JP5485932B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition containing an organic polymer having a silicon-containing functional group (hereinafter also referred to as a reactive silicon group) that can be crosslinked by forming a siloxane bond.

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

Among these polymers having reactive silicon groups, polyoxyalkylene polymers and polyisobutylene polymers have already been industrially produced and are widely used for applications such as sealing materials, adhesives and paints. .

Resin for adhesives used in interior panel adhesives, exterior panel adhesives, tile adhesives, stone adhesives, wall finish adhesives, vehicle panel adhesives, etc. If the creep resistance is poor, the adhesive layer may be deformed over time due to the weight of the adherend or external stress, and the panel, tile, stone, etc. may be displaced. Also, in the case of ceiling finishing adhesives and floor finishing adhesives, if the restoration property and creep resistance are inferior, the adhesive layer may be deformed over time, resulting in unevenness of the ceiling surface or floor surface. Furthermore, if the restoring property and creep resistance of the adhesive for assembling electrical, electronic, and precision equipment are poor, the adhesive layer may be deformed over time, leading to a reduction in equipment performance. Therefore, these adhesive compositions are required to be excellent in resilience and creep resistance.

Sealing materials are generally used for the purpose of filling watertightness and airtightness by filling joints and gaps between various members. Therefore, since followability to the use site over a long period of time is extremely important, it is demanded that the cured product has excellent resilience and durability. In particular, sealing materials for working joints (headwood, glass, windows, sashes, curtain walls, various exterior panels) for buildings with large joint width fluctuations, direct glazing, multi-layer glass, The composition used for the sealant for the SSG method is required to have excellent resilience and durability.

On the other hand, (Patent Literature 1), (Patent Literature 2), (Patent Literature 3), (Patent Literature 4), (Patent Literature 5), (Patent Literature 6), (Patent Literature 7), (Patent Literature 8), (Patent Literature 9), (Patent Literature 10), (Patent Literature 11), (Patent Literature 12), (Patent Literature 13), (Patent Literature 14), (Patent Literature 15), (Patent Literature 16), (Patent Literature 16) (Reference 17), (Patent Document 18), (Patent Reference 19), (Patent Reference 20), (Patent Reference 21), (Patent Reference 22), (Patent Reference 23), (Patent Reference 24), (Patent Reference 25) ), (Patent Document 26), (Patent Document 27), (Patent Document 28), and (Patent Document 29), an organic polymer having a reactive silicon group in which three hydrolyzable groups are bonded to silicon is essential. Although room temperature curable compositions as components are disclosed, in these prior arts, Fast curing which three hydrolyzable groups are based on the reactive silicon group bonded are mainly described, resilient creep resistance, description suggesting the durability is not disclosed.

JP-A-10-245482 JP-A-10-245484 Japanese Patent Laid-Open No. 10-251552 JP 10-324793 A JP-A-10-330630 JP 11-12473 A Japanese Patent Laid-Open No. 11-12480 JP-A-11-21463 JP-A-11-29713 JP 11-49969 A JP 11-49970 A JP-A-11-116831 JP-A-11-124509 WO 98-47939 JP 2000-34391 JP 2000-109676 JP 2000-109677 JP 2000-109678 A JP 2000-129126 A JP 2000-129145 A JP 2000-129146 A JP 2000-129147 A JP 2000-136312 A JP 2000-136313 A JP 2000-239338 A JP 2001-55503 A JP 2001-72854 A JP 2001-72855 A JP 2000-327771 A

The present invention has been made in view of the above situation, and an object of the present invention is to provide a method for improving the restoring property, durability and creep resistance of a cured product. In addition, the present invention provides an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, an adhesive for flooring, and the like, which have improved restorability, durability and creep resistance. Adhesives, wall finishing adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, direct glazing sealants, double glazing sealants, SSG construction sealants, or buildings It aims at providing the sealing material for working joints. Furthermore, this invention aims at providing the curable composition which can give the hardened | cured material excellent in restoring property, durability, and creep resistance.

As a result of diligent studies to solve such problems, the present inventors have used a silicon-containing functional group having three or more hydrolyzable groups on silicon as the reactive silicon group of this polymer. Thus, the present inventors have found that the restorability, durability and creep resistance are improved, thereby completing the present invention.

That is, the first of the present invention has a silicon-containing functional group having three or more hydrolyzable groups on silicon and capable of crosslinking by forming a siloxane bond, and the main chain skeleton is a polyoxyalkylene type An organic polymer (A1) that is at least one selected from a polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester copolymer obtained by a living radical polymerization method; and
The present invention relates to a curable composition containing a silanol condensation catalyst that is at least one selected from a carboxylic acid tin salt (C), an organotin catalyst (D), and a non-tin catalyst (E).

In a preferred embodiment, the silicon-containing functional group that can be crosslinked by forming a siloxane bond is represented by the general formula (6):
-Si (OR ⁴ ) ₃ (6)
(Wherein, three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms).

In a preferred embodiment, the curable composition is characterized in that the silicon-containing functional group capable of crosslinking by forming a siloxane bond is a triethoxysilyl group.

As a preferred embodiment, the organic polymer (A1) is an organic polymer in which an unsaturated group is introduced at the terminal, and the general formula (2):
H-SiX ₃ (2)
(In the formula, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different.) An organic polymer obtained by an addition reaction with a hydrosilane compound It is related with the said curable composition characterized by the above-mentioned.

As a preferred embodiment, the organic polymer (A1) is an organic polymer in which an unsaturated group is introduced at the terminal, and the general formula (9):
H-Si (OR ⁴ ) ₃ (9)
(Wherein three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms) and an organic polymer obtained by an addition reaction with a hydrosilane compound It relates to the curable composition.

In a preferred embodiment, the organic polymer (A1) relates to the curable composition characterized in that the organic polymer (A1) is an organic polymer that does not substantially contain an amide segment (—NH—CO—) in the main chain skeleton.

In a preferred embodiment, the curable composition is characterized in that the silanol condensation catalyst is a carboxylic acid tin salt (C) and further contains an amine compound.

As a preferred embodiment, the present invention further relates to the curable composition containing an organotin catalyst (D).

In a preferred embodiment, the organotin catalyst (D) is dialkyl tin carboxylate, dialkyl tin oxide, Q _g Sn (OZ) _4-g , and [Q ₂ Sn (OZ)] ₂ O (where Q Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is an organic having a monovalent hydrocarbon group having 1 to 20 carbon atoms or a functional group capable of forming a coordination bond to Sn inside itself. In addition, the present invention relates to the curable composition, wherein g is at least one selected from the group consisting of compounds represented by:

In a preferred embodiment, the curable composition is characterized in that the carboxylic acid tin salt (C) is a carboxylic acid tin salt (C1) in which the carbon atom adjacent to the carbonyl group is a quaternary carbon.

In a preferred embodiment, the non-tin catalyst (E) is a carboxylic acid and further contains an amine.

In a preferred embodiment, the curable composition is characterized in that the carboxylic acid is a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon.

As a preferred embodiment, the present invention further relates to the curable composition characterized by containing a fine hollow body (F).

A preferred embodiment relates to the curable composition, wherein the organic polymer (A1) is 5 to 28% by weight in the total amount of the curable composition.

As a preferred embodiment, the present invention further relates to the curable composition containing the epoxy resin (I).

As a preferred embodiment, the present invention further relates to the curable composition characterized by containing a silicate (B).

In a preferred embodiment, the curable composition is characterized in that the silicate is a condensate of tetraalkoxysilane.

As a preferred embodiment, the following formula (7):
^{_{-SiR 5 c (OR 6) 3}} -c (7)
(Wherein c R ^{5 s} are each independently a monovalent organic group having 1 to 20 carbon atoms, and 3-c R ^{6 s} are each independently a monovalent organic group having 2 to 20 carbon atoms. It is a group, and c represents 0, 1, or 2.) The amino silane coupling agent (G) which has group represented by this is contained, It is related with the said curable composition characterized by the above-mentioned.

A preferred embodiment relates to the curable composition, wherein the group represented by the general formula (7) is a triethoxysilyl group.

As a preferred embodiment, the general formula (6):
-Si (OR ⁴ ) ₃ (6)
(Wherein three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms) an organic polymer having a silicon-containing functional group capable of crosslinking by forming a siloxane bond And general formula (8):
_{^{-SiR 7 d (OCH 3) e}} (OR 8) 3-d-e (8)
(In the formula, d R ⁷ are each independently a monovalent organic group having 1 to 20 carbon atoms, and 3-de R ⁸ are each independently a monovalent organic group having 2 to 20 carbon atoms. D represents 0, 1, or 2, and e represents 1, 2, or 3, provided that 3-de ≧ 0 is satisfied. A curable composition containing an aminosilane coupling agent (H) having a curable composition, wherein the curable composition is cured in advance.

The second of the present invention is the general formula (6):
-Si (OR ⁴ ) ₃ (6)
(Wherein three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms) an organic polymer having a silicon-containing functional group capable of crosslinking by forming a siloxane bond And R ⁴ O— group of the general formula (6) and a compound (J) having at least one methoxy group capable of transesterification, which is obtained by a transesterification reaction, the general formula (10):
_{^{-Si (OCH 3) f (OR}} 4) 3-f (10)
(Wherein 3-f R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms, and f represents 1, 2, or 3). The present invention relates to a method for producing an organic polymer, which has a silicon-containing functional group that can be cross-linked.

As a preferred embodiment, an organic polymer obtained by the production method, and
The present invention relates to a curable composition containing a silanol condensation catalyst that is at least one selected from a carboxylic acid tin salt (C), an organotin catalyst (D), and a non-tin catalyst (E).

As a more preferred embodiment, the present invention relates to an adhesive for interior panels, exterior panels, or vehicle panels, which contains the curable composition.

As a further preferred embodiment, the present invention relates to a sealing material for a working joint of a building, which contains the curable composition.

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 copolymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomer, vinyl polymer obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene; graft polymer obtained by polymerizing vinyl monomer in the organic polymer; polysulfide 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-aminolaurolac by condensation polymerization of A polyamide polymer such as nylon 12 produced by ring-opening polymerization of a copolymer, a copolymer nylon having two or more components of the above-mentioned nylon; a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, for example; Examples include diallyl phthalate polymers. Among the polymers having the main chain skeleton, polyoxyalkylene polymers, hydrocarbon polymers, polyester polymers, (meth) acrylic acid ester copolymers, polycarbonate polymers, etc. are available and manufactured. It is preferable because it is easy.

Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester copolymers have a relatively low glass transition temperature. The cured product is particularly preferred because of its excellent cold resistance.

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.

The urethane-bonding component is not particularly limited, and examples thereof include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; Examples thereof include those obtained from a reaction between an isocyanate compound and the above-mentioned polyols having various main chain skeletons.

When there are many amide segments (-NH-CO-) produced | generated in a principal chain frame | skeleton based on the said urethane bond, the viscosity of an organic polymer will become high and it will become a composition with bad workability | operativity. Therefore, the amount of the amide segment in the main chain skeleton of the organic polymer is preferably 3% by weight or less, more preferably 1% by weight or less, and most preferably substantially free of the amide segment. preferable.

The reactive silicon group contained in the organic polymer having a reactive silicon group has a hydroxyl group or 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 that can be crosslinked by As the reactive silicon group, the general formula (11):
^{_{- (SiR 1 2-b X}} b O) m -SiR 2 3-a X a (11)
(Wherein R ¹ and R ² are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO—. A triorganosiloxy group, when two or more R ¹ or R ² are present, they may be the same or different, where R ′ is a monovalent carbon atom having 1 to 20 carbon atoms; Three R's may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same A is 0, 1, 2 or 3, b is 0, 1, or 2. Also, regarding _{b in} m (SiR ¹ _2-b X _b O) groups, They may be the same or different, m is It represents an integer of 19. However, a group represented by shall satisfy a + Σb ≧ 1) and the like.

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

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

In particular, the general formula (12):
-SiR ² _3-a X _a (12)
A reactive silicon group represented by the formula (wherein R ² and X are the same as described above; a is an integer of 1 to 3) is preferable because it is easily available.

Specific examples of R ¹ and R ² in the general formulas (11) and (12) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, benzyl And an aralkyl group such as a group, and a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group, or the like. Of these, a methyl group is particularly preferred.

More specific examples of the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.

In the present invention, silicon in which three or more hydrolyzable groups are bonded particularly on silicon (that is, the number of a + b × m in the general formula (11) is 3 or more) among the organic polymers of the component (A). An organic polymer having a contained functional group can be used as the component (A1).

In this component (A1), three or more hydrolyzable groups are bonded on silicon, and the cured product crosslinked by silanol condensation reaction of the reactive silicon group exhibits good restorability and not more than two. Compared to the case of a reactive silicon group-containing organic polymer having a hydrolyzable group, a remarkable creep resistance and durability improvement effect are exhibited.

The number of a + b × m in the general formula (11) of the component (A1) is more preferably 3 to 5, and particularly preferably 3. Of these, trialkoxysilyl groups are preferred because the effects of improving the restorability, durability, and creep resistance of the curable composition of the present invention are particularly great, and the availability of raw materials is good. Here, the alkoxyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, a trimethoxysilyl group and a triethoxysilyl group are most preferable. When the carbon number is larger than 20, the curability may be slow.

In general, it is known that the durability of the resulting cured product decreases as the weight percent of the reactive silicon group-containing organic polymer in the curable composition decreases. However, when the component (A1) of the present invention is used as the reactive silicon group-containing organic polymer, high durability is maintained even if the weight percent of the reactive silicon group-containing organic polymer in the curable composition is reduced. be able to. Therefore, when the proportion of the component (A1) in the curable composition is 5 to 28% by weight, more preferably 10 to 26% by weight, and particularly preferably 15 to 24% by weight, low cost and high durability are achieved. It is preferable because both can be achieved.

In the present invention, among the organic polymers of the component (A1), an organic polymer having a trialkoxysilyl group having 2 to 20 carbon atoms can be used as the component (A4). That is, general formula (6):
-Si (OR ⁴ ) ₃ (6)
(In the formula, three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms.) An organic polymer having a group represented by (A4) can be used.

