-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Although silane etc. are mention | raise | lifted, it is not limited to these.

  A silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane may cause a disproportionation reaction. 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. For this reason, when a group in which three hydrolyzable groups such as trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the synthesis method (b) or (c) can be used. preferable.

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

  In order to obtain a rubber-like cured product exhibiting high strength, high elongation and low elastic modulus, the average number of reactive silicon groups contained in the organic polymer is at least 1, preferably 1, It is good to have 1-5 pieces. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to develop good rubber elastic behavior. The reactive silicon group may be present at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the reactive silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

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

等が挙げられる。ポリオキシアルキレン系重合体の主鎖骨格は、１種類だけの繰り返し単位からなってもよいし、２種類以上の繰り返し単位からなってもよい。特にシーラント等に使用される場合には、プロピレンオキシド重合体を主成分とする重合体から成るものが非晶質であることや比較的低粘度である点から好ましい。

Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used in a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferred because it is amorphous or 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 as 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 Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. Polymerization method using double metal cyanide complex catalyst as shown in US Pat. No. 3,427,335, polymerization method using polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited.

  A method for producing a polyoxyalkylene polymer having a reactive silicon group is disclosed in Japanese Patent Publication Nos. 45-36319, 46-12154, JP-A-50-156599, 54-6096, 55-13767, JP-A-55-13468, 57-164123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution Killen polymer can be exemplified, but not particularly limited thereto.

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

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton is (1) ethylene, propylene, 1-butene, isobutylene, etc. Such as olefin-based compounds having 1 to 6 carbon atoms as the main monomer, or (2) homopolymerizing diene-based compounds such as butadiene and isoprene, or copolymerizing with the above-mentioned olefin-based compounds. After that, it can be obtained by a method such as hydrogenation. However, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are easy to introduce functional groups at the ends, easily control the molecular weight, The number can be increased, and an isobutylene polymer is particularly preferable.

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

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units or may be a copolymer with other monomers. What contains more than weight% is preferable, What contains 80 weight% or more is more preferable, What contains 90 to 99 weight% is especially preferable.

  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, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). It is known that a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.

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

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

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. 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, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trimethyl (meth) acrylate Fluoromethylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoro (meth) acrylate Methyl, (meth) acrylic acid (Trifluoromethyl) methyl, (meth) acrylic acid trifluoromethyl perfluoroethyl methyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl. In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohex Maleimide monomers such as lumaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used singly or a plurality thereof may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. 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. For general architectural use and the like, a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. 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 converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. 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 it is not limited, examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (by weight ratio of 40-50 / 20- 30/30 to 20). In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably 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.

  The method for synthesizing the (meth) acrylic acid ester polymer is not particularly limited, and may be performed by a 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 a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. 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, and has a specific functional group because it 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 Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  Examples of the method for producing a (meth) acrylic acid ester-based polymer having a reactive silicon group include chain transfer in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. A production method using a free radical polymerization method using an agent is disclosed. 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.

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

  These organic polymers having a reactive silicon group may be used alone or in combination of two or more. 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. An organic polymer obtained by blending two or more selected from the above can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto. A preferred specific example has a reactive silicon group and a molecular chain substantially having the following general formula (5):
^{_{-CH 2 -C (R 5) (}} COOR 6) - (5)
(Wherein R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkyl group having 1 to 8 carbon atoms) and a (meth) acrylate ester having an alkyl group having 1 to 8 carbon atoms A monomer unit and the following general formula (6):
—CH ₂ —C (R ⁵ ) (COOR ⁷ ) — (6)
(Wherein, R ⁵ is the same as above, and R ⁷ represents an alkyl group having 10 or more carbon atoms) represented by a (meth) acrylic acid ester 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 ^{6 in the} general formula (5) 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 ⁶ may alone, or may be a mixture of two or more.

R ^{7 in the} general formula (6) 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 10-30, preferably 10-20. And an alkyl group. The alkyl group of R ⁷ is similar to the case of R ^6, alone may or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units represented by the formulas (5) and (6). It means that the total of the monomer units of the formula (5) and the formula (6) present therein exceeds 50% by weight. The total of the monomer units of formula (5) and formula (6) is preferably 70% by weight or more.

  Further, the abundance ratio of the monomer unit of the formula (5) and the monomer unit of the formula (6) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by weight.

  Examples of monomer units other than those represented by formula (5) and formula (6) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, Monomers containing amide groups such as N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene Monomer units derived from alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

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

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

  On the other hand, the main chain skeleton of the organic polymer 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 general formula (7):
—NR ⁸ —C (═O) — (7)
(R ⁸ 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. Examples thereof include a urethane group. In the present invention, groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (7).

