JP6108514B2 - Curable composition - Google Patents

Description

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

  An organic polymer containing at least one crosslinkable silicon group in the molecule is crosslinked at room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of a reactive silicon group due to moisture or the like. It is known to have the property of being obtained. Among these polymers having a crosslinkable silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer are used for sealing materials, adhesives, paints, etc. Widely used.

  The curable composition used for sealing materials, adhesives, paints, etc. and the rubber-like cured product obtained by curing have various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing crosslinkable silicon groups.

  These curable compositions containing an organic polymer having a crosslinkable silicon group are cured using a silanol condensation catalyst. Usually, organic tin-based catalysts such as dibutyltin bis (acetylacetonate) are widely used. It is used. However, in recent years, toxicity of organotin compounds has been pointed out, and development of non-organotin catalysts has been demanded.

As this non-organotin-based catalyst, a dealcohol-free silicone composition using a titanium catalyst is already commercially available and widely used for many applications (for example, Patent Documents 1 to 3).
However, there are relatively few examples of adding a titanium catalyst to an organic polymer containing a crosslinkable silicon group, which are disclosed in Patent Documents 4 to 21 and the like. The curable compositions using these titanium catalysts have a problem that the curing rate is slow, and the curing rate is lowered and the viscosity is increased after storage.

  Moreover, the curable composition containing the organic polymer containing a crosslinkable silicon group is often used as an adhesive or a sealing material, and in that case, adhesion to various types of substrates is required. In order to ensure this adhesiveness, so-called aminosilane having a primary amino group and an alkoxyl group in the molecule is usually used. However, when an organic polymer containing a crosslinkable silicon group and a titanium catalyst are used to prepare a one-component curable composition by adding aminosilane, the composition is good after storage for a certain period, although the adhesiveness is good. If the viscosity of the product is improved and it is severe, it may harden in the container and cannot be used. Sealing materials and adhesives are not always used immediately after production, but are often stored for several months in warehouses or stores, and it is desired that their curability and viscosity be constant before and after storage. Yes.

Japanese Examined Patent Publication No. 39-27643 US Pat. No. 3,175,993 US Pat. No. 3,334,067 JP 58-17154 A JP-A-11-209538 JP-A-5-311063 JP 2001-302929 A JP 2001-302930 A JP 2001-302931 A JP 2001-302934 A JP 2001-348528 A Japanese Patent Laid-Open No. 2002-249672 JP 2003-165916 A JP 2003-147220 A JP 2005-325314 A WO2005 / 108492 WO2005 / 108498 WO2005 / 108494 WO2005 / 108499 WO2007 / 037368 JP 2008-280434 A

  An object of this invention is to provide the curable composition excellent in sclerosis | hardenability, adhesiveness, and storage stability, and excellent in safety | security without requiring an organic tin-type catalyst.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research. As a result, an isocyanate is used as a curing catalyst in an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule. By using a silane compound having a nurate ring and a titanium chelate coordinated with a β-ketoester, it is excellent in curability, adhesiveness and storage stability, and does not require an organotin catalyst and is safe. It was found that a room temperature moisture curable curable composition excellent in temperature can be obtained.

  That is, the curable composition of the present invention comprises (A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule and the main chain is not polysiloxane, (B) isocyanurate Curability comprising a silane compound having a ring, and (C) one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the following formula (1) and a titanium chelate represented by the following formula (2) A composition comprising 0.1 to 40 parts by mass of the (B) silane compound and 0.1 to 40 parts by mass of the (C) titanium catalyst with respect to 100 parts by mass of the (A) organic polymer. It is characterized by doing.

In the formula (1), n R ^{1 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R ^{2 s} are each independently a hydrogen atom or A substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R ³ and 4-n R ⁴ are each independently substituted or unsubstituted C 1-20 carbon atoms. A hydrocarbon group and n is 0, 1, 2 or 3;

In the formula (2), R ⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and two R ⁶ are independently a hydrogen atom or substituted or unsubstituted. It is a hydrocarbon group having 1 to 20 carbon atoms, and two R ⁷ and two R ⁸ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. )

  The (A) organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups on average per molecule, and 0.8 or more crosslinks on average per molecule. Selected from the group consisting of a saturated hydrocarbon polymer containing a functional silicon group and a (meth) acrylic acid ester polymer containing an average of 0.8 or more crosslinkable silicon groups in one molecule. One or more are preferable.

  It is preferable that the crosslinkable silicon group includes a trimethoxysilyl group.

  The curable composition of the present invention preferably further contains (D) a silane compound having a primary amino group.

  The (D) silane compound comprises (D1) an epoxy silane compound represented by the following formula (3) and an amino silane compound represented by the following formula (4). It is preferable that it is 1 or more types selected from the group which consists of a silane compound made to react in the range of 1.5-10 mol, and (D2) the silane compound shown by following formula (5).

In the formula (3), R ^{11 to} R ¹³ are each a hydrogen atom or an alkyl group, R ¹⁴ is an alkylene group or an alkyleneoxyalkylene group, R ¹⁵ is a monovalent hydrocarbon group, and R ¹⁶ is an alkyl group. A is 0, 1 or 2;

In the formula (4), R ^{17 to} R ²² are each a hydrogen atom or an alkyl group, R ²³ is a monovalent hydrocarbon group, R ²⁴ is an alkyl group, and b is 0 or 1.

In the formula (5), R ³¹ is a methyl group or an ethyl group, and when a plurality of R ³¹ are present, they may be the same or different, and R ³² is a methyl group or In the case where a plurality of R ³² are present, they may be the same or different, R ³³ is a hydrocarbon group having 1 to 10 carbon atoms, and m is 2 or 3 and n is 0 or 1.

  The (D1) silane compound is preferably a silane compound obtained by reacting the epoxysilane compound and the aminosilane compound at a reaction temperature of 40 to 100 ° C.

  The curable composition of the present invention preferably further contains (E) a filler. The (E) filler is preferably surface-treated calcium carbonate.

  The curable composition of the present invention preferably further contains (F) a diluent.

  The curable composition of the present invention preferably further contains a metal hydroxide. It is preferable that the metal hydroxide is aluminum hydroxide.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition excellent in sclerosis | hardenability, adhesiveness, and storage stability and excellent in safety | security without requiring an organic tin-type catalyst can be provided.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The curable composition of the present invention comprises (A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule and the main chain is not polysiloxane, and (B) an isocyanurate ring. And a curable composition comprising (C) one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the formula (1) and a titanium chelate represented by the formula (2) And 0.1 to 40 parts by mass of the (B) silane compound and 0.1 to 40 parts by mass of the (C) titanium catalyst with respect to 100 parts by mass of the (A) organic polymer. It is characterized by.

  The (A) organic polymer is an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule and the main chain is not polysiloxane, and various main chain bones excluding polysiloxane. You can use one with a rating.

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability when made into one-component compositions.

  The crosslinkable silicon group of the (A) organic polymer used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (6) is preferable.

In the formula ^{(6), R 41} is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group, or ^{R 41} 7 to 20 carbon atoms ₃ represents a triorganosiloxy group represented by SiO— (R ⁴¹ is the same as above), and when two or more R ⁴¹ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. d represents 0, 1, 2, or 3, and e represents 0, 1, or 2, respectively. Further, p in the following general formula (7) need not be the same. p shows the integer of 0-19. However, d + (sum of e) ≧ 1 is satisfied.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and d + (sum of e) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (8) is preferable because it is easily available.

In the formula (8), R ⁴¹ and X are the same as those described above, and d is an integer of 1, 2 or 3. In view of curability, in order to obtain a curable composition having a sufficient curing rate, a in the formula (8) is preferably 2 or more, and more preferably 3.

Specific examples of R ⁴¹ include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, aralkyl groups such as a benzyl group, and R ³¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxyl 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, and an alkoxyl group, an amide group, and an aminooxy group are more preferable. An alkoxyl group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among alkoxyl groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [—SiR ¹ (OR) ₂ ] is exemplified, and a high reactivity makes the trialkoxysilyl group [—Si (OR) ₃ ] preferable, and a trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

  Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

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

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

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more in one molecule of the polymer. 1.1 to 5 may be present. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to develop good rubber elastic behavior. The crosslinkable silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (9).
-R ⁴² -O- (9)
In the general formula ^{(9), R 42} is a linear or branched alkylene group having 1 to 14 carbon atoms, 1 to 14 carbon atoms, more 2 to 4, linear or branched alkylene group is preferable .

Specific examples of the repeating unit represented by the general formula (9) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used as a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-215623 can be used. Polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound and a porphyrin as shown, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336 Examples of the polymerization method using a catalyst include, but are not limited to, a polymerization method. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; The thing obtained from reaction with coalescence can be mention | raise | lifted.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has this can be mention | raise | lifted. An unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene polymer containing can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal. Examples thereof include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, JP-B No. 3-2450, JP-A No. 2005-213446, No. 2005-306891, International Publication No. WO2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.

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

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) A diene compound such as butadiene or isoprene is homopolymerized, or a copolymer with the olefin compound is copolymerized. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

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

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.

  As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but in particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843) It is known that it can be easily produced by using it, can be polymerized with a molecular weight of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and can introduce various functional groups at the molecular ends.