It is known that methanol produced by the hydrolysis reaction of the methoxysilyl group has a unique toxicity of causing optic nerve damage. On the other hand, since the component (A4) has 2 to 20 carbon atoms of the alkoxy group bonded to the silicon atom, the alcohol produced by the hydrolysis reaction of the reactive silicon group does not contain highly toxic methanol. It becomes a highly safe composition.

(A4) The carbon number of R ^{4 in} the general formula (6) of the component is more preferably 2 to 10, particularly preferably 2 to 4, and in the case of 2, the alcohol produced by hydrolysis is ethanol. And is the most preferable because of its highest safety. Specifically, a triethoxysilyl group is most preferable. When the number of carbon atoms is greater than 20, the curability of the curable composition may be slow, and the anesthetic action and stimulating action of the generated alcohol may be large.

Furthermore, in the present invention, among the organic polymers of the component (A4), those having a main chain skeleton of polyoxyalkylene can be used as the component (A5). That is, general formula (6):
-Si (OR ⁴ ) ₃ (6)
A polyoxyalkylene polymer having a group represented by the formula (wherein R ⁴ is the same as described above) can be used as the component (A5).

The average number of reactive silicon groups in the organic polymer (A) is preferably at least one per molecule, more preferably 1.1 to 5. When the number of reactive silicon groups contained in one molecule of the organic polymer (A) is less than one, the curability becomes insufficient, and good rubber elasticity behavior is hardly exhibited. The reactive silicon group may exist at the end of the molecular chain of the organic polymer (A) or may exist inside. When the reactive silicon group is present at the end of the molecular chain, the effective network chain amount of the organic polymer (A) component contained in the finally formed cured product increases, so that it has high strength, high elongation, and low elasticity. It becomes easy to obtain a rubber-like cured product showing a rate.

In the present invention, among the organic polymers of the component (A), an organic polymer having an average of 1.7 to 5 reactive silicon groups per molecule is used as the component (A2). Can do.

This component (A2) has an average number of 1.7 to 5 reactive silicon groups per molecule, and the cured product crosslinked by silanol condensation reaction of the reactive silicon group is good. It exhibits resilience and exhibits significant creep resistance and durability improvement effects as compared with organic polymers having an average number of reactive silicon groups per molecule of less than 1.7.

The number of reactive silicon groups per molecule of the component (A2) is more preferably 2-4, and particularly preferably 2.3-3. When the number of reactive silicon groups per molecule is less than 1.7, the effect of improving the restorability, durability, and creep resistance of the curable composition of the present invention may not be sufficient. If it is larger than the number, the elongation of the cured product obtained may be small.

In the present invention, among the organic polymers of the component (A), the general formula (3):
_{^{-O-R 3 -CH (CH 3}} ) -CH 2 - (SiR 1 2-b X b O) m -SiR 2 3-a X a (3)
(Wherein R ³ represents a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, oxygen, and nitrogen as a constituent atom, and R ¹ , R ² , X, An organic polymer having a structural part represented by a, b, and m is the same as described above can be used as the component (A3).

This component (A3) has a structural portion represented by the general formula (3), and the cured product crosslinked by silanol condensation reaction of the reactive silicon group exhibits good restorability, and the general formula (3) Compared to the case of an organic polymer having a terminal structure other than the above, remarkable creep resistance and durability improvement effects are exhibited.

The number of carbon atoms of R ^{3 in} the general formula (3) is more preferably 1 to 10 and particularly preferably 1 to 4 from the viewpoint of availability. Specifically, R ³ is most preferably a methylene group.

The component (A3) is represented by the general formula (5):
—O—R ³ —CH (CH ₃ ) —CH ₂ —SiX ₃ (5)
(In the formula, R ³ and X are the same as above), when the organic polymer has a structural portion represented by the above formula, improvement in resilience, durability, and creep resistance of the curable composition of the present invention. It is preferable because the effect is particularly great and the availability of raw materials is good.

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

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

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

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

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

Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. Alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane Examples thereof include, but are not limited to, ketoximate silanes. Of these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are most preferable because the hydrolyzability of the resulting curable composition is gentle and easy to handle.

Among the hydrosilane compounds, the general formula (2):
H-SiX ₃ (2)
The hydrosilane compound represented by the formula (wherein X is the same as above) is particularly effective in improving the resilience, durability, and creep resistance of a curable composition comprising an organic polymer obtained by addition reaction of the hydrosilane compound. It is preferable because it is large. Of the hydrosilane compounds represented by the general formula (2), trialkoxysilanes such as trimethoxysilane, triethoxysilane, and triisopropoxysilane are more preferable.

Among the trialkoxysilanes, a trialkoxysilane having a C 1 alkoxy group (methoxy group) such as trimethoxysilane may proceed rapidly, and the disproportionation reaction proceeds. , Quite dangerous compounds such as dimethoxysilane are produced. From the viewpoint of handling safety, the general formula (9):
H-Si (OR ⁴ ) ₃ (9)
It is preferable to use a trialkoxysilane having an alkoxy group having 2 or more carbon atoms represented by (wherein R ⁴ is the same as above). Triethoxysilane is the most preferable from the viewpoints of availability, safety in handling, restoration properties of the resulting curable composition, durability, and creep resistance.

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. Although silane etc. are mention | raise | lifted, it is not limited to these.

As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Although silane etc. are mention | raise | lifted, it is not limited to these.

As described above, a disproportionation reaction may occur in a silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane. The trialkoxysilane having one alkoxy group (methoxy group) sometimes proceeds disproportionately. As the disproportionation reaction proceeds, a rather dangerous compound such as dimethoxysilane is formed. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when a trialkoxysilyl group having a methoxy group such as a trimethoxysilyl group is used as the silicon-containing group, it is preferable to use the synthesis method (b) or (c).

In addition, as a method for obtaining an organic polymer having a silicon-containing group bonded to a methoxy group, the reactive silicon group is represented by the general formula (6) by any one of the methods (a), (b), and (c). ):
-Si (OR ⁴ ) ₃ (6)
(Wherein R ⁴ is the same as described above) After obtaining an organic polymer having a group represented by the above formula (that is, the component (A4)), a compound having at least one methoxy group capable of undergoing transesterification (J ) And a transesterification reaction in the presence or absence of a transesterification reaction catalyst, thereby giving a general formula (10):
_{^{-Si (OCH 3) f (OR}} 4) 3-f (10)
(Wherein 3-f R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms, and f represents 1, 2, or 3). A method for producing a coalescence can be mentioned. The organic polymer having a group represented by the general formula (10) exhibits faster curability than the organic polymer having a group represented by the general formula (6).

Among the above production methods, in particular, after introducing a reactive silicon group by the method (a), an organic compound having a group represented by the general formula (10) is obtained by subjecting the component (J) to a transesterification reaction. In the method for producing the polymer, a dangerous compound such as dimethoxysilane due to the disproportionation reaction does not occur during the production, and the odor is less than that of the organic polymer obtained by the method (b). It is more preferable because it becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method of

The compound (J) having at least one methoxy group capable of transesterification is not particularly limited, and various compounds can be used.

Examples of the component (J) include methanol, methyl esters of various acids such as carboxylic acid and sulfonic acid, and compounds having a silicon atom bonded to at least one methoxy group. As the compound having a silicon atom bonded to at least one methoxy group, a compound having a silicon atom bonded to 2 to 4 methoxy groups on the same silicon atom is more preferable because of a high transesterification rate. Furthermore, a compound having a silicon atom and an amino group bonded to 2 to 4 methoxy groups on the same silicon atom is particularly preferable because the transesterification rate is high.

Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, Examples include amino group-containing silanes such as γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-benzyl-γ-aminopropyltrimethoxysilane. In addition, a derivative obtained by modifying the silane compound or a condensation reaction product of the silane compound can also be used as the component (J).

The amino group-containing silanes are preferable because the transesterification proceeds even under relatively low temperature conditions of 60 ° C. or lower in the presence of a transesterification catalyst.

The component (J) used in the present invention is preferably used in the range of 0.1 to 10 parts and transesterified with respect to 100 parts of the reactive silicon group-containing organic polymer of the component (A4). In particular, it is preferably used in the range of 1 to 5 parts. The component (J) may be used alone or in combination of two or more.

The organic polymer (A) having a reactive silicon group may be linear or branched, and its number average molecular weight is about 500 to 50,000 in terms of polystyrene in GPC, more preferably 1,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 50,000, it tends to be disadvantageous in terms of workability due to high viscosity.

The reactive silicon group may be at the end or inside of the organic polymer molecular chain or at both. In particular, when the reactive silicon group is at the molecular end, the effective network chain amount of the organic polymer component contained in the finally formed cured product increases, so that a rubber-like cured product having high strength and high elongation is obtained. It is preferable from the viewpoint of being easily obtained.

The polyoxyalkylene polymer essentially has the general formula (13):

(Wherein R ⁹ is a divalent organic group, which is a linear or branched alkylene group having 1 to 14 carbon atoms), and in the general formula (13) R ⁹ is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (13) include

Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used in a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferred because it is amorphous or has a relatively low viscosity.

Examples of the method for synthesizing 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. After polymerizing such an olefinic compound having 1 to 6 carbon atoms as a main monomer, or (2) homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing with the olefinic compound However, isobutylene-based polymers and hydrogenated polybutadiene-based polymers can be easily introduced with functional groups at the terminals, the molecular weight can be easily controlled, and the number of terminal functional groups can be adjusted. An isobutylene polymer is particularly preferable because of its ease of synthesis.

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 the specifications 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.

Among the saturated hydrocarbon polymers having a reactive silicon group, the general formula (6):
-Si (OR ⁴ ) ₃ (6)
A saturated hydrocarbon polymer having a group represented by the formula (wherein R ⁴ is the same as described above) can be used as the component (A7). This component (A7) is characterized by excellent heat resistance, weather resistance, and moisture barrier properties based on a saturated hydrocarbon polymer having a main chain skeleton, and methanol accompanying a hydrolysis reaction of a reactive silicon group. In addition, the polymer is a polymer having a cured product with good resilience, durability, and creep resistance.

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

In the present invention, among the organic polymers of the component (A), those whose molecular chain is a (meth) acrylic acid ester copolymer can be used as the component (A6).

It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate Examples include (meth) acrylic acid monomers such as hexadecylethyl. In the (meth) acrylic acid ester copolymer, the following vinyl monomers 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 preferably, it is a (meth) acrylic polymer composed of an acrylate monomer and a methacrylic acid ester monomer, particularly preferably an acrylic polymer composed of an acrylate monomer, and further preferably composed of butyl acrylate. It is a polymer. 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 side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although 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 copolymer (A6), 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 copolymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio For this, 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 copolymer 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.

A cured product obtained by curing a curable composition containing a (meth) acrylic acid ester copolymer having a reactive silicon group is an organic polymer having another main chain skeleton such as a polyoxyalkylene polymer. The elongation may be low compared to a curable composition containing a coalescence. Even when the (meth) acrylic acid ester copolymer produced using the “living radical polymerization method” or the “atom transfer radical polymerization method” is used, the elongation may be insufficient and the durability may be poor. The durability of this (meth) acrylic acid ester copolymer can be remarkably improved by using a silicon-containing functional group having three or more hydrolyzable groups on silicon as a reactive silicon group. As compared with organic polymers having other main chain skeletons, the effect of improving durability is great.

As a method for producing a (meth) acrylic acid ester-based copolymer having a reactive silicon group, for example, Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, Japanese Patent Application Laid-Open No. Hei 6-221922, etc. A production method using a free radical polymerization method using a transfer 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.

Among the (meth) acrylic acid ester-based copolymers having a reactive silicon group, the general formula (6):
-Si (OR ⁴ ) ₃ (6)
A (meth) acrylic acid ester-based copolymer having a group represented by the formula (wherein R ⁴ is the same as described above) can be used as the component (A8). This component (A8) has features of excellent heat resistance, weather resistance, and chemical resistance based on a (meth) acrylic acid ester copolymer having a main chain skeleton, and hydrolysis of a reactive silicon group. There is no production of methanol due to the reaction, and the polymer is a polymer with good recovery, durability and creep resistance of the cured product.

The reactive silicon group of the component (A8) may be at the end or inside of the organic polymer molecular chain, or at both. In particular, when the reactive silicon group is at the end of the polymer main chain, the effective network chain amount of the polymer component contained in the finally formed cured product is increased, so that the rubber-like shape having high strength and high elongation is obtained. This is preferable from the viewpoint of easily obtaining a cured product.

As the polymerization method for the component (A8), the living radical polymerization method is more preferable because it has a low molecular weight distribution due to a narrow molecular weight distribution and can introduce a crosslinkable functional group at the molecular chain terminal at a high rate. The transfer radical polymerization method is particularly preferred.

The (meth) acrylic acid ester-based copolymer 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, it comprises a polyoxyalkylene polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, and a (meth) acrylic acid ester copolymer having a reactive silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester copolymer having a reactive silicon group is disclosed in JP-A-59-122541, Although proposed in Japanese Patent Laid-Open Nos. 63-112642, 6-172631, and 11-116763, the invention is not particularly limited thereto.

An organic polymer obtained by blending this polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester copolymer having a reactive silicon group can be used as a polyoxyalkylene polymer alone. It is known that the restorability is worse than that of the case. Therefore, as the polyoxyalkylene polymer component in the blended organic polymer, the above general formula (6):
-Si (OR ⁴ ) ₃ (6)
(Wherein R ⁴ is the same as above), a polyoxyalkylene polymer (A5) having a group represented by (meth) acrylic acid ester copolymer (A6) having a reactive silicon group; The blended organic polymer has excellent resilience, durability and creep resistance based on the component (A5) while exhibiting excellent weather resistance and adhesion based on the component (A6).

Preferred specific examples of the (A6) component (meth) acrylic acid ester copolymer include a reactive silicon group and a molecular chain substantially having the following general formula (14):

(Wherein R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group having 1 to 8 carbon atoms) (meth) acrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms Unit and the following general formula (15):

(Wherein R ¹⁰ is the same as described above, and R ¹² represents an alkyl group having 10 or more carbon atoms) and is a copolymer comprising a (meth) acrylate monomer unit having an alkyl group having 10 or more carbon atoms. In this method, a polymer is blended with a polyoxyalkylene polymer having a reactive silicon group.

