JP2013163787A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which is usable as a sealing material, an adhesive, and a coating material, and which exhibits fast curing properties by curing the curable composition in a certain period of time.SOLUTION: A curable composition, which includes an organic polymer (A) having a reactive silicon group containing a halogen atom (such as a chloromethyl dimethoxy silyl group), and an amine compound (B) having a primary amino group and/or a secondary amino group, is cured in a certain period of time.

Description

  In the present invention, an organic heavy group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon group capable of forming a crosslink by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). The present invention relates to a curable composition comprising a coalescence and an organic polymer thereof.

  An organic polymer having at least one reactive silicon in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of a silyl group due to moisture or the like, thereby obtaining a rubber-like cured product. It is known to have

  As these organic polymers having a reactive silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a polyisobutylene polymer have already been industrially produced, such as sealing materials, adhesives, paints, etc. Widely used in applications (Patent Document 1) and (Patent Document 2).

  When an organic polymer having a reactive silicon group is used as a curable composition such as a sealant, an adhesive, or a paint, various properties such as curability and adhesion, and mechanical properties of the cured product are required. .

  A curable composition containing an organic polymer having a reactive silicon group is usually cured using a condensation catalyst such as an organic tin compound having a carbon-tin bond, represented by dibutyltin bis (acetylacetonate). Let When it is necessary to cure the curable composition in a short time, a method such as increasing the amount of the condensation catalyst is common. However, in recent years, the toxicity of organotin compounds has been pointed out, and caution is required for their use from the viewpoint of environmental safety.

  For this reason, as condensation catalysts other than organic tin compounds, carboxylic acid tin salts, other carboxylic acid metal salts, and catalyst systems using carboxylic acids and amine compounds in combination have been proposed (Patent Document 3) and (Patent Document 4). (Patent Document 5).

  However, these catalysts are often inferior in curability as compared with organotin catalysts. On the other hand, it has been proposed that a curable composition having a high curing rate can be obtained by using a polymer having a specific terminal structure (Patent Document 6) (Patent Document 7).

JP-A-52-73998 JP-A 63-6041 JP 55-9669 A JP 2003-206410 A JP-A-5-117519 JP 2005-501146 A WO2008 / 053875 publication

  If the polymer proposed in the above (Patent Document 6) or (Patent Document 7) is used, a curable composition having high curability can be obtained even if, for example, an amine compound is used as a condensation catalyst. . In order to produce a curable composition having fast curing properties, it is necessary to pay attention to moisture management, and it is also necessary to produce in a production facility with equipment capable of reliably controlling moisture.

  In the present invention, a reactive silicon group-containing organic polymer that exhibits mild curability when producing a curable composition, can be transferred to a storage container without using special equipment and operations, and exhibits rapid curability when used. It aims at providing the curable composition containing.

  As a result of intensive studies to solve the above problems, the inventor of the present invention has succeeded in heating and curing a curable composition containing a reactive silicon group having a specific structure and an amine compound. It has been found that curability is developed, and the present invention has been completed.

That is, the present invention
(1). A composition containing an organic polymer (A) having a reactive silicon group represented by the following general formula (1) and an amine compound (B) having a primary amino group and / or a secondary amino group: A curable composition obtained by curing at 30 ° C or higher for 1 day or longer,
-SiR ¹ _a R ² _b X _c (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen on the 1-position 3-position carbon atoms, a is .R ² is been substituted with halogen A hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by R ⁰ ₃ SiO—, and three R ⁰ are A hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, X represents a hydroxyl group or a hydrolyzable group, a is 1 or 2, b is 0 or 1, and c is 1 Alternatively, the condition that 2, a + b + c = 3 is satisfied, and when there are a plurality of R ¹ and X, they may be the same or different.
(2). R ¹ in the general formula (1) is an organic group represented by the following general formula (2), the curable composition according to (1),
-CR ³ _3-d Y _d (2)
(In the formula, R ³ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 19 carbon atoms. Y represents a halogen atom. D represents 1, 2 or 3. Each of R ³ and Y When there are a plurality of them, they may be the same or different.)
(3). Y in general formula (2) is chlorine, The curable composition as described in (2) characterized by the above-mentioned,
(4). The curable composition according to (2) or (3), wherein the general formula (2) is a chloromethyl group,
(5). The curable composition according to any one of (1) to (4), wherein the general formula (1) is a (chloromethyl) dimethoxysilyl group,
(6). The main chain structure of the organic polymer (A) is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester polymer. The curable composition according to any one of (1) to (5),
(7) The curable composition according to (6), wherein the main chain structure of the organic polymer (A) is a polyoxypropylene polymer,
(8) The curable composition according to any one of (1) to (7), wherein the amine compound (B) contains a hydrolyzable silicon group,
(9). The curable composition according to any one of (1) to (8), wherein curing is performed using a moisture-proof container,
(10). (1)-1-component type sealing material containing the curable composition according to any one of (9) as a component,
(11). (1)-(9) 1 liquid type adhesives which contain the curable composition of any one of (1) as a component,
(12). (1) to a cured product obtained by curing the curable composition according to any one of (9),
About.

  The curable composition of the present invention has a moderate curability when the composition is produced, and expresses a fast curability when used.

Hereinafter, the present invention will be described in detail.
(Organic polymer (A))
The organic polymer (A) of the present invention is not particularly limited as long as it is an organic polymer having a reactive silicon group represented by the following general formula (1).