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

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

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. For example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester monomers such as 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; (meth) Cyclohexyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl ) Acrylate, dicyclopentanyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylic acid ester monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylic acid ester monomers such as ethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenylthioethyl (meth) acrylate; 2-methoxy (meth) acrylate, (meth) acrylic acid (Meth) acrylate esters such as 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate Monomer: γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxy Silyl group-containing (meth) acrylic acid ester monomers such as tildimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; (meth) acrylic acid derivatives such as ethylene oxide adducts of (meth) acrylic acid; (meth) acrylic Trifluoromethyl methyl acid, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, (meth ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) 2-perfluorohexylethyl acrylate , Fluorine-containing (meth) acrylate monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl Maleimide monomers such as maleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferably, it is a (meth) acrylic acid ester-based polymer using one or two or more (meth) acrylic acid alkyl ester monomers and optionally using other (meth) acrylic acid monomers, By using the group-containing (meth) acrylic acid ester monomer together, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled. A methacrylic acid ester polymer composed of a methacrylic acid ester monomer is particularly preferred because of its good adhesiveness. Moreover, when performing viscosity reduction, a softness | flexibility provision, and tackiness provision, it is suitable to use an acrylate ester monomer timely. In the present specification, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In the present invention, the method for obtaining the (meth) acrylic acid ester polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). And a radical polymerization method using a radical polymerization reaction is preferable. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. A reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

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

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto.
Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (10):
—CH ₂ —C (R ⁴⁵ ) (COOR ⁴⁶ ) — (10)
(Wherein, R ⁴⁵ represents a hydrogen atom or a methyl group, and R ⁴⁶ represents an alkyl group having 1 to 5 carbon atoms), and the following general formula (11):
—CH ₂ —C (R ⁴⁵ ) (COOR ⁴⁷ ) — (11)
(In the formula, R ⁴⁵ is the same as described above, and R ⁴⁷ represents an alkyl group having 6 or more carbon atoms.) A copolymer composed of a (meth) acrylate monomer unit is represented by a crosslinkable silicon group. It is a method of blending and producing a polyoxyalkylene polymer.

R ^{46 in the} general formula (10) is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group or the like, having 1 to 5 carbon atoms, preferably 1 to 4, more preferably 1 to 4. 2 alkyl groups. The alkyl group of R ⁴⁶ may alone, or may be a mixture of two or more.

R ^{47 in the} general formula (11) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7 to 30, preferably 8 to 20 Long chain alkyl groups. In addition, the alkyl group of R ⁴⁷ may be single or may be a mixture of two or more as in the case of R ⁴⁶ .

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units of the formula (10) and the formula (11), and the term “substantially” here refers to the copolymer. It means that the total of the monomer units of the formula (10) and the formula (11) present therein exceeds 50% by mass. The total of the monomer units of the formula (10) and the formula (11) is preferably 70% by mass or more.
Further, the abundance ratio of the monomer unit of the formula (10) and the monomer unit of the formula (11) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 in terms of mass ratio.

  Examples of monomer units other than the formulas (10) and (11) that may be contained in the copolymer (hereinafter also referred to as other monomer units) include α such as acrylic acid and methacrylic acid. , Β-unsaturated carboxylic acids; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc. And other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  Having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (meta ) As the acrylate polymer, for example, it has a crosslinkable silicon group described in JP-A-63-112642, and the molecular chain has substantially (1) an alkyl group having 1 to 8 carbon atoms (meta (Meth) acrylic acid ester-based copolymers containing an acrylic acid alkyl ester monomer unit and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms These (meth) acrylic acid ester copolymers can also be used.

The number average molecular weight of the (meth) acrylic acid ester polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and still more preferably 1,000 to 4,500. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved. The (meth) acrylic acid ester polymer may be used alone or in combination of two or more.
The compounding ratio of the polyoxyalkylene polymer having the crosslinkable silicon group and the (meth) acrylic acid ester polymer having the crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester The total amount of the polymer and the polyoxyalkylene polymer is preferably 100 parts by mass, and the (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, more preferably 20 to 20 parts by mass. It is in the range of 50 parts by mass, more preferably in the range of 25 to 45 parts by mass. If the amount of the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable.

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

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

  When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslink with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10-200 mass parts of the (meth) acrylic acid ester-type polymer which has a crystalline silicon group, and it is more preferable to use 20-80 mass parts.

  The (B) silane compound is not particularly limited as long as it is a silane compound having an isocyanurate ring. Specifically, a silane compound represented by the following formula (12) is preferably used.

In the formula (12), R ^{51 to} R ⁵³ are each a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, or a group represented by the following formula (13), and each of R ^{51 to} R ⁵³ At least one is a group represented by the following formula (13), and R ^{51 to} R ⁵³ are preferably groups other than hydrogen atoms.
^{_{- (CH 2) b -SiR 54}} R 55 R 56 ··· (13)
In (Formula (13), b is an integer of ^2-6, R 54 ^{to R 56} are independently an alkyl group or an alkoxyl ^group, is at least one of alkoxyl groups R 54 ^{to R 56} Is preferred.)

The substituted or unsubstituted monovalent hydrocarbon group in R ^{51 to} R ⁵³ in the formula (12) is a substituted or unsubstituted alkyl group, a substituted or unsubstituted unsaturated hydrocarbon group, a substituted or non-substituted group. Examples include substituted cyclic hydrocarbon groups. The type and number of substituents in the substituted monovalent hydrocarbon group are not limited, and examples of the substituent include an alkoxyl group, an alkoxycarbonyl group, and a cyano group.

  Examples of the (B) silane compound include silane compounds represented by the following formulas (14) to (20) and partial hydrolysates thereof.

  The blending ratio of the (B) silane compound is a blend of 0.1 to 40 parts by mass of the (B) silane compound with respect to 100 parts by mass of the (A) organic polymer. It is preferable to mix | blend a mass part, and it is more preferable to mix | blend 0.5-20 mass parts. The (B) silane compound may be used alone or in combination of two or more.

  The (C) titanium catalyst is at least one selected from the group consisting of a titanium chelate represented by the following formula (1) and a titanium chelate represented by the following formula (2).

In the formula (1), n R ^{1 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R ^{2 s} are each independently a hydrogen atom or A substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R ³ and 4-n R ⁴ are each independently substituted or unsubstituted C 1-20 carbon atoms. A hydrocarbon group and n is 0, 1, 2 or 3;

In the formula (2), R ⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and two R ⁶ are independently a hydrogen atom or substituted or unsubstituted. It is a hydrocarbon group having 1 to 20 carbon atoms, and two R ⁷ and two R ⁸ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

  Examples of the titanium chelate represented by the formula (1) or the formula (2) include titanium dimethoxide bis (ethyl acetoacetate), titanium diethoxide bis (ethyl acetoacetate), and titanium diisopropoxide bis (ethyl). Acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxide bis (t-butyl acetoacetate), titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexano) Acid), titanium diisopropoxide bis (ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium di-n-butoxide bis (ethyl acetoacetate), titanium diisobutoxide bis (ethyl acetoacetate) ), Titanium di-t-butoxide bis (ethyl acetoacetate), Titanium di-2-ethylhexoxide bis (ethyl acetoacetate), Titanium bis (1-methoxy-2-propoxide) bis (ethyl acetoacetate), Titanium bis ( 3-oxo-2-butoxide) bis (ethyl acetoacetate), titanium bis (3-diethylaminopropoxide) bis (ethyl acetoacetate), titanium triisopropoxide (ethyl acetoacetate), titanium triisopropoxide (allyl acetoacetate) Acetate), titanium triisopropoxide (methacryloxyethyl acetoacetate), 1,2-dioxyethane titanium bis (ethylacetoacetate), 1,3-dioxypropane titanium bis (ethylacetate) Acetate), 2,4-dioxypentane titanium bis (ethyl acetoacetate), 2,4-dimethyl-2,4-dioxypentane titanium bis (ethyl acetoacetate), titanium tetrakis (ethyl acetoacetate), titanium bis ( And trimethylsiloxy) bis (ethylacetoacetate), titanium bis (trimethylsiloxy) bis (acetylacetonate), and the like. Among these, titanium diethoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (ethyl acetoacetate), titanium dibutoxide bis (ethyl acetoacetate) and the like, titanium diisopropoxide bis (ethyl acetoacetate) ) Is more preferable.

  Examples of the chelating reagent capable of forming the chelate ligand of the titanium chelate include, for example, methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, acetoacetate (2-methacryloxyethyl), 3-oxo Β-ketoesters such as methyl -4,4-dimethylhexanoate and ethyl 3-oxo-4,4,4-trifluorobutanoate are mentioned, methyl acetoacetate and ethyl acetoacetate are preferred, and ethyl acetoacetate is more preferred . When two or more chelate ligands are present, each chelate ligand may be the same or different.

  The blending ratio of the (C) titanium catalyst is such that 0.1 to 40 parts by weight of the (C) titanium catalyst is blended with respect to 100 parts by weight of the (A) organic polymer, and 1 to 30 parts by weight. It is preferable to mix | blend and it is more preferable to mix | blend 1-20 mass parts. The (C) titanium catalyst may be used alone or in combination of two or more. As the method for adding the (C) titanium catalyst, in addition to adding the titanium chelate described above directly, a titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide or titanium dichloride diisopropoxide, and acetoacetic acid A method may be used in which a chelating reagent such as ethyl is added to the composition of the present invention and chelated in the composition.

