JP2012107098A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which is used as a sealing material, an adhesive, a coating material or the like and provides a cured material having high strength and excellent extensibility.SOLUTION: The curable composition contains an organic polymer (A) having a reactive silicon group having high activity (e.g., chloromethyldimethoxysilyl group or the like) and a silane coupling agent (B) having a reactive silicon group and a carbamate group in the molecule.

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 polymers proposed in the above (Patent Document 6) and (Patent Document 7) are used, a curable composition having high curability can be obtained even if, for example, an amine compound is used as a condensation catalyst. it can. When the present inventors created a curable composition using the polymers described in the examples of (Patent Document 6) and (Patent Document 7), the mechanical properties of the resulting cured product were found to be the same as that of conventional dimethoxy. It has been found that there is a tendency to have a high hardness and a low elongation as compared with a cured product obtained from a curable composition using a polymer having a methylsilyl terminal. Depending on the application, there are cases where elongation properties are required, and there is room for improvement in terms of achieving both elongation properties and curability.

  An object of the present invention is to provide a curable composition containing a reactive silicon group-containing organic polymer having excellent elongation properties even when a non-organotin-based condensation catalyst is used.

  As a result of intensive studies to solve the above problems, the present inventor uses an organic polymer having a reactive silicon group having a specific structure and a silane coupling agent having a reactive silicon group and a carbamate group in the molecule. As a result, it was found that excellent elongation physical properties were expressed, and the present invention was completed.

That is, the present invention
(1).
Reactive silicon group-containing organic polymer (A) having a reactive silicon group represented by the following general formula (1) at the molecular chain end, and a reactive silicon group and carbamate represented by the following general formula (2) A curable composition comprising a silane coupling agent (B) having a group in the molecule;
-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 at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen atom, —OR ³ , —NR ⁴ R ^5. , -N = R ⁶ , -SR ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is 1 carbon atom. A divalent substituted or unsubstituted hydrocarbon group of ˜20), a perfluoroalkyl group having 1 to 20 carbon atoms, or a group substituted with a cyano group, R ² is a carbon atom having 1 to 20 carbon atoms. A hydrogen group, 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—, wherein three R ⁰ are carbonized carbon atoms having 1 to 20 carbon atoms Are hydrogen groups, they may be the same or different X for each condition is satisfied ^{.R 1, R} 2, X to the .a showing a hydroxyl group or a hydrolyzable group 1 or 2, b is 0 or 1, c is 1 or 2, a + b + c = 3 , When they are present, they may be the same or different.)
_{^{R 9 O 2 C-NH-}} R 8 -SiX 1 3 (2)
(In the formula, R ⁸ represents a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms. In the formula, R ⁹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. Or an aryl group having 7 to 20 carbon atoms, X ¹ represents a hydroxyl group or a hydrolyzable group, and X ¹ may be the same or different.
(2).
R ¹ in the general formula (1) is an organic group represented by the following general formula (3), the curable composition according to (1),
-CR ¹⁰ _3-d Y _d (3)
(In the formula, R ¹⁰ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 19 carbon atoms. Y represents a halogen atom, —OR ³ , —NR ⁴ R ⁵ , —N═R ⁶ , —SR. ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a divalent substituted or non-substituted group having 1 to 20 carbon atoms. A substituted hydrocarbon group.), A perfluoroalkyl group having 1 to 20 carbon atoms, a group substituted with a cyano group, d represents 1, 2 or 3. For each of R ¹⁰ and Y, When there are multiple, they may be the same or different.)
(3).
The curable composition according to (2), wherein Y in the general formula (3) is a chlorine atom,
(4).
The curable composition according to (3), wherein the general formula (3) is a chloromethyl group,
(5).
The curable composition according to (4), wherein the general formula (1) is a chloromethyldimethoxysilyl group,
(6).
Y in general formula (3) is an alkoxy group, The curable composition as described in (2) characterized by the above-mentioned,
(7).
Y in the general formula (3) is at least one group selected from the group consisting of a methoxy group, an ethoxy group, and a phenoxy group, the curable composition according to (6),
(8).
The curable composition according to (7), wherein the general formula (3) is a methoxymethyl group or an ethoxymethyl group,
(9).
The curable composition according to (8), wherein the general formula (1) is a methoxymethyldimethoxysilyl group.
(10).
The main chain structure of the reactive silicon group-containing 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 (9), which has
(11).
The curable composition according to (10), wherein the main chain structure of the reactive silicon group-containing organic polymer (A) is a polyoxypropylene polymer,
(12).
The curable composition according to any one of (1) to (11), wherein the general formula (2) is (methylcarbamatemethyl) trimethoxysilane,
(13).
(1) to a sealing material containing the curable composition according to any one of (12) as a component,
(14).
(1) to an adhesive comprising the curable composition according to any one of (12) as a component;
(15).
(1) to a cured product obtained by curing the curable composition according to any one of (12),
About.