-SiR ¹ _a R ² _b X _c (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is substituted with a halogen atom. R ² Represents a hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by R ⁰ ₃ SiO—, and three R ⁰ Are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, X represents a hydroxyl group or a hydrolyzable group, a is 1 or 2, b is 0 or 1, and c is The condition that 1 or 2, a + b + c = 3 is satisfied, and when there are a plurality of R ¹ and X, they may be the same or different.
(Reactive silicon group of general formula (1))
A hydrocarbon in which at least one hydrogen atom on the 1st to 3rd carbon atoms is substituted with a halogen, together with a hydrolyzable group or a hydroxyl group, as a substituent bonded to the silicon atom in the general formula (1) A silicon group having a group is essential.

Furthermore, it is preferable that R ¹ in the general formula (1) is a substituent represented by the following general formula (2) because higher curability is exhibited.

-CR ³ _3-d Y _d (2)
(In the formula, R ³ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 19 carbon atoms. Y represents a halogen. D represents 1, 2 or 3. For each of R ³ and Y, , When they are present, they may be the same or different.)

The substituent represented by the general formula (2) is a kind of R ^{1 in} the general formula (1) and represents a hydrocarbon group having a halogen at the 1-position carbon atom.

  Y in the general formula (2) is not particularly limited, and examples thereof include halogens such as fluorine, chlorine, bromine and iodine. In these, since it has high reactivity, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a chlorine atom is more preferable from the availability of the compound used as a raw material.

Specific examples of R ¹ in the general formula (1) include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a chloromethyl group, and a dichloromethyl group. 1-chloroethyl group, 2-chloroethyl group, 3-chloropropyl group, 2-chloropropyl group, bromomethyl group, iodomethyl group, 3-iodopropyl group and the like. In these, a chloromethyl group, 1-chloroethyl group, a bromomethyl group, and an iodomethyl group are preferable from a sclerosing | hardenable point, and a chloromethyl group is more preferable from the availability of the compound used as a raw material.

  X in the general formula (1) represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include known hydrolyzable groups. Specific examples thereof 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 amino group. Examples thereof include an oxy 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. An alkoxy group such as a group is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

  Moreover, it is preferable that the reactive silicon group represented by General formula (1) has two hydrolyzable groups and two hydroxyl groups from being easy to obtain quick curability.

Specific examples of R ² in the general formula (1) include an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; Of these, a methyl group is particularly preferred.

  Specific examples of the reactive silicon group represented by the general formula (1) include a chloromethylmethoxymethylsilyl group, a bis (chloromethyl) methoxysilyl group, a chloromethyldimethoxysilyl group, and a chloromethyldiethoxysilyl group. Chloromethylalkoxysilyl group such as dichloromethyldimethoxysilyl group; chloroethyldimethoxysilyl group, chloropropyldimethoxysilyl group, bromomethylmethoxymethylsilyl group, bromomethyldimethoxysilyl group, bromomethyldiethoxysilyl group, dibromomethyldimethoxysilyl Group, iodomethylmethoxymethylsilyl group, iodomethyldimethoxysilyl group, iodomethyldiethoxysilyl group, diiodomethyldimethoxysilyl group and the like. Among these, a chloromethyldimethoxysilyl group and a chloromethyldiethoxysilyl group are preferable because of easy synthesis, and a chloromethyldimethoxysilyl group is particularly preferable.

(Main chain structure of organic polymer (A))
As the main chain structure of the reactive silicon group-containing organic polymer (A) of the present invention, specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene Copolymer, polyoxyalkylene polymer such as polyoxypropylene-polyoxybutylene copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, Copolymers of isoprene or butadiene with acrylonitrile and / or styrene, polybutadiene, copolymers of isoprene or butadiene with acrylonitrile and styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers Hydrocarbon polymers such as polymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid and glycols or ring-opening polymerization of lactones; methyl (meth) acrylate, (meth) acrylic acid (Meth) acrylate esters obtained by radical polymerization of (meth) acrylate monomers such as ethyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate (Co) polymer; (meth) acrylic acid ester monomer, vinyl copolymer obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile and styrene; in the organic polymer, (meth) Graft polymer obtained by polymerizing monomers such as acrylate monomers, vinyl acetate, acrylonitrile, styrene; 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 by condensation polymerization, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide polymer such as copolymer nylon having two or more components among the above nylons; by condensation polymerization of bisphenol A and carbonyl chloride Examples thereof include polycarbonate polymers and diallyl phthalate polymers. In the above description, for example, (meth) acrylic acid ester represents acrylic acid ester and / or methacrylic acid ester.

  Of these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester (co) polymers are relatively glass transitions. It is more preferable because the temperature is low and the resulting cured product is excellent in cold resistance. The glass transition temperature of the reactive silicon group-containing organic polymer (A) of the present invention is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. It is particularly preferred that If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease. The glass transition temperature is a value obtained by DSC measurement.

  In addition, polyoxyalkylene polymers and (meth) acrylic acid ester (co) polymers have high moisture permeability and excellent deep-part curability when made into a one-component composition, and further have excellent adhesion. Particularly preferred. Of these, polyoxyalkylene polymers are most preferred.

The polyoxyalkylene polymer is a polymer having a repeating unit represented by —R ⁴ —O— (wherein R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁴ is more preferably a linear or branched alkylene group having 2 to ⁴ carbon atoms. Specific examples of the repeating unit represented by —R ⁴ —O— include —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H _{5) O -, - CH 2} C (CH 3) (CH 3) O -, - CH 2 CH 2 CH 2 CH 2 O-, and the like, such as.