An example of an industrially easy production method of an organic polymer having an amide segment and a reactive silicon group is as follows. An organic polymer having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to produce a polyurethane-based main polymer. After forming a polymer having an isocyanate group at the chain end, or at the same time, all or a part of the isocyanate group may be represented by the general formula (8)
_{^{W-R 9 -SiR 2 3-}} c X c (8)
(In the formula, R ² , X and c are the same as described above. R ⁹ is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (unsubstituted or mono-substituted). Can be mentioned. Examples of known production methods for organic polymers related 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. No. 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) (Japanese Patent No. 5364955), Japanese Patent Laid-Open No. 10-53637 (US Pat. No. 5,757,751), Japanese Patent Laid-Open No. 11-100197, Japanese Patent Laid-Open No. 2000-169544, Japanese Patent Laid-Open No. 2000-169415, Japanese Patent Laid-Open No. 2002-212415, and Japanese Patent No. 3313360. , US Pat. No. 4,067,844, US Pat. No. 37 No. 1445, JP 2001-323040, and the like.

Further, the organic polymer having an active hydrogen-containing group at the terminal is represented by the general formula (9)
O = C = N—R ⁹ —SiR ² _3-c X _c (9)
(Wherein, R ² , R ⁹ , X, and c are the same as above), and those produced by reacting with a reactive silicon group-containing isocyanate compound. Examples of known production methods of organic polymers related to this production method include JP-A Nos. 11-279249 (US Pat. No. 5,990,257), JP-A No. 2000-119365 (US Pat. No. 6,046,270), and JP-A No. 58-. No. 29818 (US Pat. No. 4,345,053), JP-A-3-47825 (US Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002-155138, JP-A-2002-249538, WO03 / 018658, WO03 / 059981 Etc.

  Examples of the organic 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 compounds, polyamine compounds and the like. Among these, polyether polyol, polyacryl polyol, and polyolefin polyol are preferable because the obtained organic polymer has a relatively low glass transition temperature and the resulting cured product has excellent cold resistance. In particular, polyether polyols are particularly preferred because the resulting organic polymer has a low viscosity and good workability and good deep part curability. Polyacryl polyols and saturated hydrocarbon polymers are more preferred because the resulting cured organic polymer has 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 alkylene oxide produced by using a conventional alkali metal catalyst, an initiator such as a polyhydroxy compound having at least two hydroxyl groups in the presence of a double metal cyanide complex or cesium, and an alkylene oxide. An oxyalkylene polymer produced by reacting with oxyalkylene.

  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 polyacryl 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 General formula (8), when it illustrates concretely, (gamma) -aminopropyl trimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyl trimethoxysilane, (gamma)-( Amino such as N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. 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 products of various α, β-unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds, The Michael addition reaction product of can also be used as the silicon compound of general formula (8).

  The reactive silicon group-containing isocyanate compound of the general formula (9) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triexylsilylpropyl isocyanate, and γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiexylsilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate and the like. 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 (8) 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 (9).

  When there are many amide segments in the main chain skeleton of the organic polymer as the component (A) of the present invention, the viscosity of the organic polymer increases, and the composition may have poor workability. On the other hand, the amide segment in the main chain skeleton of the component (A) tends to improve the curability of the composition of the present invention. Therefore, when an organic polymer having an amide segment in the main chain skeleton is used as the component (A), the composition combined with the component (B) has a faster curability while using a non-organotin catalyst. preferable. When the main chain skeleton of the component (A) contains an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 7, and particularly preferably 2 to 5. When the number is less than 1, the curability may not be sufficient. When the number is more than 10, the organic polymer may have a high viscosity, resulting in a poor workability composition.

  In the present invention, carboxylic acid (b1) and / or carboxylic acid metal salt (b2) is used as component (B). These components (B) function as a so-called silanol condensation catalyst capable of forming a siloxane bond from a hydroxyl group or a hydrolyzable group bonded to a silicon atom contained in the organic polymer as the component (A).

  Carboxylic acid (b1) and carboxylic acid metal salt (b2) may be used alone or in combination. Any of them is preferable as a non-organotin catalyst because it has a small environmental load.

  The carboxylic acid (b1) is not limited to carboxylic acid, but also includes carboxylic acid derivatives that generate carboxylic acid by hydrolysis of carboxylic acid anhydrides, esters, amides, nitriles, acyl chlorides, and the like. The carboxylic acid (b1) is particularly preferably a carboxylic acid because of its high catalytic activity.