R ^{11 in the} general formula (14) is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc., having 1 to 8, preferably 1 to 4, More preferably, 1-2 alkyl groups are mentioned. The alkyl group of R ¹¹ may alone, or may be a mixture of two or more.

R ^{12 in the} general formula (15) is, for example, a long-chain alkyl having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10-30, preferably 10-20. Group. The alkyl group of R ¹² is same as in the case of R ^11, alone may be, or may be a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester-based copolymer is substantially composed of monomer units of the formula (14) and the formula (15), and the term “substantially” here refers to the copolymer. It means that the sum of the monomer units of formula (14) and formula (15) present therein exceeds 50% by weight. The total of the monomer units of formula (14) and formula (15) is preferably 70% by weight or more.

The ratio of the monomer unit of the formula (14) to the monomer unit of the formula (15) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, by weight.

Examples of monomer units other than those represented by formula (14) and formula (15) 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.

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

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

In the present invention, silicate can be used as the component (B). This silicate has a function of improving the resilience, durability and creep resistance of the organic polymer which is the component (A) of the present invention.

The silicate as component (B) is represented by the general formula (16)
Si (OR ¹³ ) ₄ (16)
(In the formula, each R ¹³ is independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Or a partially hydrolyzed condensate thereof.

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

The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.

Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. 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.).

The silicate (B) exhibits further improved restoring properties, durability, and creep resistance improvement effect by combining with the components (A1), (A2) and (A3) of the present invention. In particular, when combined with the component (A1), it exhibits an excellent effect of improving the resilience, durability, and creep resistance.

(B) As usage-amount of a component, 0.1-10 weight part is preferable with respect to 100 weight part of (A) component, Furthermore, 1-5 weight part is preferable. When the blending amount of the component (B) is below this range, the restoring effect, durability, and creep resistance may not be sufficiently improved. When the blending amount of the component (B) is above this range, the curing rate is increased. May be slow. The silicate may be used alone or in combination of two or more.

In the present invention, a carboxylic acid tin salt can be used as the component (C). By using this carboxylic acid tin salt as a silanol condensation catalyst of the organic polymer that is the component (A1) of the present invention, compared with other silanol condensation catalysts, the restorability, durability, and Can improve creep resistance.

The carboxylic acid tin salt (C) used in the present invention is not particularly limited, and various compounds can be used.

Here, as the carboxylic acid having an acid group of the carboxylic acid tin salt (C), a hydrocarbon-based carboxylic acid group-containing compound having 2 to 40 carbon atoms including the carbonyl carbon is preferably used, and the point of availability. To C2-20 hydrocarbon carboxylic acids 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, hydonocarbic acid, sorghumulinic acid, golphosphoric 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, speric acid, sebacic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, oxydiacetic acid and other saturated dicarboxylic acids; maleic acid, Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as aconitic acid, citric acid, and isocitric acid. Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl And aromatic polycarboxylic acids such as acetic acid and pyromellitic acid. In addition, amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, histidine and the like can be mentioned.

The carboxylic acid is preferably 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, naphthenic acid, or the like because it is particularly easy to obtain and inexpensive, and has good compatibility with the component (A1). .

When the carboxylic acid has a high melting point (high crystallinity), the carboxylic acid tin salt having an acid group also has a high melting point, which makes it 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.

Moreover, when the carbon number of the carboxylic acid is large (molecular weight is large), the carboxylic acid tin salt having the acid group becomes a solid or highly viscous liquid, which is difficult to handle (poor workability). . On the contrary, when the carbon number of the carboxylic acid is small (molecular weight is small), the carboxylic acid tin salt having the acid group contains many components that are easily volatilized by heating, and the catalytic ability of the carboxylic acid metal salt is reduced. There is a case. In particular, when the composition is thinly stretched (thin layer), volatilization by heating is large, and the catalytic ability of the carboxylic acid metal salt may be greatly reduced. Therefore, 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 the carboxylic acid tin salt, a dicarboxylic acid or monocarboxylic acid tin salt is preferable, and a monocarboxylic acid tin salt is more preferable.

As the monocarboxylic acid tin salt, the general formula (17):
Sn (OCOR) ₂ (17)
Wherein R is a substituted or unsubstituted hydrocarbon group and may contain a carbon-carbon double bond. The two RCOO— groups may be the same or different. A divalent Sn compound or a general formula (18):
Sn (OCOR) ₄ (18)
A tetravalent Sn compound represented by the formula (wherein R is the same as described above. The two RCOO- groups may be the same or different) is preferable. From the viewpoint of curability and availability, a divalent Sn compound represented by the general formula (17) is more preferable.

In addition, the carboxylic acid tin salt (C) includes a carboxylic acid tin salt (such as tin 2-ethylhexanoate) whose carbon at the α-position of the carboxyl group is a tertiary carbon, or a carboxylic acid tin salt (neodecane) whose quaternary carbon is used. Tin oxide, tin pivalate, etc.) are more preferable because of their high curing speed, and carboxylic acid tin salts in which the carbon atom adjacent to the carbonyl group is a quaternary carbon are particularly preferable.

In the present invention, among the carboxylic acid tin salt (C), a carboxylic acid tin salt in which the carbon at the α-position of the carboxyl group is a quaternary carbon is used as the component (C1).

The carboxylic acid tin salt of the component (C1) has the general formula (19):

(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a substituted or unsubstituted monovalent organic group and may contain a carboxyl group), or a chain fatty acid tin represented by Formula (20):

(Wherein R ¹⁷ is a substituted or unsubstituted monovalent organic group, R ¹⁸ is a substituted or unsubstituted divalent organic group, each of which may contain a carboxyl group) and the general formula (21 ):

(Wherein, R ¹⁹ is a substituted or unsubstituted trivalent organic group, which may contain a carboxyl group), and cyclic fatty acid tin containing the structure represented by: Specific examples of the carboxylic acid having an acid group of the carboxylic acid tin salt (C1) 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 Chain monocarboxylic acids such as -2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyl-3-hydroxypropionic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2,2 -Chain dicarboxylic acids such as dimethyl succinic acid, 2,2-diethyl succinic acid, 2,2-dimethyl glutaric acid, 3-methylisocitric acid, 4,4-dimethylaconitic acid Any chain tricarboxylic acid, 1-methylcyclopentanecarboxylic 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- Examples thereof include cyclic carboxylic acids such as 1-carboxylic acid and bicyclo [2.2.2] octane-1-carboxylic acid. Many compounds containing such structures exist in natural products, but these can also be used.

In particular, from the viewpoint of good compatibility with the component (A1) and good workability, tin monocarboxylate is more preferable, and chain monocarboxylic acid tin is more preferable. Further, tin pivalate, tin neodecanoate, tin versatate, tin 2,2-dimethyloctanoate, tin 2-ethyl-2,5-dimethylhexanoate and the like are particularly preferable because they are easily available.

In the component (C1), the divalent tin carboxylate and the tetravalent tin carboxylate can be mentioned as in the case of the component (C) described above. From the viewpoint of curability and availability, the divalent tin is included. The carboxylate salt is more preferred.

Moreover, it is preferable that carbon number of the carboxylic acid which has an acid group of (C1) component is 5-20, It is more preferable that it is 6-17, It is especially preferable that it is 8-12. If the number of carbon atoms exceeds this range, it tends to be solid and the compatibility with the component (A1) is lowered, and the catalytic activity may be lowered. On the other hand, if the number of carbon atoms is small, volatility and odor increase, and the thin layer curability of the curable composition decreases, which is not preferable.

From these points, as component (C1), tin neodecanoate (divalent), tin versatate (divalent), tin 2,2-dimethyloctanoate (divalent), 2-ethyl-2,5-dimethylhexanoic acid Tin (divalent), tin neodecanoate (tetravalent), tin versatate (tetravalent), tin 2,2-dimethyloctanoate (tetravalent), tin 2-ethyl-2,5-dimethylhexanoate (tetravalent) Is particularly preferred.

The amount of component (C) and component (C1) used is preferably about 0.01 to 20 parts by weight, more preferably about 0.5 to 10 parts by weight, per 100 parts by weight of component (A1). If the blending amount is less than this range, the curing rate may be slow, and the curing reaction may be difficult to proceed sufficiently. On the other hand, if the blending amount exceeds this range, the pot life may become too short, resulting in poor workability, and is not preferable from the viewpoint of storage stability.

Moreover, (C) component and (C1) component can be used in combination of 2 or more types besides using individually.

On the other hand, when only the component (C) and the component (C1) are low in activity and an appropriate curability cannot be obtained, an amine compound can be added as a promoter.

Examples of the various amine compounds are described in JP-A-5-287187. Specifically, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2- Aliphatic primary amines such as ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, Di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstere Aliphatic secondary amines such as rilamine; Aliphatic tertiary amines such as triethylamine, triamylamine, trihexylamine and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Laurylaniline and stearyl Aromatic amines such as aniline, triphenylamine, N, N-dimethylaniline, dimethylbenzylaniline; and other amines such as monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylenetriamine, triethylenetetramine , Tetraethylenepentamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, dodecamethylenediamine, dimethylethylene Amine, triethylenediamine, guanidine, diphenylguanidine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethylethylenediamine, 2,4,6- Examples include tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), and the like. It is not limited.

The compounding amount of the amine compound is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the organic polymer of the component (A1). If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 20 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

In the present invention, an organotin catalyst can be used as the component (D). When this organotin catalyst is used as a silanol condensation catalyst for an organic polymer having a reactive silicon group, it has a higher catalytic activity than other silanol condensation catalysts, and a curable composition having good deep curability and adhesiveness. A thing is obtained. However, the restorability, durability, and creep resistance of the cured product of the resulting curable composition are reduced depending on the amount of the organotin catalyst added.

By using the organic polymer that is the component (A1) of the present invention as the polymer component, the curable composition to which the organotin catalyst of the component (D) is added has high catalytic activity, deep curable property, and adhesive property. It is good and can maintain high restoration property, durability, and creep resistance of the obtained cured product.

On the other hand, when an adhesive or sealant containing an organic polymer having a reactive silicon group as a main component is used for an application requiring durability, the carboxylic acid tin salt of the component (C) is used as a curing catalyst. Often used. However, when this carboxylic acid tin salt is used as a curing catalyst, when the sealing material remains as a thin layer around the joint, the thin layer portion is difficult to cure, and may remain uncured particularly under conditions of high temperature and high humidity. is there. On the other hand, when the organotin catalyst (D) is used as a curing catalyst, as described above, the restorability and durability are lowered, but the curability of the thin layer portion is good. Therefore, when the organic polymer that is the component (A1) of the present invention and the organotin catalyst of the component (D) are combined, the thin layer portion of the cured product can be maintained while maintaining the high resilience and durability of the resulting cured product. Curability can be remarkably improved.

However, even when combined with the organic polymer which is the component (A1) of the present invention, the resilience and durability may be slightly lowered depending on the amount of the organotin catalyst as the component (D). Therefore, as the curing catalyst, the (D) component organotin catalyst is used in combination with the (C) component carboxylic acid tin salt, and sufficient curability, deep curability, adhesiveness, and thin layer curability are obtained. It is more preferable to reduce the amount of component (D) added to the extent.

Specific examples of the organotin catalyst (D) include dialkyltin carboxylates, dialkyltin oxides, and general formula (22):
_{Q g Sn (OZ) 4-} g, or _{[Q 2 Sn (OZ)]} 2 O (22)
(In the formula, Q is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a functional group capable of forming a coordination bond to Sn inside itself. An organic group having a functional group, and g is any one of 0, 1, 2, and 3). Also, a tetravalent tin compound such as dialkyltin oxide or dialkyltin diacetate and a low molecular silicon compound having a hydrolyzable silicon group such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane or phenyltrimethoxysilane. The reactant can also be used as component (D). Among these, compounds represented by the general formula (22), that is, chelate compounds such as dibutyltin bisacetylacetonate and tin alcoholates are more preferable because of their high activity as silanol condensation catalysts.

Specific examples of the dialkyltin carboxylates include, for example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate Dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diiso Examples include octyl malate.

Specific examples of the dialkyl tin oxides include dibutyl tin oxide, dioctyl tin oxide, a mixture of dibutyl tin oxide and phthalate ester, and the like.

Specific examples of the chelate compound include:

However, it is not limited to these. Of these, dibutyltin bisacetylacetonate is most preferred because of its high catalytic activity, low cost, and availability.

Specific examples of the tin alcoholates include:

However, it is not limited to these. Of these, dialkyltin dialkoxide is preferred. In particular, dibutyltin dimethoxide is more preferred because of its low cost and easy availability.

The amount of component (D) used is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, per 100 parts by weight of component (A1). If the blending amount is less than this range, the curing rate may be slow, and the curing reaction may be difficult to proceed sufficiently. On the other hand, if the blending amount exceeds this range, the pot life may become too short, resulting in poor workability, and is not preferable from the viewpoint of storage stability.

Moreover, as the usage-amount in the case of using together (D) component and (C) component as a curing catalyst, (C1) component: 0.5-20 weight part with respect to (A1) component 100 weight part, (D) Component: 0.01-10 parts by weight is preferable, (C) component: 1-10 parts by weight, and (D) component: 0.02-5 parts by weight are more preferable. When the blending amount of component (C) is below this range, the curing rate may be slow, and when the blending amount is above this range, the pot life may be too short and workability may be deteriorated. When the blending amount of the component (D) is less than this range, the curability, deep-curing property, adhesiveness, and thin layer curability may not be sufficiently improved. The restoration property, durability, and creep resistance of an object may deteriorate.

Moreover, (D) component can be used in combination of 2 or more type besides using it individually.

In the present invention, a non-tin catalyst can be used as the component (E). When this non-tin catalyst is used as a silanol condensation catalyst of the organic polymer which is the component (A1) of the present invention, compared to other silanol condensation catalysts, the restorability, durability, and It has a function to increase creep resistance. Further, the non-tin catalyst as the component (E) is an environment-friendly curing catalyst with high social demand.