The main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. The polyoxyalkylene polymer preferably contains 50% by weight or more of the repeating unit represented by —R ⁴ —O— in the main chain, based on all the repeating units in the main chain, and is 70% by weight or more. It is more preferable to contain.

  The main chain structure of the polyoxyalkylene polymer has a repeating unit of oxypropylene of 50% by weight or more, preferably 80% by weight or more of the polymer main chain structure, particularly when used in sealants, adhesives and the like. A polyoxypropylene polymer is preferred because it is amorphous and has a relatively low viscosity.

The main chain structure of the polyoxyalkylene polymer may be linear or may have a branched chain. It is preferable to have a branched chain because the curing time until the rapid curability is developed can be shortened.
In the case of having a branched chain, the number of branched chains is preferably 1 to 6, more preferably 1 to 4, and most preferably 1.

  The polyoxyalkylene polymer is preferably obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.

  Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, it is particularly preferable to use propylene oxide because an amorphous and relatively low viscosity polyether polymer can be obtained.

  Specific examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, Alcohols such as sorbitol; number average molecular weights of 300 to 4,000, and polyoxyalkylene polymers such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol .

  The main chain structure of the organic polymer (A) of the present invention is an organic polymer containing other bonding components such as a urethane bond and a urea bond in the main chain structure as long as the effects of the present invention are not significantly impaired. A coalescence may be used. Specific examples of such polymers include polyurethane prepolymers.

  The polyurethane prepolymer can be obtained by a known method. For example, it can be obtained by reacting a polyol compound and a polyisocyanate compound.

  Specific examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol.

  Specific examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, hexamethylene diisocyanate, and the like.

  The polyurethane prepolymer may have either a hydroxyl group or an isocyanate group at the end.

  The cured product obtained from the curable composition using a polymer having a urethane bond, a urea bond, and / or an ester bond in the main chain structure of the organic polymer (A) of the present invention has a urethane bond by heat or the like. There is a possibility that the main chain may be cleaved at the urea bond and / or the ester bond part, and the strength of the cured product may be significantly reduced.

When there are many amide bonds (—NR ⁵ —C (═O) —; R ⁵ represents a hydrogen atom or a substituted or unsubstituted organic group) in the main chain skeleton of the organic polymer (A) of the present invention, The viscosity of the coalescence tends to increase. Moreover, a viscosity may rise after storage, and workability | operativity of the composition obtained may fall. Furthermore, the amide bond may be cleaved by heat or the like.

  Therefore, when an amide bond is included in the main chain structure, the average number of amide bonds is 1 to 10 per molecule, preferably 1.5 to 5, and more preferably 2 to 3. When the number is less than 1, the curability may not be sufficient. When the number is more than 10, the polymer may have a high viscosity and may be difficult to handle.

  From these points, as the main chain structure of the organic polymer (A) of the present invention, from the point of obtaining a curable composition excellent in storage stability and workability, in the main chain structure, a urethane bond, Most preferred is a polyoxyalkylene polymer that does not contain a linking group such as a urea bond, an amide bond, or an ester bond.

  The molecular weight distribution (Mw / Mn) of the organic polymer (A) is preferably 1.6 or less, more preferably 1.5 or less, and particularly preferably 1.4 or less.

  The number average molecular weight of the organic polymer (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000. When the number average molecular weight is less than 3,000, the elongation property at break of the cured product of the obtained organic polymer (A) is lowered. When the number average molecular weight exceeds 100,000, the reactive silicon group concentration becomes too low and the curing rate is too high. Tends to slow down. In addition, the viscosity of the organic polymer (A) tends to be too high, making it difficult to handle.

  As a relative measurement method of the number average molecular weight of the organic polymer (A), a polystyrene-converted number average molecular weight (GPC molecular weight) obtained by general GPC measurement of a polyether polymer precursor and a calibration curve of the above end group molecular weights. Is obtained by converting the GPC molecular weight of the reactive silicon group-containing organic polymer (A) into a terminal group molecular weight.

  The main chain structure of the organic polymer (A) is preferably a linear or branched structure having 2 to 8 terminal groups of the organic polymer, and a linear or branched structure having 2 to 4 terminal groups. A structure is more preferable, and a linear structure having 2 terminal groups or a branched structure having 3 terminal groups is particularly preferable.

The method for introducing a reactive silicon group into the organic polymer (A) of the present invention is not particularly limited and is preferably obtained by the following methods (a) and / or (b).
(A) After converting the terminal hydroxyl group of the hydroxyl group-terminated organic polymer to an allyl group, HSiR ¹ _a R ² _b X _c (R ¹ , R ² , X, a, b, c are each described in the general formula (1). It is obtained by reacting a silane compound represented by the same formula.
(B) the terminal hydroxyl groups of the hydroxyl-terminated organic polymer, .e showing the _{^{OCN-R 6 -SiR 1 e R}} 2 f X g (R 6 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms 1 Or 2, f is 0 or 1, g is 1 or 2, and e + f + g = 3, where R ¹ , R ² , and X are the same as those in the general formula (1)). Obtained by reacting the compound.

When a polyurethane prepolymer is used, each end of at least one polyurethane prepolymer selected from the group consisting of (b1) a hydroxyl group-terminated polyurethane prepolymer, an isocyanate group-terminated polyurethane prepolymer, and an amino group-terminated polyurethane prepolymer is used. OCN—R ⁶ —SiR ¹ _e R ² _f X _g (R ⁶ represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms) in the functional group (ie, hydroxyl group, isocyanate group, amino group). Is 1 or 2, f is 0 or 1, g is 1 or 2, and e + f + g = 3, where R ¹ , R ² , and X are the same as those in the general formula (1)) A reactive silicon group-containing polyurethane prepolymer obtained by reacting an isocyanate silane compound.

