JP2011241390A - Curable composition having improved storage stability and adhesion property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which includes a non-tin-based metal catalyst and an organic polymer with a crosslinking silicon group, in particular which has improved storage stability and an adhesion property.SOLUTION: The curable composition contains: the organic polymer (A) which has a hydrolyzable group bonded to a silicon atom and has the crosslinking silicon group capable of crosslinking by forming a siloxane bond by an action of water, and in which the main chain is not a polysiloxane; and a metal compound (B) as a curing catalyst, and has an adhesion property. The metal compound (B) is a compound of one or more metals selected from a group comprised of metals except for tin, and is formed by bonding a residue of an α- or β-keto alcohol to the metal atom, wherein the α carbon is a saturated carbon, and the curable composition contains 0.1-20 pts.mass of the metal compound (B) based on 100 pts.mass of the organic polymer (A).

Description

  The present invention relates to a curable composition using an organic polymer having a crosslinkable silicon group, and particularly relates to a curable composition having improved storage stability and adhesiveness.

  An organic polymer having a crosslinkable silicon group in the molecule has a feature that it reacts with moisture in the air even at room temperature to cure in a rubbery form. Among organic polymers having a crosslinkable silicon group in the molecule, an organic polymer whose main chain skeleton is a polyoxyalkylene polymer is disclosed in Patent Document 1 and the like. This polyoxyalkylene polymer has already been industrially produced and widely used for applications such as sealing materials and adhesives. A typical example of such an organic polymer usually has a crosslinkable silicon group formed by bonding two hydrolyzable groups per silicon atom in order to maintain elongation and flexibility.

  The curable composition containing the above organic polymer is cured using a silanol condensation catalyst, and usually an organic tin catalyst such as dibutyltin bisacetylacetonate is widely used. However, in recent years, toxicity of organic tin compounds has been pointed out, and an alternative non-tin curing catalyst is desired.

  A dealcohol-free silicone composition using a titanium catalyst as the non-organotin-based catalyst is disclosed in Patent Document 2, Patent Document 3, and the like. This dealcohol-free silicone composition has already been industrially produced and widely used in many applications.

  On the other hand, Patent Documents 4 to 7 disclose curable compositions obtained by combining a titanium catalyst, an aluminum catalyst, or a zirconium catalyst as a curing catalyst with respect to an organic polymer containing a crosslinkable silicon group.

JP-A-52-73998 Japanese Examined Patent Publication No. 39-27643 (US Pat. No. 3,175,993) US Pat. No. 3,334,067 Japanese Patent Laid-Open No. 2002-249672 JP 58-17154 A (Japanese Patent Publication No. 3-57943) JP 62-146959 A (Japanese Patent Publication No. 5-45635) JP 2004-51809 A

  However, when a curable composition disclosed in Patent Document 4 or the like, that is, a titanium catalyst, an aluminum catalyst, or a zirconium catalyst is used as a curing catalyst for an organic polymer having a crosslinkable silicon group, it is generally used at present. Compared to the case of the organic tin-based compound, the curing rate is low, and it may not have practical curability.

  An object of the present invention is to provide a curable composition having a metal catalyst and an organic polymer having a crosslinkable silicon group as a curing catalyst, particularly having improved storage stability and adhesion.

  As a result of diligent studies to solve such problems, the present inventors have found that an organic polymer having a crosslinkable silicon group formed by bonding a hydrolyzable group to a silicon atom as an organic polymer having a crosslinkable silicon group. It is a non-organic tin catalyst by using a polymer and using a “metal compound in which α- or β-ketoalcohol residue is bonded to a metal atom and α-carbon is saturated carbon” as its curing catalyst. However, the inventors have found that a curable composition having improved storage stability can be obtained while maintaining sufficiently practical curability and adhesiveness, and completed the present invention.

  The curable composition of the present invention has (A) a hydrolyzable group bonded to a silicon atom, a crosslinkable silicon group that can be cross-linked by forming a siloxane bond by the action of moisture, and a main chain of which 1. A curable composition having adhesiveness containing an organic polymer that is not siloxane and (B) a metal compound as a curing catalyst, wherein the (B) metal compound is selected from the group consisting of metals other than tin. A compound of more than one kind of metal, which is a metal compound in which a residue of α- or β-ketoalcohol is bonded to the metal atom, and the α-carbon is a saturated carbon; 0.1-20 mass parts of said (B) metal compound is contained with respect to a mass part, It is characterized by the above-mentioned.

The (B) metal compound is preferably a reaction product obtained by reacting at least a metal alkoxide with a hydroxycarboxylic acid ester.
It is preferable that the hydroxycarboxylic acid ester is one or more selected from the group consisting of a lactic acid ester, a malic acid ester, and a citric acid ester.
Moreover, it is preferable that the said metal alkoxide is a metal alkoxide containing a C1-C12 alkoxide group.

  It is preferable that the metal is at least one selected from the group consisting of titanium, aluminum, zirconium, niobium, vanadium and tantalum.

  The main chain skeleton of the (A) organic polymer is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester polymer. Is preferred.

  The crosslinkable silicon group is preferably a group represented by the following formula (1).

In the formula (1), R ¹ 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, or an aralkyl group having 7 to 20 carbon atoms. When two or more R ¹ are present, they may be the same or different. X represents a hydrolyzable group, the hydrolyzable group is preferably an alkoxy group, and at least a part of the hydrolyzable group is more preferably a methoxy group. When two or more X are present, they may be the same or different. a is an integer of 1, 2, or 3, 2 or 3 is preferable, and 3 is more preferable.

  According to the present invention, including a metal catalyst that is a non-tin curing catalyst and an organic polymer having a crosslinkable silicon group, the storage stability is particularly improved, the adhesiveness is excellent, and an adhesive, a sealing material, etc. Useful curable compositions 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 has (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and has a crosslinkable silicon group that can be crosslinked by forming a siloxane bond by the action of moisture. Is a curable composition having adhesiveness containing an organic polymer that is not polysiloxane, and (B) a metal compound as a curing catalyst, wherein the metal compound is selected from the group consisting of metals other than tin A compound of the above metal, which is a metal compound in which an α- or β-ketoalcohol residue is bonded to the metal and the α carbon is a saturated carbon, and (A) 100 parts by mass of the organic polymer To (B) 0.1-20 parts by mass of the curing catalyst.