  The curable composition containing the reactive silicon group-containing organic polymer (A) of the present invention is fast curable, and the cured product has excellent elongation properties.

Hereinafter, the present invention will be described in detail.
(Reactive silicon group-containing organic polymer (A))
The reactive silicon group-containing 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 at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen atom, —OR ³ , —NR ⁴ R ^5. , -N = R ⁶ , -SR ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is 1 carbon atom. A divalent substituted or unsubstituted hydrocarbon group of ˜20), a perfluoroalkyl group having 1 to 20 carbon atoms, or a group substituted with a cyano group, R ² is a carbon atom having 1 to 20 carbon atoms. A hydrogen group, 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—, wherein three R ⁰ are carbonized carbon atoms having 1 to 20 carbon atoms Are hydrogen groups, they may be the same or different X for each condition is satisfied ^{.R 1, R} 2, X to the .a showing a hydroxyl group or a hydrolyzable group 1 or 2, b is 0 or 1, c is 1 or 2, a + b + c = 3 , When they are present, they may be the same or different.)

(Reactive silicon group of general formula (1))
As a substituent bonded to a silicon atom in the general formula (1), together with a hydrolyzable group or a hydroxyl group, at least one hydrogen atom on the carbon atoms from position 1 to position 3 is a halogen atom, -OR ^3, —NR ⁴ R ⁵ , —N═R ⁶ , —SR ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R ⁶ Is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A perfluoroalkyl group having 1 to 20 carbon atoms, or a silicon group having a hydrocarbon group substituted with a cyano group (hereinafter referred to as “a silicon group”). A heteroatom-containing reactive silicon group). The organic polymer (A) of the present invention has a reactive silicon group having an unsubstituted hydrocarbon group such as a methyl group (for example, a dimethoxymethylsilyl group) by having a heteroatom-containing reactive silicon group. Fast curability compared to organic polymers.

Furthermore, it is preferable that R ¹ in the general formula (1) is a substituent represented by the following general formula (3) because it exhibits higher curability.

-CR ¹⁰ _3-d Y _d (3)
(In the formula, Y is a halogen atom, —OR ³ , —NR ⁴ R ⁵ , —N═R ⁶ , —SR ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a carbon atom number of 1 to 20 substituted or unsubstituted hydrocarbon groups, R ⁶ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.), A perfluoroalkyl group having 1 to 20 carbon atoms, a cyano group R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 19 carbon atoms, d represents 1, 2 or 3. When a plurality of R ¹⁰ and Y are present, They may be the same or different.)

Incidentally, the substituent represented by the general formula (3) is a general formula (1) one of R ¹ in, are a hydrocarbon group having a hetero atom at the 1-position carbon atoms.

  Y in the general formula (3) is not particularly limited, and examples thereof include halogen atoms; oxygen-based substituents such as alkoxy groups and acyloxy groups; nitrogen-based substituents such as amino groups, alkylamino groups, and ureido groups; acyl Group, alkoxycarbonyl group, nitro group, cyano group, sulfonyl group, perfluoroalkyl group, electron-withdrawing aryl group, and the like.

  More specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-butoxy group, tert- Alkoxy groups such as butyloxy, octoxy, lauryloxy, phenoxy, and benzyloxy; acyloxy groups such as acetoxy, propanoyloxy, and benzoyloxy; amino, methylamino, dimethylamino, and ethylamino Substituted amino groups such as a group, diethylamino group, propylamino group, dipropylamino group, diphenylamino group; groups bonded by urethane bond or urea bond such as ureido group, carbamate group; acetyl group, propanoyl group, octanoyl group, laurylyl Group, an acyl group such as benzoyl group; Alkoxycarbonyl groups such as xycarbonyl group and tert-butyloxycarbonyl group; nitro group; cyano group; isocyanate group; sulfonyl groups such as methylsulfonyl group and toluenesulfonyl group; trifluoromethyl group, pentafluoroethyl group, perfluoropropyl Groups, perfluoroalkyl groups such as perfluorohexyl groups and perfluorooctyl groups; and electron withdrawing aryl groups such as difluorophenyl groups and pentafluorophenyl groups. Of these, halogen atoms, alkoxy groups, substituted or unsubstituted amino groups, and trifluoromethyl groups are preferred because the resulting polymer exhibits high curability, and halogen atoms, alkoxy groups, substituted or unsubstituted amino groups are preferred. A group is more preferable, and a halogen atom and an alkoxy group are particularly preferable.