  The curable composition of the present invention uses the titanium catalyst (C) as a curing catalyst, but other curing catalysts can be used in combination so as not to reduce the effects of the present invention. Examples of other curing catalysts include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate. Organotin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reaction products of dibutyltin oxide and phthalate, etc. ; Titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethylate Organoaluminum compounds such as acetoacetate and diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Organic acid lead such as lead octylate and lead naphthenate; Bismuth octylate Organic acid bismuth such as bismuth neodecanoate and bismuth rosinate; other acidic catalysts and basic catalysts known as silanol condensation catalysts. However, the toxicity of the resulting curable composition may increase depending on the amount of the organotin compound added.

  The curable composition of the present invention preferably further contains (D) a silane compound having a primary amino group. (D) By adding a silane compound, storage stability and tensile physical properties can be further improved.

  As the (D) silane compound, a known silane compound having a primary amino group can be widely used, but one hydrolyzable silicon group per molecule and a primary amino group. A silane compound having a azo group is preferred. In the silane compound (D), when a hydrolyzed silicon group-containing silane compound is used, a known hydrolyzable group excluding a primary amino group can be used as the hydrolyzable group bonded to the silicon atom. Alkoxyl groups are preferred. In the component (D), in consideration of storage stability and tensile physical properties, the hydrolyzable silicon group is preferably a trialkoxysilyl group or a dialkoxysilyl group, and more preferably a trialkoxysilyl group.

  Examples of the silane compound having one hydrolyzable silicon group and one primary amino group in one molecule include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, Alkoxysilanes containing a phenyl group such as 2-carboxyethylphenylbis (2-methoxyethoxy) silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane; 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxy Alkoxysilanes containing epoxy groups such as lan; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxy Alkoxysilanes containing isocyanate groups such as silane, (isocyanatemethyl) dimethoxymethylsilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy Silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltri Alkoxysilanes containing mercapto groups such as toxisilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; 2-carboxyethyltriethoxysilane, N-2- (carboxymethyl) aminoethyl-3-aminopropyltrimethoxysilane, etc. Carboxysilanes; alkoxysilanes containing vinyl unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane An alkoxysilane containing a halogen such as 3-chloropropyltrimethoxysilane; an isocyanurate such as tris (3-trimethoxysilylpropyl) isocyanurate; N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N, N ′ -Secondary amino group and / or tertiary amino group such as bis [3- (trimethoxysilyl) propyl] ethylenediamine, bis (3-trimethoxysilylpropyl) amine, N-ethyl-3-aminoisobutyltrimethoxysilane Contained alkoxysilane; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl)- Ketimine type silane such as 1-propanamine; tetramethoxysilane Tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t -Tetraalkoxysilanes (tetraalkyl silicates) such as butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, Trialkoxysilanes such as decyltrimethoxysilane and trifluoropropyltrimethoxysilane; dialkoxysilanes such as dimethyldimethoxysilane and diethyldimethoxysilane And the like can be given: trimethyl methoxy silane, mono-alkoxy silane such as trimethyl silane; dimethyl isopropenoxysilane silane, alkyl isopropenoxysilane silane such as methyltrimethoxysilane isopropenoxysilane silane.

  As the (D) silane compound, (D1) an epoxy silane compound represented by the following formula (3) and an amino silane compound represented by the following formula (4) are used with respect to 1 mol of the amino silane compound. One or more selected from the group consisting of a silane compound obtained by reacting a silane compound in the range of 1.5 to 10 mol and (D2) a silane compound represented by the following formula (5) is particularly preferably used.

In the formula (3), R ^{11 to} R ¹³ are each a hydrogen atom or an alkyl group, preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom. R ¹⁴ is an alkylene group or alkyleneoxyalkylene group, and is a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, methyleneoxyethylene group, methyleneoxypropylene group, methyleneoxybutylene. Group, ethyleneoxyethylene group and ethyleneoxypropylene group are preferable, butylene group, octylene group and methyleneoxypropylene group are more preferable. R ¹⁵ is a monovalent hydrocarbon group, preferably an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkenyl group such as a vinyl group, an allyl group or a butenyl group; an aryl group such as a phenyl group or a tolyl group; Groups are more preferred. When a plurality of R ¹⁵ are present, they may be the same or different. R ¹⁶ is an alkyl group, preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group or an ethyl group. When a plurality of R ¹⁶ are present, they may be the same or different. a is 0, 1 or 2, and 0 is preferable.

In the formula (4), R ^{17 to} R ²² are each a hydrogen atom or an alkyl group, preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom. R ²³ is a monovalent hydrocarbon group, preferably an alkyl group or an alkoxyl group, more preferably a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group, and even more preferably a methoxy group or an ethoxy group. R ²⁴ is an alkyl group, preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group or an ethyl group. b is 0 or 1. (3-b) pieces of R ²⁴ may be the same or different.

In the formula (5), R ³¹ is a methyl group or an ethyl group, and when a plurality of R ³¹ are present, they may be the same or different. R ³² is a methyl group or an ethyl group, and when a plurality of R ³² are present, they may be the same or different. R ³³ is a hydrocarbon group having 1 to 10 carbon atoms. m is 2 or 3, and 3 is more preferable. n is 0 or 1.

  In the (D1) silane compound, examples of the epoxy silane compound include 4-oxiranylbutyltrimethoxysilane, 8-oxiranyloctyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycol. Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. are mentioned.

  In the (D1) silane compound, examples of the aminosilane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane. Can be mentioned.

In the (D1) silane compound, the reaction condition between the epoxysilane compound and the aminosilane compound is that the primary amino group of the aminosilane compound reacts with the epoxysilane compound, and the primary amino group is a secondary amino group or What is necessary is just to make it react so that it may become a tertiary amino group and this primary amino group does not remain | survive.
As the reaction conditions for that purpose, for example, the aminosilane compound and the epoxysilane compound are mixed in the presence or absence of a solvent, and 25 ° C to 100 ° C, preferably 30 ° C to 90 ° C, more preferably 40 ° C. It is suitable to make it react at the reaction temperature of -80 degreeC. By setting the reaction temperature within the above range, the reaction can proceed stably without causing runaway. When the reaction temperature is less than 25 ° C., the activity is low, the time required to achieve a sufficient reaction is lengthened, and the efficiency is poor. The reaction time can be appropriately set in consideration of the reaction temperature and the like. For example, under the above conditions, the reaction time is usually 1 to 336 hours, preferably 24 to 72 hours. Is preferred.
The reaction ratio (molar ratio) of the epoxysilane compound and the aminosilane compound is 1.5 to 10 mol, preferably 1.6 to 5.0 mol, more preferably 1.7 mol of the epoxysilane compound with respect to 1 mol of the aminosilane compound. It is made to react so that it may become -2.4 mol.

In the (D1) silane compound, the epoxysilane compound and the aminosilane compound are heated and reacted at a reaction temperature of preferably 40 ° C. or higher, more preferably 40 to 100 ° C., and even more preferably 40 to 80 ° C. To cleave the epoxy ring of the epoxysilane compound and cyclize by an alcohol exchange reaction between the hydroxyl group generated by this reaction and the alkoxyl group in the aminosilane compound to obtain a carbacyltolane derivative represented by the following formula (21) Can do. The carbacyltolane derivative represented by the following formula (21) is a compound having a peak from −60 ppm to −70 ppm in ²⁹ Si-NMR.

In the formula (21), R ^{11 to} R ¹⁶ and a are the same as the formula (3), R ^{17 to} R ²² are the same as the formula (4), and b in the formula (4) is In the case of 0, R ²⁵ is the same as OR ^{24 in the} formula (2), and when b in the formula (4) is 1, R ²⁵ is the same as R ^{23 in the} formula (4). In addition, the alkoxyl group bonded to the silicon atom may be partially substituted by an alcohol exchange reaction, and the silicon atom-bonded alkoxyl group of the raw material and the silicon atom-bonded alkoxyl group in the carbacyltran derivative generated by the reaction May not be the same.

  Examples of the (D2) silane compound include dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, decyltri Alkyltrialkoxysilanes such as methoxysilane; alkoxysilanes containing phenyl groups such as phenyltrimethoxysilane and phenyltriethoxysilane; alkoxysilanes containing vinyl type unsaturated groups such as vinyltrimethoxysilane and vinyltriethoxysilane; Examples include alkoxysilanes containing an epoxy group such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, and alkoxysilanes containing a phenyl group. It is more preferable.

  The blending ratio of the (D) silane compound is not particularly limited, but it is preferable to blend 0.1 to 40 parts by mass of the (D) silane compound with respect to 100 parts by mass of the (A) organic polymer. It is more preferable to mix 0.3-30 mass parts, and it is further more preferable to mix 0.5-20 mass parts. The (D) silane compound may be used alone or in combination of two or more.

The curable composition of the present invention preferably further contains (E) a filler. (E) A hardened | cured material can be reinforced by mix | blending a filler.
As the (E) filler, known fillers can be widely used and are not particularly limited. For example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate , Silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, zeolite and the like, among which calcium carbonate is preferable, and surface-treated calcium carbonate is more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, etc. can be used. Among them, an acrylic balloon is more preferable from the viewpoint that the decrease in elongation after curing of the composition is small.