  The (A) organic polymer having a crosslinkable silicon group used in the present invention is an organic polymer whose main chain is not polysiloxane, and those having various main chain skeletons excluding polysiloxane can be used.

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

  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 more preferable because it is excellent in cold resistance.

  Moreover, when the addition amount of the (B) curing catalyst used in the present invention is large, the deep curability of the resulting composition may be lowered. Therefore, the polyoxyalkylene polymer and the (meth) acrylic acid ester polymer are particularly preferable because they are highly moisture-permeable and have excellent deep-curing properties when made into a one-component composition. Most preferred.

  (A) The crosslinkable silicon group of the organic polymer having a crosslinkable silicon group used in the present invention has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. It is. As the crosslinkable silicon group, for example, a group represented by the following general formula (2) is preferable.

In Formula (2), R ¹ 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 having 7 to 20 carbon atoms, or R ^1. ₃ represents a triorganosiloxy group represented by SiO— (R ¹ is the same as above), and when two or more R ¹ 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. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2, respectively. Further, p in the following general formula (3) need not be the same. p shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) 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 (1) is preferable because it is easily available.

In the formula (1), R ¹ and X are the same as described above, and a 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 (1) is preferably 2 or more, and more preferably 3.

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ 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 alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases 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.

The specific structure of the crosslinkable silicon group includes dialkoxy such as trialkoxysilyl group [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, methyldimethoxysilyl group and methyldiethoxysilyl group. And a silyl group [—SiR ¹ (OR) ₂ ]. 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 at least 1, preferably 1, It is good to have 1-5 pieces. If the number of crosslinkable silicon groups contained in the molecule is less than 1 on average, the curability becomes insufficient and it becomes difficult to exhibit 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 (4).
—R ² —O— (4)
In the general formula (4), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. .

Specific examples of the repeating unit represented by the general formula (4) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used 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 high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution 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 mentioned.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be applied to a polyoxyalkylene polymer having a functional group such as an unsaturated group, hydroxyl group, epoxy group or 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 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. Or an olefinic compound having 2 to 6 carbon atoms as a main monomer, or (2) a diene compound such as butadiene or isoprene is homopolymerized or copolymerized with the olefinic compound. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

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

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units or may be a copolymer with other monomers. 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, 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 various functional groups can be introduced at the molecular ends.

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

  The 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. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (Meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2- -Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl) methyl, (meth) acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acid.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, 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 styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. In applications such as general construction, a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferred to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve the low temperature characteristics without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / -2-methoxyethyl acrylate (40-50 / 20 by mass ratio). To 30/30 to 20). In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in a mass ratio of 40% or more. . In the above expression format, for example, (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 synthesis method described in JP-A-2003-313397), 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.

<Free radical polymerization method>
When using a free radical polymerization method, it is preferable to make it react at 0 to 200 degreeC using a chain transfer agent and an initiator. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the free radical polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 1 to 144 hours, preferably It is preferable to set within a range of 2 to 8 hours.

  As the chain transfer agent, known chain transfer agents can be widely used, and there is no particular limitation. However, a thiol compound is preferable, and a thiol compound having a reactive silyl group is more preferable. For example, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethyltripropoxysilane, mercaptomethylmethyldisilane Propoxysilane, mercaptomethyldimethylpropoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysilane, 3-mercaptopropyl -Dimethylmonomethoxysilane, 3-mercaptopropyl-monomethyldiethoxysilane, 4- Rukaputobuchiru - trimethoxysilane and 3-mercaptopropyl butyl - trimethoxysilane. These may be used alone or in combination of two or more.

  The chain transfer agent can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a usual amount, specifically, 100 mol parts of a polymerizable unsaturated compound to be polymerized. The amount is usually 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

  The initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, an ionic initiator, and a redox initiator. These may be used alone or in combination of two or more.

  Examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis. (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries, Ltd.), 1,1′-azobis (cyclohexane-1-carbonitrile) (V-40, Wako Pure) Yakuhin Kogyo Co., Ltd.), 1-[(1-cyano-1-methylethyl) azo] formamide (V-30, Wako Pure Chemical Industries, Ltd.), 2-phenylazo-4-methoxy-2,4 -Dimethyl-valeronitrile (V-19, manufactured by Wako Pure Chemical Industries, Ltd.) Nitrile compound, 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] (VA-080, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [ 2-methyl-N- [2- (1-hydroxybutyl)]-propionamide] (VA-085, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- (2 -Hydroxyethyl) -propionamide] (VA-086, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries, Ltd.) ), 2, 2'- Zobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (N-butyl-2-methylpropionamide) (VAm -110, manufactured by Wako Pure Chemical Industries, Ltd.), azoamide compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (VAm-111, manufactured by Wako Pure Chemical Industries, Ltd.), 2 2,2′-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropane) (VR-160, Wako Pure Chemical) And alkylazo compounds such as those manufactured by Kogyo Co., Ltd.