The non-tin catalyst that is the component (E) that can be used in the present invention is not particularly limited, but carboxylic acid, carboxylic acid metal salts other than tin carboxylate, organic sulfonic acid, acidic phosphate esters, Examples thereof include organometallic compounds containing Group 3B and Group 4A metals.

As carboxylic acid, the above-mentioned various carboxylic acid which has the acid group of the carboxylic acid tin salt which is (C) component can be illustrated.

The carboxylic acid, like the carboxylic acid tin salt (C), preferably contains 2 to 20 carbon atoms, more preferably 6 to 17 carbon atoms, including 8 to 12 carbon atoms. It is particularly preferred. Further, 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. Further, the carboxylic acid is a carboxylic acid (2-ethylhexanoic acid or the like) in which the carbon at the α-position of the carboxyl group is a tertiary carbon, or a carboxylic acid (neodecanoic acid, pivalic acid or the like) in which the carbon is a quaternary carbon. Is more preferable, and a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is particularly preferable.

As the carboxylic acid, 2-ethylhexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid and 2-ethyl-2,5-dimethylhexanoic acid are particularly preferable from the viewpoints of availability, curability and workability. .

As the carboxylic acid metal salt other than the carboxylic acid tin salt, the aforementioned metal salts of various carboxylic acids can be suitably used.

Among carboxylic acid metal salts other than the carboxylic acid tin salt, bismuth carboxylate, calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate , Cobalt carboxylate, zirconium carboxylate, cerium carboxylate are preferable from the viewpoint of high catalyst activity, bismuth carboxylate, calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate More preferable are manganese carboxylate and zirconium carboxylate, and bismuth carboxylate, calcium carboxylate, vanadium carboxylate, iron carboxylate, titanium carboxylate, and zirconium carboxylate are more preferable. Carboxylic acid bismuth, iron carboxylate, titanium carboxylate is most preferred.

In addition, bismuth carboxylate, calcium carboxylate, vanadium carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, nickel carboxylate, cobalt carboxylate, zirconium carboxylate are obtained curable compositions. More preferable from the viewpoint of less coloring and the heat resistance and weather resistance of the resulting cured product, bismuth carboxylate, calcium carboxylate, titanium carboxylate, potassium carboxylate, barium carboxylate, and zirconium carboxylate are more preferable. .

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

Examples of the monocarboxylic acid metal salt include general formulas (23) to (35):
Bi (OCOR) ₃ (23)
Ca (OCOR) ₂ (24)
V (OCOR) ₃ (25)
Fe (OCOR) ₂ (26)
Fe (OCOR) ₃ (27)
Ti (OCOR) ₄ (28)
K (OCOR) (29)
Ba (OCOR) ₂ (30)
Mn (OCOR) ₂ (31)
Ni (OCOR) ₂ (32)
Co (OCOR) ₂ (33)
Zr (O) (OCOR) ₂ (34)
Ce (OCOR) ₃ (35)
Wherein R is a substituted or unsubstituted hydrocarbon group and may contain a carbon-carbon double bond. The two RCOO— groups may be the same or different. Carboxylic acid metal salts are preferred.

Examples of the carboxylic acid group of the carboxylic acid metal salt other than the carboxylic acid tin salt include acid groups of various carboxylic acid tin salts exemplified as the component (C).

Specific examples of preferable carboxylic acid metal salts from the viewpoint of availability of raw materials and compatibility include bismuth 2-ethylhexanoate (trivalent), iron 2-ethylhexanoate (divalent), and iron 2-ethylhexanoate. (Trivalent), titanium 2-ethylhexanoate (tetravalent), vanadium 2-ethylhexanoate (trivalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent), 2 -Barium ethylhexanoate (divalent), manganese 2-ethylhexanoate (divalent), nickel 2-ethylhexanoate (divalent), cobalt 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate ( Tetravalent), cerium 2-ethylhexanoate (trivalent), bismuth neodecanoate (trivalent), iron neodecanoate (divalent), iron neodecanoate (trivalent), titanium neodecanoate Tetravalent), vanadium neodecanoate (trivalent), calcium neodecanoate (divalent), potassium neodecanoate (monovalent), barium neodecanoate (divalent), zirconium neodecanoate (tetravalent), cerium neodecanoate (trivalent) ), Bismuth oleate (trivalent), iron oleate (divalent), iron oleate (trivalent), titanium oleate (tetravalent), vanadium oleate (trivalent), calcium oleate (divalent), Potassium oleate (monovalent), barium oleate (divalent), manganese oleate (divalent), nickel oleate (divalent), cobalt oleate (divalent), zirconium oleate (tetravalent), oleic acid Cerium (trivalent), bismuth naphthenate (trivalent), iron naphthenate (divalent), iron naphthenate (trivalent), titanium naphthenate (tetravalent), naphtho Vanadium oxide (trivalent), calcium naphthenate (divalent), potassium naphthenate (monovalent), barium naphthenate (divalent), manganese naphthenate (divalent), nickel naphthenate (divalent), naphthenic acid Examples include cobalt (divalent), zirconium naphthenate (tetravalent), cerium naphthenate (trivalent), and the like.

From the viewpoint of catalytic activity, bismuth 2-ethylhexanoate (trivalent), iron 2-ethylhexanoate (divalent), iron 2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate (tetravalent), Bismuth neodecanoate (trivalent), iron neodecanoate (divalent), iron neodecanoate (trivalent), titanium neodecanoate (tetravalent), bismuth oleate (trivalent), iron oleate (divalent), oleic acid More preferred are iron (trivalent), titanium oleate (tetravalent), bismuth naphthenate (trivalent), iron naphthenate (divalent), iron naphthenate (trivalent), and titanium naphthenate (tetravalent). -Especially preferred are iron iron hexanoate (trivalent), iron neodecanoate (trivalent), and iron naphthenate (trivalent).

From the viewpoint of coloring, bismuth 2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate (tetravalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent) , Barium 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate (tetravalent), bismuth neodecanoate (trivalent), titanium neodecanoate (tetravalent), calcium neodecanoate (divalent), potassium neodecanoate (Monovalent), barium neodecanoate (divalent), zirconium neodecanoate (tetravalent), bismuth oleate (trivalent), titanium oleate (tetravalent), calcium oleate (divalent), potassium oleate (1 Valent), barium oleate (divalent), zirconium oleate (tetravalent), bismuth naphthenate (trivalent), titaniate naphthenate Beam (tetravalent), calcium naphthenate (divalent), potassium naphthenate (monovalent), barium naphthenate (divalent), zirconium naphthenate (tetravalent) is more preferable.

Examples of the organic sulfonic acid include toluene sulfonic acid and styrene sulfonic acid.

An acidic phosphate ester is a phosphate ester containing a -OP (= O) OH moiety, and includes acidic phosphate esters as shown below. Organic acidic phosphate compounds are preferred in terms of compatibility and curing catalyst activity.

Organic acidic phosphoric acid ester _{^{compound, (R 20 -O) h -P}} (= O) - represented by _{(OH) 3-h} (wherein h is 1 or ^{2, R 20} represents an organic residue) .

Specific examples are given below.
_{(CH 3 O) 2 -P (} = O) (- OH), (CH 3 O) -P (= O) (- OH) 2, (C 2 H 5 O) 2 -P (= O) (- _{OH), (C 2 H 5} O) -P (= O) (- OH) 2, (C 3 H 7 O) 2 -P (= O) (- OH), (C 3 H 7 O) -P _{(= O) (- OH)} 2, (C 4 H 9 O) 2 -P (= O) (- OH), (C 4 H 9 O) -P (= O) (- OH) 2, (C _{8 H 17 O) 2 -P (} = O) (- OH), (C 8 H 17 O) -P (= O) (- OH) 2, (C 10 H 21 O) 2 -P (= O) (—OH), (C ₁₀ H ₂₁ O) —P (═O) (— OH) ₂ , (C ₁₃ H ₂₇ O) ₂ —P (═O) (— OH), (C ₁₃ H ₂₇ O) _{-P (= O) (- OH} ) 2, (C 16 H 33 O) 2 -P (= O) _{-OH), (C 16 H 33} O) -P (= O) (- OH) 2, (HO-C 6 H 12 O) 2 -P (= O) (- OH), (HO-C 6 H _{12 O) -P (= O)} (- OH) 2, (HO-C 8 H 16 O) -P (= O) (- OH), (HO-C 8 H 16 O) -P (= O) (—OH) ₂ , {(CH ₂ OH) (CHOH) O} ₂ —P (═O) (— OH), {(CH ₂ OH) (CHOH) O} —P (═O) (— OH) _{2, {(CH 2 OH)} (CHOH) C 2 H 4 O} 2 -P (= O) (- OH), {(CH 2 OH) (CHOH) C 2 H 4 O} -P (= O) (—OH) _{2 and the} like can be mentioned, but are not limited to the above exemplified substances.

Addition of an amine compound as a co-catalyst when the activity is low only with carboxylic acid, metal carboxylate other than tin carboxylate, organic sulfonic acid, and acidic phosphoric acid esters, and adequate curability cannot be obtained. be able to.

As the various amine compounds, the above-described various amine compounds described as promoters for the carboxylic acid tin salt (C) can be used.

The compounding amount of the amine compound is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the organic polymer of the component (A1). If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 20 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

Examples of the non-tin metal compounds include organic metal compounds containing Group 3B and Group 4A metals, in addition to carboxylic acid metal salts other than the above-mentioned carboxylic acid tin salts, organic titanate compounds, organic aluminum compounds, and organic zirconium compounds. A compound, an organic boron compound, and the like are preferable from the viewpoint of activity, but are not limited thereto.

Examples of the organic titanate compound include titanium alkoxides such as tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate, tetra (2-ethylhexyl titanate), triethanolamine titanate, titanium tetraacetylacetonate, titanium ethylacetoacetate, octylene. Examples thereof include chelate compounds such as titanium chelates such as glycolate and titanium lactate.

Examples of the organoaluminum compounds include aluminum alkoxides such as aluminum isopropylate, monosec-butoxyaluminum diisopropylate, and aluminum sec-butyrate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, and the like. Aluminum chelates.

Examples of the zirconium compound include zirconium alkoxides such as zirconium tetraisopropoxide, zirconium tetra-n-propylate, and zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, and zirconium acetylacetonate. Zirconium chelates such as bisethyl acetoacetate and zirconium acetate.

These organic titanate compounds, organoaluminum compounds, organozirconium compounds, organoboron compounds, and the like can be used together, but in particular, the activity is enhanced by the combined use with the amine compound or acidic phosphate compound. Therefore, it is preferable from the viewpoint of reducing the amount of the catalyst used, and more preferable from the viewpoint of adjusting curability at high temperature and pot life at normal temperature.

The amount of component (E) used is preferably about 0.01 to 20 parts by weight, more preferably about 0.5 to 10 parts by weight, based on 100 parts by weight of component (A1). If the blending amount is less than this range, the curing rate may be slow, and the curing reaction may be difficult to proceed sufficiently. On the other hand, if the blending amount exceeds this range, the pot life may become too short, resulting in poor workability, and is not preferable from the viewpoint of storage stability.

Moreover, (E) component can be used in combination of 2 or more type besides using it individually.

In the present invention, a fine hollow body can be used as the component (F). When this micro hollow body is used, as described in JP-A-11-35923 and JP-A-11-310772, the workability (stringing property, thixotropy) of the composition is remarkably improved. It is known that the composition can be reduced in weight and cost. However, it is known that the restorability and durability of the cured product of the resulting curable composition are reduced depending on the amount of the micro hollow body added.

By using the organic polymer that is the component (A1) of the present invention as the polymer component, the curable composition to which the micro hollow body of the component (F) is added significantly improves workability (stringiness). However, the restorability and durability of the resulting cured product can be maintained high.

The minute hollow body (hereinafter referred to as balloon) which is the component (F) of the present invention has a diameter of 1 mm or less, preferably 500 μm, as described in, for example, “Latest Technology of Functional Filler” (CMC Corporation). It is a hollow body composed of the following inorganic or organic materials. The component (F) is not particularly limited, and various known balloons can be used.

The average particle density of the balloon is preferably 0.01 to 1.0 g / cm ^3, more preferably ^{0.03~0.7g / cm 3, 0.1~0.5g / cm} 3 It is particularly preferred that If the average particle density is below this range, the tensile strength of the cured product may be reduced. On the other hand, if the average particle density is above this range, the workability improvement effect may not be sufficient.

From the viewpoints of resilience and durability, inorganic balloons are preferable to organic balloons.

Examples of the inorganic balloons include silicate balloons and non-silicate balloons, silicate balloons include shirasu balloons, perlite, glass balloons, silica balloons, fly ash balloons, etc., and non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons. Specific examples of these inorganic balloons include Shirasu balloons made by Idichi Kasei Co., Ltd., Sankilite made by Sanki Kogyo Co., Ltd., and glass balloons made by Nippon Sheet Glass Co., Ltd., Sumitomo 3M Co., Ltd. ) Cellstar Z-28, EMERSON & CUMING Co., Ltd. MICRO BALLON, PITTS BURGGE CORNING Co., Ltd. CELAMIC GLASSMODULES, 3M Co., Ltd. GLASS BUBBLES, Fuji Silicia Chemical Co., Ltd. Q-CEL manufactured by Asahi Glass Co., Ltd., silicia manufactured by Fuji Silysia Chemical Co., Ltd., fly ash balloon, CEROSPHERES manufactured by PFAMARKETING, FILLITE U. S. FILLITE manufactured by A Co., Ltd., BW manufactured by Showa Denko Co., Ltd. as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA Co., Ltd. as a zirconia balloon, Kureha Fair Co., Ltd., GENERAL TECHNOLOGIES Co., Ltd. manufactured as a carbon balloon A car boss fair is commercially available.

Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting balloon includes a phenol balloon, an epoxy balloon, and a urea balloon. The thermoplastic balloon includes a saran balloon, a polystyrene balloon, Examples thereof include polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. A crosslinked thermoplastic balloon can also be used. The balloon here may be a balloon after foaming, or a balloon containing a foaming agent may be foamed after blending.