  Specific examples of the carboxylic acid (b1) include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl Linear saturated fatty acids such as acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, and laccellic acid; undecylenic acid, lindelic acid, tuzu Acid, fizeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid , Erucic acid, brassic acid, ceracoray Monoene unsaturated fatty acids such as acid, ximenoic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linoleic acid, 10,12-octadecadienoic acid , Hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,8,11, 14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, succinic acid, nisic acid, Polyene unsaturated fatty acids such as docosahexaenoic acid; 2-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, Branched fatty acids such as valeric acid, tuberculostearic acid, pivalic acid, neodecanoic acid, 2-phenylbutyric acid; triples such as propiolic acid, taliphosphoric acid, stearolic acid, crepenic acid, xymenic acid, 7-hexadesinic acid Fatty acids having a bond; alicyclic carboxylic acids such as naphthenic acid, malvalic acid, sterlic acid, hydnocarbic acid, sorghumulinic acid, gorulinic acid; acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid , 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambretoleic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9 , 10-jihi Oxygenated fatty acids such as loxyoctadecanoic acid, ricinoleic acid, camlorenic acid, ricanoic acid, ferronic acid and cerebronic acid; halogen substituted products of monocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid and chlorobenzoic acid . Examples of the aliphatic dicarboxylic acid include adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, oxydiacetic acid and other saturated dicarboxylic acids; maleic acid, Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as aconitic acid, citric acid, and isocitric acid. Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl And aromatic polycarboxylic acids such as acetic acid and pyromellitic acid. In addition, amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, histidine and the like can be mentioned.

  Carboxylic acid (b1) is 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, naphthenic acid, etc. because it is particularly easy to obtain and inexpensive and has good compatibility with component (A). Is preferred.

  When the melting point of carboxylic acid is high (crystallinity is high), the resulting curable composition tends to be difficult to handle (poor workability). Accordingly, the melting point of the carboxylic acid (b1) is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.

  Also, when the carbon number of the carboxylic acid is large (molecular weight is large), it becomes a solid or highly viscous liquid and is difficult to handle (poor workability). On the contrary, when the carbon number of the carboxylic acid (b1) is small (molecular weight is small), it is likely to volatilize by heating, so that the catalytic ability may be lowered. In particular, when the composition is thinly stretched (thin layer), volatilization due to heating is large, and the catalytic ability may be greatly reduced. Accordingly, the carboxylic acid (b1) preferably has 2 to 20 carbon atoms including carbon of the carbonyl group, more preferably 6 to 17, and particularly preferably 8 to 12.

  From the viewpoint of easy handling (workability and viscosity) of the carboxylic acid (b1), a dicarboxylic acid or a monocarboxylic acid is preferable, and a monocarboxylic acid is more preferable.

  Further, the carboxylic acid (b1) is a carboxylic acid (such as 2-ethylhexanoic acid) in which the carbon atom adjacent to the carbonyl group is a tertiary carbon or a carboxylic acid (neodecanoic acid, pivalic acid, etc.) that is a quaternary carbon. A carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is particularly preferable because of its high curing rate. Moreover, the carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon tends to be excellent in adhesiveness as compared with other carboxylic acids.

  As the carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon, the general formula (10):

（式中、Ｒ¹⁰、Ｒ¹¹およびＲ¹²はそれぞれ独立した置換あるいは非置換の１価炭化水素基であり、カルボキシル基を含んでいてもよい。）で表される鎖状脂肪酸、または一般式（１１）：

(Wherein R ¹⁰ , R ¹¹ and R ¹² are each independently a substituted or unsubstituted monovalent hydrocarbon group, which may contain a carboxyl group), or a general formula (11):

（式中、Ｒ¹³は置換あるいは非置換の１価炭化水素基、Ｒ¹⁴は置換あるいは非置換の２価炭化水素基であり、それぞれカルボキシル基を含んでいてもよい。）および一般式（１２）：

(Wherein R ¹³ is a substituted or unsubstituted monovalent hydrocarbon group, R ¹⁴ is a substituted or unsubstituted divalent hydrocarbon group, each of which may contain a carboxyl group) and a general formula (12 ):

（式中、Ｒ¹⁵は置換あるいは非置換の３価炭化水素基であり、カルボキシル基を含んでいてもよい。）で表される構造を含有する環状脂肪酸が挙げられる。具体的に例示すると、ピバル酸、２，２−ジメチル酪酸、２−エチル−２−メチル酪酸、２，２−ジエチル酪酸、２，２−ジメチル吉草酸、２−エチル−２−メチル吉草酸、２，２−ジエチル吉草酸、２，２−ジメチルヘキサン酸、２，２−ジエチルヘキサン酸、２，２−ジメチルオクタン酸、２−エチル−２，５−ジメチルヘキサン酸、ネオデカン酸、バーサチック酸、２，２−ジメチル−３−ヒドロキシプロピオン酸などの鎖状モノカルボン酸、ジメチルマロン酸、エチルメチルマロン酸、ジエチルマロン酸、２，２−ジメチルこはく酸、２，２−ジエチルこはく酸、２，２−ジメチルグルタル酸などの鎖状ジカルボン酸、３−メチルイソクエン酸、４，４−ジメチルアコニット酸などの鎖状トリカルボン酸、１−メチルシクロペンタンカルボン酸、１，２，２−トリメチル−１，３−シクロペンタンジカルボン酸、１−メチルシクロヘキサンカルボン酸、２−メチルビシクロ［２．２．１］−５−ヘプテン−２−カルボン酸、２−メチル−７−オキサビシクロ［２．２．１］−５−ヘプテン−２−カルボン酸、１−アダマンタンカルボン酸、ビシクロ［２．２．１］ヘプタン−１−カルボン酸、ビシクロ［２．２．２］オクタン−１−カルボン酸などの環状カルボン酸などが挙げられる。このような構造を含有する化合物は天然物に多く存在するが、もちろんこれらも使用できる。