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. 2-chloroethyl group, 3-chloropropyl group, 2-chloropropyl group, bromomethyl group, iodomethyl group, 3-iodopropyl group, methoxymethyl group, ethoxymethyl group, phenoxymethyl group, aminomethyl group, N-methylamino Examples thereof include a methyl group, N, N-dimethylaminomethyl group, N-ethylaminomethyl group, N, N-diethylaminomethyl group, acetoxymethyl group, methylcarbamate group, 2-cyanoethyl group and the like. Among these, from the viewpoint of curability, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group are more preferable.

  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.

  In addition, the heteroatom-containing reactive silicon group preferably has two hydrolyzable groups and two hydroxyl groups because it is easy to obtain fast 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 heteroatom-containing reactive silicon group represented by the general formula (1) include, for example, a chloromethylmethoxymethylsilyl group, a bis (chloromethyl) methoxysilyl group, a chloromethyldimethoxysilyl group, and a chloromethyldisilane. Chloromethylalkoxysilyl groups such as ethoxysilyl group and dichloromethyldimethoxysilyl group; methoxymethylalkoxysilyl groups such as chloroethyldimethoxysilyl group, chloropropyldimethoxysilyl group, methoxymethyldimethoxysilyl group and methoxymethyldiethoxysilyl group; ethoxy Methyldimethoxysilyl group, aminomethyldimethoxysilyl group, N, N-dimethylaminomethyldimethoxysilyl group, N, N-diethylaminomethyldimethoxysilyl group, N, N-diethylaminomethyldiethoxysilyl group N- (2-aminoethyl) aminomethyldimethoxysilyl group, 3-aminopropyldimethoxysilyl group, N-methylaminopropyldimethoxysilyl group, N, N-dimethylaminopropyldimethoxysilyl group, 3- (2-aminoethyl) Examples include aminopropyldimethoxysilyl group, 3,3,3-trifluoropropyldimethoxysilyl group, acetoxymethyldimethoxysilyl group, acetoxymethyldiethoxysilyl group and the like. Among these, chloromethyldimethoxysilyl group, methoxymethyldimethoxysilyl group, methoxymethyldiethoxysilyl group, N, N-diethylaminomethyldiethoxysilyl group, and 3,3,3-trifluoropropyldimethoxysilyl group are synthesized. It is preferable because it is easy, and a chloromethyldimethoxysilyl group and a methoxymethyldimethoxysilyl group are particularly preferable.

(About the main chain structure of the reactive silicon group-containing 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 polyoxyalkylene polymer having a repeating unit represented by —R ¹¹ —O— (wherein R ¹¹ is a linear or branched alkylene group having 1 to 14 carbon atoms). R ¹¹ is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by —R ¹¹ —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 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. 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 .

  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. 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, can be mentioned, but not particularly limited, manufacturing cost and, because of such the polymer having a narrow molecular weight distribution is obtained, by the polymerization method is more preferred composite metal cyanide complex catalyst.

  In addition, as the main chain structure of the reactive silicon group-containing organic polymer (A) of the present invention, other bonding components such as a urethane bond and a urea bond are included in the main chain structure as long as the effects of the present invention are not significantly impaired. You may use the organic polymer containing. 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.

  A cured product obtained from a curable composition using a polymer having a urethane bond, a urea bond, and / or an ester bond in the main chain structure of the reactive silicon group-containing organic polymer (A) of the present invention, The main chain may be cleaved at the urethane bond, urea bond, and / or ester bond portion due to heat or the like, and the strength of the cured product may be significantly reduced.

An amide bond (—NR ¹² —C (═O) —; R ¹² represents a hydrogen atom or a substituted or unsubstituted organic group) in the main chain skeleton of the reactive silicon group-containing organic polymer (A) of the present invention. When there is much, there exists a tendency for the viscosity of a polymer to become high. 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 reactive silicon group-containing organic polymer (A) of the present invention, in the main chain structure from the viewpoint of obtaining a curable composition excellent in storage stability and workability. Is most preferably a polyoxyalkylene polymer not containing a linking group such as a urethane bond, a urea bond, an amide bond or an ester bond.

(Reactive silicon group-containing organic polymer)
The reactive silicon group-containing organic polymer (A) of the present invention is preferably obtained by the following method (a) and / or (b).
(A) After converting the terminal hydroxyl group of the hydroxyl group-terminated polyether polymer to an allyl group, HSiR ¹ _a R ² _b X _c (R ¹ , R ² , X, a, b, c are each represented by the general formula (1) A reactive silicon group-containing polyether polymer obtained by reacting a silane compound represented by the same formula.
(B) OCN—CH ₂ —SiR ¹ _f R ² _g X _h (f is 1 or 2, g is 0 or 1, h is 1 or 2, f + g + h = 3 A reactive silicon group-containing polyether polymer obtained by reacting an isocyanate methylsilane compound represented by the general formula (1) with R ¹ , R ² and X being the same as described in the general formula (1) .
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. A functional group (that is, a hydroxyl group, an isocyanate group, or an amino group) has OCN—CH ₂ —SiR ¹ _f R ² _g X _h (f is 1 or 2, g is 0 or 1, h is 1 or 2, and f + g + h = 3. A reactive silicon group-containing polyurethane prepolymer obtained by reacting an isocyanate methylsilane compound represented by the general formula (1) with R ¹ , R ² and X being the same as described in the general formula (1).