  Examples of the peroxide initiator include methyl ethyl ketone peroxide (Permec H, manufactured by NOF Corporation), cyclohexanone peroxide species (Perhexa H, manufactured by NOF Corporation), methylcyclohexanone peroxide (Perhexa Q). , Manufactured by NOF Corporation), methylacetoacetate peroxide (Percure SA, manufactured by NOF Corporation), ketone peroxides such as acetylacetone peroxide (Percure A, manufactured by NOF Corporation), 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation), 1,1-bis (t-hexylperoxy) cyclohexane (Perhexa HC, NOF Corporation ), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 3M, manufactured by NOF Corporation, 1,1-bis (t-butylperoxy) cyclohexane (Perhexa C, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclododecane (Perhexa CD-R, manufactured by NOF Corporation), 2,2′-bis (t-butylperoxy) butane (Perhexa 22, manufactured by NOF Corporation), n-butyl 4,4-bis (t -Butylperoxy) valerate) Perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (Pertetra A, manufactured by NOF Corporation), etc. Peroxyketals, t-butyl hydroperoxide (Perbutyl H-69, manufactured by NOF Corporation), p-menthane hydroperoxide (Permenta H, manufactured by NOF Corporation), diisopropylbenzene hydroperoxide ( Pa Cumyl P, manufactured by NOF Corporation, 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Perk Mill H-80, NOF Corporation) Co., Ltd.), hydroperoxides such as t-hexyl hydroperoxide (Perhexyl H, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (Perhexin 25B, manufactured by NOF Corporation), di-t-butyl peroxide (Perbutyl DR, manufactured by NOF Corporation), t-butyl cumyl peroxy species (Perbutyl C, manufactured by NOF Corporation) ), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation), Dicumyl Peroxy species (Park Mill DR, manufactured by NOF Corporation), α, α'-bis (t-bu Dialkyl peroxides such as luperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation), octanoyl peroxy species (Perroyl O, manufactured by NOF Corporation), lauroyl peroxy species (Perroyl L, NOF Corporation) Co., Ltd.), stearoyl peroxy species (Perroyl S, manufactured by NOF Corporation), succinic acid peroxy species (Perloyl SA, manufactured by NOF Corporation), benzoyl peroxide (Nyper BW, NOF Corporation) )), Isobutyryl peroxide (Perroyl IB, manufactured by NOF Corporation), 2,4-dichlorobenzoyl peroxy species (Nyper CS, manufactured by NOF Corporation), 3,5,5-trimethylhexanoyl Diacyl peroxides such as peroxy species (Perroyl 355, manufactured by NOF Corporation), di-n-propyl peroxydicarbonate (Perroyl) NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (Perroyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, NOF Corporation) ), Di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by NOF Corporation), di-2-ethoxyhexyl peroxydicarbonate (Perloyl OPP, manufactured by NOF Corporation), Di-2-methoxybutyl peroxydicarbonate (Perroyl MBP, manufactured by NOF Corporation), di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perloyl SOP, manufactured by NOF Corporation), etc. Peroxydicarbonates, α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Nyper ND-R, JP Fatty Co., Ltd.), cumyl peroxyneodecanoate (Park Mill ND-R, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (Perocta ND-R) , Manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxyneodecanoate (percyclo ND-R, manufactured by NOF Corporation), t-hexylperoxyneodecanoate (perhexyl ND-) R, manufactured by NOF Corporation), t-butyl peroxyneodecanoate (perbutyl ND-R, manufactured by NOF Corporation), t-hexyl peroxypivalate (perhexyl PV, manufactured by NOF Corporation) ), T-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, NOF Corporation) Made) 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corporation), t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexanoate (perbutyl) O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF Corporation), t-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corporation), t-butylperoxy 3,5,5-trimethylhexanoate (Perbuthi 355, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane ( Perhexa 25MT, manufactured by NOF Corporation, t-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E, NOF Corporation) )), T-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF Corporation) T-butyl peroxyacetate (Perbutyl A, manufactured by NOF Corporation), t-butyl peroxy-m-toluoyl benzoate (Perbutyl ZT, manufactured by NOF Corporation) Peroxyesters such as t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation), bis (t-butylperoxy) isophthalate (Perbutyl IF, manufactured by NOF Corporation), t-butyl Peroxyallyl monocarbonate (Peromer AC, manufactured by NOF Corporation), t-butyltrimethylsilyl peroxide (Perbutyl SM, manufactured by NOF Corporation), 3,3′-4,4′-tetra (t-butyl) Peroxycarbonyl) benzophenone (BTTB-50, manufactured by NOF Corporation), 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, manufactured by NOF Corporation) and the like.

  Examples of the ionic initiator include 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2 -[N- (4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyphenyl) amidino] Propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, Wako Pure Chemical Industries, Ltd.) 2,2′-azobis [2- (N-allylamidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-amidinop) Pan) dihydrochloride (VA-50, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyethyl) amidino] propane} dihydrochloride (VA-558, Wako Pure) Yakuhin Kogyo Co., Ltd.), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries, Ltd.), 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (4,5, 6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (3,4) , 5,6-Tetrahydropyrimidine 2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2- Yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} Dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, manufactured by Wako Pure Chemical Industries, Ltd.) And anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries, Ltd.) and ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries, Ltd.).

  Such redox initiators include, for example, systems based on organic peroxides and tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as cumene hydroperoxide. And systems based on cobalt naphthate.

  The initiator can be appropriately set in consideration of the molecular weight, molecular weight distribution, etc., but can be used in a normal amount, specifically, in 100 mol parts of the polymerizable unsaturated compound to be polymerized. On the other hand, it is usually used in an amount of 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

<Addition-cleavage transfer reaction polymerization method>
When the addition-cleavage transfer reaction polymerization method is used, it is preferable to react at 0 ° C. to 200 ° C. using a chain transfer agent and an initiator. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the addition-cleavage transfer reaction polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 30 minutes to 144. It is preferable to set the time, preferably within the range of 1 to 24 hours.