Specific examples of these organic balloons include UCAR and PHENOLIC MICROBALLONS manufactured by Union Carbide as phenolic balloons, ECCOSPHERES manufactured by EMERSON & CUMING Co., Ltd. as epoxy balloons, and ECCOSPHERES VF-O manufactured by EMERSON & CUMING Co., Ltd. as urea balloons. SARAN MICROSPHERES manufactured by DOW CHEMICAL Co., Ltd. as a Saran balloon, EXPANSELL manufactured by Nippon Filament Co., Ltd., Matsumoto Microsphere manufactured by Matsumoto Yushi Seiyaku Co., Ltd., DYLITE EXPANDABLE POLYSTYRENE manufactured by ARCO POLYMERS Co., Ltd. as a polystyrene balloon EXPA manufactured by BASF WYANDOTE DABLE POLYSTYRENE BEADS, crosslinked styrene - the acrylic acid balloon made by Japan Synthetic Rubber (Ltd.) SX863 is (P), it is commercially available.

The balloons may be used alone or in combination of two or more. In order to improve the dispersibility and the workability of the compound by using fatty acid, fatty acid ester, rosin, rosin lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. on the surface of these balloons. The processed one can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

The amount of the balloon used is preferably about 0.1 to 50 parts by weight, more preferably about 0.5 to 30 parts by weight with respect to 100 parts by weight of component (A1). If the blending amount is less than this range, the workability improvement effect may not be sufficient, and if the blending amount exceeds this range, the tensile strength of the cured product may be reduced, and the resilience and durability may be deteriorated. .

In the present invention, as the component (G), the general formula (7):
^{_{-SiR 5 c (OR 6) 3}} -c (7)
(Wherein c R ^{5 s} are each independently a monovalent organic group having 1 to 20 carbon atoms, and 3-c R ^{6 s} are each independently a monovalent organic group having 2 to 20 carbon atoms. And c represents 0, 1, or 2.) and an aminosilane coupling agent having a group represented by the following formula can be used. This (G) component is represented by the general formula (6) as the component (A4) of the present invention:
-Si (OR ⁴ ) ₃ (6)
By adding to the organic polymer having a group represented by the formula (wherein R ⁴ is the same as above), it has excellent resilience, durability, and creep resistance, and also exhibits excellent adhesion. Composition. In addition, since the reactive silicon group of component (G) does not have a methoxy group as an alkoxy group bonded to a silicon atom, after mixing with component (A4), the reaction between component (G) and component (A4) Even if the transesterification reaction between the reactive silicon groups proceeds, a highly reactive methoxysilyl group is not generated on the reactive silicon group of the component (A4). Therefore, the curable composition containing the component (G) and the component (A4) becomes a curable composition with little change in the curing rate before and after storage. Further, since the reactive silicon group of the component (G) and the component (A4) has 2 to 20 carbon atoms of the alkoxy group bonded to the silicon atom, the reactive silicon group is used when the curable composition is condensed and cured. The alcohol produced by the hydrolysis reaction does not contain highly toxic methanol, resulting in a highly safe composition.

The curable composition comprising the component (G) and the component (A4) can be used as a one-component type or a multi-component type composition such as a two-component type. This is more preferable because the effect of reducing the change in the curing rate before and after storage is great.

The component (G) is a compound having a reactive silicon group and an amino group represented by the general formula (7). Specific examples of the reactive silicon group represented by the general formula (7) include triethoxysilyl group, methyldiethoxysilyl group, dimethylethoxysilyl group, ethyldiethoxysilyl group, triisopropoxysilyl group, methyldiiso Examples thereof include a propoxysilyl group. The alkoxy group bonded to the silicon atom of the reactive silicon group is preferably an ethoxysilyl group or isopropoxysilyl, and more preferably an ethoxysilyl group, from the viewpoint of the toxicity of the alcohol generated in the hydrolysis reaction. The number of alkoxy groups bonded to one silicon atom of the reactive silicon group is preferably 2 or more, more preferably 3 from the viewpoint of curing speed. A triethoxysilyl group is most preferable from the viewpoint of the toxicity of the alcohol generated in the hydrolysis reaction and the curing rate.

Specific examples of the component (G) include γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltriisopropoxysilane, γ-ureido Propylmethyldiethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-benzyl-γ-aminopropyltriethoxysilane, Nn-butyl-γ-aminopropyltriethoxysilane, N-vinylbenzyl-γ -Aminopropyltriethoxy Amino such as lan, N, N′-bis (γ-triethoxysilylpropyl) ethylenediamine, bis (triethoxysilylpropyl) amine, γ- [2- (2-aminoethyl) aminoethyl] aminopropyltriethoxysilane, etc. Group-containing silanes can be mentioned. A derivative obtained by modifying the silane compound or a condensation reaction product of the silane compound can also be used as the component (G).

(G) component used for this invention is used in 0.1-10 parts with respect to 100 parts of organic polymers of (A4) component. In particular, it is preferably used in the range of 1 to 5 parts. The component (G) may be used alone or in combination of two or more.

When the composition composed of the component (A4) and the component (G) is a one-component composition, a dehydrating agent may be added. The dehydrating agent is not particularly limited, and various compounds can be used. As a dehydrating agent, a silicon compound that has an alkoxysilyl group and does not contain an amino group, after curing due to a slow transesterification reaction with the reactive silicon group of the component (A4) during curing at a relatively low temperature The change in physical properties is small and the dehydration effect is high. A silicon compound having a trialkoxysilyl group and not containing an amino group is preferred because of its higher dehydration effect, and a silicon compound having a trimethoxysilyl group and not containing an amino group is particularly preferred. Specifically, alkyltrialkoxysilanes such as vinyltrimethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane are preferable from the viewpoint of dehydration effect, curability, availability, and tensile properties of the cured product.

In the present invention, as the component (H), the general formula (8):
^{_{-SiR 7 d (OCH 3) e}} (OR 8) 3-d-e (8)
(In the formula, d R ^{7 s} are each independently a monovalent organic group having 1 to 20 carbon atoms, and 3-de R ^{8 s} are each independently a monovalent organic group having 2 to 20 carbon atoms. An organic group, d represents 0, 1, or 2, and e represents 1, 2, or 3, provided that 3-de ≧ 0 is satisfied. The aminosilane coupling agent which has can be used. This (H) component is represented by the general formula (6) as the component (A4) of the present invention:
-Si (OR ⁴ ) ₃ (6)
When the curable composition added to the organic polymer having a group represented by the formula (wherein R ⁴ is the same as above) is cured in advance, the methoxysilyl group of the component (H) and the reactive silicon group of the component (A4) The transesterification reaction proceeds with the reaction, and a highly reactive methoxysilyl group is generated in the reactive silicon group of the component (A4). The resulting curable composition has excellent adhesion, resilience, durability, and creep resistance, and becomes a fast-curing curable composition.

Preferred curing conditions for the curable composition comprising the component (H) and the component (A4) are the presence or absence of an ester exchange reaction catalyst and the amount added, and the reactive silicon group ester of the component (H) and the component (A4). Since it varies depending on the exchange reaction activity, etc., it cannot be generally determined. However, when the organotin catalyst or the Ti-based catalyst is contained in the system in an amount of about 0.5 to 3 parts as the transesterification reaction catalyst, 10 to 30 ° C. It is preferable to cure for one week or longer under the relatively low temperature condition, and it is preferable to cure for one day or more under the high temperature condition of 30 ° C. or higher.

The curable composition comprising the component (H) and the component (A4) can be used as a one-component or multi-component composition such as a two-component type. Since the change of the hardening rate by curing is remarkable, it is more preferable.

The component (H) is a compound having a reactive silicon group and an amino group represented by the general formula (8). Specific examples of the reactive silicon group represented by the general formula (8) include trimethoxysilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, ethoxydimethoxysilyl group, dimethylmethoxysilyl group, diethylmethoxysilyl group, dioxysilane. And ethoxymethoxysilyl group. The number of alkoxy groups bonded to one silicon atom of the reactive silicon group is preferably 2 or more, more preferably 3 from the viewpoint of the transesterification reaction rate. Therefore, a trimethoxysilyl group is most preferable.

Specific examples of the component (H) include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethoxydimethoxysilane, and γ- (2-aminoethyl). Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylethyldimethoxysilane, γ- (2-aminoethyl) aminopropylethoxydimethoxysilane, γ- Ureidopropyltrimethoxysilane, γ-ureidopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, Nn-butyl-γ-aminopropyltrimethoxy Run, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, N, N′-bis (γ-trimethoxysilylpropyl) ethylenediamine, bis (trimethoxysilylpropyl) amine, γ- [2- (2-aminoethyl) And amino group-containing silanes such as aminoethyl] aminopropyltrimethoxysilane. In addition, a derivative obtained by modifying the silane compound or a condensation reaction product of the silane compound can also be used as the component (H).

(H) component used for this invention is used in 0.1-10 parts with respect to 100 parts of organic polymers of (A4) component. In particular, it is preferably used in the range of 1 to 5 parts. The component (H) may be used alone or in combination of two or more.

In the present invention, an epoxy resin can be used as the component (I). This epoxy resin has a function of improving the impact strength and toughness of the organic polymer as the component (A4) of the present invention and further improving the resilience, durability, and creep resistance.

Examples of the epoxy resin used as the component (I) of the present invention include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as tetrabromobisphenol A glycidyl ether, novolak type epoxy resin, water Bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin , Various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene Examples include glycidyl ethers of polyhydric alcohols such as recall diglycidyl ether and glycerin, epoxidized products of unsaturated polymers such as hydantoin-type epoxy resins, petroleum resins, etc., but are not limited to these. The used epoxy resin can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins. These epoxy resins (I) and reactive silicon group-containing organic polymers (A4) are used in a weight ratio of (A4) / epoxy resin = 100/1 to 1/100. When the ratio of (A4) / epoxy resin is less than 1/100, the effect of improving the impact strength, toughness, resilience, durability, and creep resistance of the cured epoxy resin becomes difficult to obtain, and (A4 ) / Epoxy resin ratio exceeding 100/1, the strength of the organic polymer cured product becomes insufficient. The preferred use ratio varies depending on the use of the curable composition, etc., and thus cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, The component (A4) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the strength of the cured product of the component (A4), 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, particularly 5 to 100 parts by weight of the epoxy resin with respect to 100 parts by weight of the component (A4). 50 parts by weight should be used.

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

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

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

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

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

You may mix | blend various fillers other than the micro hollow body of (F) component with the curable composition of this invention. The filler is not particularly limited, and includes, for example, reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc And fillers such as titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and hydrogenated castor oil; and fibrous fillers such as asbestos, glass fibers and filaments.

When it is desired to obtain a curable composition having high strength with these fillers, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc A preferable result can be obtained by using a filler selected from flower and the like in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A). In addition, when a curable composition having low strength and large elongation is desired, a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, etc. A preferable result is obtained if it is used in the range of 5 to 200 parts by weight per 100 parts by weight of the combined body (A). Of course, these fillers may be used alone or in combination of two or more.

In the curable composition of the present invention, when a plasticizer is used in combination with a filler, the elongation of the cured product can be increased or a large amount of filler can be mixed, which is more effective.

Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate and dibutyl sebacate; diethylene glycol dibenzoate and pentaerythritol ester. Glycol esters such as; butyl oleate, aliphatic esters such as methyl acetyl ricinoleate; phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate; epoxidized soybean oil, epoxidized linseed oil, Epoxy plasticizers such as epoxy benzyl stearate; Polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; Polyethers such as polypropylene glycol and its derivatives Polystyrenes such as poly-α-methylstyrene and polystyrene; plasticizers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and chlorinated paraffins alone or in the form of a mixture of two or more types; Can be used arbitrarily. When the amount of the plasticizer is 100 parts by weight or less with respect to 100 parts by weight of the organic polymer (A), preferable results are obtained.

Moreover, a polymeric plasticizer can be used. When using a high-molecular plasticizer, compared to the case of using a low-molecular plasticizer that does not contain a polymer component in the molecule, the initial physical properties are maintained over a long period of time, and an alkyd paint is applied to the cured product. The dryness (also called paintability) 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. Polyethers and vinyl polymers are preferred. Of these, vinyl polymers are preferred from the viewpoints 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 and molecular weight distribution (Mw / Mn) of the polymer plasticizer are measured by the GPC method (polystyrene conversion).

The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight thereof must be lower than that of the polymer of component (A).

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

The amount of the plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of component (A). If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

In the curable composition of the present invention, in order to further increase the activity of the condensation catalyst, the general formula R _a Si (OR) _4-a (wherein R is independently substituted or non-substituted having 1 to 20 carbon atoms). A substituted hydrocarbon group, and a is any one of 0, 1, 2, and 3). The silicon compound is not limited, but R in the general formula such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, The aryl group having 6 to 20 aryl groups is preferable because the effect of accelerating the curing reaction of the composition is large. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are particularly preferable because of low cost and easy availability. The compounding amount of the silicon compound is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A). When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. The said physical property modifier may be used independently and may be used together 2 or more types.

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

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

The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A).

A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight per 100 parts by weight of component (A).

In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of component (A).

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

A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toa Gosei Chemical Co., Ltd.)
Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Addition of sensitizers such as ketones and nitro compounds and accelerators such as amines may enhance the effect. The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of component (A). When the amount is 20 parts by weight or more, the cured product becomes too hard and cracks are generated.

An antioxidant (antiaging agent) can be used in the composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. 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 Geigy Japan); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all above Also manufactured by Adeka Argus Chemical Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Co., Ltd.) A hindered amine light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is 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).

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.

In the composition of the present invention, when an unsaturated acrylic compound is used as the photocurable substance, a tertiary amine-containing hindered amine light stabilizer is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use an agent for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 119FL (all manufactured by Ciba Geigy Japan, Inc.); MARKLA-57, LA-62, LA-67, LA-63 (all above Adeka Argus Examples 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).

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.

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. In addition, by appropriately combining these components, a multi-component compound such as a one-component type or a two-component type can be made and used.

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

When using the curable composition of the present invention, if necessary, an adhesion improver other than aminosilane, a physical property modifier, a storage stability improver, an ultraviolet absorber, a metal deactivator, and ozone degradation. Various additives such as an inhibitor, a light stabilizer, an amine radical chain inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added.