  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.

  Regarding the introduction of reactive silicon groups by the method (a), JP-B Nos. 45-36319, 46-12154, JP-A-50-156599, 54-6096, 55-13767, 55 No. 13468, 57-164123, Japanese Patent Publication No. 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. High molecular weights having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less proposed in Japanese Patent Publications Nos. 61-197631, 61-215622, 61-215623, and 61-218632 In which a reactive silicon group is introduced into a polyoxypropylene polymer having a narrow molecular weight distribution by hydrosilylation or the like, Those proposed in JP 2527 can be exemplified.

  The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing 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 reactive silicon group-containing 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 characteristics at break of the cured product of the obtained reactive silicon group-containing organic polymer (A) are lowered, and when it exceeds 100,000, the reactive silicon group concentration is lowered. It tends to slow down the curing rate. Moreover, the viscosity of the reactive silicon group-containing organic polymer (A) tends to be too high, making it difficult to handle.

  The number average molecular weight of the reactive silicon group-containing organic polymer (A) is directly determined by titration analysis based on the method for measuring the hydroxyl value of JIS K 1557 and the method for measuring the iodine value defined in JIS K 0070. The molecular weight corresponding to the number average molecular weight (terminal group molecular weight) determined in consideration of the structure of the polyether polymer (the degree of branching determined by the polymerization initiator used) was measured.

  As a relative measurement method of the number average molecular weight of the reactive silicon group-containing organic polymer (A), the polystyrene-equivalent number average molecular weight (GPC molecular weight) obtained by general GPC measurement of the polyether polymer precursor and the above-mentioned terminal are used. It is possible by preparing a calibration curve of the base molecular weight and obtaining the GPC molecular weight of the reactive silicon group-containing organic polymer (A) by converting it to the terminal group molecular weight.

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

  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 an average of 1.1 or more per molecule, and the upper limit is It is preferably less than 85% of the number of hydroxyl groups in the rod polymer. Specifically, for example, when the number of terminal hydroxyl groups of the precursor polymer of the reactive silicon group-containing organic polymer (A) is 2, the number of reactive silicon groups is 1.1 on average per molecule. -1.7 are preferable, and 1.2-1.6 are more preferable. Moreover, when the precursor polymer number of the precursor polymer of the reactive silicon group-containing organic polymer (A) is 3, the number of reactive silicon groups is preferably 1.1 to 2.5 on average per molecule. 1.2-2.4 are more preferable.

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

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

  The silane coupling agent (B) is a compound having a reactive silicon group and a carbamate group in the molecule (hereinafter referred to as carbamate silane). By using this, the curable composition excellent in the elongation physical property of hardened | cured material is provided. It is also a compound that can function as a dehydrating agent and a physical property adjusting agent.

  The hydrolyzable group of the hydrolyzable silicon group of the silane coupling agent 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, and an amino group. Amide group, acid amide group, aminooxy group, mercapto group and the like. 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 the silicon atom in the carbamate silane is preferably 3 in order to ensure excellent elongation properties.

  Specific examples of carbamate silane include (methyl carbamate methyl) trimethoxy silane, (methyl carbamate methyl) triethoxy silane, (ethyl carbamate methyl) triethoxy lane, (phenyl carbamate methyl) trimethoxy silane, (methyl carbamate propyl) tri Carbamate silanes such as methoxy silane and (ethyl carbamate propyl) triethoxy silane can be mentioned.

Of these, (methylcarbamatemethyl) trimethoxysilane, (ethylcarbamatemethyl) triethoxylane, and (methylcarbamatepropyl) trimethoxysilane are preferred because they are easy to synthesize, and (methylcarbamatemethyl) trimethoxysilane is cured. From the point which ensures the storage stability of an adhesive composition.
The amount of carbamate silane is preferably about 0.5 to 20 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing organic polymer (A). If the blending amount is less than 0.5 parts by weight, excellent elongation physical properties may not be exhibited, and storage stability may be deteriorated. On the other hand, if the blending amount exceeds 20 parts by weight, the cured product becomes brittle and sufficient strength cannot be obtained, and the curing rate may be slow.