(Wherein, R ¹⁵ is a substituted or unsubstituted trivalent hydrocarbon group, which may contain a carboxyl group), and cyclic fatty acids having a structure represented by: Specific examples include pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, Chain monocarboxylic acids such as 2,2-dimethyl-3-hydroxypropionic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2, Chain dicarboxylic acids such as 2-dimethylglutaric acid, chain tricarboxylic acids such as 3-methylisocitric acid and 4,4-dimethylaconitic acid, 1-methylcyclopentane Rubonic acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo [2.2.1] -5-heptene-2-carboxylic acid, 2- Methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2.2. 2] Cyclic carboxylic acids such as octane-1-carboxylic acid. Many compounds containing such structures exist in natural products, but of course they can also be used.

  Among these, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, and 2-ethyl-2,5-dimethylhexanoic acid are particularly preferable from the viewpoint of easy handling and availability.

  On the other hand, as carboxylate metal salt (b2), tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, carboxylic acid Vanadium, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate are preferred because of their high catalytic activity, and furthermore, tin carboxylate, lead carboxylate, bismuth carboxylate, titanium carboxylate, carboxylic acid Iron and zirconium carboxylate are more preferred, tin carboxylate is particularly preferred, and divalent tin carboxylate is most preferred.

  Examples of the carboxylic acid having an acid group of the carboxylic acid metal salt (b2) include various carboxylic acids exemplified for the carboxylic acid (b1).

  Moreover, when the carboxylic acid metal salt (b2) is used, a curable composition having good resilience, durability, and creep resistance can be obtained. In addition, it can be expected to be effective for water-resistant adhesion, adhesion durability under high temperature and high humidity conditions, residual tack, dust adhesion, contamination, surface weather resistance, heat resistance, concrete adhesion, and the like.

  (B) As usage-amount of a component, 0.01-20 weight part is preferable with respect to 100 weight part of (A) component, Furthermore, 0.1-15 weight part is more preferable, Especially 1-10 weight part Is preferred. When the blending amount of the component (B) is below this range, a practical curing rate may not be obtained, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (B) exceeds this range, the pot life tends to be too short, resulting in poor workability and poor storage stability.

  In the present invention, a germanium compound having a reactive group is used as the component (C). The carboxylic acid and / or carboxylic acid metal salt as component (B) is used as the silanol condensation catalyst of the present invention, but these components (B) are more curable than organic tin compounds such as dibutyltin bisacetylacetonate. In some cases, it was inferior. Therefore, an effect of improving curability can be obtained by combining the germanium compound of component (C) with component (B).

  Specific examples of the component (C) germanium compound include tetraalkoxygermane such as tetramethoxygermane, tetraethoxygermane, tetraisopropoxygermane, tetrabutoxygermane; siloxygermane such as tetrakistrimethylsiloxygermane; methyltriethoxygermane, Organic alkoxygermane such as ethyltriethoxygermane, diethyldiethoxygermane, triethylmethoxygermane; Halogenated germane such as tetrabromogermane, tetrachlorogermane, tetrafluorogermane, tetraiodogermane, dibutyldichlorogermane; and dimethylaminotrimethylgermane , Dibutyldiacetoxygermane, diphenyldimethylgermane, hydroxygermatran, dibutylgermane, etc. It is.

As can be seen from the above exemplary compounds, the compound (C) has reactivity, and as the reactive group, an alkoxy group, a siloxy group, a halogen, a substituted or unsubstituted amino group, a carboxyl group, a phenyl group, A hydrogen atom, a hydroxyl group, etc. are mentioned. Among these, tetraalkoxygermane represented by the following formula (1) is preferable from the viewpoint of high curability improving effect, ease of handling, and availability, and tetraethoxygermane can be more preferably used.
Ge (OR ¹ ) ₄ (1)
(Wherein R ¹ is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms)
When the carboxylic acid (b1) is used, the effect of improving the curability by the component (C) is obtained more remarkably.

  (C) As usage-amount of (A) component, 0.01-20 weight part is preferable with respect to 100 weight part of (A) component, Furthermore, 0.1-10 weight part is more preferable, Especially 0.5-5 weight Part is preferred. When the blending amount of component (C) is below this range, a sufficient effect of improving curability cannot be expected. On the other hand, even if the blending amount of the component (C) exceeds this range, a linear improvement effect cannot be obtained and the blending cost becomes high.

  In addition, by adding the component (C), effects such as improvement in adhesion, improvement in workability, improvement in strength, improvement in durability, and improvement in creep resistance can be expected.

  On the other hand, the amine compound which is (D) component can be added as a promoter. By adding the component (D), the curability tends to be further improved.