The curable composition of the present invention includes pressure-sensitive adhesives, sealants for buildings, ships, automobiles, roads, adhesives, mold preparations, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spray materials, etc. Can be used for Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, powder coating materials, casting materials, medical rubber materials, medical adhesives , Medical equipment sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot melt materials, potting agents for electrical and electronic equipment, films , Gaskets, various molding materials, and a variety of liquid sealants used in rustproof and waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), automotive parts, electrical parts, various machine parts, etc. It can be used for various purposes. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, since the curable composition of the present invention is excellent in resilience, durability, and creep properties, it can be used as an interior panel adhesive, an exterior panel adhesive, a tile adhesive, a stone adhesive, and a ceiling finish. Adhesives, floor finishing adhesives, wall finishing adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, direct glazing sealing materials, double glazing sealing materials, SSG construction sealing It is particularly preferable when used as a material or a sealing material for a working joint of a building.

The curable composition of the present invention is excellent in resilience, durability, and creep resistance.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Synthesis Example 1)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene triol having a molecular weight of about 3,000 as an initiator, and a number average molecular weight of about 26,000 (using a Tosoh HLC-8120GPC as a liquid feeding system, The column used TSK-GEL H type manufactured by Tosoh, and the solvent obtained was a polystyrene oxide (polystyrene equivalent molecular weight measured using THF). Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by devolatilization under reduced pressure. 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.

100 parts by weight of the allyl-terminated polypropylene oxide was reacted with 1.4 parts by weight of methyldimethoxysilane for 5 hours at 90 ° C. using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex as a catalyst. A base terminal polyoxyalkylene polymer (A-1) was obtained. ^{As a} result of measurement by ¹ H-NMR (measured in CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal methyldimethoxysilyl groups was 2.3 on average per molecule.

(Examples 1-4 and Comparative Examples 1-2)
In accordance with the formulation shown in Table 1, 100 parts by weight of the organic polymer (A-1) having a reactive silicon group obtained in Synthesis Example 1, and 120 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Hakushinka CCR) , 20 parts by weight of titanium oxide (Ishihara Sangyo, Type R-820), 55 parts by weight of DIDP, 2 parts by weight of a thixotropic agent (manufactured by Enomoto Kasei, Disparon 6500), 1 part by weight of a light stabilizer (Sankyo LS770) , 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of an antioxidant (manufactured by Ouchi Shinsei Chemical Industry, Nocrack SP), dehydrating agent vinyltrimethoxysilane (manufactured by Nihon Unicar, A- 171) 2 parts by weight, adhesion-imparting agent N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (manufactured by Nihon Unicar, A-1120) 3 parts by weight, 2 parts by weight of the silicate described in Table 1 (Colcoat, ethyl silicate 28; Colcoat, ethyl silicate 40; Colcoat, methyl silicate 51), the curing catalyst described in Table 1 (manufactured by Nitto Kasei, dibutyltin bis Acetylacetonate (trade name: U-220); Nitto Kasei, tin neodecanoate (divalent) (trade name: U-50); Japan Epoxy Resin, neodecanoic acid (trade name: Versatic 10); Wako Jun 1 part of laurylamine (manufactured by Yakuhin Kogyo Co., Ltd.) is added and kneaded in a substantially moisture-free state under dehydrating conditions, and then sealed in a moisture-proof container and is a one-component curable composition Got.

(Tensile property of cured product)
Each composition of Table 1 was cured at 23 ° C. × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of about 3 mm. This sheet was punched out into a No. 3 dumbbell mold and subjected to a tensile test at a pulling speed of 200 mm / min. M50: 50% tensile modulus (MPa), Tb: strength at break (MPa), Eb: elongation at break (%) did. The results are shown in Table 1.

(Restoration rate)
Each composition of Table 1 was cured at 23 ° C. × 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 fixed at 60 ° C. for 24 hours in a state where 20 mm between the marked lines was pulled to 40 mm (100% elongation). This was opened at 23 ° C., and the restoration rate was measured from the rate at which the marked line was restored after 1 hour. A larger restoration rate indicates better restoration. The results are shown in Table 1.

(Creep measurement using dumbbell pieces)
Each composition of Table 1 was cured at 23 ° C. × 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 shape and marked with a 20 mm gap. One end of this dumbbell piece was fixed in an oven at 60 ° C., and the dumbbell piece was suspended. On the lower end of the suspended dumbbell piece, a load 0.4 times the M50 value obtained by the tensile property measurement of the cured product was applied. The displacement difference of the distance between marked lines was measured immediately after applying the load and after 200 hours. The smaller the displacement difference, the better the creep resistance. The results are shown in Table 1.

As shown in Comparative Example 1 of Table 1, when no silicate is added, when organotin (U-220) is used as a curing catalyst, the restoration rate is particularly low and the creep resistance is poor. However, as shown in Example 1, the resilience and creep resistance are remarkably improved by the addition of silicate. In addition, as shown in Comparative Example 2, when organotin (U-220) is not used as a curing catalyst and a carboxylic acid tin salt (Neostan U-50) is used, good resilience and resistance even when silicate is not added. Although the creep property was shown, as shown in Examples 2 to 4, even better resilience and creep resistance were exhibited by the addition of silicate. Ethyl silicate 40 and methyl silicate 51 used in Examples 3 to 4 were condensates of tetraethoxysilane and tetramethoxysilane, respectively, and exhibited particularly excellent effects.

(Synthesis Example 2)
Synthesis Example 1 using a hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 14,500 obtained by polymerizing propylene oxide using a polyoxypropylene glycol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst. Allyl-terminated polypropylene oxide was obtained by the same procedure. This allyl-terminated polypropylene oxide is reacted with trimethoxysilane in the same procedure as in Synthesis Example 1 to give a polyoxyalkylene polymer (A-2) having an average of 1.5 trimethoxysilyl groups at the ends. Obtained.

(Synthesis Example 3)
The allyl-terminated polypropylene oxide obtained in Synthesis Example 2 is reacted with triethoxysilane in the same procedure as in Synthesis Example 1, and has an average of 1.5 triethoxysilyl groups at the terminals. (A-3) was obtained.

(Synthesis Example 4)
The allyl-terminated polypropylene oxide obtained in Synthesis Example 2 is reacted with methyldimethoxysilane in the same procedure as in Synthesis Example 1, and a polyoxyalkylene polymer having an average of 1.5 methyldimethoxysilyl groups at the terminals. (A-4) was obtained.

(Examples 5-11 and Comparative Examples 3-5)
According to the formulation shown in Table 2, 100 parts by weight of the organic polymer having reactive silicon groups (A-2 to 4) obtained in Synthesis Examples 2 to 4, surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Shiraka Hana CCR) ) 120 parts by weight, titanium oxide (Ishihara Sangyo, Tyco R-820) 20 parts by weight, DIDP 12 parts by weight, thixotropic agent (Tsubakimoto Kasei, Disparon 6500) 2 parts by weight, light stabilizer (Sankyo, Sanol LS770) ) 1 part by weight, 1 part by weight of UV absorber (manufactured by Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of antioxidant (NOUCL SP, manufactured by Ouchi Shinsei Chemical Industry), dehydrating agent vinyltrimethoxysilane (Nihon Unicar) A-171) 2 parts by weight, adhesion-imparting agent N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (manufactured by Nihon Unicar, A-1 120) 3 parts by weight, silicate (manufactured by Colcoat, methyl silicate 51) as the number of parts described in Table 2, curing catalyst for component (D) described in Table 2 (manufactured by Nitto Kasei, dibutyltin bisacetylacetonate (trade name: U -220); Sansha Co., Ltd., dibutyltin dilaurate (trade name: STANN BL)) or (C) component curing catalyst (manufactured by Nitto Kasei, tin neodecanoate (divalent) (trade name: U-) 50)) and amine (manufactured by Wako Pure Chemical Industries, Laurylamine) are added in the number of parts shown in Table 2 and kneaded in a substantially moisture-free condition under dehydration conditions, and then sealed in a moisture-proof container. A one-component curable composition was obtained.

Using each composition of Table 2, a tensile test was performed in the same manner as described above, and M50: 50% tensile modulus (MPa), Tb: strength at break (MPa), and Eb: elongation at break (%) were measured. The results are shown in Table 2.

Using each composition in Table 2, the restoration rate was measured by the same method as described above. However, this time, the 100% stretched state was fixed at 23 ° C. for 24 hours, this was opened at 23 ° C., and the restoration rate was measured from the rate at which the marked line was restored after 1 hour. The results are shown in Table 2.

(Creep measurement using shear sample)
Using each composition of Table 2, a shear sample having an area of 20 mm × 25 mm and a thickness of 1 mm was prepared, and the one cured at 23 ° C. × 3 days + 50 ° C. × 4 days was subjected to a 0.1 MPa load in a 60 ° C. oven, The displacement difference between immediately after applying the load and after 140 hours was measured. A sample having a displacement difference of less than 0.4 mm was marked with ◯, and a sample having a displacement difference of 0.4 mm or more was marked with ×. The results are shown in Table 2.

From the comparison between Examples 5 to 9 and Comparative Examples 3 to 5 in Table 2, the organic polymer (A-2 to 3) in which the terminal reactive silicon group is a trialkoxysilyl group is used to significantly recover. And creep resistance are improved. In addition, Example 10 in which silicate was added and Example 11 in which a carboxylic acid tin salt (Neostan U-50) was used as a curing catalyst showed a further excellent restoration rate.

(Synthesis Example 5)
The allyl-terminated polypropylene oxide obtained in Synthesis Example 1 is reacted with methyldimethoxysilane in the same procedure as in Synthesis Example 1, and a polyoxyalkylene polymer having an average of two methyldimethoxysilyl groups at the terminals (A -5) was obtained.

(Synthesis Example 6)
A hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 26,000 obtained by polymerizing propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a polyoxypropylene triol having a molecular weight of about 3,000 as an initiator is used. A methallyl-terminated polypropylene oxide was obtained in the same procedure as in Synthesis Example 1 except that methallyl chloride was used. For 100 parts by weight of this methallyl-terminated polypropylene oxide, 0.5 parts of an isopropanol solution containing 3 wt% platinum in a platinum vinylsiloxane complex is used as a catalyst, and sulfur is 1 eq / Pt 1 eq in a nitrogen atmosphere containing 6 vol% oxygen. The mixture was mixed and reacted with 3.2 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours to obtain a polyoxyalkylene polymer (A-6) having an average of 2.8 methyldimethoxysilyl groups at the terminals.

(Examples 12 to 14 and Comparative Example 6)
According to the formulation shown in Table 3, 100 parts by weight of the organic polymer (A-1, A-4-6) having a reactive silicon group obtained in Synthesis Example 1 and Synthesis Examples 4-6, surface-treated colloidal carbonate 120 parts by weight of calcium (manufactured by Shiraishi Kogyo Co., Ltd., CCR), 20 parts by weight of titanium oxide (manufactured by Ishihara Sangyo, Tyco R-820), 55 parts by weight of DIDP, 2 parts by weight of thixotropic agent (manufactured by Enomoto Kasei, Disparon 6500), light 1 part by weight of a stabilizer (Sankyo, Sanol LS770), 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of an antioxidant (manufactured by Ouchi Shinsei Chemical Industry, Nocrack SP), dehydration Agent vinyltrimethoxysilane (Nihon Unicar, A-171) 2 parts by weight, adhesion promoter N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane ( Nippon Unicar, A-1120) 3 parts by weight, as a curing catalyst, carboxylic acid tin salt (manufactured by Nitto Kasei, tin neodecanoate (divalent) (trade name: U-50)) 3.4 parts by weight, carboxylic acid ( Made of Japan Epoxy Resin, 1.2 parts by weight of neodecanoic acid (trade name: Versatic 10), and 0.75 parts by weight of amine (manufactured by Wako Pure Chemical Industries, Ltd., laurylamine) were added, and substantially under dehydrating conditions. After kneading in the absence of moisture, it was sealed in a moisture-proof container to obtain a one-component curable composition.

Using each composition in Table 3, a tensile test was performed in the same manner as described above, and M50: 50% tensile modulus (MPa), Tb: strength at break (MPa), and Eb: elongation at break (%) were measured. The results are shown in Table 3.

Using each composition in Table 3, the restoration rate was measured by the same method as described above. However, this time, the 100% stretched state was fixed at 60 ° C. for 24 hours, this was opened at 23 ° C., and the restoration rate was measured from the rate at which the marked line was restored after 1 hour. The results are shown in Table 3.

Using each composition in Table 3, creep measurement using dumbbell pieces was performed in the same manner as in Examples 1 to 4, and the displacement difference between the marked lines immediately after applying the load and after 200 hours was determined. It was measured. The results are shown in Table 3.

From comparison between Examples 12 to 14 and Comparative Example 6 in Table 3, the organic polymers (A-1, A-5 to 6) having a large number of reactive silicon groups per molecule were found to have resilience and creep resistance. It turns out that it is excellent in property.

(Synthesis Example 7)
Synthesis Example 6 using a hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 28,500 obtained by polymerizing propylene oxide using a polyoxypropylene glycol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst A methallyl-terminated polypropylene oxide was obtained by the same procedure as that described above. This methallyl-terminated polypropylene oxide is reacted with methyldimethoxysilane in the same procedure as in Synthesis Example 6 to obtain a polyoxyalkylene polymer (A-7) having an average of 1.9 methyldimethoxysilyl groups at the ends. Obtained.

(Synthesis Example 8)
The polyoxyalkylene polymer having an average of 1.5 methyldimethoxysilyl groups at the ends is reacted with methyldimethoxysilane in the same procedure as in Synthesis Example 6 for the methallyl-terminated polypropylene oxide obtained in Synthesis Example 7. (A-8) was obtained.

(Synthesis Example 9)
Synthesis Example 1 using a hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 28,500 obtained by polymerizing propylene oxide using a polyoxypropylene glycol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst. Allyl-terminated polypropylene oxide was obtained by the same procedure. This allyl-terminated polypropylene oxide is reacted with methyldimethoxysilane in the same procedure as in Synthesis Example 1 to obtain a polyoxyalkylene polymer (A-9) having an average of 1.5 methyldimethoxysilyl groups at the ends. Obtained.