  The curable composition of the present invention further includes a condensation catalyst (D) for the purpose of accelerating the reaction of hydrolyzing and condensing the reactive silicon group of the reactive silicon group-containing organic polymer (A). An amine compound (D1) or an organic dialkyltin compound (D2) having an alkyl group having 5 to 20 carbon atoms can be added.

  Examples of the amine compound (D1) include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearyl Aliphatic primary amines such as amine and cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine Aliphatic secondary amines such as dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine Aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Fragrances such as aniline, laurylaniline, stearylaniline and triphenylamine Group amines; 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-diazabicyclo (2,2, 2) Nitrogen-containing heterocyclic compounds such as octane (DABCO) and aziridine; DBU phenol salt (specifically, trade name: U-CAT SA1 (manufactured by San Apro)), DBU octylate (specifically, , Trade name: U-CAT SA102 (manufactured by San Apro), p-toluenesulfonate of DBU (specifically, trade name: U-CAT SA506 (manufactured by San Apro)), octylate of DBN (specifically, Is a salt derived from a nitrogen-containing heterocyclic compound such as trade name: U-CAT 1102 (manufactured by San Apro)), and other amines such as monoethanolamine, die Noramine, triethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, diethylenetriamine, triethylene Tetramine, 2- (2-aminoethylamino) ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3 -Amines such as morpholinopropylamine, 2- (1-piperazinyl) ethylamine, xylylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol; guanidine, phenylguanidine Guanidines such as diphenyl guanidine; Buchirubiguanido, biguanides such as 1-o-tolylbiguanide and 1-phenyl biguanide, and the like.

  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.

  The amine compound (D1) 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.

  In the present invention, an amino group-containing silane coupling agent (hereinafter sometimes referred to as aminosilane) can also be used as the amine compound (D1) used in the condensation catalyst (D). 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 Examples thereof include trimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.

  Among the aminosilanes, aminosilanes having an amino group (—NH 2) are preferable from the viewpoint of curability, and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxy are preferable from the viewpoint of availability. Silane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane is preferred.

  A ketimine compound that generates the amine compound by hydrolysis can also be used as a condensation catalyst.

  Examples of the organic dialkyltin compound (D2) having an alkyl group having 5 to 20 carbon atoms include dialkyltin bis (trialkoxysilicate) represented by the following general formula (4) and dialkyl represented by the following general formula (5). Tin oxide, dialkyltin dialkoxide represented by the following general formula (6), dialkyltin dicarboxylate represented by the following general formula (7), dialkyltin dicarboxylate oxide represented by the following general formula (8), A tetravalent dialkyl organotin compound such as a dialkyltin bis (maleic acid monoester) salt represented by the formula (9) and a dialkyltin bis (thioglycolic acid monoester) salt represented by the following general formula (10) is preferred.

R ¹² ₂ Sn [OSi (OR ¹³ ) ₃ ] ₂ (4)
R ¹² ₂ SnO (5)
R ¹² ₂ Sn (OR ¹⁴ ) ₂ (6)
R ¹² ₂ Sn (OCOR ¹⁴ ) ₂ (7)
[R ¹² ₂ Sn (OCOR ¹⁴ )] ₂ O (8)
R ¹² ₂ Sn (OCOCH = CHCOOR ¹⁴ ) ₂ (9)
R ¹² ₂ Sn (SCH ₂ COOR ¹⁴ ) ₂ (10)
(In the formula, R ¹² represents a monovalent hydrocarbon group having 5 to 20 carbon atoms, R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁴ represents a monovalent organic group. When there are a plurality of each of R ¹² , R ¹³ and R ¹⁴ , they may be the same or different.

In the tetravalent organic dialkyltin compounds represented by the general formulas (4) to (10), R ¹² is more preferably a monovalent hydrocarbon group having 8 to 12 carbon atoms, particularly preferably an octyl group and / or a dodecyl group.

  Specific examples of tetravalent organic dialkyltin compounds include, for example, dioctyltin bis (triethoxysilicate) and the like as specific examples of general formula (4); dioctyltin oxide and the like as specific examples of general formula (5); Specific examples of formula (6) include dioctyltin dimethoxide, dioctyltin diacetylacetonate, etc .; specific examples of general formula (7) include dioctyltin diacetate, dioctyltin dioctoate, dioctyltin diversate, dioctyltin dilaurate, dioctyltin distearate , Dioctyltin dibehenate, dioctyltin diolate, etc .; specific examples of general formula (8) include bis (dioctyltin acetate) oxide, bis (dioctyltin octoate) oxide, bis (dioctyltin versatate) oxide, bis (dioctyltin Urate) oxide, bis (dioctyltin stearate) oxide, bis (dioctyltin behenate) oxide, etc .; specific examples of general formula (9) include dioctyltin bis (ethylmalate), dioctyltin bis (octylmalate), etc. Specific examples of the formula (10) include dioctyltin bisisooctyl thioglycolate.