  Specific examples of the amine compound of component (D) include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, Aliphatic primary amines such as cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, Aliphatic secondary amines such as dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, etc. Aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Aromatics such as laurylaniline, stearylaniline and triphenylamine And other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, diethylenetriamine, triethylenetetramine, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3 -Dimethylaminopropylamine, 3-diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, , 6-Tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), 1,5- Examples thereof include, but are not limited to, diazabicyclo (4,3,0) nonene-5 (DBN).

  As these (D) components, the cocatalyst ability varies greatly depending on the structure of the (D) component itself and the compatibility with the (A) component. Therefore, a suitable compound should be selected according to the type of the (A) component to be used. Is preferred. For example, when a polyoxyalkylene polymer is used as the component (A), primary amines such as octylamine and laurylamine are preferable from the viewpoint of high cocatalyst ability, and hydrocarbons having at least one heteroatom. An amine compound having a group is preferred. Examples of heteroatoms include N, O, S and the like, but are not limited thereto. Examples of such amine compounds include those exemplified for the above-mentioned other amines. Among these, an amine compound having a hydrocarbon group having a hetero atom on the 2nd to 4th carbon atoms is more preferable. Examples of such amine compounds include ethylenediamine, ethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, 3-methoxypropylamine, 3-lauryloxypropylamine, N-methyl-1,3-propane. Examples include diamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3- (1-piperazinyl) propylamine, and 3-morpholinopropylamine. Of these, 3-diethylaminopropylamine and 3-morpholinopropylamine are more preferable because of their high promoter ability. 3-Diethylaminopropylamine is particularly preferred because it tends to give a curable composition with good adhesion, workability and storage stability. When an isobutylene polymer is used as the component (A), relatively long-chain aliphatic secondary amines such as dioctylamine and distearylamine and aliphatic secondary amines such as dicyclohexylamine are used as promoters. It is preferable because of its high performance.

  The compounding amount of the amine compound as the component (D) is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the organic polymer of the component (A). . If the compounding amount of the amine compound is less than 0.01 parts by weight, a sufficient curing rate may not be obtained, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 20 parts by weight, the pot life tends to be too short, and the workability tends to deteriorate. Conversely, the curing rate may be slow.

  To the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and (isocyanatemethyl) trimethoxysilane. , Isocyanate group-containing silanes such as (isocyanatomethyl) dimethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ -Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane Γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2 -(2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureido Propyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxy Silane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine Amino group-containing silanes such as: N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine and other ketimine type silanes; γ-mercaptopropyltrimethoxysilane, γ-mercapto Mercapto group-containing silanes such as propyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltri Epoxy group-containing silanes such as ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane , Vinyl-type unsaturated group-containing silanes such as vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing γ-chloropropyltrimethoxysilane Orchids; it can be exemplified tris isocyanurate silanes such as (trimethoxysilyl) isocyanurate. Moreover, the condensate which condensed the said silane partially 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 silane coupling agent used for this invention is normally used in 0.1-20 weight part with respect to 100 weight part of organic polymers (A) which have a reactive silicon group. In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  The effects of the silane coupling agent added to the curable composition of the present invention include various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used for organic base materials such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving the adhesion to various adherends is particularly remarkable. Although it does not specifically limit as a specific example other than a silane coupling agent, For example, an epoxy resin, a phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate etc. are mentioned. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesiveness-imparting agents, the adhesion to the adherend can be improved.

  In the present invention, the carboxylic acid and / or carboxylic acid metal salt of the component (B) is used as the curing catalyst, but other curing catalysts can be used in combination to the extent that the effects of the present invention are not reduced. Specific examples include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin Dioctate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), Dibutyltin bis (tridecylmaleate), dibutyltin bis (benzylmaleate), dibutyltin diacetate, dioctyltin bis (ethylmaleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, di Tiltin bis (nonylphenoxide), dibutyltin oxide, dibutenyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, dibutyltin oxide Tetravalent organotin compounds such as reaction products of phthalates with phthalates; organoaluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium tetrakis ( Zirconium compounds such as acetylacetonate). By using these curing catalysts in combination, the catalytic activity is increased, and an effect of improving deep part curability, thin layer curability, adhesiveness and the like can be expected. However, the organotin compound has a tendency to reduce the restorability, durability, and creep resistance of the cured product of the resulting curable composition depending on the amount of addition, and may increase toxicity.

  A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenol resin and vinylidene chloride Examples include fillers such as resin organic microballoons, PVC powder, PMMA powder, and the like; fibrous fillers such as asbestos, glass fibers, and filaments. When the filler is used, the amount used is 1 to 250 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the polymer of component (A).