  Examples of the chain transfer agent include benzoyl-1-pyrrolecarbodithioate, benzoyldithiobenzoate, cyanoisopropyldithiobenzoate, cumyldithiobenzoate, methoxycarbonylphenylmethyldithiobenzoate. Eat, cyanobenzyldithiobenzoate, 1-phenylethyldithiobenzoate, t-butyldithiobenzoate S- (thiobenzyl) thioglycolic acid, 1-phenylethylphenyldithiobenzoate, 3-benzyl Sulfanylthiocarbonylsulfanyl-propionic acid, 2- (benzylsulfanylthiocarbonylsulfanyl) ethanol, 3-benzylsulfanylthiocarbonylsulfanylpropionic acid, S- (1-ethoxycarbonylethyl) O-ethylxanthate, ethyl -2- (2-trifluoroethoxythiocarbonylsulfanyl) propionate, ethyl-2- (1-diethoxyphosphonyl-2,2,2-trifluoroethoxythiocarbonylsulfanyl) propionate, bisthiobenzoyl disulfide Bis (2,6-dimethylthiobenzoyl) disulfide, bis (2,4-dimethylthiobenzoyl) disulfide, bis (4-methoxythiobenzoyl) disulfide, bis (2,4dimethoxythiobenzoyl) disulfide, bis (4- Fluorothiobenzoyl) disulfide, bis (2,4-difluorothiobenzoyl) disulfide, bis (4-cyanothiobenzoyl) disulfide, bis (3,5-dicyanothiobenzoyl) disulfide, bis (3,5-bis (trifluoro) Mechi ) Dithiobenzoate) disulfide, bis (2,3,4,5,6-pentafluorothiobenzoyl) disulfide, bis (4-phenylthiobenzoyl) disulfide, bis (2-naphthylthionyl) disulfide, bis (1-naphthyl) Thionyl) disulfide, triphenylmethyldithioisonicotinate, 2-cyanoisopropyl (2,6-dimethyl) dithiobenzoate, 2-cyanoisopropyl (2,4-dimethyl) dithiobenzoate, 2-cyanoisopropyl (4 -Methoxy) dithiobenzoate, 2-cyanoisopropyl (2,4-dimethoxy) dithiobenzoate, 2-cyanoisopropyl (4-fluoro) dithiobenzoate, 2-cyanoisopropyl (2,4-difluoro) dithiobenzoate, 2-Cyanoisopro Pyrdithioisonicotinate, 2-cyanoisopropyl 4-cyanodithiobenzoate, 2-cyanoisopropyl 3,5-dicyanodithiobenzoate, 2-cyanoisopropyl 3,5-bis (trifluoromethyl) dithiobenzoate, 2-cyanoisopropyl 2,3,4,5,6-pentafluorodithiobenzoate, 2-cyanoisopropyl 4-pyridinium dithiocarboxylate 4-toluenesulfonate salt, 2-cyanoisopropyl (4-phenyl) ) Dithiobenzoate, 2-cyanoisopropyl-2-naphthyldithiolate, 2-cyanoisopropyl-1-naphthyldithiolate, 2-cyano-4-methylpent-2-yldithiobenzoate, 2- Cyano-4-methylpent-2-yl-4-cyanodithiobenzoate, - cyano-4-methylpent-2-yl 3,5-bis-trifluoromethyl dithiobenzoate et - DOO, 2-cyano-4-methylpent-2-yl-4-methoxy sulfonyl dithiobenzoate et - include bets. These may be used alone or in combination of two or more.

  The chain transfer agent can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a usual amount, specifically, 100 mol parts of a polymerizable unsaturated compound to be polymerized. The amount is usually 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

  The initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, and an ionic initiator. These may be used alone or in combination of two or more.

  Examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis. (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries, Ltd.), 1,1′-azobis (cyclohexane-1-carbonitrile) (V-40, Wako Pure) Yakuhin Kogyo Co., Ltd.), 1-[(1-cyano-1-methylethyl) azo] formamide (V-30, Wako Pure Chemical Industries, Ltd.), 2-phenylazo-4-methoxy-2,4 -Dimethyl-valeronitrile (V-19, manufactured by Wako Pure Chemical Industries, Ltd.) Nitrile compound, 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] (VA-080, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [ 2-methyl-N- [2- (1-hydroxybutyl)]-propionamide] (VA-085, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- (2 -Hydroxyethyl) -propionamide] (VA-086, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries, Ltd.) ), 2, 2'- Zobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (N-butyl-2-methylpropionamide) (VAm -110, manufactured by Wako Pure Chemical Industries, Ltd.), azoamide compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (VAm-111, manufactured by Wako Pure Chemical Industries, Ltd.), 2 2,2′-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropane) (VR-160, Wako Pure Chemical) And alkylazo compounds such as those manufactured by Kogyo Co., Ltd.

  Examples of the peroxide initiator include methyl ethyl ketone peroxide (Permec H, manufactured by NOF Corporation), cyclohexanone peroxide species (Perhexa H, manufactured by NOF Corporation), methylcyclohexanone peroxide (Perhexa Q). , Manufactured by NOF Corporation), methylacetoacetate peroxide (Percure SA, manufactured by NOF Corporation), ketone peroxides such as acetylacetone peroxide (Percure A, manufactured by NOF Corporation), 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation), 1,1-bis (t-hexylperoxy) cyclohexane (Perhexa HC, NOF Corporation ), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 3M, manufactured by NOF Corporation, 1,1-bis (t-butylperoxy) cyclohexane (Perhexa C, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclododecane (Perhexa CD-R, manufactured by NOF Corporation), 2,2′-bis (t-butylperoxy) butane (Perhexa 22, manufactured by NOF Corporation), n-butyl 4,4-bis (t -Butylperoxy) valerate) Perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (Pertetra A, manufactured by NOF Corporation), etc. Peroxyketals, t-butyl hydroperoxide (Perbutyl H-69, manufactured by NOF Corporation), p-menthane hydroperoxide (Permenta H, manufactured by NOF Corporation), diisopropylbenzene hydroperoxide ( Pa Cumyl P, manufactured by NOF Corporation, 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Perk Mill H-80, NOF Corporation) Co., Ltd.), hydroperoxides such as t-hexyl hydroperoxide (Perhexyl H, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (Perhexin 25B, manufactured by NOF Corporation), di-t-butyl peroxide (Perbutyl DR, manufactured by NOF Corporation), t-butyl cumyl peroxy species (Perbutyl C, manufactured by NOF Corporation) ), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation), Dicumyl Peroxy species (Park Mill DR, manufactured by NOF Corporation), α, α'-bis (t-bu Dialkyl peroxides such as luperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation), octanoyl peroxy species (Perroyl O, manufactured by NOF Corporation), lauroyl peroxy species (Perroyl L, NOF Corporation) Co., Ltd.), stearoyl peroxy species (Perroyl S, manufactured by NOF Corporation), succinic acid peroxy species (Perloyl SA, manufactured by NOF Corporation), benzoyl peroxide (Nyper BW, NOF Corporation) )), Isobutyryl peroxide (Perroyl IB, manufactured by NOF Corporation), 2,4-dichlorobenzoyl peroxy species (Nyper CS, manufactured by NOF Corporation), 3,5,5-trimethylhexanoyl Diacyl peroxides such as peroxy species (Perroyl 355, manufactured by NOF Corporation), di-n-propyl peroxydicarbonate (Perroyl) NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (Perroyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, NOF Corporation) ), Di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by NOF Corporation), di-2-ethoxyhexyl peroxydicarbonate (Perloyl OPP, manufactured by NOF Corporation), Di-2-methoxybutyl peroxydicarbonate (Perroyl MBP, manufactured by NOF Corporation), di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perloyl SOP, manufactured by NOF Corporation), etc. Peroxydicarbonates, α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Nyper ND-R, JP Fatty Co., Ltd.), cumyl peroxyneodecanoate (Park Mill ND-R, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (Perocta ND-R) , Manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxyneodecanoate (percyclo ND-R, manufactured by NOF Corporation), t-hexylperoxyneodecanoate (perhexyl ND-) R, manufactured by NOF Corporation), t-butyl peroxyneodecanoate (perbutyl ND-R, manufactured by NOF Corporation), t-hexyl peroxypivalate (perhexyl PV, manufactured by NOF Corporation) ), T-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, NOF Corporation) Made) 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corporation), t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexanoate (perbutyl) O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF Corporation), t-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corporation), t-butylperoxy 3,5,5-trimethylhexanoate (Perbuthi 355, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane ( Perhexa 25MT, manufactured by NOF Corporation, t-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E, NOF Corporation) )), T-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF Corporation) T-butyl peroxyacetate (Perbutyl A, manufactured by NOF Corporation), t-butyl peroxy-m-toluoyl benzoate (Perbutyl ZT, manufactured by NOF Corporation) Peroxyesters such as t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation), bis (t-butylperoxy) isophthalate (Perbutyl IF, manufactured by NOF Corporation), t-butyl Peroxyallyl monocarbonate (Peromer AC, manufactured by NOF Corporation), t-butyltrimethylsilyl peroxide (Perbutyl SM, manufactured by NOF Corporation), 3,3′-4,4′-tetra (t-butyl) Peroxycarbonyl) benzophenone (BTTB-50, manufactured by NOF Corporation), 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, manufactured by NOF Corporation) and the like.