As the calcium carbonate, any of heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, ground calcium carbonate and the like can be used, but colloidal calcium carbonate is more preferable. These calcium carbonates may be used alone or in combination of two or more.
The primary particle diameter of the calcium carbonate is preferably 0.5 μm or less, and more preferably 0.01 to 0.1 μm. By using such fine powdered calcium carbonate having a small particle diameter, thixotropy can be imparted to the curable composition.

  Further, among calcium carbonates, surface-treated calcium carbonate is preferable, and surface-treated fine calcium carbonate is more preferable from the viewpoint of imparting thixotropy and reinforcing effect on a cured product (cured film). Furthermore, surface-treated fine powdered calcium carbonate is used in combination with other calcium carbonates such as heavy calcium carbonate that has not been surface-treated and has a large particle size, or surface-treated calcium carbonate with a large particle size. May be. When the surface-treated fine calcium carbonate and other calcium carbonate are used in combination, the ratio (mass ratio) between the surface-treated fine calcium carbonate and the other calcium carbonate is preferably 1: 9 to 9: 1, and 3: 7. ~ 7: 3 is more preferred.

  In the said surface treatment calcium carbonate, there is no restriction | limiting in particular in the surface treatment agent used, A well-known surface treatment agent can be used widely. Examples of the surface treatment agent include higher fatty acid compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, nonionic surfactants, paraffin, and titanate couplings. And higher fatty acid compounds and paraffin are more preferable. These surface treatment agents may be used alone or in combination of two or more.

  As the surface-treated calcium carbonate, known surface-treated calcium carbonate can be widely used, and is not particularly limited. For example, Vigot 15 (manufactured by Shiraishi Calcium Co., Ltd., light carbonate surface-treated with a fatty acid) Surface treated light calcium carbonate such as calcium, primary particle diameter 0.15 μm; Vigot 10 (manufactured by Shiraishi Calcium Co., Ltd., colloidal calcium carbonate surface treated with fatty acid, primary particle diameter 0.10 μm), white sinter flower DD (Shiraishi calcium Colloidal calcium carbonate surface-treated with resin acid, primary particle size 0.05 μm, Carlex 300 (manufactured by Maruo Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, primary particle size 0. 05μm), Neolite SS (manufactured by Takehara Chemical Industry Co., Ltd., surface-treated with fatty acid) Dal calcium carbonate, average particle size 0.04 μm), Neolite GP-20 (manufactured by Takehara Chemical Industry Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, average particle size 0.03 μm), Calsees P (Kamishima Chemical Industry) Surface-treated colloidal calcium carbonate such as colloidal calcium carbonate surface-treated with fatty acid manufactured by Co., Ltd .; MC Coat P1 (manufactured by Maruo Calcium Co., Ltd., heavy carbonate surface-treated with paraffin) Calcium, primary particle size 3.3 μm), AFF-95 (manufactured by Pfematech Co., Ltd., heavy calcium carbonate surfaced with a cationic polymer, primary particle size 0.9 μm), AFF-Z (manufactured by Pmatech) , Heavy calcium carbonate surfaced with a cationic polymer and an antistatic agent, and a surface-treated heavy coal such as a primary particle size of 1.0 μm) Calcium and the like.

  The blending ratio of the (E) filler is not particularly limited, but it is preferable to blend 0 to 500 parts by mass of the (E) filler with respect to 100 parts by mass of the (A) organic polymer. It is more preferable to mix 250 parts by mass, and it is even more preferable to mix 5 to 125 parts by mass. The (E) filler may be used alone or in combination of two or more.

The curable composition of the present invention preferably further contains (F) a diluent. (F) Physical properties, such as a viscosity, can be adjusted by mix | blending a diluent.
(F) As a diluent, a well-known diluent can be widely used and there is no restriction | limiting in particular, For example, saturated hydrocarbon type solvents, such as normal paraffin and isoparaffin, a linearlen dimer (Idemitsu Kosan Co., Ltd. brand name) Α-olefin derivatives such as toluene, xylene and other aromatic hydrocarbon solvents, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, diacetone alcohol and other alcohol solvents, ethyl acetate, butyl acetate, acetic acid Various solvents such as ester solvents such as amyl and cellosolve acetate, citrate solvents such as acetyltriethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are listed.

The flash point of the diluent (F) is not particularly limited, but in view of the safety of the resulting curable composition, it is desirable that the curable composition has a high flash point. Volatile substances from the curable composition Is preferably less.
Therefore, the flash point of the (F) diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. When two or more (F) diluents are mixed and used, the flash point of the mixed diluent is preferably 70 ° C. or higher. However, generally, a diluent having a high flash point tends to have a low dilution effect on the curable composition, and therefore, the flash point is preferably 250 ° C. or lower.

  In consideration of both safety and dilution effect of the curable composition of the present invention, as the diluent (F), a saturated hydrocarbon solvent is preferable, and normal paraffin and isoparaffin are more preferable. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number 11, flash point 68 ° C), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number) 12, flash point 85 ° C.), IP solvent 2028 (isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C.) and the like.

  The blending ratio of the (F) diluent is not particularly limited, but 0 to 50 parts by weight of the (F) diluent is preferably blended with respect to 100 parts by weight of the (A) organic polymer. It is more preferable to mix 1 to 30 parts by mass, and further preferable to mix 0.1 to 15 parts by mass. The said (F) diluent may be used by 1 type, and may be used in combination of 2 or more type.

The curable composition of the present invention preferably further contains a metal hydroxide. By mix | blending the said metal hydroxide, a flame retardance can be provided, workability | operativity can be improved, and hardened | cured material can be reinforced. Furthermore, the metal hydroxide also has an effect of higher safety than other flame retardants such as halogen flame retardants. In particular, by using a metal hydroxide and surface-treated calcium carbonate in combination, workability (thixotropic properties) can be further improved and flame retardancy can be imparted. The metal hydroxide may be a metal hydroxide surface-treated with a surface treatment agent.
Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide, and aluminum hydroxide is more preferable.

  The blending ratio of the metal hydroxide is not particularly limited, but it is preferable to blend 0 to 500 parts by weight of the metal hydroxide with respect to 100 parts by weight of the (A) organic polymer, and 2 to 250 parts by weight. More preferably, it is more preferably 5 to 125 parts by mass. The said metal hydroxide may be used independently and may be used together 2 or more types. Moreover, you may use together another well-known flame retardant.

  In addition to the above-described components, the curable composition of the present invention includes an ultraviolet absorber, an antioxidant, an anti-aging agent, an adhesiveness imparting agent, a physical property modifier, a plasticizer, a thixotropic agent, and a dehydration agent as necessary. You may mix substances such as additives (storage stability improvers), flame retardants, tackifiers, anti-sagging agents, colorants, radical polymerization initiators, and blend with other compatible polymers. Good.

  The antioxidant is used to prevent oxidation of the curable composition to improve weather resistance and heat resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. It is done.

  The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the curable composition, for example, ultraviolet absorption of benzotriazole, triazine, benzophenone, benzoate, etc. Agents and the like.

  The anti-aging agent is used to prevent heat deterioration of the curable composition and improve heat resistance. For example, an anti-aging agent such as an amine-ketone type and an aromatic secondary amine type are used. Antiaging agents, benzimidazole type antiaging agents, thiourea type antiaging agents, phosphorous acid type antiaging agents and the like can be mentioned.

  The plasticizer is added for the purpose of improving elongation properties after curing or adjusting the hardness to reduce the modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate Aliphatic esters such as butyl oleate; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives Polyoxyethylene alkyl ethers such as tetraethylene glycol diethyl ether; polystyrene oligomers such as poly-α-methylstyrene; hydrocarbon oligomers such as polybutadiene; chlorinated paraffins; UP-1080 ( Acrylic plasticizers such as Toagosei Co., Ltd., UP-1110 (Toagosei Co., Ltd.), UP-1061 (Toagosei Co., Ltd.); UP-2000 (Toagosei Co., Ltd.) ), UHE-2012 (manufactured by Toagosei Co., Ltd.) and the like; hydroxyl group-containing acrylic plasticizers such as UC-3510 (manufactured by Toagosei Co., Ltd.); carboxyl group-containing acrylic polymers such as UG-4000 (Toagosei) Epoxy group-containing acrylic polymers such as Synthetic Co., Ltd .; less than 0.8, such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.), preferably Examples include acrylic polymers containing less than 0.4 silyl groups; oxyalkylene resins containing less than 0.8, preferably less than 0.4 silyl groups.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include zeolite, calcium oxide, magnesium oxide, and zinc oxide.

  Examples of the flame retardant include phosphorus flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide flame retardants such as antimony trioxide; bromine flame retardants; chlorine flame retardants and the like.

  The curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type. The curable composition of the present invention can be cured at normal temperature by moisture in the atmosphere, and is suitably used as a normal temperature moisture-curable curable composition, but if necessary, curing is accelerated by heating as appropriate. You may let them.

  The method for producing the curable composition of the present invention is not particularly limited. For example, a predetermined amount of the components (A) to (C) is blended, and other blending substances are blended as necessary, followed by deaeration and stirring. Can be manufactured. In addition, the reaction between the epoxysilane compound and the aminosilane compound in the (B) silane compound is carried out using the (B) silane compound obtained by reacting the epoxysilane compound and the aminosilane compound in advance. And other compounding materials may be blended to prepare a curable composition, or a mixture in which some or all of the epoxysilane compound, aminosilane compound, and other compounding materials are mixed is prepared in the mixture. The curable composition may be prepared by reacting an epoxysilane compound and an aminosilane compound.

