JP2014080532A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition providing a cured material exhibiting physical properties such as low modulus and high elongation.SOLUTION: In the curable composition including: 100 pts.wt. of an organic polymer (A) having a silicon-containing group represented by general formula (1): -SiRX(Ris alkyl group or the like, and X is hydrolyzable group or the like, and a is 1 to 3); 0.01-10 pts.wt. of a carboxylic acid (B); and less than 1 pts.wt. of a low-molecular compound (C) having a molecular weight of 100-1,000, which has the silicon-containing group, where the value of a of the general formula (1) is 3, (1) a curable composition (I) is characterized in that the (A) component is an organic polymer (A1) having on average 1.1-2.5 silicon-containing groups per one molecule and further, it contains 0.1-10 pts.wt. of a low molecular weight compound (D) having a molecular weight of 100-1,000, which has one silicon-containing group, where the value of a of the general formula (1) is 2, per one molecule, or (2) a curable composition (II) is characterized in that the (A) component is an organic polymer (A2) having on average 1.1-1.5 silicon-containing groups, where the value of a of the general formula (1) is 2, per one molecule and further, the curable composition (II) contains less than 0.1 pts.wt. of the (D) component.

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.

  An organic polymer containing at least one reactive silicon group in the molecule is crosslinked at room temperature by forming 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 a reactive silicon group, an organic polymer whose main chain skeleton is a polyoxyalkylene polymer is disclosed in (Patent Document 1), and has already been industrially produced and sealed. Widely used in applications such as materials, adhesives and paints.

  Sealing materials are generally used for the purpose of filling water-tightness and airtightness by filling joints and gaps between various members. Therefore, as a physical property of the cured product, a low modulus and high elongation tensile property is required.

  These curable compositions containing an organic polymer having a reactive silicon group are cured using a silanol condensation catalyst, and organotin catalysts and divalent tin carboxylate catalysts are widely used. . As other curing catalysts, (Patent Document 2), (Patent Document 3), (Patent Document 4), and the like disclose techniques using a carboxylic acid as a catalyst.

  Moreover, the curable composition containing the organic polymer which has these reactive silicon groups has improved storage stability and adhesiveness using various silane coupling agents, and generally has a trialkoxysilyl group. The silane coupling agent which has is used.

  On the other hand, (Patent Document 5), (Patent Document 6), and the like disclose techniques for obtaining a cured product having a low modulus and flexibility.

JP-A-52-73998 JP-A-5-117519 WO04-031300 WO08-133265 JP-A-9-95619 Japanese Patent Laid-Open No. 11-80533

  However, even when the curable compositions described in (Patent Document 5) and (Patent Document 6) are used, flexibility and elongation performance are not sufficient, and improvement has been desired.

  An object of this invention is to provide the curable composition which has the organic polymer which has a reactive silicon group as a main component, Comprising: It has a low modulus and high elongation physical property.

  As a result of diligent studies to solve such problems, the present inventor contains an organic polymer (A) having a reactive silicon group and a carboxylic acid (B), and has three hydroxyl groups or hydrolyzable groups. In the curable composition which does not substantially contain the silicon-containing low molecular weight compound, (1) a specific silicon-containing low molecular weight compound is added, or (2) the component (A) has a specific structure, thereby reducing the The present inventors have found that a curable composition having a cured product having a high modulus and a high elongation can be obtained, thereby completing the present invention.

That is, the present invention
The number average molecular weight is 1000 to 50000, and the general formula (1):
-SiR ¹ _3-a X _a (1)
(In the formula, each of 3-a R ¹ 's independently represents 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 SiO— (wherein R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and a number of X is each Independently, it is a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3) with respect to 100 parts by weight of the organic polymer (A) having a silicon-containing group. 1 to 10 parts by weight of a low molecular weight compound (C) having a molecular weight of 100 to 1000 having 0.01 to 10 parts by weight of a carboxylic acid (B) as a condensation catalyst and a silicon-containing group in which the value of a in the general formula (1) is 3. Curable composition containing less than part Because
(1) The component (A) is an organic polymer (A1) having an average of 1.1 to 2.5 silicon-containing groups per molecule, and further, the value of a in the general formula (1) A curable composition (I) characterized by containing 0.1 to 10 parts by weight of a low molecular compound (D) having a molecular weight of 100 to 1000 and having one silicon-containing group of 2 per molecule, or ,
(2) The component (A) is an organic polymer (A2) having an average of 1.1 to 1.5 silicon-containing groups per molecule where the value of a in the general formula (1) is 2. Further, the present invention relates to a curable composition (II) characterized by containing less than 0.1 part by weight of the component (D).
It is preferable that content of a tin compound is less than 1 weight part with respect to 100 weight part of (A) component.
(A) It is preferable to contain 0.01-20 weight part of amine compounds (E) with respect to 100 weight part of component.
The main chain skeleton of the organic polymer (A) is preferably at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester polymer. .
The main chain skeleton of the component (A) is more preferably polypropylene oxide.
The silicon-containing group of the component (A1) is preferably a silicon-containing group having a value a of 2 in the general formula (1).
The component (A2) is a mixture of an organic polymer (A2a) having two or more silicon-containing groups per molecule and an organic polymer (A2b) having one silicon-containing group per molecule, and the component (A2a) It is preferable that the molar ratio of the component (A2b) is 1/1 to 1/10.
A cured product can be obtained by curing the curable composition described above.