(Examples 15 to 16 and Comparative Examples 7 to 8)
According to the formulation shown in Table 4, 100 parts by weight of an organic polymer (A-4, A-7-9) having a reactive silicon group obtained in Synthesis Example 4 and Synthesis Examples 7-9, surface-treated colloidal carbonate 120 parts by weight of calcium (manufactured by Shiraishi Kogyo Co., Ltd., CCR), 20 parts by weight of titanium oxide (manufactured by Ishihara Sangyo, Tyco R-820), 55 parts by weight of DIDP, 2 parts by weight of thixotropic agent (manufactured by Enomoto Kasei, Disparon 6500), light 1 part by weight of a stabilizer (Sankyo, Sanol LS770), 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of an antioxidant (manufactured by Ouchi Shinsei Chemical Industry, Nocrack SP), dehydration Agent vinyltrimethoxysilane (Nihon Unicar, A-171) 2 parts by weight, adhesion promoter N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane ( Nippon Unicar, A-1120) 3 parts by weight, curing catalyst dibutyltin bisacetylacetonate (Nitto Kasei, Neostan U-220) 2 parts by weight, in a state substantially free of moisture under dehydration conditions After kneading, it was sealed in a moisture-proof container to obtain a one-component curable composition.

Using each composition in Table 4, a tensile test was performed in the same manner as described above, and M50: 50% tensile modulus (MPa), Tb: strength at break (MPa), and Eb: elongation at break (%) were measured. The results are shown in Table 4.

Using each composition in Table 4, the restoration rate was measured by the same method as described above. However, this time, the 100% stretched state was fixed at 23 ° C. for 24 hours, this was opened at 23 ° C., and the restoration rate was measured from the rate at which the marked line was restored after 24 hours. The results are shown in Table 4.

Using each composition in Table 4, creep measurement using dumbbell pieces was performed in the same manner as in Examples 1 to 4, and the displacement difference between the marked lines immediately after applying the load and after 45 hours was determined. It was measured. The results are shown in Table 4.

From comparison between Examples 15 to 16 and Comparative Examples 7 to 8 in Table 4, the organic polymer (A-7 to 8) in which a reactive silicon group was introduced into the methallyl group-terminated organic polymer was found to have resilience and resistance. It turns out that it is excellent in creep property.

(Synthesis Example 10)
The allyl-terminated polypropylene oxide obtained in Synthesis Example 1 is reacted with triethoxysilane in the same procedure as in Synthesis Example 1, and a polyoxyalkylene polymer having an average of 2.3 triethoxysilyl groups at the terminal is obtained. (A-10) was obtained.

(Example 17 and Comparative Examples 9 to 10)
According to the formulation shown in Table 5, 100 parts by weight of the organic polymer (A-1, A-10) having a reactive silicon group obtained in Synthesis Example 1 and Synthesis Example 10, surface-treated colloidal calcium carbonate (manufactured by Solvay) , Winnofil SPM) 120 parts by weight, titanium oxide (manufactured by Kerr-McGee, RFK-2) 20 parts by weight, DIUP 50 parts by weight, thixotropy imparting agent (manufactured by Cray Valley, Crayvallacsuper) 5 parts by weight, light stabilizer (manufactured by Sankyo, 1 part by weight of Sanol LS770), 1 part by weight of UV absorber (Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of antioxidant (NOUCL SP, manufactured by Ouchi Shinsei Chemical Industry), vinyltrimethoxysilane as a dehydrating agent (Nippon Unicar, A-171) 2 parts by weight, component (G) as an adhesion-imparting agent 3 parts by weight of γ-aminopropyltriethoxysilane (Nihon Unicar, A-1100) or N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (Nihon Unicar, A-1120), curing catalyst dibutyltin bis Add 2 parts by weight of acetylacetonate (Nitto Kasei, Neostan U-220), knead in the absence of moisture under dehydrating conditions, seal in a moisture-proof container, and cure one-component Sex composition was obtained.

Using each composition in Table 5, the restoration rate was measured by the same method as described above. However, this time, the 100% stretched state was fixed at 60 ° C. for 24 hours, this was opened at 23 ° C., and the restoration rate was measured from the rate at which the marked line was restored after 1 hour. The results are shown in Table 5.

Using each composition in Table 5, creep measurement using a shear sample was performed in the same manner as in Examples 5 to 11, and the displacement difference between the marked lines immediately after applying the load and after 140 hours was measured. It was measured. The evaluation criteria were ◯ when the displacement difference was less than 0.4 mm, and x when the displacement difference was 0.4 mm or more. The results are shown in Table 5.

(Curability of curable composition)
Each composition of Table 5 was thinned to a thickness of about 3 mm, and the time until the surface was skinned (skinning time) was measured under conditions of 23 ° C. and humidity 50% RH. The shorter the skinning time, the better the curability. The results are shown in Table 5.

As shown in Example 17 of Table 5, a polymer having a triethoxysilyl group at the end of the component (A4) is used as the organic polymer, and a triethoxysilyl group as the component (G) is used as the adhesion promoter. When aminosilane is combined, the change in the skin time before and after storage is small and the storage stability is good, while being excellent in resilience and creep resistance.

(Example 18 and Comparative Examples 11-12)
According to the formulation shown in Table 6, 100 parts by weight of the organic polymer (A-2) having a reactive silicon group obtained in Synthesis Example 2, 30 parts by weight of DIDP, triethoxysilane as a dehydrating agent (manufactured by Colcoat, ethyl silicate) 28) 2 parts by weight, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (manufactured by Nihon Unicar, A-1120) or N-β- (aminoethyl) as component (H) as an adhesion-imparting agent -Γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-603) 3 parts by weight, curing catalyst dibutyltin bisacetylacetonate (manufactured by Nitto Kasei, Neostan U-220) 2 parts by weight, and glass substituted with nitrogen Sealed in a container to obtain a one-component curable composition. In Comparative Example 11, the skinning time was measured under conditions of 23 ° C. and 50% RH without curing this one-component curable composition. In Example 18 and Comparative Example 12, after promoting the transesterification reaction between reactive silicon groups by curing these one-component curable compositions at 50 ° C. for 7 days, the conditions were 23 ° C. and 50% RH. The skinning time was measured below. The results are shown in Table 6.

As shown in Example 18 of Table 6, a polymer having a triethoxysilyl group at the end of the component (A4) is used as the organic polymer, and an aminosilane having a methoxysilyl group as the component (H) as an adhesion promoter. When the transesterification reaction is accelerated by curing, the curability of the organic polymer can be remarkably improved.

(Examples 19 to 20 and Comparative Example 13)
100 parts by weight of the organic polymer (A-10) having a reactive silicon group obtained in Synthesis Example 10, 120 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiruka Hana CCR), titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipei) R-820) 20 parts by weight, DIDP 55 parts by weight, thixotropic agent (Tsubakimoto Kasei, Disparon 6500) 2 parts, light stabilizer (Sankyo, Sanol LS770) 1 part by weight, UV absorber (Ciba Specialty) Chemicals, Tinuvin 327) 1 part by weight, antioxidant (Ouchi Shinsei Chemical Industry, NOCRACK SP) 1 part by weight, dehydrating agent vinyltrimethoxysilane (Nihon Unicar, A-171) 2 parts by weight, adhesion promoter 3 parts by weight of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (Nihon Unicar, A-1120) and various hard materials described below The catalyst was added and kneaded in a substantially moisture-free condition under dehydrating conditions, and then sealed in a moisture-proof container to obtain a one-pack curable composition. As a curing catalyst, 6 parts by weight of neodecanoic acid (manufactured by Japan Epoxy Resin, Versatic 10) and 0.75 parts by weight of amine (manufactured by Wako Pure Chemical Industries, laurylamine), which are non-tin catalysts as component (E), were added. The product obtained in Example 19 was prepared by adding 8.5 parts by weight of isopropoxytitanium bis (ethylacetoacetate) (manufactured by Matsumoto Kosho Co., Ltd., ORGATICS TC-750). Further, Comparative Example 13 was obtained by adding 2 parts by weight of dibutyltin bisacetylacetonate (Nitto Kasei, Neostan U-220).

As a result of measuring the restoration rate in the same manner as described above using each of these compositions, the cured products of Example 19 and Example 20 showed a higher restoration rate than the cured product of Comparative Example 13.

(Synthesis Example 11)
Synthesis Example 1 using a hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 25,500 obtained by polymerizing propylene oxide using a polyhexylene glycol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst. Allyl-terminated polypropylene oxide was obtained by the same procedure. This allyl-terminated polypropylene oxide is reacted with triethoxysilane in the same procedure as in Synthesis Example 1 to obtain a polyoxyalkylene polymer (A-11) having an average of 1.5 triethoxysilyl groups at the ends. Obtained.

(Synthesis Example 12)
The allyl-terminated polypropylene oxide obtained in Synthesis Example 11 is reacted with methyldimethoxysilane in the same procedure as in Synthesis Example 1, and a polyoxyalkylene polymer having an average of 1.5 methyldimethoxysilyl groups at the terminals. (A-12) was obtained.

(Example 21 and Comparative Examples 14-15)
95 parts by weight of the organic polymer (A-11, A-12) having a reactive silicon group obtained in Synthesis Example 11 and Synthesis Example 12, 60 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Hakujyo Hana CCR), Surface treated colloidal calcium carbonate (Shiraishi Kogyo, Viscolite R) 60 parts by weight, heavy calcium carbonate (Shiraishi calcium, Whiten SB) 20 parts by weight, DOP 40 parts by weight, epoxy plasticizer (Nippon Nippon Chemical Co., Ltd., Sanso) sizer E -P S) 20 parts by weight, thixotropic agent (Kusumoto Chemicals Ltd., Disparon 305) 3 parts by weight, the photo-curable resin (manufactured by Toagosei Co., Aronix M-309) 3 parts by weight of a light stabilizer (manufactured by Sankyo , Sanol LS770) 1 part by weight, UV absorber (Ciba Specialty Chemicals, Tinuvin 327) 1 part by weight, antioxidant (Ciba Specialty Weigh 1 part by weight of Mikaru's, Irganox 1010) and 0 or 20 parts of the hollow hollow body (Fuji Silysia Chemical, Fuji Balloon H-40) as component (F), and knead well with three paint rolls. And used as the main agent. In addition, it was set as Example 21 using 20 parts of micro hollow bodies using (A-11) as an organic polymer. Moreover, what used (A-12) as an organic polymer, added 0 part of a micro hollow body as Comparative Example 14, used (A-11) as an organic polymer, and added 20 parts of a micro hollow body. Was referred to as Comparative Example 15.

As a curing agent, a mixture of tin 2-ethylhexanoate (divalent) (manufactured by Nitto Kasei Co., Ltd., U-28) and 0.75 parts by weight of amine (manufactured by Wako Pure Chemical Industries, Ltd., laurylamine) was used. The main agent and the curing agent were mixed uniformly to evaluate workability (stringiness) and durability.

The composition of Example 21 had better workability than Comparative Example 14 and better durability than Comparative Example 15.

(Example 22 and Comparative Example 16)
70 parts by weight of the organic polymer (A-10) having a reactive silicon group obtained in Synthesis Example 10 or 95 parts by weight of the organic polymer (A-1) having a reactive silicon group obtained in Synthesis Example 1; 60 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Shiraka Hana CCR), 60 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Viscolite R), 20 parts by weight of heavy calcium carbonate (manufactured by Shiroishi Co., Ltd., Whiten SB) Parts, 40 parts by weight of DOP, 20 parts by weight of epoxy plasticizer (manufactured by Nippon Seika, Sanso Sizer EP-S), 3 parts by weight of thixotropic agent (manufactured by Enomoto Kasei, Disparon 305), photo-curing resin (manufactured by Toagosei) , Aronix M-309) 3 parts by weight, light stabilizer (Sankyo, Sanol LS770) 1 part, UV absorber (Ciba Specialty Chemicals, Tinuvin 32) ) 1 part by weight of an antioxidant (manufactured by Ciba Specialty Chemicals Ltd., Irganox 1010) 1 part by weight were weighed, respectively, and the main agent and well kneaded with a three-roll paint. In addition, what added 70 parts of (A-10) as an organic polymer was made into Example 22, and what added 95 parts of (A-1) as an organic polymer was made into the comparative example 16. As a curing agent, a mixture of 3 parts by weight of 2-ethylhexanoic acid tin (divalent) (manufactured by Nitto Kasei, U-28) and 0.75 parts by weight of amine (Wako Pure Chemical Industries, laurylamine) is added to the main agent. It was added and the recovery rate was measured.

The composition of Example 22 showed a higher restoration rate than Comparative Example 16 while keeping the weight percent of the organic polymer low.

(Example 23 and Comparative Example 17)
95 parts by weight of the organic polymer (A-10) having a reactive silicon group obtained in Synthesis Example 10, 60 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiraka Hana CCR), surface-treated colloidal calcium carbonate (Shiraishi Kogyo) Manufactured by Viscolite R), 60 parts by weight, 20 parts by weight of heavy calcium carbonate (Shiraishi Calcium, Whiteon SB), 40 parts by weight of DOP, 20 parts by weight of an epoxy plasticizer (Shinso Rika, Sanso Sizer EP-S) , 3 parts by weight of a thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., Disparon 305), 3 parts by weight of a photocurable resin (manufactured by Toagosei Co., Ltd., Aronix M-309), 1 part by weight of a light stabilizer (manufactured by Sankyo, Sanol LS770), ultraviolet light 1 part by weight of absorbent (Ciba Specialty Chemicals, Tinuvin 327), antioxidant (Ciba Specialty Chemicals, Irganox) 010) 1 part by weight, and the epoxy resin (Japan Epoxy Resin, Epikote 828) 0 parts or 5 parts were each weighed, and the main agent and well kneaded with a three-roll paint. Note that Example 23 was obtained by adding 5 parts of epoxy resin. Further, Comparative Example 17 was obtained by adding 0 part of epoxy resin. As a curing agent, a mixture of 3 parts by weight of 2-ethylhexanoic acid tin (divalent) (manufactured by Nitto Kasei, U-28) and 0.75 parts by weight of amine (Wako Pure Chemical Industries, laurylamine) is added to the main agent. It was added and the recovery rate was measured.