  When you want to obtain a hardened material with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and if used in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. Favorable results are obtained. Also, when you want to obtain a cured product with low strength and large elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the organic polymer (A) having a reactive silicon group, preferable results are obtained. 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 calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

  Addition of an organic balloon or an inorganic balloon is preferable in order to improve the workability of the composition (such as sharpness) and to make the surface of the cured product matt. 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 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 adhesive for an outer wall tile, because the cured product has good chemical resistance. However, it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, a high-quality outer wall is used as the outer wall by mixing sputter coating, colored aggregates, and the like. When a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, is blended in the composition of the present invention, the cured product is in harmony with such a high-quality outer wall. However, since the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular substance is used, the surface becomes sandy or sandstone-like rough, and when a scaly substance is used, the surface is uneven.

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

  A diameter is 0.1 mm or more, Preferably it is about 0.1-5.0 mm, The thing of a suitable magnitude | size is used according to the material, pattern, etc. of an 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 scale-like 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 into 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 is 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. The preferable diameter, blending amount, material, etc. of the balloon are as follows as described in JP-A-10-251618.

  The balloon is a spherical filler with a hollow inside. Examples of the material of the balloon 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 balloons 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, only the viscosity of the composition is increased, and a rough feeling may not be exhibited. The blending amount of the balloon can be easily determined depending on the degree of roughness of the target 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 No. 2000-154368 and the surface of a cured product as described in JP-A No. 2001-164237 are matted to give an uneven state. An amine compound for obtaining a state can be added, particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher.

  Specific examples of the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.

  Even when the composition of the present invention contains particles of cured sealant, the cured product can form irregularities on the surface and improve the design. 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 about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

  Moreover, a silicate can be used for the composition of this invention. This silicate acts as a crosslinking agent and has a function of improving the resilience, durability and creep resistance of the organic polymer which is the component (A) of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When silicate is used, the amount used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer of component (A).

  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.

  The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance of the present invention are greater than those 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. Moreover, the commercially available thing can be used for the partial hydrolysis-condensation product of an organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

  A plasticizer can be added to the 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 composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and 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; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also called paintability) when an alkyd paint is applied to the cured product can be improved. 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, etc., but are not limited thereto is not.

  Of these polymer plasticizers, those compatible with the polymer of component (A) are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, it is preferable because deep-part curability is improved and curing delay after storage does not occur, and polypropylene glycol is more preferable. 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 preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. 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 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer flows out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, 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 is 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 GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, it is measured by molecular weight distribution (Mw / Mn) 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, more preferably 0.8 or less on average per molecule. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight thereof must be lower than that of the polymer of component (A).

  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 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer of component (A). 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.

  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 modifier, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Examples include alkoxy silanes having an unsaturated group such as alkyl isopropenoxy silane such as silane, vinyl trimethoxy silane, vinyl dimethyl methoxy silane; silicone varnishes; polysiloxanes. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. 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 mention | raise | lifted. Further, compounds that are derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, that generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis, and trimethylol described in JP-A-11-241029 Examples thereof include 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.

Further, there may be mentioned also compounds which 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 used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group.

  A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging preventing 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. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group.

  In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. 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, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group.

A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a 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 Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toa Gosei Chemical Co., Ltd.)
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 Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as 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 photocurable material is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. When the amount is less than 1 part by weight, there is no effect of increasing the weather resistance, and when the amount is more than 20 parts by weight, the cured product tends to be too hard and tends to crack.

  An oxygen curable substance can be used in the 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 prevent 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 and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene 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 preferred. Moreover, 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 preferably 0.1 to 20 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, an oxygen curable substance is preferably used in combination with a photocurable substance.

  An antioxidant (anti-aging agent) can be used in the 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 from Asahi Denka Kogyo Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all from Sankyo Corporation) It is also possible to use hindered amine light stabilizers shown in 1. 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 preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. Parts by weight.

  A light stabilizer can be used in the 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 light stabilizer is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. Parts by weight. Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARKLA-57, LA-62, LA-67, LA-63 (all above) Asahi Denka Kogyo Co., Ltd.); light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Co., Ltd.).

  An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be increased. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. 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 composition of the present invention. A composition to which an epoxy resin is added is particularly preferred 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 preferred are bisphenol A type epoxy resins or novolac type epoxy resins. The use ratio of these epoxy resins and the organic polymer (A) having a reactive silicon group is in the range of (A) / epoxy resin = 100/1 to 1/100 in terms of weight ratio. When the ratio of (A) / epoxy resin is less than 1/100, the effect of improving the impact strength and toughness of the cured epoxy resin is difficult to obtain, and the ratio of (A) / epoxy resin exceeds 100/1. And the intensity | strength of organic type polymer cured material will become inadequate. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The component (A) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the intensity | strength of the hardened | cured material of (A) component, it is good to use 1-200 weight part of epoxy resins with respect to 100 weight part of (A) component, More preferably, 5-100 weight part is used. .

  When an epoxy resin is added, the composition of the present invention can naturally 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 ; Fe Lumpur acids; 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. Further, the curing agents may be used alone or in combination of two or more.