  The curable composition of the present invention has a low modulus and a high elongation property.

  The present invention will be described in detail below.

  The main chain skeleton of the organic polymer (A) 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 A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers. Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product Is more preferable because of its excellent cold resistance.

  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.

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

  The reactive silicon group contained in the organic polymer having a reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and forms a siloxane bond by a reaction accelerated by a silanol condensation catalyst. It is a group capable of crosslinking.

As the reactive silicon group, the general formula (1):
-SiR ¹ _3-a X _a (1)
(In the formula, each of 3-a R ¹ 's independently represents 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 SiO— (wherein R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and a number of X is each Independently, it is a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3).

  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.

That is, the general formula (2):
-SiR ¹ _3-a (OR ² ) _a (2)
(Wherein, a and R ¹ are the same as described above. A R ^{2 s} are each independently a hydrocarbon group having 1 to 8 carbon atoms.) It is preferable because it is easy to handle.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and 2 or 3 is preferable from the viewpoint of curability. When two or more hydrolyzable groups or hydroxyl groups are bonded to the silicon atom, they may be the same or different. A reactive silicon group having three hydroxyl groups or hydrolyzable groups on a silicon atom has high activity and good curability, and is excellent in resilience, durability and creep resistance of the resulting cured product. This is preferable. That is, the value of a in the general formulas (1) and (2) is preferably 2 or 3, and more preferably 3, from the viewpoints of curability and restorability. On the other hand, a reactive silicon group having two hydroxyl groups or hydrolyzable groups on a silicon atom is preferable because it is excellent in storage stability and the obtained cured product has high elongation and high strength. That is, the value of a in the general formulas (1) and (2) is preferably 2 from the viewpoints of storage stability and physical properties of the cured product.

Specific examples of R ^{1 in} the general formulas (1) and (2) 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, and a benzyl 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 and elongation property. 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.

  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. , Methyldimethoxysilane, phenyldimethoxysilane, alkoxysilanes such as 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyldiacetoxysilane Examples thereof include, but are not limited to, acyloxysilanes such as: ketoximate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the obtained organic polymer has high curability, storage stability, elongation characteristics, and tensile strength. Trimethoxysilane is particularly preferable from the viewpoints of curability and restorability of the resulting curable composition.

  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 generation 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. Examples include, but are not limited to, silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.

  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. Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  A silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane may undergo a disproportionation reaction. As the disproportionation reaction proceeds, fairly dangerous compounds such as dimethoxysilane and tetrahydrosilane are produced. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, 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) may be used. preferable.

On the other hand, general formula (3):
H- (SiR ³ ₂ O) _m SiR ³ ₂ -R ⁴ -SiX ₃ (3)
(In the formula, X is the same as above. 2 × m + 2 R ^{3 s} are each independently a hydrocarbon group or —OSi (R ″) ₃ (R ″ is independently from 1 carbon atom) And a hydrocarbon group having 1 to 20 carbon atoms, and from the viewpoint of availability and cost, it is preferably 1 to 8 carbon atoms. The hydrocarbon group is more preferably a hydrocarbon group having 1 to 4 carbon atoms, and R ⁴ is a divalent organic group, and is divalent having 1 to 12 carbon atoms from the viewpoint of availability and cost. A divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon group having 2 carbon atoms is particularly preferable, and m is an integer of 0 to 19. 1 from the viewpoint of availability and cost) The disproportionation reaction does not proceed with the silane compound. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (a), the silane compound represented by the general formula (3) should be used. Is preferred. Specific examples of the silane compound represented by the general formula (3) include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxy). Silyl) propyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane.

  The organic polymer having a reactive silicon group may be linear or branched, and its number average molecular weight is 1,000 to 50,000 in terms of polystyrene in GPC, particularly preferably 3,000 to 3,000. 30,000. If the number average molecular weight is less than 1000, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 50,000, it tends to be inconvenient in terms of workability due to high viscosity.

  In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, the average number of reactive silicon groups contained in the organic polymer is at least 1, preferably 1, .1-5, more preferably 1.3-4, and even more preferably 1.5-3. 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 exhibit good rubber elastic behavior.

  The reactive silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the reactive silicon group is at the end of the main chain of the molecular chain, the effective network chain 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 ⁵ —O— (4)
(Wherein R ⁵ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁵ in the general formula (4) is a carbon atom. A linear or branched alkylene group having 1 to 14 or 2 to 4 is preferable. Specific examples of the repeating unit represented by the general formula (4) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used in sealants and the like, a polymer composed mainly of a propylene oxide polymer having a propylene oxide repeating unit of 50% by weight or more is amorphous or has a relatively low viscosity. It is preferable from the point.

  Examples of the method for synthesizing the 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. No. 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 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 JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. JP-A-55-13468, JP-A-57-16123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a narrow molecular weight distribution with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less 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, or the like. Such an olefinic compound having 2 to 6 carbon atoms is polymerized as a main monomer, or (2) a diene compound such as butadiene or isoprene is homopolymerized or copolymerized with the olefinic compound. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

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

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. 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 particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). It is known that 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, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (Meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2- -Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl) methyl, (meth) acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acid. 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 alone or a plurality of these 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. In applications such as general construction, 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 alkyl group in the side chain 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 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 (40-50 / 20 by weight) 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.