  The blending order of the components (A) to (C) is not particularly limited, but the components (B) and (C) are mixed in advance to obtain a mixture containing the components (B) and (C), and then the mixture. And a component (A) are preferably blended, and a curing catalyst obtained by aging a mixture containing the components (B) and (C) at a predetermined temperature is more preferably blended with the component (A). Here, aging means transesterification of a part of the alkoxyl group of the (C) titanium catalyst and a part of the alkoxyl group of the (B) silane compound and / or moisture contained in the air ( B) This means that a part of the silane compound is hydrolyzed with the titanium catalyst (C) and oligomerized. It is preferable to reach the state of chemical equilibrium by the aging.

  When a mixture in which the (B) silane compound and the (C) titanium catalyst are mixed in advance is used, the mixing ratio of the (B) silane compound and the (C) titanium catalyst is 1 mol of the (C) titanium catalyst. On the other hand, the range of 0.1-30 mol of said (B) silane compound is preferable, the range of 0.5-5.0 mol is more preferable, The range of 0.5-3.0 mol is further more preferable. The (C) titanium catalyst and the (B) silane compound may be used singly or in combination of two or more.

  The method of obtaining the mixture of the (B) silane compound and the (C) titanium catalyst is obtained by using the (B) silane compound obtained by reacting an epoxy silane compound and an aminosilane compound in advance. The compound and (C) titanium catalyst may be mixed to obtain a mixture, or an epoxy silane compound, an amino silane compound, and (C) a mixture of titanium catalyst are prepared, and the epoxy silane compound and amino silane compound in the mixture And (B) a mixture of a silane compound and (C) a titanium catalyst may be obtained.

  The reaction temperature condition for aging the mixture containing the (B) silane compound and the (C) titanium catalyst is not particularly limited, but the (B) silane compound and the (C) titanium catalyst are heated at 30 ° C to 100 ° C. It is preferable to make it react, 30 to 90 degreeC is more preferable, and 40 to 80 degreeC is further more preferable. By setting the reaction temperature within the above range, the reaction can proceed stably without causing runaway. When the reaction temperature is less than 30 ° C., the activity is low, the time required to achieve a sufficient reaction is lengthened, and the efficiency is poor. The reaction time can be appropriately set in consideration of the reaction temperature and the like, but it is desirable to carry out the reaction until at least an equilibrium state is reached. For example, the reaction time is usually 1 to 336 hours under the above conditions, preferably Is preferably set within a range of 72 to 168 hours.

  The blending order of other blending substances other than components (A) to (C) is not particularly limited, and may be determined as appropriate. When using a mixture in which the components (B) and (C) are mixed in advance, the mixture may be obtained by mixing other compounding substances together with the components (B) and (C). The components (B) and (C) After blending one of the above and the other blending substance, the other of components (B) and (C) may be blended to obtain a mixture, and other blends may be added to the mixture containing components (B) and (C). Substances may be added. In the case of using a curing catalyst obtained by aging a mixture containing components (B) and (C), other compounding substances are added before the aging step, and the mixture contains components (B), (C) and other compounding substances. A ripening step may be performed, or other compounding substances may be added after the aging process, or other compounding substances may be added after the aging process and further ripened at a predetermined temperature. Moreover, you may age | cure | ripen at the predetermined temperature further with respect to the composition which mix | blended all the compounding substances.

  When the component (D) is blended as another blending substance, there is no particular limitation in the blending order, but after obtaining a mixture in which the components (C) and (D) are mixed in advance, the mixture and the components (A) and ( After obtaining the mixture which mix | blended B) or mixed component (B)-(D) previously, this mixture and component (A) are mix | blended, etc., and the mixture containing component (C) and (D) is obtained. After that, it is preferable to blend the remaining compounding substances.

  When the (D1) silane compound is used as the (D) silane compound, the reaction between the epoxysilane compound and the aminosilane compound in the (D1) silane compound was obtained by reacting the epoxysilane compound and the aminosilane compound in advance ( D1) Using the silane compound, the curable compound may be prepared by blending the (D1) silane compound and other compounding substances, or a part of the epoxysilane compound, aminosilane compound, and other compounding substances Alternatively, a mixture in which all are mixed may be prepared, and an epoxysilane compound and an aminosilane compound may be reacted in the mixture to prepare a curable composition.

  When a mixture in which the (C) titanium catalyst and the (D) silane compound are mixed in advance is used, the mixing ratio of the (C) titanium catalyst and the (D) silane compound is 1 mol of the (C) titanium catalyst. On the other hand, the range of 0.1-30 mol of said (D) silane compound is preferable, the range of 0.5-5.0 mol is more preferable, The range of 0.5-3.0 mol is further more preferable. The (C) titanium catalyst and the (D) silane compound may be used singly or in combination of two or more.

  When a silane compound having an alkoxysilyl group is used as the component (D), a curing catalyst obtained by aging a mixture containing the components (C) and (D) at a predetermined temperature may be blended with the remaining compounding substances. preferable. Here, the term “ripening” means that a part of the alkoxyl group of the (C) titanium catalyst and a part of the alkoxyl group of the (D) silane compound are subjected to a transesterification reaction and / or the moisture contained in the air ( D) It means that a part of the silane compound is hydrolyzed with the titanium catalyst (C) and oligomerized. It is preferable to reach the state of chemical equilibrium by the aging.

  The reaction temperature condition for aging the mixture containing the (C) titanium catalyst and the (D) silane compound is not particularly limited, but the (C) titanium catalyst and the (D) silane compound are heated at 30 ° C to 100 ° C. It is preferable to make it react, 30 to 90 degreeC is more preferable, and 40 to 80 degreeC is further more preferable. By setting the reaction temperature within the above range, the reaction can proceed stably without causing runaway. When the reaction temperature is less than 30 ° C., the activity is low, the time required to achieve a sufficient reaction is lengthened, and the efficiency is poor. The reaction time can be appropriately set in consideration of the reaction temperature and the like, but it is desirable to carry out the reaction until at least an equilibrium state is reached. For example, the reaction time is usually 1 to 336 hours under the above conditions, preferably Is preferably set within a range of 72 to 168 hours.

  In the present invention, the ripening of the components (B) and (C) and the ripening of the components (C) and (D) may or may not be performed, but at least one of the aging is performed. It is preferable to perform both aging. In the case of aging, there is no restriction on the order of aging, but since the production process is simplified, from the viewpoint of workability, aging is simultaneously performed at a predetermined temperature for the mixture in which components (B) to (D) are mixed. In view of storage stability, rate of change in curing time, and the like, after aging a mixture containing one of components (B) and (D) and component (C) at a predetermined temperature, A method in which the other of (B) and (D) is blended and aged again at a predetermined temperature as necessary, a component (B) and a component (C) are aged, a component (B) and a component (D ) Is preferably mixed, and if necessary, the mixed mixture is further aged. By performing the aging step, the storage stability can be further improved.

  When the component (E) is blended as another blending substance, there is no particular limitation on the blending order, and it may be determined as appropriate. When the components (B) and (C) are aged and the components (C) and (D) are aged, it is preferable to add the component (E) after the aging step.

  When component (F) is blended as another blending substance, there is no particular limitation on the order of blending, but in addition to one or both of components (B) and (D) and component (C), component (F) is added. It is preferable to age the mixture at a predetermined temperature. In this case, the mixture containing one or both of the components (B) and (D), the component (C), and the component (F) may be simultaneously aged at a predetermined temperature. A mixture containing one or both of D) and the component (C) is aged at a predetermined temperature at the same time, and then the component (F) is blended in the mixture and aged again at a predetermined temperature, for example, a plurality of times. An aging step may be performed. In particular, by blending the component (F) after the aging step of the components (B) to (D) and further performing the aging step, the rate of change in the curing time after storage can be reduced, which is more preferable. By performing the aging step, the storage stability can be further improved.

  The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. Since the curable composition of the present invention is excellent in adhesiveness, storage stability, and curability, it is particularly preferable to use it as an adhesive, but for various other buildings, automobiles, civil engineering, electric / electronics. It can be used for fields.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

Analysis and measurement in Synthesis Examples, Examples and Comparative Examples were performed according to the following methods.
1) Measurement of number average molecular weight It measured on the following conditions by the gel permeation chromatography (GPC). In the present invention, the maximum frequency molecular weight measured by GPC under the measurement conditions and converted with standard polyethylene glycol is referred to as the number average molecular weight.
THF solvent measuring device / analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millenium data processing device (manufactured by Waters)
Column: Plgel GUARD + 5 μmMixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by Polymer Lab)
・ Flow rate: 1 mL / min ・ Converted polymer: Polyethylene glycol ・ Measurement temperature: 40 ° C.
FT-NMR measuring apparatus: JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.
FT-IR measuring device: FT-IR460Plus manufactured by JASCO Corporation

2) Storage stability test, curability (TFT) test, and thixotropy test Viscosity, curing time, and structural viscosity index (SVI value) immediately after blending the curable composition were measured. The conditions were referred to as initial, and the measured viscosity, curing time, and SVI value were defined as initial viscosity, initial TFT, and initial SVI value, respectively.