  Examples of the ionic initiator include 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2 -[N- (4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyphenyl) amidino] Propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, Wako Pure Chemical Industries, Ltd.) 2,2′-azobis [2- (N-allylamidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-amidinop) Pan) dihydrochloride (VA-50, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyethyl) amidino] propane} dihydrochloride (VA-558, Wako Pure) Yakuhin Kogyo Co., Ltd.), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries, Ltd.), 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (4,5, 6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (3,4) , 5,6-Tetrahydropyrimidine 2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2- Yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} Dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, manufactured by Wako Pure Chemical Industries, Ltd.) And anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries, Ltd.) and ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries, Ltd.).

  The initiator can be appropriately set in consideration of the molecular weight, molecular weight distribution, etc., but can be used in a normal amount, specifically, in 100 mol parts of the polymerizable unsaturated compound to be polymerized. On the other hand, it is usually used in an amount of 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

<Polymerization method using a thiol compound having a reactive silyl group and a metallocene compound>
It is preferable to use a metallocene compound as a metal catalyst and to react at 0 ° C. to 150 ° C. using a thiol compound having at least one reactive silyl group in the molecule. More preferably, it is particularly preferably set within the range of 25 ° C to 120 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 1 to 12 hours, preferably 2 It is preferable to set within a range of ˜8 hours.

  The metallocene compound is not particularly limited, and examples thereof include dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluoropheny. -1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophen-1-yl Dicyclopentadiene-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2 , 3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3 5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3 Titanocene compounds such as-(pyr-1-yl) -phen-1-yl; dicyclopentadienyl-Zr-dichloride, dicyclopentadiene-Zr-bisphenyl, dicyclopentadiene-Zr-bis-2,3 , 4,5,6-pentafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,5 , 6-trifluorophen-1-yl, dicyclopentadiene-Zr-bis-2,6-difluorophen-1-yl, dicyclopentadiene -Zr-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl- Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis Zirconocene compounds such as 2,6-difluoro-3- (pyr-1-yl) -phen-1-yl); dicyclopentadienyl-V-chloride, bismethylcyclopentadienyl-V-chloride, Bispentamethylcyclopentadienyl-V-chloride, dicyclopentadienyl-Ru-chloride, dicyclopentadienyl-Cr-chloro Can be mentioned. These may be used alone or in combination of two or more.

  The metallocene compound can be used in a usual catalytic amount. Specifically, it is usually 0.1 to 0.00001 mol part, preferably 100 to 100 mol part of the polymerizable unsaturated compound to be polymerized, preferably Used in an amount of 0.0001-0.00005 mol parts.

  The thiol compound having a reactive silyl group is not particularly limited. For example, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercapto Methyldimethylethoxysilane, mercaptomethyltripropoxysilane, mercaptomethylmethyldipropoxysilane, mercaptomethyldimethylpropoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxy Silane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysila , 3-mercaptopropyl - dimethyl mono silane, 3-mercaptopropyl - monomethyl diethoxy silane, 4-mercaptomethyl-butyl - trimethoxysilane and 3-mercaptopropyl butyl - and tri methoxy silane. These may be used alone or in combination of two or more.

  The amount of the thiol compound having a reactive silyl group can be appropriately set in consideration of the molecular weight of the polymer to be obtained, the polymerization rate, etc., but the reaction proceeds smoothly and does not cause the reaction to run away. The metallocene compound and the thiol compound having a reactive silyl group are usually used in a molar ratio within the range of 100: 1 to 1: 50000, preferably 10: 1 to 1: 10000.

<Radical polymerization using transition metal complex>
When using the radical polymerization method using a transition metal complex, it is preferable to make it react at 0 to 200 degreeC using a transition metal complex, an organic halide, and / or a ligand. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the addition-cleavage transfer reaction polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 30 minutes to 144. It is preferable to set the time, preferably within the range of 1 to 24 hours.