  It does not specifically limit as a synthesis method of a (meth) acrylic acid ester type polymer, What is necessary is just to carry out by a well-known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a 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 described 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 6) (}} COOR 7) - (5)
(Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 1 to 8 carbon atoms) and a (meth) acrylic acid ester having an alkyl group having 1 to 8 carbon atoms A monomer unit and the following general formula (6):
—CH ₂ —C (R ⁶ ) (COOR ⁸ ) — (6)
(Wherein, R ⁶ is the same as above, and R ⁸ represents an alkyl group having 10 or more carbon atoms) From the (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 ^{7 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 to 2 alkyl groups. The alkyl group R ⁷ may alone, or may be a mixture of two or more.

R ^{8 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 to 30, preferably 10 to 20 And an alkyl group. The alkyl group of R ⁸ is similar to the case of R ^7, individually may or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based polymer is substantially composed of monomer units of the formulas (5) and (6), and the term “substantially” as used herein means that in the copolymer Means that the total of the monomer units of formula (5) and formula (6) present in the formula 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 an amide group such as N-methylol methacrylamide, an epoxy group such as glycidyl acrylate and glycidyl methacrylate, and an amino group 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 polymer having a reactive silicon group are disclosed in JP-A-1-168774 and JP-A-2000-186176. However, it is not particularly limited to these.

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

  On the other hand, the main chain skeleton of the organic polymer (A) 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 ⁹ —C (═O) — (7)
(R ⁹ is a hydrogen atom or a monovalent organic group, preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 8 carbon atoms. An unsubstituted monovalent hydrocarbon group).

  Specifically, the amide segment includes a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between the isocyanate group and an amino group; a thiol formed by a reaction between the isocyanate group and a mercapto group. A urethane group etc. can be mentioned. In the present invention, 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).

  Examples of industrially easy production methods for polyoxyalkylene polymers having an amide segment and a reactive silicon group include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557) and Japanese Patent Application Laid-Open No. 58-109529 (US Pat. 4374237), JP-A-62-143030 (US Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-11-100197, JP-A-2000-169544, JP-A-2000-169545, JP-A-2002. -212415, Patent 331336 No. 4, U.S. Pat. No. 4,067,844, U.S. Pat. No. 3,711,445, JP-A No. 2001-32340, JP-A No. 11-279249 (US Pat. No. 5,990,257), JP-A No. 2000-119365 (US Pat. No. 6,046,270), 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-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981. 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. , JP 2 No. 00-119365 (U.S. Pat. No. 6,046,270), and the like.

<< carboxylic acid (B) >>
In the present invention, a carboxylic acid is used as the component (B). The component (B) acts 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).

  The carboxylic acid used in the present invention is not particularly limited, and various compounds can be used.

  Here, as the carboxylic acid, a hydrocarbon carboxylic acid having 2 to 40 carbon atoms including carbonyl carbon is preferably used, and a hydrocarbon carboxylic acid having 2 to 20 carbon atoms from the viewpoint of availability. Can be used particularly preferably.

  Specifically, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic 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, seracole Monoene unsaturated fatty acids such as acid, ximenic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linoleic acid, 10,12-octadecadiene 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; 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberc Branched fatty acids such as stearic acid, pivalic acid, neodecanoic acid; fatty acids having triple bonds such as propiolic acid, taliphosphoric acid, stearolic acid, crepenic acid, ximenic acid, 7-hexadesinic acid; naphthenic acid, malvalic acid Alicyclic carboxylic acids such as sterlic acid, hydnocarpsic 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-dihydroxyoctadecanoic acid, ricinoleic acid, Muroren acid, licanic, Feron acid, oxygenated fatty acids, such as cerebronic acid; chloroacetic acid, 2-chloro-acrylic acid, halogen substitution products of monocarboxylic acids such as chlorobenzoic acid. Examples of the aliphatic dicarboxylic acid include adipic acid, azelaic acid, pimelic acid, suberic 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.

  Particularly, the carboxylic acid is preferably 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, or naphthenic acid because it is easily available and inexpensive, and has good compatibility with the component (A). .

  When the melting point of the carboxylic acid is high (crystallinity is high), it becomes difficult to handle (poor workability). Therefore, the melting point of the carboxylic acid is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.

  Further, when the number of carbon atoms of the carboxylic acid is large (molecular weight is large), it becomes a solid or highly viscous liquid and difficult to handle (poor workability). On the other hand, when the number of carbon atoms of the carboxylic acid is small (molecular weight is small), a component that easily volatilizes by heating may be included, and the catalytic ability of the carboxylic acid may decrease. In particular, when the composition is thinly stretched (thin layer), volatilization due to heating is large, and the catalytic ability of the carboxylic acid may be greatly reduced. Accordingly, the carboxylic acid 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 carboxylic acid, dicarboxylic acid or monocarboxylic acid is preferable, and monocarboxylic acid is more preferable.