  Among these methods, the polymer obtained by the method (a) can obtain a polymer having a lower viscosity than the polymer obtained by the method (b) or (b1). The method (b) can obtain a polymer having a high silyl group introduction rate in a relatively short reaction time.

  In order to obtain a good rubber-like cured product, the number of reactive silicon groups in the reactive silicon group-containing organic polymer (A) is preferably 1.1 to 2.5 on average per molecule. 2 to 2.4 is more preferable.

  The reactive silicon group may be present at either the main chain terminal, the side chain terminal, or both of the organic polymer (A). In particular, when the reactive silicon group is at the end of the main chain, the molecular weight between the cross-linking points becomes long, so that it is easy to obtain a rubber-like cured product having high strength and high elongation.

The average number of reactive silicon groups in the organic polymer (A) is defined as the average number obtained by a method of quantifying protons on carbon to which reactive silicon groups are directly bonded by high resolution ¹ H-NMR measurement. ing. In the calculation of the average number of reactive silicon groups in the organic polymer (A) in the present invention, when the reactive silicon group is introduced into the polyether polymer precursor before the reactive silicon group is introduced. In addition, the same main chain structure is applied to the polyether polymer precursor in which no reactive silicon group is introduced and the modified polyether polymer precursor in which no by-product reactive silicon group is introduced. It is considered that it is a part of the component of the reactive silicon group-containing organic polymer (A) and it is included in the parameter (number of molecules) when calculating the average number of reactive silicon groups in one molecule.

The amine compound (B) having a primary amine and / or a secondary amine in the molecule is not particularly limited as long as it is a compound having an amino group represented by the following general formula (4). Never happen.
-NR ⁷ R ⁸ (4)
(In the formula, R ⁷ or R ⁸ represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ⁷ and R ⁸ may be the same. , May be different.)

Although it does not specifically limit as an amine compound, R < ⁷ > in General formula (4) and R < ⁸ > are either the primary amine whose R < ⁸ > is a hydrogen atom, R < ⁷ >, or R < ⁸ > is a hydrogen atom. It is preferable that the other is a secondary amine which is an alkyl group other than a hydrogen atom, and a primary amine is particularly preferable because a fast-curing curable composition can be obtained early after curing.

  Specific examples of the amine compound (B) are not particularly limited, and methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, pentadecylamine. Aliphatic primary amines such as cetylamine, laurylamine, stearylamine, cyclohexylamine, and primary amines having aromatic groups such as aniline, laurylaniline, stearylaniline; dimethylamine, diethylamine, dipropylamine, Diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearyl Amine, methyl stearylamine, stearylamine, aliphatic secondary amines, such as butyl stearylamine, phenylpropylamine, secondary amines having an aromatic group such as phenyl butyl amine. Of these, aliphatic primary amines such as butylamine, pentylamine, hexylamine, and octylamine are preferred because the reactive silicon group-containing organic polymer (A) exhibits high curability.

  Amines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU and DBN; guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide , Biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide are not included.

  In the present invention, it is also possible to use an amino group-containing silane coupling agent (hereinafter sometimes referred to as aminosilane) as the amine compound (B). An aminosilane is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter sometimes referred to as a hydrolyzable silicon group) and a substituted or unsubstituted amino group.

  The substituent of the substituted amino group is not particularly limited, and examples thereof include an alkyl group, an aralkyl group, and an aryl group.

  The hydrolyzable silicon group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, An aminooxy group, a mercapto group, etc. are mention | raise | lifted. Of these, halogen atoms, alkoxy groups, alkenyloxy groups, and aryloxy groups are preferred because of their high activity. A chlorine atom and an alkoxy group are preferable because they can be easily introduced. Alkoxy groups such as a methoxy group and an ethoxy group are more preferable because the hydrolyzability is mild and easy to handle, and a methoxy group and an ethoxy group are particularly preferable. In addition, the ethoxy group and the isopropenoxy group are preferably removed from the reaction by ethanol and acetone, respectively, from the viewpoint of safety. The number of hydrolyzable groups bonded to silicon atoms in aminosilane is preferably 2 or more, particularly 3 or more.

  The aminosilane is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldisilane. Ethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N- β-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltriisopropoxysilane, N-β- (β-aminoethyl) aminoethyl-γ-aminopropyltrimethoxysilane N-6-aminohexyl-γ-amino Propyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Trimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, bis (trimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) Pill) such as an amine, and the like.

Among the aminosilanes, aminosilanes having a primary amino group (—NH ₂ ) are preferable from the viewpoint of curability, and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Aminopropylmethyldimethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane are preferred.

  About 1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the compounding quantity of an amine compound (B), 1.5-10 weight part is more preferable. If the blending amount is less than 1 part by weight, fast curing may not be exhibited even if the moisture-proof container is cured for a certain period. On the other hand, if the blending amount exceeds 20 parts by weight, the cured product becomes brittle and sufficient strength may not be obtained.

  The curable composition containing the organic polymer (A) and the amine compound (B) of the present invention needs to be cured in a moisture-proof container at 30 ° C. or higher. The curing temperature is preferably 30 ° C or higher, more preferably 35 ° C to 80 ° C, and most preferably 40 to 80 ° C because the curing period can be shortened. When the curing temperature is less than 30 ° C., long-term curing may be required to develop fast curability. On the other hand, when the curing temperature exceeds 80 ° C., the viscosity of the curable composition may increase.