It does not specifically limit as said transition metal complex, For example, what is described in WO97 / 18247 can be utilized. Among these, a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel is preferable. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When using cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, if necessary, zero-valent copper, cuprous chloride Dicopper, cupric bromide, and cupric iodide can also be used.
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  When using a copper compound as a catalyst, the ligand described in WO97 / 18247 can be used as the ligand. Although not particularly limited, amine-based ligands are preferable, and bipyridyl compounds such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, hexamethyltriethylenetetraamine, bispicolylamine , Ligands such as aliphatic amines such as trialkylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine. In the present invention, among these, polyamine compounds, particularly aliphatic polyamines such as pentamethyldiethylenetriamine and hexamethyl (2-aminoethyl) amine are preferred. Moreover, when using a polyamine compound, a pyridine-type compound, or an aliphatic amine compound as a ligand in the case of using a copper compound as a catalyst, these ligands must have three or more amino groups. Is preferred. The amino group in the present invention represents a group having a nitrogen atom-carbon atom bond, and among these, a group in which a nitrogen atom is bonded only to a carbon atom and / or a hydrogen atom is preferable. The metallocene compounds listed above can also be used.

  The amount of the ligand as described above is determined from the number of coordination sites of the transition metal and the number of groups coordinated by the ligand under the conditions of normal atom transfer radical polymerization, so that they are almost equal. Is set to For example, the amount of 2,2'-bipyridyl and its derivatives added to CuBr is usually twice as much as the molar ratio, and in the case of pentamethyldiethylenetriamine, it is once as high as the molar ratio. In the present invention, when a ligand is added to initiate polymerization, and / or when a catalyst activity is controlled by adding a ligand, there is no particular limitation, but the metal atom is excessive relative to the ligand. Is preferred. The ratio between the coordination position and the coordinating group is preferably 1.2 times or more, more preferably 1.4 times or more, particularly preferably 1.6 times or more, and particularly preferably 2 times or more. It is.

As an initiator, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position) or a sulfonyl halide is used. Used.
If Specific _{examples, C 6 H 5 -CH 2 X} , C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2, XCH 2 - _{C 6 H 5 -CH 2 X,} XC (H) (CH 3) -C 6 H5-C (H) (CH 3) X ( where in the above _formula, C 6 _{H 5} is a phenyl group, X is chlorine , bromine or ^{_{iodine), R 3 -C (H)}} (X) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C, (H) (X) _{^{-C (O) R 4, R}} 3 -C (CH 3) (X) -C (O) R 4, R 3 -C 6 H 4 -SO 2 X ( ^wherein, R 3, ^{R 4} is a hydrogen atom Or a C1-C20 alkyl group, an aryl group, or an aralkyl group, X is chlorine, a bromine, or an iodine) etc. are mentioned.

  In radical polymerization methods using transition metal complexes, aluminum trial chelates such as triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-t-butoxyaluminum, trisec-butoxyaluminum and dioctyltin And divalent tin compounds such as diethylhexyltin and dibutyltin, and organic substances such as glucose and ascorbic acid can be used as additives for activating the polymerization.

  In the synthesis of the (meth) acrylic acid ester polymer, the polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene, xylene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketone solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, etc., nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ethyl acetate, butyl acetate, etc. Polyoxyalkylene polymers such as ester solvents, carbonate solvents such as ethylene carbonate and propylene carbonate, and the like can be mentioned, and these can be used alone or in admixture of two or more.

  Further, by using a polyoxyalkylene polymer, a saturated hydrocarbon polymer or the like as a solvent, a subsequent degassing step or the like can be eliminated.

  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 (5):
—CH ₂ —C (R ⁵ ) (COOR ⁶ ) — (5)
(Wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 8 carbon atoms) (meth) acrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms Unit and the following general formula (6):
—CH ₂ —C (R ⁵ ) (COOR ⁷ ) — (6)
(Wherein R ⁵ is the same as described above, and R ⁷ represents an alkyl group having 10 or more carbon atoms) and is a copolymer comprising a (meth) acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms. In this method, a polymer is blended with a polyoxyalkylene polymer having a crosslinkable silicon group.

As R ^{6 in the} general formula (5), for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc., 1 to 8, preferably 1 to 4, More preferred are 1 to 2 alkyl groups. The alkyl group of R ⁶ may alone, or may be a mixture of two or more.

R ^{7 in the} general formula (6) is, for example, a long-chain alkyl having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10 to 30, preferably 10 to 20 Group. The alkyl group of R ⁷ is similar to the case of R ^6, alone may or may be a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based copolymer is substantially composed of monomer units of the formulas (5) and (6), and the term “substantially” here refers to the copolymer. It means that the total of the monomer units of the formula (5) and the formula (6) present therein exceeds 50% by mass. The total of the monomer units of the formula (5) and the formula (6) is preferably 70% by mass or more.

  The abundance ratio of the monomer unit of formula (5) and the monomer unit of formula (6) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, in terms of mass ratio.

  Examples of monomer units other than those represented by formulas (5) and (6) that may be contained in the copolymer include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; acrylamide and methacrylamide , N-methylol acrylamide, amide groups such as N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, monomers containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitriles, Examples thereof include monomer units derived from styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

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

  In the present invention, the curing catalyst for the component (B) is a compound of one or more metals selected from the group consisting of metals other than tin, and an α- or β-ketoalcohol residue is bonded to the metal. A metal compound in which the α carbon is saturated carbon is used. These catalysts function as a curing catalyst for the organic polymer as component (A). Conventionally, organic tin compounds such as dibutyltin dilaurate and dibutyltin bisacetylacetonate have been used as curing catalysts for organic polymers having a crosslinkable silicon group as component (A). ), A curable composition having improved storage stability while maintaining sufficiently practical curability and adhesiveness while being a non-organotin catalyst can be obtained.

As said (B) metal compound, the metal compound represented by following formula (7) is used suitably, for example.
MZx (OR ⁸ ) y (7)

In the formula (7), M represents a metal atom selected from metals other than tin, preferably titanium, aluminum, zirconium, niobium, vanadium, or tantalum, and more preferably titanium, aluminum, or zirconium. Z is an alkoxide group represented by the following formula (8), and when there are a plurality of Z, they may be the same or different. R ⁸ is a substituted or unsubstituted organic group having 1 to 30 carbon atoms, wherein —OR ⁸ represents a group that is not a residue of α- or β-ketoalcohol, and R ⁸ is preferably an isopropyl group. If -OR ⁸ groups are a plurality, it may be the same or different and a plurality of -OR ⁸ groups together may be made to the polyol residue, at least one of -OR ⁸ carbon It is preferable that it is a C1-C30 alkoxy group.