  The carboxylic acid may be a carboxylic acid having a tertiary carbon atom adjacent to the carbonyl group (such as tin 2-ethylhexanoate) or a carboxylic acid having a quaternary carbon (such as tin neodecanoate or tin pivalate). A carboxylic acid having a quaternary carbon as the carbon atom adjacent to the carbonyl group is particularly preferred because of its high curing rate. Moreover, the carboxylic acid whose carbon atom adjacent to a carbonyl group is a quaternary carbon is excellent also in adhesiveness compared with other carboxylic acid. Here, the tertiary carbon indicates a carbon atom bonded to three carbon atoms, and the quaternary carbon indicates a carbon atom bonded to four carbon atoms.

  As the carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon, the general formula (8):

(Wherein R ¹⁰ , R ¹¹ and R ¹² are each independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and may contain a carboxyl group). Chain fatty acid or general formula (9):

(Wherein R ¹³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ¹⁴ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, And may contain a group) and general formula (10):

(Wherein, R ¹⁵ is a substituted or unsubstituted trivalent hydrocarbon group having 1 to 20 carbon atoms and may contain a carboxyl group), and a cyclic fatty acid 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.

  In particular, monocarboxylic acids are more preferable, and chain monocarboxylic acids are more preferable from the viewpoint of good compatibility with the component (A) and easy handling. In addition, pivalic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid and the like are particularly preferable because they are easily available.

  In addition, the number of carbon atoms of the carboxylic acid in which the carbon atom adjacent to such a carbonyl group is a quaternary carbon is preferably 5 to 20, more preferably 6 to 17, and 8 to 12. Is particularly preferred. If the number of carbon atoms exceeds this range, it tends to become solid and it becomes difficult to achieve compatibility with the component (A), and the activity tends not to be obtained. On the other hand, when the number of carbon atoms is small, it tends to volatilize and the odor tends to become strong. From these points, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, and 2-ethyl-2,5-dimethylhexanoic acid are most preferable.

  Moreover, each said carboxylic acid can be used in combination of 2 or more type besides using individually.

  The carboxylic acid (B) is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the component (A). Used in part range. If the blending amount is below this range, the curability may not be sufficient. On the other hand, if the blending amount exceeds this range, the pot life may become too short and workability may deteriorate, and storage stability tends to deteriorate.

  Although the carboxylic acid (B) is used as the curing catalyst of the present invention, other curing catalysts can be used in combination to such an extent that the effects of the present invention are not reduced. Specific examples include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, carboxyl Various carboxylic acid metal salts such as iron acid, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, di Titanium compounds such as isopropoxytitanium bis (ethyl acetocetate); dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethyl) Xanoate), dibutyl tin bis (methyl maleate), dibutyl tin bis (ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl Tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide), dibutenyl tin oxide, dibutyl tin Tetravalent organic tin such as oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, etc. Compound; Al Niumutorisu (acetylacetonate), aluminum tris (ethylacetoacetate), an organoaluminum compound such as diisopropoxy aluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate) and the like.

  However, when a curing catalyst other than the component (B) is added, the amount of the curing catalyst other than the component (B) may not be exhibited depending on the amount added. Is less than 0.5 parts by weight with respect to 100 parts by weight of component (A), preferably less than 0.1 parts by weight, more preferably less than 0.01 parts by weight, and especially not substantially contained. preferable.

<< Amine compound (E) >>
On the other hand, when only the component (B) is low in activity and an appropriate curability cannot be obtained, an amine compound as the component (E) can be added as a promoter.

  Specific examples of the component (E) amine compound 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, bis (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 4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), 1,5 -Diazabicyclo (4, 3, 0) nonene-5 (DBN) etc. are mentioned, However, It is not limited to these.

  As these (E) components, the cocatalyst ability varies greatly depending on the structure of the (E) component itself and the compatibility with the (A) component. Therefore, in the present invention, octylamine, lauryl are used because of their high cocatalyst ability. Primary amines such as amines are preferred, and amine compounds having a hydrocarbon group having at least one heteroatom are 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 any one of 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 provides a curable composition with good adhesion, workability, and storage stability.

  The compounding amount of the amine compound as component (E) is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, and more preferably 1 to 5 parts per 100 parts by weight of component (A). Part by weight is particularly preferred. If the blending amount is below this range, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, if the blending amount exceeds this range, the pot life becomes too short, and the workability tends to deteriorate. On the contrary, the curing speed may be slow.

<< Silicon-containing low molecular weight compound (C) having three hydroxyl groups or hydrolyzable groups >>
In the present invention, the low molecular compound (C) having a molecular weight of 100 to 1000 having a silicon-containing group having a value of a of 3 in the general formula (1) is not contained, or (100) part by weight of component (A) ( It is essential that the component C) be less than 1 part by weight.

  When the component (C) is used, if the amount added is large, the physical property improving effect of the present invention may be difficult to express. Therefore, the amount of the component (C) used is 100 parts by weight of the component (A). Is preferably less than 0.5 part by weight, more preferably less than 0.1 part by weight, still more preferably less than 0.01 part by weight, and particularly preferably not substantially contained.