The viscosity is measured with a BS rotational viscometer (rotor No. 7-10 rpm) when the viscosity of the curable composition is 160 Pa · s or higher, and the BH type when the viscosity of the curable composition is less than 160 Pa · s. It measured with the rotational viscometer (rotor No.7-20rpm) (measurement temperature 23 degreeC).
As for the curing time, the touch drying time (TFT) was measured in an environment of RH 50% at 23 ° C. according to JIS A 1439 5.19 tack-free test.
The SVI value is calculated by dividing the viscosity at 1 rpm by the viscosity at 10 rpm using a BS type rotational viscometer (rotor No. 7) when the viscosity of the curable composition is 160 Pa · s or more. When the viscosity of the product was less than 160 Pa · s, it was calculated by dividing the viscosity at 2 rpm by the viscosity at 20 rpm using a BH type rotational viscometer (rotor No. 7) (measurement temperature 23 ° C.). The obtained SVI value was used as an index indicating thixotropy.

Next, the curable composition in the sealed glass container was left in an atmosphere of 50 ° C. for 1, 2 or 4 weeks, and the viscosity, the curing time, and the SVI value were measured. The measured viscosity, curing time, and SVI value were the viscosity after storage, the TFT after storage, and the SVI value after storage, respectively.
The viscosity increase ratio was calculated by dividing the viscosity after storage by the initial viscosity. Moreover, the thickening rate after 1 week storage was evaluated according to the following evaluation criteria.
A: 0.90 to 1.40, O: 1.41 to 1.50, Δ: 1.51 to 1.60, x: 1.61 to 0.89.
The rate of change was calculated by dividing the TFT after storage by the initial TFT. The rate of change after storage for 1 week was evaluated according to the following evaluation criteria.
A: 0.90 to 1.10, B: 0.80 to 0.89, or 1.11 to 1.30, Δ: 1.31 to 1.40, or 0.70 to 0.79 Hereinafter, x: 1.41 or more or 0.69 or less.

3) Surface Curability Test A cured product of a curable composition having a size of 100 mm × 100 mm × 3 mm was prepared by leaving it in an environment of 23 ° C. and RH 50% for 7 days, and judged by finger touch. The evaluation criteria are as follows.
A: Not sticky at all, ○: Not sticky, △: Sticky, ×: Very sticky.

4) Adhesion test 0.2 g of the curable composition was uniformly applied on the adherend, and immediately bonded in an area of 25 mm × 25 mm. After bonding, the adhesive strength was measured according to the tensile shear adhesive strength test method of a rigid adherend immediately after pressing with a small eyeball clip for 7 days in an atmosphere of 23 ° C. and RH 50%. As an adherend, hard vinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), ABS resin (ABS), acrylic resin (PMMA), nylon 6 (6-Ny), cold rolled steel plate (SPCC), Alternatively, anodized aluminum (Al) was used. Further, the fracture state of the adhesive surface was evaluated according to the following evaluation criteria.
CF: cohesive failure, AF: adhesive failure, C10A90 to C90A10: The area of the fractured state of CF and AF is expressed as an approximate percentage. CnA (100-n) is CFn%, AF (100-n)% It means the destruction state.

(Synthesis Example 1)
Hydroxyl value obtained by reacting propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst with ethylene glycol as initiator in a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser A polyoxypropylene triol having a reduced molecular weight of 24,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, and methanol is distilled off under reduced pressure by heating to convert the terminal hydroxyl group of the polyoxypropylene triol into sodium alkoxide to obtain a polyoxyalkylene polymer M1. It was.

Next, the polyoxyalkylene polymer M1 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer A1 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group by GPC, the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 2)
Hydroxyl value obtained by reacting propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst with ethylene glycol as initiator in a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser A polyoxypropylene diol having a converted molecular weight of 11000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene triol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M2. It was.

Next, the polyoxyalkylene polymer M2 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride, and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer A2 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group by GPC, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

  In Table 1, the compounding quantity of each compounding substance is shown by g. The polyoxyalkylene polymers M1 and M2 are the polyoxyalkylene polymers M1 and M2 obtained in Synthesis Examples 1 and 2, respectively.

(Synthesis Example 3)
As shown in Table 2, 40.00 g of ethyl acetate, 70.00 g of methyl methacrylate, 2-ethylhexyl methacrylate (Tokyo Chemical Industry Co., Ltd.) were added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. )) 30.00 g, 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 12.00 g, and titanocene diclide 0.10 g as a metal catalyst were charged and nitrogen gas was introduced into the flask. The contents of the flask were heated to 80 ° C. while introducing. Next, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 4.30 g of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Further, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After the additional addition of 4.30 g of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. . After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product was returned to room temperature, 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, and a vinyl system having a trimethoxysilyl group A polymer A3 was obtained. The peak top molecular weight was 4000, and the molecular weight distribution was 2.4. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.00 per molecule.

  In Table 2, the compounding quantity of each compounding substance is shown by g.

(Synthesis Example 4)
To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser at the mixing ratio shown in Table 3, KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., Tris (3-trimethoxysilylpropyl) ) Isocyanurate), and ORGATICS TC-750 [Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxy bis (ethyl acetoacetate)], and aged by heating and stirring at 70 ° C. for 168 hours to obtain titanium catalyst G1 Obtained. About the obtained titanium catalyst G1, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 5)
To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser at the mixing ratio shown in Table 3, KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., Tris (3-trimethoxysilylpropyl) ) Isocyanurate), ORGATICS TC-750 [Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetoacetate)] and KBM-103 (Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) The mixture was aged by heating and stirring at 70 ° C. for 168 hours to obtain a titanium catalyst G2. About the obtained titanium catalyst G2, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Examples 6-9)
As shown in Table 3, titanium catalysts G3 to G6 were obtained by the same method as in Synthesis Example 4 except that the blending ratio of the blended materials was changed. About the obtained titanium catalysts G3-G6, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Examples 10-15)
As shown in Table 3, titanium catalysts G7 to G12 were obtained in the same manner as in Synthesis Example 5 except that the component (D) was changed. About the obtained titanium catalysts G7-G12, the change of the peak was confirmed from ²⁹ Si-NMR.

In Table 3, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are as follows.
KBM 9659: trade name, Tris (3-trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.
TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: ORGATICS TC-750, titanium diisopropoxybis (ethyl acetoacetate).
KBM-103: trade name, phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-403: 3-Glycidoxypropyltrimethoxysilane Z-6366: Trade name, methyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd.
KBM-1003: Trade name, vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
A-LINK (registered trademark) 35: Trade name, 3-isocyanatopropyltrimethoxysilane, manufactured by Momentive Performance Materials Japan GK.
KBM-503: trade name, 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

(Synthesis Example 16)
To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser at a blending ratio shown in Table 4, KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., Tris (3-trimethoxysilylpropyl) ) Isocyanurate), ORGATICS TC-750 [Matsumoto Fine Chemical Co., Ltd., N-11 (trade name, normal paraffin made by JX Nippon Mining & Energy Co., Ltd.) is added and stirred at 70 ° C. for 168 hours. The titanium catalyst G13 was obtained. About the obtained titanium catalyst G13, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 17)
To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser at a blending ratio shown in Table 4, KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., Tris (3-trimethoxysilylpropyl) ) Isocyanurate), ORGATICS TC-750 [Matsumoto Fine Chemical Co., Ltd., KBM-103 (Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane), and N-11 (JX Nippon Mining & Energy Corporation) And aged by heating and stirring at 70 ° C. for 168 hours to obtain a titanium catalyst G14. About the obtained titanium catalyst G14, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 18)
To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser at a blending ratio shown in Table 4, KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., Tris (3-trimethoxysilylpropyl) ) Isocyanurate), ORGATICS TC-750 [Matsumoto Fine Chemical Co., Ltd., and KBM-103 (Shin-Etsu Chemical Co., Ltd., Phenyltrimethoxysilane) are added and heated and stirred at 70 ° C. for 168 hours. After aging, N-11 (trade name, normal paraffin manufactured by JX Nippon Oil & Energy Corporation) was added and aged by heating and stirring at 70 ° C. for 168 hours to obtain a titanium catalyst G15. About the obtained titanium catalyst G15, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Examples 19-21)
As shown in Table 4, titanium catalysts G16 to G18 were obtained in the same manner as in Synthesis Example 17 except that the blending ratio of component (B) and component (D) were changed. About the obtained titanium catalysts G16-G18, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 22)
To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, 100 g of 3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Toray Dow Corning Co., Ltd.), 3 -276 g of glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Toray Dow Corning Co., Ltd.) was added and stirred at 50 ° C. for 72 hours to obtain a silane compound D-1.
About the obtained silane compound D-1, the disappearance of the peak resulting from the epoxy group near 910 cm ⁻¹ was confirmed by FT-IR, the peak of the secondary amine near 1140 cm ⁻¹ was confirmed, and ²⁹ Si From -NMR, the appearance of a new peak from -60 ppm to -70 ppm was confirmed.