  In the formula (7), x and y are numbers satisfying the valence of x + y = metal atom M, the average value of x in the composition is a positive number, and the average value of y in the composition is 0. Or it is a positive number. In addition, the valence of titanium and zirconium is 4, and the valence of aluminum is 3. In this invention, 0.1-4.0 are preferable and, as for the average value of x in a composition, 0.3-3.0 are more preferable.

In the formula (8), R ⁹ represents a hydrogen atom or a substituted or unsubstituted organic group having 1 to 30 carbon atoms, and two R ⁹ may be the same or different. R ¹⁰ represents a hydrogen atom or a substituted or unsubstituted organic group having 1 to 30 carbon atoms, and two R ¹⁰ may be the same or different. R ¹¹ represents a substituted or unsubstituted organic group having 1 to 30 carbon atoms, preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 30 carbon atoms, and further preferably an ethoxy group. n represents 0 or 1, and n is preferably 0.

One of R ^{9 in} the formula (8) is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and the other of R ⁹ is preferably a methyl group or a substituted methyl group. . The substituent of the substituted methyl group is preferably an ethoxycarbonyl group (—C (═O) OC ₂ H ₅ ), or an ethoxycarbonyl group (—C (═O) OC ₂ H ₅ ) and a hydroxyl group. is there. In addition, one of R ^{9 in} the formula (8) is an ethoxycarbonyl group (—C (═O) OC ₂ H ₅ ), and the other of R ⁹ is a methyl group (—CH ₂ C) substituted with an ethoxycarbonyl group. (= O) OC ₂ H ₅ ) is preferred.

  The method for producing the metal compound used for the (B) curing catalyst is not particularly limited, but at least one selected from the group consisting of titanium alkoxide, aluminum alkoxide, zirconium alkoxide, niobium alkoxide, vanadium alkoxide and tantalum alkoxide. A reaction product obtained by reacting a metal alkoxide with one or more hydroxycarboxylic acid esters is preferred.

  The (B) curing catalyst is preferably a titanium compound in which a residue of α- or β-keto alcohol is bonded to a titanium atom, and the α carbon is a saturated carbon. As the titanium compound, a reaction product obtained by reacting at least a titanium alkoxide and a hydroxycarboxylic acid ester is preferable, and a reaction product obtained by reacting at least a titanium alkoxide and an α-hydroxycarboxylic acid ester is more preferable from the viewpoint of curability. preferable. The (B) curing catalyst is preferably an aluminum compound in which an α- or β-ketoalcohol residue is bonded to an aluminum atom and the α carbon is a saturated carbon. The aluminum compound is preferably a reaction product obtained by reacting at least an aluminum alkoxide and a hydroxycarboxylic acid ester, and a reaction product obtained by reacting at least an aluminum alkoxide and an α-hydroxycarboxylic acid ester is more preferable from the viewpoint of curability. preferable.

  Examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraallyl oxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetraisobutoxide, and titanium tetra sec. -Butoxide, titanium tetra-t-butoxide, titanium tetra n-pentyl oxide, titanium tetracyclopentyl oxide, titanium tetrahexyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, titanium tetraoctyl oxide, titanium tetrakis (2-ethylhexyl oxide), Titanium tetradecyl oxide, titanium tetradodecyl oxide, Titanium tetrastearyl oxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyl oxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolato), titanium bis (2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolato), titanium tetrakis (2-chloroethoxide), titanium tetrakis (2-bromoethoxide), titanium tetrakis (2-methoxyethoxide), titanium tetrakis (2-ethoxy) Ethoxide), titanium butoxide trimethoxide, titanium dibutoxide dimethoxide, titanium butoxide triethoxide, titanium dibutoxide diethoxide, titanium butoxide triisopropoxide, titanium Nium dibutoxide diisopropoxide, titanium tetraphenoxide, titanium tetrakis (o-chlorophenoxide), titanium tetrakis (m-nitrophenoxide), titanium tetrakis (p-methylphenoxide), titanium tetrakis (trimethylsilyloxide), etc. . These may be used alone or in combination. Among these, a titanium alkoxide containing an alkoxide group having 1 to 12 carbon atoms is preferable, and a titanium alkoxide containing an alkoxide group having 1 to 6 carbon atoms is more preferable. From the viewpoints of easy handling, availability, and curability, titanium. Tetraisopropoxide, titanium tetra n-butoxide, and titanium tetra t-butoxide are most preferred.

  Examples of the aluminum alkoxide include aluminum trimethoxide, aluminum triethoxide, aluminum triallyl oxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum triisobutoxide, aluminum trisec. -Butoxide, aluminum tri-t-butoxide, aluminum tri-n-pentyl oxide, aluminum tricyclopentyl oxide, aluminum trihexyl oxide, aluminum tricyclohexyl oxide, aluminum tribenzyl oxide, aluminum trioctyl oxide, aluminum tris (2-ethylhexyl oxide), Aluminum tridecyl oxide, aluminum tridodecyloxy , Aluminum tristearyl oxide, aluminum tributoxide dimer, aluminum tris (8-hydroxyoctyl oxide), aluminum isopropoxide bis (2-ethyl-1,3-hexanediolato), aluminum diisopropoxide (2-ethyl- 1,3-hexanediolato), aluminum (2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolato), aluminum bis (2-ethylhexyloxy) (2-ethyl-1,3-hexanediol) Lato), aluminum tris (2-chloroethoxide), aluminum tris (2-bromoethoxide), aluminum tris (2-methoxyethoxide), aluminum tris (2-ethoxyethoxide), aluminum butoxide dimethoxide, aluminum Minium methoxide dibutoxide, aluminum butoxide diethoxide, aluminum ethoxide dibutoxide, aluminum butoxide diisopropoxide, aluminum isopropoxide dibutoxide, aluminum triphenoxide, aluminum tris (o-chlorophenoxide), aluminum tris (m-nitrophenoxide) , Aluminum tris (p-methylphenoxide), and the like. These may be used alone or in combination.