  Specific examples of the component (C) include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) triethoxysilane, and other isocyanate group-containing silanes; -Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxy Silane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ- Ure Dopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, etc. Amino group-containing silanes; Ketimine type silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltri Ethoxysilane, mercap Mercapto group-containing silanes such as tomethyltrimethoxysilane and mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltri Carboxysilanes such as methoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxypropyltrimethoxy Vinyl type unsaturated group-containing silanes such as silane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; tris (3-trimethoxysilylpropyl) ) Isocyanurate silanes such as isocyanurate. Further, the reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, partial condensates of various silane coupling agents, and the like can also be mentioned as the component (C).

  A so-called silicate which is a tetraalkoxysilane or a partially hydrolyzed condensate thereof can also be mentioned as the component (C).

  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.

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

<< Silicon-containing low molecular compound (D) having two hydroxyl groups or hydrolyzable groups >>
In the present invention, a low molecular compound (D) having a molecular weight of 100 to 1000 and having one silicon-containing group per molecule having a value of a of 2 in the general formula (1) can be used.

  Specific examples of component (D) include isocyanate group-containing silanes such as γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, (isocyanatemethyl) methyldimethoxysilane, and (isocyanatemethyl) methyldiethoxysilane. Γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl); Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiisopropoxysilane, γ- (6-aminohexyl) aminopropylmethyldimethoxysilane, 3- (N-ethylamino) -2 Methylpropylmethyldimethoxysilane, γ-ureidopropylmethyldimethoxysilane, γ-ureidopropylmethyldiethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-benzyl-γ-aminopropylmethyldimethoxysilane, N-vinyl Amino group-containing silanes such as benzyl-γ-aminopropylmethyldiethoxysilane, N-cyclohexylaminomethylmethyldiethoxysilane, N-phenylaminomethylmethyldimethoxysilane, (2-aminoethyl) aminomethylmethyldimethoxysilane; N -(1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, etc. Ketimine Silanes; mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane; γ-glycidoxypropylmethyldimethoxysilane, Epoxy group-containing silanes such as γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane; -Carboxysilanes such as carboxyethylmethyldiethoxysilane and N-β- (carboxymethyl) aminoethyl-γ-aminopropylmethyldimethoxysilane; vinylmethyldimethoxysilane, vinylmethyldiethoxy Vinyl type such as lan, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, methacryloyloxymethylmethyldimethoxysilane Unsaturated group containing silanes; Halogen containing silanes such as γ-chloropropylmethyldimethoxysilane.

  The curable composition of the present invention is a curable composition containing 0.01 to 10 parts by weight of component (B) and less than 1 part by weight of component (C) with respect to 100 parts by weight of component (A). However, the tensile properties of the cured product obtained by further adding (1) 0.1 to 10 parts by weight of the component (D) or by limiting the component (2) (A) to a specific structure. Can be remarkably improved.

  That is, in the present invention, the curable composition (I) of the <first embodiment> and the <second embodiment, respectively, due to the difference in the component (A) and / or the difference in the amount of the component (D) added. Embodiment> of the curable composition (II). (B) component and (C) component can be used in common with the curable composition of each aspect. Various additives other than the component (A), the component (B), the component (C), and the component (D) can also be used in common for the curable compositions of the respective embodiments.

  Although it is not clear as a mechanism by which the curable composition of the present invention is remarkably improved at a low modulus and a high elongation, it is estimated as follows. The curable composition (I) of <first embodiment> contains a component (D) and a silicon-containing group (hereinafter referred to as “D end group”) in which the value of a in formula (1) is 2. In the molecule). On the other hand, the curable composition (II) of the <second aspect> contains a polymer containing the component (A2) and having one D terminal group in the molecule. These components having only one D terminal group in the molecule are considered to form a unique crosslinking structure in the presence of a carboxylic acid (B) catalyst and to form a chain-extending crosslinking point. As a result, the obtained cured product becomes a cured product having a large molecular weight between cross-linking points, and gives physical properties of low modulus and low elongation.

  Hereinafter, the curable composition of each aspect is demonstrated.

<First embodiment> curable composition (I):
The first aspect of the present invention is a silanol condensation catalyst with respect to 100 parts by weight of the organic polymer (A) having a number average molecular weight of 1,000 to 50,000 and having a reactive silicon group represented by the general formula (1). Less than 1 part by weight of the low molecular weight compound (C) having a molecular weight of 100 to 1000 having 0.01 to 10 parts by weight of the carboxylic acid (B) and a silicon-containing group in which the value of a in the general formula (1) is 3. A curable composition containing,
The component (A) is an organic polymer (A1) having an average of 1.1 to 2.5 silicon-containing groups per molecule, and the value of a in the general formula (1) is 2 It is a curable composition (I) characterized by containing 0.1 to 10 parts by weight of a low molecular compound (D) having a molecular weight of 100 to 1000 and having one silicon-containing group per molecule.

  The number average molecular weight of the component (A1) is essential to be 1,000 to 50,000 in terms of polystyrene in GPC, preferably 3,000 to 40,000, and particularly preferably 10,000 to 30,000. If the number average molecular weight is less than 1000, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 50,000, the viscosity tends to be inconvenient because of high viscosity.

  The component (A1) may be linear or branched, but is preferably linear from the viewpoint of the elongation characteristics of the cured product.