  Of these, dialkyltin bis (trialkoxysilicate) represented by the general formula (4) is preferable from the viewpoint of curability, and dioctyltin bis (triethoxysilicate) is more preferable from the viewpoint of availability. This compound is commercially available (trade name: Neostan S-1, manufactured by Nitto Kasei Co., Ltd.).

  These organic dialkyl tin compounds (D2) having an alkyl group having 5 to 20 carbon atoms may be used alone or in combination of two or more.

  It is also possible to use a condensation catalyst other than the condensation catalyst (D) 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; aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate); various metals such as tetrabutoxyhafnium Examples thereof include alkoxide compounds; organic acidic phosphates; organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid, and boronic acid.

  Among these condensation catalysts, an amine compound (D1) or an organic dialkyltin compound (D2) having an alkyl group having 5 to 20 carbon atoms is particularly preferable from the viewpoints of curability and environmental burden.

  The amount of the condensation catalyst (D) used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing organic polymer (A). 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 may be insufficient, and the curing reaction may not proceed sufficiently. On the other hand, when the amount of the condensation catalyst used exceeds 20 parts by weight, the curing rate is too fast, and therefore the time that the curable composition can be used tends to be short, resulting in poor workability and poor storage stability.

  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 reactive silicon group-containing 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 a plasticizer having a reactive silicon group, particularly a polyether polymer having a reactive silicon group, the number average molecular weight must be lower than that of the reactive silicon group-containing 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 reactive silicon group-containing 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-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N -Β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropy Triethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxy Amino group-containing silanes such as silane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl Mercapto group-containing silanes such as methyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxysilane) Epoxy group-containing silanes such as (rohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane Carboxysilanes such as N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyl Vinyl type unsaturated group-containing silanes such as triethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate Can. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. .

  0.1-20 weight part is preferable with respect to 100 weight part of reactive silicon group containing 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, based on 100 parts by weight of the reactive silicon group-containing 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 thereof is 1 to 200 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing organic polymer (A). preferable.

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

  The amount of the spherical hollow body used is preferably 0.01 to 30 parts by weight, particularly preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the reactive silicon group-containing organic polymer (A). 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 reactive silicon group-containing 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; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); 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 reactive silicon group containing 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 reactive silicon group containing 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 reactive silicon group containing 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 a Tosoh 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. 1.51 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 5 and a number average molecular weight of 21,100 was obtained.

(Synthesis Example 2)
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 14,600 (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, with respect to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene polymer, 72 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 2.01 parts by weight of trimethyl orthoformate were added and stirred. Then, 2.35 parts by weight of chloromethyldimethoxysilane was slowly added dropwise. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted chloromethyldimethoxylane was distilled off under reduced pressure, whereby the terminal was a chloromethyldimethoxysilyl group, and the average number of silicon groups per molecule was 1. Five linear reactive silicon group-containing polyoxypropylene polymers (A-2) having a number average molecular weight of 14,600 were obtained.

(Synthesis Example 3)
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 4)
Polymerization of propylene oxide using 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 14,600 (using a Tosoh HLC-8120GPC as a liquid feeding system) The column used a Tosoh TSK-GEL H type, and the solvent was a polyoxypropylene glycol 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 group-terminated polyoxypropylene glycol 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 allyl group-terminated polyoxypropylene polymer, 36 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 2.01 parts by weight of trimethyl orthoformate were added and stirred. Then, 2.28 parts by weight of the synthesized methoxymethyldimethoxysilane 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. Five linear reactive silicon group-containing polyoxypropylene polymers (A-3) having a number average molecular weight of 14,600 were obtained.

(Synthesis Example 5)
Polymerization of propylene oxide was performed using a polyoxypropylene diol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight was 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, while adding 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, 1.15 parts by weight of dimethoxymethylsilane was slowly added while stirring. And dripped. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby the terminal was a dimethoxymethylsilyl group and an average of 1.5 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 6)
71.1 g (0.88 mol) of potassium cyanate was placed in the reactor, and the atmosphere was purged with nitrogen. Then, 500 ml of N, N-dimethylformamide was added and the mixture was stirred well to obtain 128.0 g (0.002 mol) of (chloromethyl) trimethoxysilane. 75 mol) and 50.2 g (1.56 mol) of methanol were added and heated to 90 ° C. Thereafter, the mixture was heated to 120 ° C. over 4 hours, and further stirred for 3 hours. The precipitated potassium chloride was removed by filtration, N, N-dimethylformamide was distilled off with an evaporator, and then purified by distillation to obtain (methylcarbamatemethyl) trimethoxysilane (carbamatesilane-B1) in a yield of 116.2 g. Obtained.