As shown in Table 4, the titanium catalyst G19 was prepared in the same manner as in Synthesis Example 17 except that the blending ratio of the component (B) was changed and the component (D) was changed to the obtained silane compound D-1. Obtained. About the obtained titanium catalyst G19, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 23)
In a 1000 cc three-necked flask, 100 g of triallyl isocyanurate (manufactured by Nippon Kasei Chemical Co., Ltd.) and 400 mL of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred, while trimethoxysilane (Tokyo Kasei ( 98 g) was added dropwise, and then 0.6 g of a platinum-divinyltetramethylsiloxane complex (manufactured by Chisso Corp.) was added, followed by a heating reaction at 120 ° C. for 4 hours. All of this reaction was performed in a nitrogen atmosphere. Then, the silane compound B-1 shown by following formula (22) was obtained by distilling a toluene solution off.

As shown in Table 4, a titanium catalyst G20 was obtained in the same manner as in Synthesis Example 17 except that the obtained silane compound B-1 was used as the component (B). About the obtained titanium catalyst G20, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 24)
As shown in Table 4, a titanium catalyst G21 was obtained by the same method as in Synthesis Example 5 except that the blending ratio of component (B) was changed. About the obtained titanium catalyst G21, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 25)
As shown in Table 4, a titanium catalyst G22 was obtained in the same manner as in Synthesis Example 17 except that the blending ratio of component (B) was changed. About the obtained titanium catalyst G22, the change of the peak was confirmed from ²⁹ Si-NMR.

(Synthesis Example 26)
As shown in Table 4, a titanium catalyst G23 was obtained by the same method as in Synthesis Example 5 except that the blending ratio of component (B) was changed. About the obtained titanium catalyst G23, the change of the peak was confirmed from ²⁹ Si-NMR.

In Table 4, the compounding quantity of each compounding substance is shown by g. The silane compound D-1 is the silane compound D-1 obtained in Synthesis Example 22, the silane compound B-1 is the silane compound B-1 obtained in Synthesis Example 23, and details of other compounding substances are as follows. It is as follows.
KBM 9659: trade name, Tris (3-trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.
TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: ORGATICS TC-750, titanium diisopropoxybis (ethyl acetoacetate).
KBM-103: trade name, phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-403: 3-Glycidoxypropyltrimethoxysilane Z-6366: Trade name, methyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd.
N-11: Trade name, normal paraffin manufactured by JX Nippon Oil & Energy Corporation.

Example 1
As shown in Table 5, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of the polyoxyalkylene polymer A2 obtained in the above and 35 g of vinyl polymer A3 obtained in Synthesis Example 3 in terms of solid content were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, 2.9 g of KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., tris (3-trimethoxysilylpropyl) isocyanurate), Olgatics TC-750 [trade name of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis] 4.0 g of (ethyl acetoacetate)] was added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 6 shows the results of the curability test and the storage stability test of the curable composition, and Table 7 shows the adhesive results.

(Example 2)
As shown in Table 5, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of the polyoxyalkylene polymer A2 obtained in the above and 35 g of vinyl polymer A3 obtained in Synthesis Example 3 in terms of solid content were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, 2.9 g of KBM 9659 (manufactured by Shin-Etsu Chemical Co., Ltd., tris (3-trimethoxysilylpropyl) isocyanurate), Olgatics TC-750 [trade name of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis] 4.0 g of (ethyl acetoacetate)] and 5.0 g of KBM103 (manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) were added and deaerated and stirred at 25 ° C. to obtain a curable composition. Table 6 shows the results of the curability test and the storage stability test of the curable composition, and Table 7 shows the adhesive results.

(Example 3)
As shown in Table 5, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of the polyoxyalkylene polymer A2 obtained in the above and 35 g of vinyl polymer A3 obtained in Synthesis Example 3 in terms of solid content were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, 6.9 g of the titanium catalyst G1 obtained in Synthesis Example 4 was added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 6 shows the results of the curability test and the storage stability test of the curable composition, and Table 7 shows the adhesive results.

(Examples 4 to 7)
As shown in Table 5, a curable composition was obtained in the same manner as in Example 3 except that a predetermined amount of titanium catalysts G2 to G5 was blended instead of the titanium catalyst G1. Table 6 shows the results of the curability test and the storage stability test of the curable composition, and Table 7 shows the adhesive results.

In Table 5, the compounding quantity of each compounding substance is shown by g, and polymer A3 is shown by the compounding quantity of solid content conversion. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively, the polymer A3 is the vinyl polymer A3 obtained in Synthesis Example 3, and the titanium catalysts G1 to G5. Are titanium catalysts G1 to G5 obtained in Synthesis Examples 4 to 8, respectively, and details of other compounding substances are as follows.
KBM 9659: trade name, tris (3-trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.
TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: ORGATICS TC-750, titanium diisopropoxybis (ethyl acetoacetate).
KBM-103: trade name, phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

(Comparative Examples 1-3)
As shown in Table 8, a curable composition was obtained in the same manner as in Example 2 except that the compounding substances were changed. The results of the curability test and the storage stability test of the curable composition are shown in Table 9, and the adhesion results are shown in Table 10.

(Comparative Example 4)
As shown in Table 8, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of vinyl polymer A3 obtained in Synthesis Example 3 were mixed in terms of solid content. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, (E) 20 g of Carlex 300 (manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm) as surface-treated calcium carbonate, Whiteon SB (Shiraishi Calcium Co., Ltd.) Made, heavy calcium carbonate, average particle size 2.2 μm) 40 g, 1 g of NOCLACK CD as an anti-aging agent, heated (100 ° C.), degassed, stirred for 1 hour, returned to room temperature (25 ° C.), (F) 10 g of N-11 (trade name, normal paraffin manufactured by JX Nippon Mining & Energy Co., Ltd.) as a diluent, Olgatrix TC-750 [Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate) Acetate)] was added, and the mixture was further degassed and stirred to obtain a curable composition. The results of the curability test and the storage stability test of the curable composition are shown in Table 9, and the adhesion results are shown in Table 10.

(Comparative Example 5)
As shown in Table 8, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of vinyl polymer A3 obtained in Synthesis Example 3 were mixed in terms of solid content. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, (E) 20 g of Carlex 300 (manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm) as surface-treated calcium carbonate, Whiteon SB (Shiraishi Calcium Co., Ltd.) Made, heavy calcium carbonate, average particle size 2.2 μm) 40 g, 1 g of NOCLACK CD as an anti-aging agent, heated (100 ° C.), degassed, stirred for 1 hour, returned to room temperature (25 ° C.), (F) 10 g of N-11 (trade name, normal paraffin manufactured by JX Nippon Mining & Energy Co., Ltd.) as a diluent, Olgatrix TC-750 [Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate) Acetate)] 4.0 g and KBM-103 (Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) 5 Put 0 g, to obtain a further degassed stirring curable composition. The results of the curability test and the storage stability test of the curable composition are shown in Table 9, and the adhesion results are shown in Table 10.

In Table 8, the compounding quantity of each compounding substance is shown by g, and the polymer A3 is shown by the compounding quantity of solid content conversion. Polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively, and details of other compounding substances are as follows.
TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: ORGATICS TC-750, titanium diisopropoxybis (ethyl acetoacetate).
KBM-103: trade name, phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
Whiteon SB: trade name, heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., average particle size 2.2 μm.
Carlex 300: trade name manufactured by Maruo Calcium Co., Ltd., surface-treated calcium carbonate, treatment agent: fatty acid, primary particle diameter (electron microscope) 0.05 μm.
N-11: Trade name, normal paraffin manufactured by JX Nippon Oil & Energy Corporation.
KBM-903: trade name, 3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
Anti-aging agent: manufactured by Ouchi Shinko Co., Ltd., trade name: NOCRACK CD, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

(Example 8)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 20 g of the polyoxyalkylene polymer A2 obtained in the above and 35 g of vinyl polymer A3 obtained in Synthesis Example 3 in terms of solid content were mixed. The mixture was heated (120 ° C.), degassed under reduced pressure, residual monomer and ethyl acetate contained in the vinyl polymer A3 were removed, and cooled to room temperature (25 ° C.). Thereafter, 10 g of Isopar M as a diluent (F) and 8.9 g of the titanium catalyst G6 obtained in Synthesis Example 9 were added and further deaerated and stirred to obtain a curable composition. Table 12 shows the results of the curability test and the storage stability test of the curable composition, and Table 13 shows the adhesion results.

(Examples 9 to 14)
As shown in Table 11, a curable composition was obtained in the same manner as in Example 8, except that a predetermined amount of titanium catalysts G7 to G12 was blended instead of the titanium catalyst G6. Table 12 shows the results of the curability test and the storage stability test of the curable composition, and Table 13 shows the adhesion results.

In Table 11, the compounding quantity of each compounding substance is shown by g, and polymer A3 is shown by the compounding quantity of solid content conversion. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively, the polymer A3 is the vinyl polymer A3 obtained in Synthesis Example 3, and the titanium catalysts G6 to G12. Are titanium catalysts G6 to G12 obtained in Synthesis Examples 9 to 15, respectively, and details of other compounding substances are as follows.
Isopar M: trade name, isoparaffin, manufactured by ExxonMobil Co., Ltd.