  It is essential that the average number of reactive silicon groups of the component (A1) be 1.1 to 2.5 per molecule, preferably 1.3 to 2.3, and particularly preferably 1. 5 to 2.0. When the number of reactive silicon groups contained in the molecule is less than this range, the curability may be insufficient and it may be difficult to develop good rubber elastic behavior. On the other hand, if the number of reactive silicon groups contained in the molecule exceeds this range, the elongation performance tends to deteriorate.

  The silicon-containing group of the component (A1) is preferably a silicon-containing group having a value a of 2 in the general formula (1) from the viewpoint of elongation characteristics.

  (D) It is essential that the number average molecular weight of a component is 100-1000, Preferably it is 120-500, Most preferably, it is 150-250. If the number average molecular weight is less than 100, the volatile component in the curable composition tends to increase, and if it exceeds 1000, the viscosity tends to be inconvenient because of high viscosity.

  (D) The compounding quantity of a component uses 0.01-10 weight part as an essential component with respect to 100 weight part of (A) component, Preferably it is 0.1-10 weight part, More preferably, it is 1-5. Used in the range of parts by weight. If the blending amount is below this range, the elongation characteristics of the cured product may not be sufficient. On the other hand, if the blending amount exceeds this range, the curing rate tends to be slow.

  Various additives other than the components (A) to (E) will be described later.

Curable composition (II) of <second aspect>:
The second aspect of the present invention is a silanol condensation catalyst with respect to 100 parts by weight of the organic polymer (A) having a number average molecular weight of 1,000 to 50,000 and having a reactive silicon group represented by the general formula (1). Less than 1 part by weight of the low molecular weight compound (C) having a molecular weight of 100 to 1000 having 0.01 to 10 parts by weight of the carboxylic acid (B) and a silicon-containing group in which the value of a in the general formula (1) is 3. A curable composition containing,
The component (A) is an organic polymer (A2) having an average of 1.1 to 1.5 silicon-containing groups per molecule, wherein the value of a in the general formula (1) is 2. The curable composition (II) containing less than 0.1 part by weight of the component (D).

  The number average molecular weight of the component (A2) is essential to be 1,000 to 50,000 in terms of polystyrene in GPC, preferably 3,000 to 40,000, and particularly preferably 10,000 to 30,000. If the number average molecular weight is less than 1000, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 50,000, the viscosity tends to be inconvenient because of high viscosity.

  The component (A2) may be linear or branched, but is preferably linear from the viewpoint of the elongation characteristics of the cured product.

  It is essential that the reactive silicon group of the component (A2) is a silicon-containing group in which the value of a in the general formula (1) is 2.

  Further, it is essential that the reactive silicon group of the component (A2) has an average of 1.1 to 1.5 per molecule, preferably 1.2 to 1.4, particularly preferably 1.3 to 1.4. When the number of reactive silicon groups contained in the molecule is less than this range, the curability may be insufficient and it may be difficult to develop good rubber elastic behavior. On the other hand, if the number of reactive silicon groups contained in the molecule exceeds this range, the elongation performance tends to deteriorate.

  From the viewpoint of elongation characteristics, the component (A2) is a mixture of an organic polymer (A2a) having two or more silicon-containing groups per molecule and an organic polymer (A2b) having one silicon-containing group per molecule. The molar ratio of the component (A2a) to the component (A2b) is preferably 1/1 to 1/10.

  (D) It is essential that the number average molecular weight of a component is 100-1000, Preferably it is 120-500, Most preferably, it is 150-250. If the number average molecular weight is less than 100, the volatile component in the curable composition tends to increase, and if it exceeds 1000, the viscosity tends to be inconvenient because of high viscosity.

  The amount of component (D) is not contained, or it is essential that it is less than 0.1 parts by weight, preferably less than 0.01 parts by weight, substantially less than 100 parts by weight of component (A). It is particularly preferable not to contain it. If the blending amount exceeds this range, the curing rate tends to be slow.

  Various additives other than the components (A) to (E) will be described later.

<< Other various additives >>
<< Plasticizer >>
A plasticizer can be added to the composition of the present invention. By adding a 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, di (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 referred to as 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, and the like, 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, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are 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 will flow 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).

  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 plasticizer is used in the range of 10 to 200 parts by weight, preferably 20 to 120 parts by weight, and more preferably 30 to 80 parts by weight with respect to 100 parts by weight of component (A). If the blending amount is below this range, the plasticizing effect may not be sufficient. On the other hand, if the blending amount exceeds this range, the cured product properties may be deteriorated.

<< Filler >>
A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fume 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, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin powders such as resin organic microballoons, PVC powder, and PMMA powders; and fibrous fillers such as asbestos, glass fibers, and filaments.

  The filler is used in the range of 10 to 500 parts by weight, preferably 50 to 300 parts by weight, and more preferably 100 to 200 parts by weight with respect to 100 parts by weight of component (A). If the blending amount is below this range, the strength of the cured product may not be sufficient. On the other hand, if the blending amount exceeds this range, the elongation characteristics of the cured product may deteriorate.