Example 1
Fatty acid-treated calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Shiraishi Hana CCR), heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd. : Whiten SB Red) 50 parts by weight were mixed and sufficiently kneaded, and then passed once through three paint rolls and dispersed. 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, the formulation was filled into a moisture-proof cartridge-type container.

(Evaluation)
The tensile properties of the prepared blends were measured by the method shown below.

(Tensile properties)
The composition was extruded from the cartridge under an atmosphere of 23 ° C. and a relative humidity of 50%, and 5.7 parts by weight of the synthesized carbamate silane (carbamate silane-B1) with respect to 100 parts by weight of the polymer (A-1). 3-aminopropyltrimethoxysilane (product name: A-1110, 3 parts by weight) as a condensation catalyst, DBU (product of Wako Pure Chemical Industries, Ltd., product name: 1,8-diazabicyclo [5, 4,0] undecene-7) After adding 0.3 parts by weight, it was mixed well. The mixture was filled into a polyethylene mold having a thickness of 3 mm so as not to contain air bubbles, and cured at 23 ° C. and a relative humidity of 50% for 3 days, and further at 50 ° C. for 4 days to obtain a cured product. From the resulting cured product, No. 3 dumbbell was punched in accordance with JIS K 6251, and a tensile test (tensile speed 200 mm / min, 23 ° C., relative humidity 50%) was performed. 100% elongation stress (M100), fracture The time stress (TB) and the elongation at break (EB) were measured. The results are shown in Table 1.

(Example 2)
In Example 1, a curable composition was prepared in the same manner except that dioctyltin bis (triethoxysilicate) (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan S-1) was used instead of DBU as the condensation catalyst. did.

(Example 3)
In Example 1, the curable composition was produced similarly except having used the polymer (A-3) instead of the polymer (A-1).

(Comparative Example 1)
A curable composition was prepared in the same manner as in Example 1 except that vinyltrimethoxysilane (manufactured by Momentive Inc., trade name: A-171) was used instead of carbamatesilane-B1.

(Comparative Example 2)
A curable composition was prepared in the same manner as in Example 1 except that vinyltrimethoxysilane was used instead of carbamatesilane-B1, and dioctyltin bis (triethoxysilicate) was used instead of DBU as the condensation catalyst.

(Comparative Example 3)
A curable composition was prepared in the same manner as in Example 1 except that the polymer (A-3) was used instead of the polymer (A-1), and vinyltrimethoxysilane was used instead of the carbamatesilane-B1.

(Comparative Example 4)
In Example 1, the polymer (C-1) is used instead of the polymer (A-1), and dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., Neostan U-220H) is used instead of DBU as the condensation catalyst. A curable composition was prepared in the same manner except that.

(Comparative Example 5)
In Example 1, polymer (C-1) was used instead of polymer (A-1), vinyltrimethoxysilane was used instead of carbamatesilane-B1, and dibutyltin diacetylacetonate was used instead of DBU. Thus, a curable composition was prepared.

Example 4
For 100 parts by weight of polymer (A-2), 45 parts by weight of a plasticizer (manufactured by Jay Plus Co., Ltd., trade name: DIDP), calcium carbonate treated with fatty acid (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Hakusuka CCR) 120 parts by weight, titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name: Taipei R-820) 20 parts by weight, sagging inhibitor (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500), 2 parts by weight, 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. After that, it was dispersed by passing three times through three paint rolls. Thereafter, dehydration under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, 4.2 parts by weight of carbamate silane (carbamate silane-B1), and γ-aminopropyltrimethoxysilane (Momentive Co., Ltd.) as an adhesion-imparting agent. ), Product name: A-1110) 1.5 parts by weight, and N-β-aminoethyl-γ-aminopropyltrimethoxysilane (Mentive Co., Ltd., product name: A-1122) 1.5 parts by weight Then, 1.5 parts by weight of 1-phenylguanidine (manufactured by Nippon Carbide Industries Co., Ltd.) as a condensation catalyst was added and kneaded, kneaded in a substantially moisture-free state, and then filled into a moisture-proof cartridge type container And sealed to obtain a one-component curable composition.

(Evaluation)
The tensile properties of the prepared blends were measured by the method shown below.

(Skinning time)
Each curable composition is extruded from the cartridge in an atmosphere of 23 ° C. and 50% relative humidity, filled into a mold with a thickness of about 5 mm using a spatula, and the time when the surface is flattened is set as the curing start time. It was. 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 2.