(Example 15)
As shown in Table 14, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of vinyl polymer A3 obtained in Synthesis Example 3 were mixed in terms of solid content. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, (E) 40 g of whiten SB (manufactured by Shiraishi Calcium Co., Ltd., heavy calcium carbonate, average particle size 2.2 μm) as a filler, (E) Carlex 300 (Maruo Calcium Co., Ltd.) as surface-treated calcium carbonate ), Fatty acid surface-treated calcium carbonate, primary particle size (electron microscope) 0.05 μm) 20 g, NOCLACK CD 1 g as an anti-aging agent, heated (100 ° C.), degassed and stirred for 1 hour, 25 deg. The results of the curability test and the storage stability test of the curable composition are shown in Table 15, and the adhesion results are shown in Table 16.

(Example 16)
As shown in Table 14, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of vinyl polymer A3 obtained in Synthesis Example 3 were mixed in terms of solid content. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, (E) 40 g of whiten SB (manufactured by Shiraishi Calcium Co., Ltd., heavy calcium carbonate, average particle size 2.2 μm) as a filler, (E) Carlex 300 (Maruo Calcium Co., Ltd.) as surface-treated calcium carbonate ), Fatty acid surface-treated calcium carbonate, primary particle size (electron microscope) 0.05 μm) 20 g, NOCLACK CD 1 g as an anti-aging agent, heated (100 ° C.), degassed and stirred for 1 hour, 25 g), 20 g of the titanium catalyst G13 obtained in Synthesis Example 16 and 5.0 g of KBM103 (manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) are added, and the mixture is further deaerated and stirred to obtain a curable composition. Obtained. The results of the curability test and the storage stability test of the curable composition are shown in Table 15, and the adhesion results are shown in Table 16.

(Examples 17 to 23)
As shown in Table 14, a curable composition was obtained in the same manner as in Example 15 except that a predetermined amount of titanium catalysts G14 to G20 was blended instead of the titanium catalyst G13. The results of the curability test and the storage stability test of the curable composition are shown in Table 15, and the adhesion results are shown in Table 16.

In Table 14, the compounding quantity of each compounding substance is shown by g, and polymer A3 is shown by the compounding quantity of solid content conversion. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively, the polymer A3 is the vinyl polymer A3 obtained in Synthesis Example 3, and the titanium catalysts G13 to G20. Are titanium catalysts G13 to G20 obtained in Synthesis Examples 16 to 23, respectively, and details of other compounding substances are as follows.
KBM-103: trade name, phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
Whiteon SB: trade name, heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., average particle size 2.2 μm.
Carlex 300: trade name manufactured by Maruo Calcium Co., Ltd., surface-treated calcium carbonate, treatment agent: fatty acid, primary particle diameter (electron microscope) 0.05 μm.
Anti-aging agent: manufactured by Ouchi Shinko Co., Ltd., trade name: NOCRACK CD, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

(Example 24)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 35 g of the polyoxyalkylene polymer A2 obtained in 1 above and 20 g in terms of solid content of the vinyl polymer A3 obtained in Synthesis Example 3 were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomers and ethyl acetate contained in the vinyl polymer A3, and cooled to room temperature. Thereafter, (E) 17.5 g of Carlex 300 (manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm) as surface-treated calcium carbonate, MC coat S-1 (Maruo) Calcium Co., Ltd., fatty acid surface-treated heavy calcium carbonate, primary particle size 3.4 μm) 40 g, Nocrack CD 5 g as an anti-aging agent, heated (100 ° C.), degassed and stirred for 1 hour at room temperature Return to (25 ° C.), (F) 10 g of N-11 (trade name, normal paraffin manufactured by JX Nippon Oil & Energy Corporation) as a diluent and 11 g of the titanium catalyst G21 obtained in Synthesis Example 25, Further, the mixture was deaerated and stirred to obtain a curable composition. The results of the curability test and the storage stability test of the curable composition are shown in Table 18, and the adhesion results are shown in Table 19.

(Examples 25 to 28)
As shown in Table 17, a curable composition was obtained in the same manner as in Example 24 except that the compounding substances were changed. The results of the curability test and the storage stability test of the curable composition are shown in Table 18, and the adhesion results are shown in Table 19.

(Example 29)
A curable composition was obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 17. The results of the curability test and the storage stability test of the curable composition are shown in Table 18, and the adhesion results are shown in Table 19.

In Table 17, the compounding quantity of each compounding substance is shown by g, and the polymer A3 is shown by the compounding quantity of solid content conversion. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively, the polymer A3 is the vinyl polymer A3 obtained in Synthesis Example 3, and the titanium catalysts G21 to G23. Are titanium catalysts G21 to G23 obtained in Synthesis Examples 24 to 26, respectively, and details of other compounding substances are as follows.
KBM 9659: trade name, Tris (3-trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.
TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: ORGATICS TC-750, titanium diisopropoxybis (ethyl acetoacetate).
Whiteon SB: trade name, heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., average particle size 2.2 μm.
Carlex 300: trade name manufactured by Maruo Calcium Co., Ltd., surface-treated calcium carbonate, treatment agent: fatty acid, primary particle diameter (electron microscope) 0.05 μm.
MC Coat S-1: Trade name manufactured by Maruo Calcium Co., Ltd., surface-treated heavy calcium carbonate, treatment agent: fatty acid, primary particle size 3.4 μm.
MC coat P-1: Trade name manufactured by Maruo Calcium Co., Ltd., surface-treated heavy calcium carbonate, treatment agent: paraffin wax, primary particle size 3.3 μm.
MS-100M: trade name manufactured by Maruo Calcium Co., Ltd., surface-treated calcium carbonate, treatment agent: fatty acid / resin acid, primary particle diameter (electron microscope) 0.05 μm.
Calfine 200M: trade name manufactured by Maruo Calcium Co., Ltd., surface-treated colloidal calcium carbonate, treatment agent: fatty acid, primary particle size 0.05 μm.
Armorix B316: trade name, aluminum hydroxide, average particle diameter of 18 μm, manufactured by Armorix Co., Ltd.
N-11: Trade name, normal paraffin manufactured by JX Nippon Oil & Energy Corporation.
Isopar M: trade name, isoparaffin, manufactured by ExxonMobil Co., Ltd.
Anti-aging agent: manufactured by Ouchi Shinko Co., Ltd., trade name: NOCRACK CD, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

  As shown in Tables 5 to 19, in Examples 1 to 29, the storage stability and curing delay were improved while imparting adhesiveness, and curing excellent in adhesiveness, storage stability and curability. Sex composition was obtained. The curable composition of the present invention showed excellent adhesion particularly to metals such as Al.

Claims (10)

(A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule and the main chain is not polysiloxane;
(B) a silane compound having any isocyanurate ring represented by the following formula (14) to the following formula (20) , and (C) a titanium chelate represented by the following formula (1) coordinated with a β-ketoester; One or more titanium catalysts selected from the group consisting of titanium chelates represented by the following formula (2):
A curable composition comprising
0.1 to 40 parts by mass of (B) silane compound and 0.1 to 40 parts by mass of (C) titanium catalyst are blended with respect to 100 parts by mass of (A) organic polymer. Curable composition.
(In the formula (1), n R ^{1 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R ^{2 s} are independently hydrogen atoms. Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R ³ and 4-n R ⁴ are independently substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms. And n is 0, 1, 2 or 3.)
(In the formula (2), R ⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and the two R ⁶ are independently a hydrogen atom or substituted or unsubstituted. And 2 R ⁷ and 2 R ⁸ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.)   The (A) organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups on average per molecule, and 0.8 or more crosslinks on average per molecule. Selected from the group consisting of a saturated hydrocarbon polymer containing a functional silicon group and a (meth) acrylic acid ester polymer containing an average of 0.8 or more crosslinkable silicon groups in one molecule. It is 1 or more types, The curable composition of Claim 1 characterized by the above-mentioned.   The curable composition according to claim 1 or 2, wherein the crosslinkable silicon group contains a trimethoxysilyl group.   (D) The curable composition according to any one of claims 1 to 3, further comprising a silane compound not containing a primary amino group. The (D) silane compound comprises (D1) an epoxy silane compound represented by the following formula (3) and an amino silane compound represented by the following formula (4). 5. The silane compound obtained by reacting in a range of 1.5 to 10 mol, and (D2) one or more selected from the group consisting of silane compounds represented by the following formula (5): The curable composition as described.
(In the formula (3), R ^{11 to} R ¹³ are each a hydrogen atom or an alkyl group, R ¹⁴ is an alkylene group or an alkyleneoxyalkylene group, R ¹⁵ is a monovalent hydrocarbon group, and R ¹⁶ is An alkyl group, and a is 0, 1 or 2.)
(In the formula (4), R ^{17 to} R ²² are each a hydrogen atom or an alkyl group, R ²³ is a monovalent hydrocarbon group, R ²⁴ is an alkyl group, and b is 0 or 1. )
(In the formula (5), R ³¹ is a methyl group or an ethyl group, and when a plurality of R ³¹ are present, they may be the same or different, and R ³² is a methyl group. Or when there are a plurality of R ^{32 s} , they may be the same or different, R ³³ is a hydrocarbon group having 1 to 10 carbon atoms, and m is 2 Or 3 and n is 0 or 1.) (E) The curable composition according to any one of claims 1 to 5, further comprising a filler.   The curable composition according to claim 6, wherein the filler (E) is a surface-treated calcium carbonate.   (F) The curable composition according to any one of claims 1 to 7, further comprising a diluent.   The curable composition according to claim 1, further comprising a metal hydroxide.   The curable composition according to claim 9, wherein the metal hydroxide is aluminum hydroxide.