<< Solvent >>
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, ether solvents, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. In the case of using a solvent, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. 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. Accordingly, the blending amount of the solvent is preferably less than 1 part by weight, more preferably less than 0.1 part by weight with respect to 100 parts by weight of the component (A), and the solvent is not substantially contained. Most preferably, it is a solvent type.

<< Thixotropic agent >>
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 anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight per 100 parts by weight of component (A).

<< Antioxidant >>
An antioxidant (antiaging 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 Co., Ltd.) 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 in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of component (A).

<< light stabilizer >>
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 by weight, based on 100 parts by weight of component (A). 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, CHIMASSORB 119FL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (and above) Examples thereof include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Corporation).

<< UV absorber >>
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 enhanced. 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 ultraviolet absorber is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of component (A). It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

<< Other various additives >>
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, epoxy resins, epoxy resin curing agents, photocurable materials, oxygen curable materials, silanol-containing compounds, tackifiers, thermoplastic elastomers, flame retardants, and curing modifiers. , Radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, ant-proofing agents, fungicides, and the like. 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.

<< Method for adjusting curable composition >>
The curable composition of the present invention can be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured at room temperature by the moisture in the air after construction. It can also be prepared as a two-component type in which components such as a filler, a plasticizer, and water are blended and the blended 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 for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, the storage stability is further improved by adding a lower alcohol such as methanol or ethanol.

  The amount of the dehydrating agent used is in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight of component (A).

  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.

<< Usage >>
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. It can be used for coating materials and waterproofing coating films. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and elongation characteristics, among these, it is more preferable to use it as a sealing material, an adhesive, a coating material, and a waterproof coating material. preferable.

  Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical equipment sealants, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, primers, conductive materials for shielding electromagnetic waves , Heat conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), automotive parts, It can be used for various applications such as liquid sealants used in electrical parts and various machine parts. 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 includes 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.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.

  In the following synthesis examples, “number average molecular weight” was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). Tosoh HLC-8120GPC was used as the liquid feeding system, the column was TOS-GEL H type manufactured by Tosoh, and the solvent was measured using THF.

(Synthesis Example 1)
Polymerization of propylene oxide using polyoxypropylene triol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain polypropylene oxide having a number average molecular weight of about 26,000 and a molecular weight distribution of 1.3 It was. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polypropylene oxide to distill off the methanol, and a 1.2-fold equivalent of allyl chloride was added to remove the terminal hydroxyl group. Converted to 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 trifunctional polypropylene oxide having a number average molecular weight of about 26,000 and having an allyl group at the end was obtained (hereinafter referred to as polymer <P1>).

The polymer <P1> is reacted with 1.1 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours using 150 parts by weight of an isopropanol solution containing 3 wt% of platinum as a catalyst with respect to 100 parts by weight of a platinum vinylsiloxane complex. A polyoxypropylene polymer (A-1) was obtained. Further, when the silyl group introduction rate was examined using ¹ H-NMR, the number of terminal methyldimethoxysilyl groups was 1.9 on average per molecule.

(Synthesis Example 2)
Hydroxyl terminal having a number average molecular weight of about 28,500 and a molecular weight distribution of 1.3, obtained by polymerizing propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene glycol having a molecular weight of about 2,000 as an initiator. Using polypropylene oxide, an allyl-terminated polypropylene oxide was obtained in the same procedure as in Synthesis Example 1 (this is referred to as polymer <P2>).

  With respect to 100 parts by weight of the polymer <P2>, 150 ppm of a platinum content of a platinum vinylsiloxane complex having a platinum content of 3 wt% as a catalyst was reacted with 1.5 parts by weight of trimethoxysilane at 90 ° C. for 5 hours. A polyoxypropylene polymer (A-2) having 6 trimethoxysilyl groups was obtained.

(Synthesis Example 3)
With respect to 100 parts by weight of the polymer <P2>, 150 ppm of a platinum content of a platinum vinylsiloxane complex having a platinum content of 3 wt% as a catalyst was reacted with 1.0 part by weight of methyldimethoxysilane at 90 ° C. for 5 hours. A polyoxypropylene polymer (A-3) having 6 methyldimethoxysilyl groups was obtained.

(Synthesis Example 4)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was added dropwise to an isobutanol solution of the following monomer mixture heated to 90 ° C. over 7 hours. After performing “post-polymerization”, the solvent was distilled off. A (meth) acrylic acid ester polymer (A-4) having a number average molecular weight of about 19,000 and a molecular weight distribution of 2.8 and having an average of 1.9 methyldimethoxysilyl groups at the end of the side chain is obtained. It was.

  n-butyl acrylate: 68.2 parts by weight, ethyl acrylate: 14.5 parts by weight, stearyl methacrylate: 14.9 parts by weight, γ-methacryloyloxypropylmethyldimethoxysilane: 2.4 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 0.4 parts by weight.

(Synthesis Example 5)
An allyl-terminated polypropylene oxide was obtained in the same procedure as in Synthesis Example 1 using a hydroxyl group-terminated polypropylene glycol having a number average molecular weight of about 4,500 and a molecular weight distribution of 1.4. This allyl-terminated polypropylene oxide is reacted with 6 parts by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 1, and a polyoxypropylene polymer having an average of 1.6 methyldimethoxysilyl groups at the ends (A- 5) was obtained.