(Tensile properties)
Each curable composition was extruded from the cartridge in an atmosphere of 23 ° C. and a relative humidity of 50%, and filled in a polyethylene mold having a thickness of 3 mm so as not to enter air bubbles. Thereafter, the cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the resulting cured product, No. 3 dumbbell was punched in accordance with JIS K 6251, and a tensile test (tensile speed 200 mm / min, 23 ° C., relative humidity 50%) was performed. 100% elongation stress (M100), fracture The time stress (TB) and the elongation at break (EB) were measured. The results are shown in Table 2.

(Viscosity increase rate)
In order to evaluate the storage stability of the prepared one-component curable composition, each curable composition was extruded from a cartridge stored at 23 ° C. for 1 week and a cartridge stored at 50 ° C. for 4 weeks. The rate of increase was measured.
Under an atmosphere of 23 ° C. and 50% relative humidity, a BS viscometer, rotor No. 7 (manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity when the rotation speed was 2 rpm, and the curability after 1 week. Table 2 shows the increase rate of the viscosity of the curable composition stored at 50 ° C. for 4 weeks with respect to the viscosity of the composition.

  In the results of Tables 1 and 2, curing by using vinyltrimethoxysilane as a dehydrating agent by using a combination of an organic polymer (A) having a reactive silicon group having a specific structure and carbamate silane (B). It can be seen that the strength and elongation of the cured product are sufficiently large compared to the product. It can also be seen that when carbamate silane is used as a dehydrating agent for a one-component curable composition, a curable composition having good storage stability is obtained.

Claims (15)

Reactive silicon group-containing organic polymer (A) having a reactive silicon group represented by the following general formula (1) at the molecular chain end, and a reactive silicon group and carbamate represented by the following general formula (2) A curable composition comprising a silane coupling agent (B) having a group in the molecule.
-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 at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen atom, —OR ³ , —NR ⁴ R ^5. , -N = R ⁶ , -SR ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is 1 carbon atom. A divalent substituted or unsubstituted hydrocarbon group of ˜20), a perfluoroalkyl group having 1 to 20 carbon atoms, or a group substituted with a cyano group, R ² is a carbon atom having 1 to 20 carbon atoms. A hydrogen group, 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—, wherein three R ⁰ are carbonized carbon atoms having 1 to 20 carbon atoms Are hydrogen groups, they may be the same or different X for each condition is satisfied ^{.R 1, R} 2, X to the .a showing a hydroxyl group or a hydrolyzable group 1 or 2, b is 0 or 1, c is 1 or 2, a + b + c = 3 , When they are present, they may be the same or different.)
_{^{R 9 O 2 C-NH-}} R 8 -SiX 1 3 (2)
(In the formula, R ⁸ represents a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms. In the formula, R ⁹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. Or an aralkyl group having 7 to 20 carbon atoms, X ¹ represents a hydroxyl group or a hydrolyzable group, and when a plurality of X ¹ are present, they may be the same or different. 2. 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 (3).
-CR ¹⁰ _3-d Y _d (3)
(In the formula, R ¹⁰ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 19 carbon atoms. Y represents a halogen atom, —OR ³ , —NR ⁴ R ⁵ , —N═R ⁶ , —SR. ⁷ (R ³ , R ⁴ , R ⁵ , R ⁷ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a divalent substituted or non-substituted group having 1 to 20 carbon atoms. A substituted hydrocarbon group.), A perfluoroalkyl group having 1 to 20 carbon atoms, a group substituted with a cyano group, d represents 1, 2 or 3. For each of R ¹⁰ and Y, When there are multiple, they may be the same or different.) Y in general formula (3) is a chlorine atom, The curable composition of Claim 2 characterized by the above-mentioned. The curable composition according to claim 3, wherein the general formula (3) is a chloromethyl group. The curable composition according to claim 4, wherein the general formula (1) is a chloromethyldimethoxysilyl group. Y in general formula (3) is an alkoxy group, The curable composition of Claim 2 characterized by the above-mentioned. The curable composition according to claim 6, wherein Y in the general formula (3) is at least one group selected from the group consisting of a methoxy group, an ethoxy group, and a phenoxy group. The curable composition according to claim 7, wherein the general formula (3) is a methoxymethyl group or an ethoxymethyl group. The curable composition according to claim 8, wherein the general formula (1) is a methoxymethyldimethoxysilyl group. The main chain structure of the reactive silicon group-containing 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. It has a curable composition of any one of Claims 1-9 characterized by the above-mentioned. The curable composition according to claim 10, wherein the main chain structure of the reactive silicon group-containing organic polymer (A) is a polyoxypropylene polymer. The curable composition according to any one of claims 1 to 11, wherein the general formula (2) is (methylcarbamatemethyl) trimethoxysilane. The sealing material which contains the curable composition of any one of Claims 1-12 as a component. The adhesive agent which contains the curable composition of any one of Claims 1-12 as a component. Hardened | cured material obtained by hardening the curable composition of any one of Claims 1-12.