  The moisture-proof container is a known container and is not particularly limited as long as it can block moisture. Examples thereof include a paper cartridge, a plastic cartridge, and an aluminum container. The moisture content of the curable composition before curing in the moisture-proof container is preferably 2000 ppm or less, and more preferably 1000 ppm or less.

  The curing period is not particularly limited, preferably about 1 day to 2 months, more preferably about 3 days to 1.5 months, and most preferably about 1 week to 1 month. The curing period may be shortened by raising the curing temperature.

  In the curable composition of the present invention, for the purpose of adjusting the condensation reaction rate after curing of the organic polymer (A), as a condensation catalyst, an amine compound other than a primary amine and a secondary amine is used. Can be added.

  Examples of amine compounds include aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aniline, laurylaniline, stearylaniline, Aromatic amines such as phenylamine; pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2-piperidinemethanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo (5,4 0) Undecene-7 (DBU) 6- (dibutylamino) -1,8-diazabicyclo (5,4,0) undecene-7 (DBA-DBU), 1,5-diazabicyclo (4,3,0) nonene-5 (DBN), 1,4 -Nitrogen-containing heterocyclic compounds such as diazabicyclo (2,2,2) octane (DABCO) and aziridine; phenol salt of DBU (specifically, trade name: U-CAT SA1 (manufactured by San Apro)), octyl of DBU Acid salt (specifically, trade name: U-CAT SA102 (San Apro)), DBU p-toluenesulfonate (specifically, trade name: U-CAT SA506 (San Apro)), DBN As salts derived from nitrogen-containing heterocyclic compounds such as octylate (specifically, trade name: U-CAT 1102 (manufactured by San Apro)), and other amines, Noethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, Diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylamino Amines such as propylamine, 3-morpholinopropylamine, 2- (1-piperazinyl) ethylamine, xylylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol; And guanidines such as gin, phenylguanidine and diphenylguanidine; and biguanides such as butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide.

  Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU and DBN; guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1 Biguanides such as -o-tolyl biguanide and 1-phenyl biguanide are preferable because they exhibit high activity, and aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness. preferable.

Further, the amine compound is basic, but an amine compound having a pKa value of the conjugate acid of 11 or more is preferably high in catalytic activity, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and the like are particularly preferable because the pKa value of the conjugate acid is 12 or more and high catalytic activity is exhibited.
The compounding amount of the amine compound other than the primary amine and the secondary amine is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the organic polymer (A). Is more preferable, and 0.05 to 1 part by weight is particularly preferable. If the amount of the condensation catalyst used is less than 0.001 part by weight, the curing rate after curing may be too fast to control. On the other hand, when the usage-amount of a condensation catalyst exceeds 10 weight part, there exists a tendency for the hardening rate after curing to become slow.

  Moreover, it is also possible to use a condensation catalyst other than the above as long as the physical properties of the curable composition and the cured product of the present invention are not affected. Specifically, for example, carboxylic acid such as 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, or naphthenic acid; tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, Carboxylic acid metal salts such as barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, Titanium compounds such as tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); dibutyltin dilaurate, dib Rutin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate) , Dibutyltin bis (octyl maleate), dibutyltin bis (tridecylmaleate), dibutyltin bis (benzylmaleate), dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide Dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate, etc. Tin compounds; dioctyltin bis (triethoxysilicate), dioctyltin oxide, dioctyltin dimethoxide, dioctyltin diacetylacetonate, dioctyltin diacetate, dioctyltin dioctoate, dioctyltin diversate, dioctyltin dilaurate, dioctyltin distearate, dioctyltin dibehenate , Dioctyltin dioleate, Bis (dioctyltin acetate) oxide, Bis (dioctyltin octoate) oxide, Bis (dioctyltin versateate) oxide, Bis (dioctyltin laurate) oxide, Bis (dioctyltin stearate) oxide, Bis (dioctyltin) Behenate) oxide, dioctyltin bis (ethylmalate), dioctyltin bis (octylmalate), dioctyltin bisiso Dioctyltin compounds such as octylthioglycolate; Aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; Zirconium compounds such as zirconium tetrakis (acetylacetonate); Examples thereof include various metal alkoxide compounds such as tetrabutoxyhafnium; organic acidic phosphate esters; organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid, and boronic acid.

  Of these condensation catalysts, amine compounds or dioctyltin compounds are particularly preferred from the viewpoints of curability and environmental load.

  The amount of the condensation catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the organic polymer (A). Is particularly preferred.

  If necessary, the curable composition of the present invention may contain a plasticizer, an adhesion promoter, a filler, a physical property modifier, a sagging inhibitor (thixotropic agent), a stabilizer, and the like.

  A plasticizer can be added to the curable composition of the present invention. By adding the plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, and the like; bis (2-ethylhexyl) ) Terephthalic acid ester compounds such as 1,4-benzenedicarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributy acetyl citrate Aliphatic polycarboxylic acid ester compounds such as butyl; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl ester (specifically, trade name: Mesamol (manufactured by LANXESS)); Phosphate ester compounds such as cresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil and epoxybenzyl stearate And epoxy plasticizers.

  Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low-molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule is used. Furthermore, the drying property (paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizers 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; number average molecular weight of 500 or more Furthermore, more than 1,000 polyether polyols such as polyethylene glycol polypropylene glycol and polytetramethylene glycol, or the hydroxy group of these polyether polyols are esterified Polyethers such as derivatives converted to ether groups; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. It is not something.