The composition of Example 23 showed a higher restoration rate than Comparative Example 17.

(Example 24 and Comparative Example 18)
95 parts by weight of the organic polymer (A-10) having a reactive silicon group obtained in Synthesis Example 10, 60 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiraka Hana CCR), surface-treated colloidal calcium carbonate (Shiraishi Kogyo) Manufactured by Viscolite R), 60 parts by weight, 20 parts by weight of heavy calcium carbonate (Shiraishi Calcium, Whiteon SB), 40 parts by weight of DOP, 20 parts by weight of an epoxy plasticizer (Shinso Rika, Sanso Sizer EP-S) , 3 parts by weight of a thixotropic agent (manufactured by Enomoto Kasei, Disparon 305), 3 parts by weight of a photocurable resin (Aronix M-309, manufactured by Toagosei Co., Ltd.), 1 part by weight of a light stabilizer (Sankyo LS 770) 1 part by weight of absorbent (Ciba Specialty Chemicals, Tinuvin 327), antioxidant (Ciba Specialty Chemicals, Irganox) 010) 1 part by weight were weighed, respectively, and the main agent and well kneaded with a three-roll paint.

Tin 2-ethylhexanoate (divalent) (manufactured by Nitto Kasei, U-28) and 0.75 parts by weight of amine (manufactured by Wako Pure Chemical Industries, laurylamine) and dibutyltin bisacetylacetonate (manufactured by Nitto Kasei, Neostann U-220) 0.1 wt part mixture was used as a curing agent in Example 24, tin 2-ethylhexanoate (divalent) (manufactured by Nitto Kasei, U-28) 3 parts by weight and amine ( A comparative example 18 was prepared by using 0.75 parts by weight of a mixture of Wako Pure Chemical Industries, Ltd. (laurylamine) as a curing agent. The main agent and the curing agent were mixed uniformly, and the restoration rate and thin layer curability were evaluated.

The composition of Example 24 exhibited better thin layer curability than Comparative Example 18, while exhibiting a high recovery rate.

(Synthesis Example 13)
An allyl-terminated polyisobutylene obtained according to the production example of JP-A-11-209039 is reacted with triethoxysilane in the presence of a Pt catalyst to give a polyisobutylene having a triethoxysilyl group at the terminal (A-13). Got.

(Synthesis Example 14)
The allyl-terminated polyisobutylene obtained in Synthesis Example 13 was reacted with methyldimethoxysilane in the presence of a Pt catalyst to obtain polyisobutylene (A-14) having a methyldimethoxysilyl group at the terminal.

(Example 25 and Comparative Example 19)
Dibutyltin bisacetylacetonate (manufactured by Nitto Kasei, Neostan U-220) with respect to 100 parts by weight of the organic polymer (A-13, A-14) having a reactive silicon group obtained in Synthesis Example 13 and Synthesis Example 14 2 parts by weight were added to obtain a cured product. In addition, the thing using (A-13) as an organic polymer was made into Example 25, and the thing using (A-14) was made into the comparative example 19. The cured product of Example 25 showed a higher restoration rate than Comparative Example 19.

(Synthesis Example 15)
CuBr (4.2 g) and acetonitrile (27.3 g) were added to a reaction vessel equipped with a stirrer, and the mixture was stirred at 65 ° C. for 15 minutes in a nitrogen atmosphere. To this, n-butyl acrylate (100 g), diethyl 2,5-dibromoadipate (8.8 g) and acetonitrile (16.6 g) were added and mixed well with stirring. Pentamethyldiethylenetriamine (0.17 g) was added to initiate the polymerization. While heating and stirring at 70 ° C., n-butyl acrylate (400 g) was continuously added dropwise. Triamine (0.68 g) was added in portions during the dropwise addition of n-butyl acrylate.

When the monomer reaction rate reached 96%, the remaining monomer and acetonitrile were devolatilized at 80 ° C., and then 1,7-octadiene (53.7 g), acetonitrile (132 g), triamine (1.69 g) were added, Subsequently, the mixture was heated and stirred at 70 ° C. to obtain a mixture containing a polymer having an alkenyl group.

Acetonitrile and unreacted 1,7-octadiene in the mixture were devolatilized by heating and diluted with methylcyclohexane. Insoluble polymerization catalyst was removed by sedimentation in a centrifuge. To 100 parts of polymer, 6 parts of adsorbent (3 parts of KYOWARD 500SH / 3 parts of KYOWARD 700SL: both manufactured by Kyowa Chemical Co., Ltd.) are added to the methylcyclohexane solution of the polymer, and in an oxygen / nitrogen mixed gas atmosphere. Stir with heating. The insoluble matter was removed, and the polymer solution was concentrated to obtain a polymer having an alkenyl group (polymer [P1]).

The obtained polymer [P1] was heated and devolatilized with stirring at 180 ° C. for 12 hours (the degree of vacuum was 10 torr or less), and further 100 parts of the polymer was diluted with 400 parts of methylcyclohexane to remove solids, The solution was concentrated to obtain a polymer [P2]. The number average molecular weight of this polymer [P2] was 24800, and the molecular weight distribution was 1.36. The number of alkenyl groups introduced per polymer molecule was 1.8.

To this polymer [P2], methyl orthoformate (1 molar equivalent with respect to the alkenyl group), platinum catalyst (as platinum metal amount 10 mg with respect to 1 kg of polymer), 1- (2-trimethoxysilylethynyl) -1 , 1,3,3-tetramethyldisiloxane (1.5 molar equivalents with respect to the alkenyl group) were added in order and mixed, and the mixture was heated and stirred at 100 ° C. for 0.5 hours in a nitrogen atmosphere. It was confirmed by ¹ H-NMR that the alkenyl group had disappeared by the reaction, and the reaction mixture was concentrated to obtain the target trimethoxysilyl group-containing polymer (A-15). The number average molecular weight was 27900, and the molecular weight distribution was 1.32. The number of silyl groups introduced per polymer molecule was 1.7.

(Synthesis Example 16)
For the polymer [P2] obtained in Synthesis Example 15, triethoxysilane instead of 1- (2-trimethoxysilylethynyl) -1,1,3,3-tetramethyldisiloxane used in Synthesis Example 15 A triethoxysilyl group-containing polymer (A-16) was obtained in the same manner as in Synthesis Example 15 except that (3 molar equivalents relative to the alkenyl group) was used. The number average molecular weight was 28600, and the molecular weight distribution was 1.48. The number of silyl groups introduced per polymer molecule was 1.5.

(Synthesis Example 17)
For the polymer [P2] obtained in Synthesis Example 15, methyldimethoxysilane was used instead of 1- (2-trimethoxysilylethynyl) -1,1,3,3-tetramethyldisiloxane used in Synthesis Example 15. A methyldimethoxysilyl group-containing polymer (A-17) was obtained in the same manner as in Synthesis Example 15 except that (3 molar equivalents relative to the alkenyl group) was used. The number average molecular weight was 28400, and the molecular weight distribution was 1.51. The number of silyl groups introduced per polymer molecule was 1.5.

(Examples 26 to 28 and Comparative Example 20)
150 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiruka Hana CCR), 20 parts by weight of heavy calcium carbonate (manufactured by Maruo Calcium, Nanox 25A), 100 parts by weight of organic polymer having a reactive silicon group, titanium oxide (Ishihara Sangyo, Typek R-820) 10 parts by weight, DIDP 60 parts by weight, thixotropy imparting agent (Tsubakimoto Kasei, Disparon 6500) 2 parts by weight, light stabilizer (Sankyo, Sanol LS765) 1 part by weight, UV absorption 1 part by weight of the agent (manufactured by Ciba Specialty Chemicals, Tinuvin 213), 2 parts by weight of the dehydrating agent vinyltrimethoxysilane (manufactured by Nihon Unicar, A-171), the adhesion-imparting agent N-β- (aminoethyl) -γ-amino 2 parts by weight of propyltrimethoxysilane (manufactured by Nihon Unicar, A-1120), dibutyltin bisacetate as a curing catalyst Add 0.2 parts by weight of tylacetonate (Nitto Kasei, Neostan U-220), knead under dehydrating conditions in a substantially water-free state, and then seal in a moisture-proof container. A mold curable composition was obtained. In addition, as an organic polymer having a reactive silicon group, an organic polymer having 100 parts by weight of the acrylate polymer (A-15) having a trimethoxysilyl group obtained in Synthesis Example 15 was used as Example 26. Example using 100 parts by weight in total of a mixture of 50 parts by weight of (A-15) and 50 parts by weight of polyoxyalkylene polymer (A-4) having a methyldimethoxysilyl group obtained in Synthesis Example 4 27 using 100 parts by weight of the acrylate polymer (A-16) having a triethoxysilyl group obtained in Synthesis Example 16 as Example 28, and methyldimethoxysilyl obtained in Synthesis Example 17 A comparative example 20 was obtained by using 100 parts by weight of an acrylic ester polymer (A-17) having a group. The hardened | cured material of Examples 26-28 showed the higher restoration rate than the comparative example 20. FIG.

The curable composition of the present invention is excellent in resilience, durability, and creep resistance.

Claims (19)

On the silicon having three hydrolyzable groups, have a silicon-containing functional group capable of crosslinking by forming siloxane bonds, the main chain skeleton is a polyoxyalkylene polymer organic polymer (A1),
Ca carboxylic acid tin salts (C), the silanol condensation catalyst is at least one selected from the organotin catalyst (D) and non-tin catalyst (E), and,
Containing a micro hollow body (F), and
A curable composition characterized by not containing an epoxy resin containing two or more epoxy groups in the molecule . A silicon-containing functional group that can be cross-linked by forming a siloxane bond has the general formula (6):
-Si (OR ⁴ ) ₃ (6)
The curable composition according to claim 1, wherein the three R ⁴ are each independently a monovalent organic group having 2 to 20 carbon atoms. The curable composition according to claim 1 or 2, wherein the silicon-containing functional group capable of crosslinking by forming a siloxane bond is a triethoxysilyl group. The organic polymer (A1) is an organic polymer in which an unsaturated group is introduced at the terminal, and the general formula (2):
H-SiX ₃ (2)
(In the formula, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different.) An organic polymer obtained by an addition reaction with a hydrosilane compound It is a curable composition of any one of Claims 1-3 characterized by the above-mentioned. The organic polymer (A1) is an organic polymer in which an unsaturated group is introduced at the terminal, and the general formula (9):
H-Si (OR ⁴ ) ₃ (9)
(Wherein three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms) and an organic polymer obtained by an addition reaction with a hydrosilane compound The curable composition of any one of Claims 1-4. The organic polymer (A1) is an organic polymer that does not substantially contain an amide segment (-NH-CO-) in the main chain skeleton. Curable composition. The curable composition according to any one of claims 1 to 6, wherein the silanol condensation catalyst is a carboxylic acid tin salt (C) and further contains an amine compound. Furthermore, the organotin catalyst (D) is contained, The curable composition of Claim 7 characterized by the above-mentioned. Organotin catalyst (D) is a dialkyl tin carboxylates, dialkyltin _{oxide, Q g Sn (OZ) 4} -g, and _[Q 2 Sn (OZ)] in ₂ O (wherein, Q is C1-20 Z represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or an organic group having a functional group capable of forming a coordination bond to Sn inside itself. 9 is at least one selected from the group consisting of compounds represented by the formula: g is 0, 1, 2, or 3). Curable composition. Curing according to any one of claims 1 to 8, wherein the tin carboxylate (C) is a tin carboxylate (C1) in which the carbon atom adjacent to the carbonyl group is a quaternary carbon. Sex composition. The curable composition according to claim 1, wherein the non-tin catalyst (E) is a carboxylic acid and further contains an amine. The curable composition according to claim 11, wherein the carboxylic acid is a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon. The curable composition according to any one of claims 1 to 12, wherein the organic polymer (A1) is 5 to 28% by weight in the total amount of the curable composition. Furthermore, general formula (7):
_{^{-SiR 5 c (OR 6) 3}} -c (7)
(Wherein c R ^{5 s} are each independently a monovalent organic group having 1 to 20 carbon atoms, and 3-c R ^{6 s} are each independently a monovalent organic group having 2 to 20 carbon atoms. The aminosilane coupling agent (G) which has group represented by the group represented by c is 0, 1 or 2, and is represented by any one of Claims 2-12 characterized by the above-mentioned. Curable composition. The curable composition according to claim 14 , wherein the group represented by the general formula (7) is a triethoxysilyl group. General formula (6):
-Si (OR ⁴ ) ₃ (6)
(Wherein three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms) an organic polymer having a silicon-containing functional group capable of crosslinking by forming a siloxane bond And general formula (8):
_{^{-SiR 7 d (OCH 3) e}} (OR 8) 3-d-e (8)
(In the formula, d R ⁷ are each independently a monovalent organic group having 1 to 20 carbon atoms, and 3-de R ⁸ are each independently a monovalent organic group having 2 to 20 carbon atoms. D represents 0, 1, or 2, and e represents 1, 2, or 3, provided that 3-de ≧ 0 is satisfied. It is a curable composition containing the aminosilane coupling agent (H) which has this, Comprising: This curable composition is hardened | cured previously, The curable composition of any one of Claims 2-12 characterized by the above-mentioned. object. The organic polymer (A1) is represented by the general formula (6):
-Si (OR ⁴ ) ₃ (6)
(Wherein three R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms) having a silicon-containing functional group capable of crosslinking by forming a siloxane bond, Transesterification of an organic polymer whose chain skeleton is a polyoxyalkylene polymer and a compound (J) having at least one methoxy group capable of transesterification with the R ⁴ O— group of the general formula (6) General formula (10):
_{^{-Si (OCH 3) f (OR}} 4) 3-f (10)
(Wherein 3-f R ^{4 s} are each independently a monovalent organic group having 2 to 20 carbon atoms, and f represents 1, 2, or 3). The curable composition according to claim 1, which has a silicon-containing functional group that can be cross-linked, and the main chain skeleton is a polyoxyalkylene polymer . An adhesive for interior panels, exterior panels, or vehicle panels, comprising the curable composition according to any one of claims 1 to 17 . A sealing material for a working joint of a building, comprising the curable composition according to any one of claims 1 to 17 .