  When the epoxy resin curing agent is used, the amount used is in the range of 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 a ketimine 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. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyltri Tokishishiran, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane; and 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; acetone , Aliphatic ketones such as 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, dimethyl malonate , Β-dicarbonyl compounds such as 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 are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

  In the composition of the present invention, a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketone solvents, alcohol solvents such as methanol, ethanol, and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.

  However, when the amount of the solvent is large, toxicity to the human body may be increased, and volume shrinkage of the cured product may be observed. Therefore, the blending amount of the solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less, and substantially contains the solvent with respect to 100 parts by weight of the organic polymer of the component (A). Most preferably not.

  Various additives 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 cured product. Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include 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 curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 100 parts by weight of organic polymer (A) having a reactive silicon group, preferably A range of 0.5 to 10 parts by weight is preferred.

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

  When exposed to the atmosphere, the 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 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, a paint, and a spray material. Can be used for etc. 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, powder coating materials, casting materials, medical rubber materials, medical adhesives , Medical equipment sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot melt materials, potting agents for electrical and electronic equipment, films , Gaskets, various molding materials, and a variety of liquid sealants used in rustproof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), automotive parts, electrical parts, various machine parts, etc. It can be used for various purposes. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can 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, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)
Polyoxypropylene diol having a molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 25,500 (using a Tosoh HLC-8120GPC as a liquid feeding system, The column used TSK-GEL H type manufactured by Tosoh, and the solvent obtained was a polystyrene oxide (polystyrene equivalent molecular weight measured using THF). 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. 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 further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. Thus, a bifunctional polypropylene oxide having a number average molecular weight of about 25,500 having an allyl group at the end was obtained.

100 parts by weight of the allyl-terminated polypropylene oxide was reacted with 0.9 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex as a catalyst. A base terminal polyoxypropylene polymer (A-1) was obtained. ^{As a} result of measurement by ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL Ltd.), the average number of terminal methyldimethoxysilyl groups was about 1.3 per molecule.

(Synthesis Example 2)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of a polyoxypropylene diol having a molecular weight of about 2,000 and a polyoxypropylene triol having a molecular weight of about 3,000 as an initiator. Using the obtained hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 19,000, allyl-terminated polypropylene oxide was obtained in the same procedure as in Synthesis Example 1. 100 parts by weight of this allyl-terminated polypropylene oxide is reacted with 1.35 parts by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 1, and polyoxypropylene having an average of about 1.7 methyldimethoxysilyl groups at the ends. A system polymer (A-2) was obtained.

(Examples 1 and 2, Comparative Examples 1 to 5)
As the component (A), the reactive silicon group-containing polyoxyalkylene polymer (A-1) obtained in Synthesis Example 1 was used, and the filler, titanium oxide, plasticizer, and sauce were added according to the formulation shown in Table 1. An inhibitor, an ultraviolet absorber, a light stabilizer, and an antioxidant were weighed and kneaded well with a three-paint roll to obtain a main agent.

  Next, under a constant temperature and humidity condition of 23 ° C. and 50% RH, the silanol condensation catalyst, germanium compound, and amine compound shown in Table 1 were weighed with respect to the main agent, and well stirred and mixed for 3 minutes using a spatula. After mixing, it was filled into a mold having a thickness of about 5 mm, and the surface was made flat. This time was taken as the curing start time, and the surface was touched with a spatula every minute, and the time when the compound no longer adhered to the spatula was measured as the skinning time.

  The results are shown in Table 1.

カルボン酸（バーサチック１０）およびカルボン酸金属塩（ネオスタンＵ−５０）を触媒とした場合、テトラエトキシゲルマンを添加することで、硬化性が向上した。特にカルボン酸を使用した場合に硬化性の向上が大きい。一方、触媒として、有機錫化合物（ネオスタンＵ−２２０）を用いた場合には、テトラエトキシゲルマンを添加しても硬化性は向上しなかった。また、テトラエトキシゲルマンのみを使用した場合には、硬化しなかった。

When carboxylic acid (Versatic 10) and carboxylic acid metal salt (Neostan U-50) were used as catalysts, the curability was improved by adding tetraethoxygermane. In particular, when a carboxylic acid is used, the curability is greatly improved. On the other hand, when an organotin compound (Neostan U-220) was used as a catalyst, the curability did not improve even when tetraethoxygermane was added. Moreover, when only tetraethoxygermane was used, it did not harden.

(Examples 3 and 4, Comparative Example 6)
As the component (A), the reactive silicon group-containing polyoxyalkylene polymer (A-2) obtained in Synthesis Example 2 was used, and according to the formulation shown in Table 2, a filler, titanium oxide, plasticizer, sauce The inhibitor, ultraviolet absorber, and light stabilizer were weighed, and well kneaded with three paint rolls to form the main agent.

  Next, the dehydrating agent, the adhesion imparting agent, the carboxylic acid, the germanium compound, and the amine compound shown in Table 2 were weighed against the main agent, and the skinning time was measured in the same manner as described above.