  Among these polymer plasticizers, those compatible with the organic polymer (A) are preferable. From this point, a polyether polymer and a vinyl polymer are preferable. Further, when a polyether polymer is used as a plasticizer, it is preferable because surface curability and deep part curability are improved and curing delay after storage does not occur, and polypropylene glycol is more preferable. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers such as poly (meth) acrylic acid alkyl esters are particularly 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 a (meth) acrylic acid alkyl ester monomer described in JP-A No. 2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000. 5,000. Most preferred is 1,000 to 3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, and the initial physical properties cannot be maintained over a long period of time. 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 of the polymer plasticizer is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer may or may not have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. When it has a reactive silicon group, it is preferably 1 or less, more preferably 0.8 or less on average per molecule. When using the plasticizer which has a reactive silicon group, especially the polyether polymer which has a reactive silicon group, the number average molecular weight needs to be lower than an organic polymer (A).

  The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (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. 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.

  In the curable composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and α-isocyanatemethyltrimethoxysilane. , Isocyanate group-containing silanes such as α-isocyanatomethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Mercapto group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyl Epoxy group-containing silanes such as dimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β- Carboxysilanes such as carboxyethylphenylbis (β-methoxyethoxy) silane; vinyl type non-vinyl such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane Saturated group-containing silanes; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; Moreover, silylated amino polymers, silylated polyesters, and the like, which are derivatives obtained by modifying these, can also be used as silane coupling agents.

  0.1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the usage-amount of a silane coupling agent, 0.5-10 weight part is especially preferable.

  Various fillers can be mix | blended with the curable composition of this invention. Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, Resin powder such as magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, PVC powder, PMMA powder And fillers such as asbestos, glass fibers and filaments.

  The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the organic polymer (A).

  When you want to obtain a hardened material with high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment A filler selected from fine calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and the amount used is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. Fatty acid surface-treated colloidal calcium carbonate and heavy calcium carbonate that has not been surface-treated such as calcium carbonate having a particle size of 1 μm or more can be used in combination.

  A spherical hollow body such as a balloon can be added to the curable composition of the present invention for the purpose of reducing the weight (reducing specific gravity) of the composition.

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

  The particle size of the balloon is preferably 3 to 200 μm, and particularly preferably 10 to 110 μm. If the thickness is less than 3 μm, the contribution to weight reduction is small, so a large amount of addition is necessary, and if it is 200 μm or more, the surface of the cured sealing material tends to be uneven or the elongation tends to decrease.

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

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

  0.01-30 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the usage-amount of a spherical hollow body, 0.1-20 weight part is especially preferable. If it is less than 0.01 part by weight, there is no workability improvement effect, and if it exceeds 30 parts by weight, the elongation and breaking strength of the cured product tend to be low.

  An anti-sagging agent may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging inhibitor 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 anti-sagging agents may be used alone or in combination of two or more.

  The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  An antioxidant (antiaging agent) can be used in the curable 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; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by Ciba Japan Co., Ltd.); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 All are manufactured by ADEKA Corporation); 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 Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

  0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the usage-amount of antioxidant, 0.2-5 weight part is especially preferable.

  A light stabilizer can be used in the curable composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.

  0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the usage-amount of a light stabilizer, 0.2-5 weight part is especially preferable.

  When a photocurable substance is blended in the curable composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a contained hindered amine light stabilizer for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB119FL (all are manufactured by Ciba Japan Co., Ltd.); Adeka Stub LA-57, LA-62, LA-67, LA-63 (all above) Light stabilizers such as SANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

  An ultraviolet absorber can be used for the curable composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. Furthermore, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.

  0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the usage-amount of a ultraviolet absorber, 0.2-5 weight part is especially preferable.

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

  The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use.

  The curable composition of the present invention can be used as a building sealing material or an industrial adhesive. Moreover, it can be used as a sealant for buildings, ships, automobiles, roads and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. it can. In addition to a normal adhesive, it can also be used as a contact adhesive. Furthermore, it is also useful as a food packaging material, cast rubber material, molding material, and paint.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.
The chloromethyldimethoxysilane used in the following synthesis examples was synthesized with reference to the methods described in Example 41 and Example 55 of WO2010 / 004948.

(Synthesis Example 1)
Polymerization of propylene oxide with a polyoxypropylene diol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 21,100 (using Tosoh's HLC-8120GPC as the liquid feeding system) The column used the TSK-GEL H type made from Tosoh, and the solvent obtained the polyoxypropylene diol of the polystyrene conversion molecular weight measured using THF. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, with respect to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, 72 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 1.29 parts by weight of trimethyl orthoformate were added and stirred. 1.41 parts by weight of methyldimethoxysilane was slowly added dropwise. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted chloromethyldimethoxysilane was distilled off under reduced pressure, whereby the terminal was a chloromethyldimethoxysilyl group, and the average number of silicon groups per molecule was 1. A linear reactive silicon group-containing polyoxypropylene polymer (A-1) having a number average molecular weight of 21,100 was obtained.

(Synthesis Example 2)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene diol having a number average molecular weight of about 3,000 as an initiator, and a number average molecular weight of 21,100 (calculated in the same manner as in Synthesis Example 1) Of polyoxypropylene diol was obtained. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 36 parts by weight of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) was added to 100 parts by weight of the allyl group-terminated polyoxypropylene polymer, and 1.06 parts by weight of methyldimethoxysilane was stirred. Was slowly added dropwise. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted methyldimethoxylane was distilled off under reduced pressure, whereby a terminal was a methyldimethoxysilyl group, and an average of 1.4 silicon groups per molecule. A linear reactive silicon group-containing polyoxypropylene polymer (C-1) having a number average molecular weight of 21,100 was obtained.