(Synthesis Example 6)
100 parts by weight of the polymer <P2> was reacted with 0.8 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. A polyoxypropylene polymer (A-6) having three methyldimethoxysilyl groups was obtained.

(Examples 1-13, Comparative Examples 1-21)
According to the formulations shown in Tables 1 to 4, the reactive silicon group-containing organic polymer, the filler, the plasticizer, the reactive silicon group-containing low molecular weight compound, the silanol condensation catalyst, and the like are weighed and dehydrated using a mixer. After kneading in a state substantially free of moisture, it was sealed in a moisture-proof container (aluminum cartridge) to obtain a one-component curable composition. The one-component compositions in Tables 1 to 4 were each extruded from each cartridge at the time of use, and evaluated below. Examples 1 to 12 and Comparative Examples 1 to 20 described in Tables 1 to 3 are examples and comparative examples for the curable composition (I) of the present invention. Example 13 and Comparative Examples 9 and 21 listed in Table 4 are examples and comparative examples for the curable composition (II) of the present invention.

In addition, what was shown below was used for the various compounding agents in Tables 1-4.
<Plasticizer> Sansosizer DIDP (Nippon Nippon Chemical Co., Ltd., diisodecyl phthalate)
<Filler> Shiraka Hana CCR (manufactured by Shiraishi Kogyo Co., Ltd.
<Reactive silicon group-containing low molecular weight compound>
Geniosil XL12 (from Wacker, vinylmethyldimethoxysilane)
KBM-202SS (manufactured by Shin-Etsu Chemical Co., Ltd., diphenyldimethoxysilane)
KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane)
A-171 (Momentive Performance Materials, vinyltrimethoxysilane)
A-1120 (Momentive Performance Materials, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane)
<Silanol condensation catalyst>
Versatic 10 (Japan epoxy resin, neodecanoic acid)
Diethylaminopropylamine (Wako Pure Chemical Industries)
Neostan U-50 (Nitto Kasei, tin neodecanoate (divalent))
Neostan U-220H (manufactured by Nitto Kasei, dibutyltin bisacetylacetonate).

(Tensile property of cured product)
Each composition shown in Tables 1 to 4 was cured at 23 ° C./50% RH × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of about 3 mm. This sheet was punched into a No. 3 dumbbell mold and subjected to a tensile test at a pulling speed of 200 mm / min. 50% elongation stress: M50 (MPa), breaking strength: Tb (MPa), breaking elongation: Eb (%) It was measured. The results are shown in Tables 1-4. In addition, since the measurement limit of the elongation physical property of the used testing machine was 2000%, when the elongation physical property exceeded 2000%, the breaking strength and the breaking elongation could not be measured.

As shown in Tables 1 to 3, it can be seen that the curable composition (I) of the present invention exhibits low modulus and high elongation properties.

  As shown in Table 4, it can be seen that the curable composition (II) of the present invention exhibits low modulus and high elongation properties.

Claims (8)

The number average molecular weight is 1000 to 50000, and the general formula (1):
-SiR ¹ _3-a X _a (1)
(In the formula, each of 3-a R ¹ 's independently represents 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 SiO— (wherein R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and a number of X is each Independently, it is a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3) with respect to 100 parts by weight of the organic polymer (A) having a silicon-containing group. 1 to 10 parts by weight of a low molecular weight compound (C) having a molecular weight of 100 to 1000 having 0.01 to 10 parts by weight of a carboxylic acid (B) as a condensation catalyst and a silicon-containing group in which the value of a in the general formula (1) is 3. Curable composition containing less than part Because
(1) The component (A) is an organic polymer (A1) having an average of 1.1 to 2.5 silicon-containing groups per molecule, and further, the value of a in the general formula (1) A curable composition (I) characterized by containing 0.1 to 10 parts by weight of a low molecular compound (D) having a molecular weight of 100 to 1000 and having one silicon-containing group of 2 per molecule, or ,
(2) The component (A) is an organic polymer (A2) having an average of 1.1 to 1.5 silicon-containing groups per molecule where the value of a in the general formula (1) is 2. The curable composition (II) further contains less than 0.1 parts by weight of the component (D). The curable composition according to claim 1, wherein the content of the tin compound is less than 1 part by weight with respect to 100 parts by weight of the component (A). (A) 0.01-20 weight part of amine compounds (E) are further contained with respect to 100 weight part of components, The curable composition of Claim 1 or 2 characterized by the above-mentioned. 2. The main chain skeleton of the organic polymer (A) is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer. 4. The curable composition according to any one of items 1 to 3. The curable composition according to any one of claims 1 to 4, wherein the main chain skeleton of the component (A) is polypropylene oxide. The curable composition according to any one of claims 1 to 5, wherein the silicon-containing group of the component (A1) is a silicon-containing group having a value a of 2 in the general formula (1). The component (A2) is a mixture of an organic polymer (A2a) having two or more silicon-containing groups per molecule and an organic polymer (A2b) having one silicon-containing group per molecule, and the component (A2a) The molar ratio of the component (A2b) is 1/1 to 1/10, and the curable composition according to any one of claims 1 to 6. Hardened | cured material obtained from the curable composition in any one of Claims 1-7.