  In addition, the compound was placed in close contact with various adherends (glass, anodized aluminum, steel plate, stainless steel plate), cured for 7 days under constant temperature and humidity conditions of 23 ° C. and 50% RH, and then a 90 ° hand. A peel test was performed. The destruction state of the cured product was observed, and the cohesive failure rate (CF rate) was measured.

  The results are shown in Table 2. In the table, a CF ratio of 100% is indicated by ◎, 50% or more and less than 100% is indicated by ○, 10% or more and less than 50% is indicated by Δ, and less than 10% is indicated by ×.

前述と同様に、テトラエトキシゲルマンを添加することで、添加しない場合に比べ、硬化性が向上した。また、各種被着体への接着性も向上した。

As described above, the addition of tetraethoxygerman improved the curability as compared with the case where it was not added. In addition, adhesion to various adherends was also improved.

(Example 5, Comparative Example 7)
As the component (A), a reactive silicon group-containing polyoxyalkylene polymer (A-2) is used, and according to the formulation shown in Table 3, a filler, titanium oxide, plasticizer, sagging inhibitor, ultraviolet absorber, As a light stabilizer, a dehydrating agent, an adhesion-imparting agent, a crosslinking agent, and a curing catalyst, the carboxylic acid (B), the germanium compound (C), and the amine compound (D) are weighed, and a one-component curable composition is prepared using a mixer. Prepared and enclosed in an aluminum cartridge.

After the cartridge was prepared, it was stored for 7 days at a constant temperature of 23 ° C., and then various evaluations were performed.
(Curing test)
Each curable composition was extruded from the cartridge, filled into a mold having a thickness of about 5 mm using a spatula, the surface was flattened, and the skinning time was measured under constant temperature and humidity conditions of 23 ° C. and 50% RH.
(Dumbell tensile test)
First, a curable composition is filled into a sheet-like mold having a thickness of 3 mm, and the surface is flattened, and the temperature is kept constant at 23 ° C. and 50% RH for 3 days, and then in a 50 ° C. dryer for 4 days. Curing was performed to create a sheet-like cured product. The cured product was punched into a 2 (1/3) type dumbbell-shaped test piece (JIS K 7113), using a Shimadzu autograph, modulus at 50% elongation, strength at break, and elongation at break (measurement environment: 23 ° C., (Tensile speed: 200 mm / min) was measured.
(Restoration rate measurement)
Moreover, the sheet-like hardened | cured material of thickness 3mm was created similarly to the above, and the hardened | cured material was pierce | punched to the No. 3 type | mold dumbbell-type test piece (JIS K 6251). A marked line having a width of 20 mm was drawn on the constricted portion of the test piece, and the test piece was stretched to 100% so that the gap between the marked lines became 40 mm, and fixed under constant temperature conditions at 60 ° C. After 24 hours, the fixation was released and the sample was allowed to stand in a 23 ° C. constant temperature room. After 6 days, the distance between the marked lines (xmm) was measured, and the restoration rate was measured from the following formula.

Restoration rate (%) = ((40−x) / 20) × 100
(Adhesion test)
The one-component curable composition was extruded to adhere to various adherends (glass, anodized aluminum, steel plate, PVC steel plate, hard PVC), and cured for 7 days under constant temperature and humidity conditions of 23 ° C. and 50% RH. Thereafter, a 90 degree hand peel test was conducted. The destruction state of the cured product was observed, and the cohesive failure rate (CF rate) was measured. In the table, a CF ratio of 100% is indicated by ◎, 50% or more and less than 100% is indicated by ○, 10% or more and less than 50% is indicated by Δ, and less than 10% is indicated by ×.

  Various test results are shown in Table 3.

前記と同様に、テトラエトキシゲルマンの添加による、硬化性向上効果が得られた。さらに、各種被着体への良好な接着性も得られた。

Similarly to the above, the effect of improving the curability by adding tetraethoxygerman was obtained. Furthermore, good adhesion to various adherends was also obtained.

Claims (9)

(A) an organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond as a component;
(B) carboxylic acid and / or carboxylic acid metal salt,
(C) A curable composition comprising a germanium compound having a reactive group.   The main chain skeleton of the organic polymer (A) is at least one heavy selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer. The curable composition according to claim 1 which is a coalescence.   The curable composition according to claim 2, wherein the polyoxyalkylene polymer is a polyoxypropylene polymer.   (B) A component is carboxylic acid, The curable composition in any one of Claims 1-3.   The curable composition according to claim 4, wherein the component (B) is a carboxylic acid having a quaternary carbon atom adjacent to the carbonyl group. Component (C) is represented by the general formula (1):
Ge (OR ¹ ) ₄ (1)
The curable composition according to any one of claims 1 to 5, which is an alkoxygermane represented by (wherein R ¹ is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms).   Furthermore, the curable composition in any one of Claims 1-6 containing an amine compound as (D) component.   The sealing material which uses the curable composition in any one of Claims 1-7.   The adhesive agent using the curable composition in any one of Claims 1-7.