(Synthesis Example 3)
Polyoxypropylene diol having a number average molecular weight of about 3,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 28,500 (Tosoh HLC-8120GPC The column was a TSK-GEL H type manufactured by Tosoh, and the solvent was a polyoxypropylene diol having a molecular weight in terms of polystyrene measured using THF. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and TES (triethoxysilane) 1.33 was added while stirring. The parts by weight were slowly added dropwise. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted TES was distilled off under reduced pressure. Furthermore, 20 parts by weight of methanol and 12 ppm of HCl are added to convert the terminal ethoxy group into a methoxy group, whereby the terminal is a trimethoxysilyl group, an average of 1.4 silicon groups per molecule, and a number average molecular weight of 28 500, a linear reactive silicon group-containing polyoxypropylene polymer (C-2) was obtained.

(Synthesis Example 4)
To methoxymethyltrimethoxysilane produced by referring to the method described in Example 2 of JP-T-2007-513203, 0.02 molar equivalent of zinc chloride was used as a catalyst and 4 molar equivalents of acetyl chloride were allowed to act. . Reaction was carried out for 36 hours under heating and refluxing conditions to synthesize methoxymethyltrichlorosilane.

  Distilled and purified methoxymethyltrichlorosilane and 1 molar equivalent of methyldichlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd .: LS-50) were mixed, 0.05 molar equivalent of methyltributylammonium chloride was added, and the mixture was reacted under heating under reflux conditions for 3 hours. . Methoxymethyldichlorosilane was obtained with a conversion of about 50%.

2.5 mol equivalent of trimethyl orthoacetate was charged into the reaction vessel with respect to the distilled and purified methoxymethyldichlorosilane, and methoxymethyldichlorosilane was slowly added while stirring well. The addition rate was adjusted so that the temperature of the reaction solution did not exceed 50 ° C. After completion of the addition, by using The ¹ HNMR spectrum (JEOL Ltd. JNM-LA400 that methoxymethyl dichlorosilane is converted almost quantitatively methoxymethyl dimethoxy silane, a peak of the measurement .CHCL ₃ in CDCL ₃ solvent 7. It was analyzed as 26 ppm.) Purification by vacuum distillation gave methoxymethyldimethoxysilane.
¹ H NMR spectrum assignment: δ 4.52 (t, 1H), 3.60 (s, 6H), 3.35 (s, 3H), 3.19 (d, 2H).

(Synthesis Example 5)
Polymerization of propylene oxide with a polyoxypropylene diol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 21,100 (using Tosoh's HLC-8120GPC as the liquid feeding system) The column used the TSK-GEL H type made from Tosoh, and the solvent obtained the polyoxypropylene diol of the polystyrene conversion molecular weight measured using THF. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 72 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 1.29 parts by weight of trimethyl orthoformate were added to 100 parts by weight of the resulting allyl group-terminated polyoxypropylene, and the mixture was stirred. 1.36 parts by weight of methoxymethyldimethoxysilane synthesized in Example 4 was slowly added dropwise. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted methoxymethyldimethoxysilane was distilled off under reduced pressure, whereby the terminal was a methoxymethyldimethoxysilyl group, and the average number of silicon groups per molecule was 1. Four linear, reactive silicon group-containing polyoxypropylene polymers (C-3) having a number average molecular weight of 21,100 were obtained.

Example 1
100 parts by weight of polymer (A-1), plasticizer (BASF, trade name: Hexamol DINCH) 30 parts by weight, fatty acid-treated calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Hakujoka CCR) 50 weights Parts, heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten SB red) 160 parts by weight, thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500) 3 parts by weight, ultraviolet After 1 part by weight of an absorbent (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumisorb 400) and 1 part by weight of a light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS770) are mixed and kneaded thoroughly. The mixture was dispersed once through three paint rolls. Next, the mixture was kneaded for 2 hours while being dehydrated by a planetary mixer under reduced pressure at 120 ° C. and 0.2 mmHg. After cooling to room temperature, 4 parts by weight of a dehydrating agent (Mentive Co., Ltd., trade name: A-171) and 3 parts by weight of amine compound (B) (Mentive Co., Ltd., trade name: A-1110) are mixed. After sufficiently kneading, the curable composition was filled into a moisture-proof cartridge type container.

(Healing)
After filling the cartridge with the curable composition, the skinning time of the curable composition cured at 50 ° C. for 4 weeks was measured by the following method.
(Skinning time)
The composition was extruded from the cartridge under an atmosphere of 23 ° C. and a relative humidity of 50%, filled in a mold having a thickness of about 5 mm using a spatula, and the time when the surface was flattened was defined as the curing start time. The surface was touched with a spatula, and the curing time was measured with the time until the composition no longer adhered to the spatula as the skinning time. The results are shown in Table 1.
(Viscosity change rate)
Under an atmosphere of 23 ° C. and 50% relative humidity, a BS viscometer and rotor No. 7 (manufactured by Toki Sangyo Co., Ltd.) were used to measure the viscosity when the rotational speed was 2 rpm. When the viscosity ratio after curing to the viscosity before curing was 2 or less, “◯” was given, and when it was 2 or more, “x” was given. The results are shown in Table 1.

(Example 2),
In Example 1, a curable composition was prepared and evaluated in the same manner except that 1.7 parts by weight of hexylamine was used instead of A-1110 as the amine compound (B).

(Example 3)
In Example 1, a curable composition was prepared and evaluated in the same manner except that 3.1 parts by weight of dihexylamine was used instead of A-1110 as the amine compound (B).

Example 4
The curable composition was the same as in Example 1 except that 0.5 part by weight of DBU (manufactured by Wako Pure Chemical Industries, Ltd., 1,8-diazabicyclo [5,4,0] undecene-7) was added as a condensation catalyst. A product was prepared and evaluated.

(Example 5)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that 0.3 part by weight of 1-phenylguanidine (manufactured by Nippon Carbide Industries Co., Ltd.) was added as a condensation catalyst.

(Example 6)
For 100 parts by weight of polymer (A-1), 55 parts by weight of plasticizer (manufactured by J-Plus Co., Ltd., trade name: DIDP), fatty acid-treated calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Hakucho Hana CCR ) 120 parts by weight, 20 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Taipei P-820), 2 parts by weight of a thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500), 1 part by weight of an ultraviolet absorber (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumisorb 400) and 1 part by weight of a light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS770) were mixed and kneaded sufficiently. Thereafter, the mixture was dispersed once by passing through three paint rolls. Next, the mixture was kneaded for 2 hours while being dehydrated by a planetary mixer under reduced pressure at 120 ° C. and 0.2 mmHg. After cooling to room temperature, 3 parts by weight of a dehydrating agent (manufactured by Momentive Co., Ltd., trade name: A-171), 1.5 parts by weight of compound (B) (manufactured by Momentive Co., Ltd., trade name: A-1110), and Compound (B) (product of Momentive Co., Ltd., trade name: A-1122) 1.5 parts by weight, dibutyltin dilaurate (product of Nitto Kasei Co., Ltd., trade name: Neostan U-100) 0.2 as a condensation catalyst A curable composition was prepared and evaluated in the same manner as in Example 1 except that parts by weight were used.

(Comparative Example 1)
In Example 6, the polymer (C-1) instead of the polymer (A-1), 4 parts by weight of the dehydrating agent A-171, 3 parts by weight of A-1110 as the amine compound, and dibutyltin as the condensation catalyst A curable composition was similarly prepared and evaluated except that 2 parts by weight of diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was used.

(Comparative Example 2)
In Example 1, a curable composition was prepared and evaluated in the same manner except that the polymer (C-1) was used instead of the polymer (A-1) and 2 parts by weight of U-220H was used as a condensation catalyst. Went.

(Comparative Example 3)
In Example 1, a curable composition was prepared in the same manner except that the polymer (C-2) was used instead of the polymer (A-1) and 0.3 part by weight of 1-phenylguanidine was used as the condensation catalyst. And evaluated.

(Comparative Example 4)
In Example 1, a curable composition was prepared and evaluated in the same manner except that the polymer (C-3) was used instead of the polymer (A-1) and 1 part by weight of 1-phenylguanidine was used as the condensation catalyst. Went.

(Comparative Example 5)
Evaluation was performed in the same manner except that the amine compound (B) was not used in Example 5.

In the results shown in Table 1, a curable composition was prepared by using a combination of an organic polymer (A) having a reactive silicon group having a specific structure and a compound (B) having an amino group in the molecule and curing for a certain period of time. It turns out that it becomes quicker than the skinning time just after, and shows quick-hardening property.

Claims (12)

A composition containing an organic polymer (A) having a reactive silicon group represented by the following general formula (1) and an amine compound (B) having a primary amino group and / or a secondary amino group: A curable composition obtained by curing at 30 ° C. or higher for 1 day or longer.
-SiR ¹ _a R ² _b X _c (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen on the 1-position 3-position carbon atoms, a is .R ² is been substituted with halogen A hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by R ⁰ ₃ SiO—, and three R ⁰ are A hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, X represents a hydroxyl group or a hydrolyzable group, a is 1 or 2, b is 0 or 1, and c is 1 Alternatively, the condition that 2, a + b + c = 3 is satisfied, and when there are a plurality of R ¹ and X, they may be the same or different. The curable composition according to claim 1, wherein R ¹ in the general formula (1) is an organic group represented by the following general formula (2).
-CR ³ _3-d Y _d (2)
(In the formula, R ³ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 19 carbon atoms. Y represents a halogen atom. D represents 1, 2 or 3. Each of R ³ and Y When there are a plurality of them, they may be the same or different.) Y in general formula (2) is a chlorine atom, The curable composition of Claim 2 characterized by the above-mentioned. The curable composition according to claim 2 or 3, wherein the general formula (2) is a chloromethyl group. The curable composition according to any one of claims 1 to 4, wherein the general formula (1) is a (chloromethyl) dimethoxysilyl group. The main chain structure of the organic polymer (A) is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester polymer. The curable composition according to any one of claims 1 to 5. The curable composition according to claim 6, wherein the main chain structure of the organic polymer (A) is a polyoxypropylene polymer. The curable composition according to any one of claims 1 to 7, wherein the amine compound (B) contains a hydrolyzable silicon group. Curing is performed using a moisture-proof container, The curable composition according to any one of claims 1 to 8. The one-component type sealing material which contains the curable composition of any one of Claims 1-9 as a component. A one-component adhesive comprising the curable composition according to any one of claims 1 to 9 as a component. Hardened | cured material obtained by hardening the curable composition of any one of Claims 1-9.