  Examples of the zirconium alkoxide include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraallyl oxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, zirconium tetraisobutoxide, zirconium tetra sec. -Butoxide, zirconium tetra-t-butoxide, zirconium tetra n-pentyl oxide, zirconium tetracyclopentyl oxide, zirconium tetrahexyl oxide, zirconium tetracyclohexyl oxide, zirconium tetrabenzyl oxide, zirconium tetraoctyl oxide, zirconium tetrakis (2-ethylhexyl oxide), Zirconium tetradecyloxy Zirconium tetradodecyl oxide, zirconium tetrastearyl oxide, zirconium tetrabutoxide dimer, zirconium tetrakis (8-hydroxyoctyl oxide), zirconium diisopropoxide bis (2-ethyl-1,3-hexanediolato), zirconium bis ( 2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolato), zirconium tetrakis (2-chloroethoxide), zirconium tetrakis (2-bromoethoxide), zirconium tetrakis (2-methoxyethoxide), Zirconium tetrakis (2-ethoxyethoxide), zirconium butoxide trimethoxide, zirconium dibutoxide dimethoxide, zirconium butoxide triethoxide, zirconium di Toxide diethoxide, zirconium butoxide triisopropoxide, zirconium dibutoxide diisopropoxide, zirconium tetraphenoxide, zirconium tetrakis (o-chlorophenoxide), zirconium tetrakis (m-nitrophenoxide), zirconium tetrakis (p-methylphenoxide) , Etc. These may be used alone or in combination.

  Examples of the niobium alkoxide include niobium pentamethoxide, niobium pentaethoxide, niobium pentalyl oxide, niobium penta n-propoxide, niobium pentaisopropoxide, niobium penta n-butoxide, niobium pentaisobutoxide, niobium penta sec-butoxide, Niobium penta-toxide, niobium penta-n-pentyl oxide, niobium pentacyclopentyl oxide, niobium pentahexyl oxide, niobium pentacyclohexyl oxide, niobium pentabenzyl oxide, niobium pentaoctyl oxide, niobium penta (2-ethylhexyl oxide), niobium pentadecyl oxide, niobium Pentadodecyl oxide, niobium pentastearyl oxide, niobium pentaboxide dimer, niobium penta ( -Hydroxyoctyl oxide), niobium diisopropoxide bis (2-ethyl-1,3-hexanediolato), niobiumbis (2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolato), niobium penta ( 2-chloroethoxide), niobium penta (2-bromoethoxide), niobium penta (2-methoxyethoxide), niobium penta (2-ethoxyethoxide), niobium butoxide tetramethoxide, niobium dibutoxide trimethoxide, niobium butoxide tetra Ethoxide, niobium dibutoxide triethoxide, niobium butoxide tetraisopropoxide, niobium tetrabutoxide diisopropoxide, niobium pentaphenoxide, niobium penta (o-chlorophenoxide), niobium penta (m-nitrophenoxide) Niobium pentakis (p- methyl phenoxide), and the like. These may be used alone or in combination.

  Examples of the vanadium alkoxide include vanadium pentamethoxide, vanadium pentaethoxide, vanadium pentalyl oxide, vanadium penta n-propoxide, vanadium pentaisopropoxide, vanadium penta n-butoxide, vanadium pentaisobutoxide, vanadium penta sec. -Butoxide, vanadium penta-toxide, vanadium penta-n-pentyl oxide, vanadium pentacyclopentyl oxide, vanadium pentahexyl oxide, vanadium pentacyclohexyl oxide, vanadium pentabenzyl oxide, vanadium pentaoctyl oxide, vanadium penta (2-ethylhexyl oxide), Vanadium pentadecyl oxide, vanadium pentadodecyl oxide, vanadium Palladium pentastearyl oxide, vanadium pentaboxide dimer, vanadium penta (8-hydroxyoctyl oxide), vanadium diisopropoxide bis (2-ethyl-1,3-hexanediolato), vanadium bis (2-ethylhexyloxy) bis ( 2-ethyl-1,3-hexanediolato), vanadium penta (2-chloroethoxide), vanadium penta (2-bromoethoxide), vanadium penta (2-methoxyethoxide), vanadium penta (2-ethoxyethoxy) ), Vanadium butoxide tetramethoxide, vanadium dibutoxide trimethoxide, vanadium butoxide tetraethoxide, vanadium dibutoxide triethoxide, vanadium butoxide tetraisopropoxide, vanadium teto Butoxy blunder isopropoxide, vanadium penta phenoxide, vanadium penta (o-chloro phenoxide), vanadium penta (m-nitrophenoxide), vanadium pentakis (p- methyl phenoxide), and the like. These may be used alone or in combination.

  Examples of the tantalum alkoxide include tantalum pentamethoxide, tantalum pentaethoxide, tantalum pentalyl oxide, tantalum penta n-propoxide, tantalum pentaisopropoxide, tantalum penta n-butoxide, tantalum pentaisobutoxide, tantalum penta sec. -Butoxide, tantalum penta-tert-butoxide, tantalum penta-n-pentyl oxide, tantalum pentacyclopentyl oxide, tantalum pentahexyl oxide, tantalum pentacyclohexyl oxide, tantalum pentabenzyl oxide, tantalum pentaoctyl oxide, tantalum penta (2-ethylhexyl oxide), Tantalum pentadecyl oxide, Tantalum pentadodecyl oxide, Tantalum pentastearyl oxide, Tanta Pentaboxide dimer, tantalum penta (8-hydroxyoctyl oxide), tantalum diisopropoxide bis (2-ethyl-1,3-hexanediolato), tantalum bis (2-ethylhexyloxy) bis (2-ethyl-1,3) -Hexanediolato), tantalum penta (2-chloroethoxide), tantalum penta (2-bromoethoxide), tantalum penta (2-methoxyethoxide), tantalum penta (2-ethoxyethoxide), tantalum butoxide tetramethoxy Tantalum dibutoxide trimethoxide, tantalum butoxide tetraethoxide, tantalum dibutoxide triethoxide, tantalum butoxide tetraisopropoxide, tantalum tetrabutoxide diisopropoxide, tantalum pentaphenoxide, tantalum Printer (o-chloro phenoxide), tantalum penta (m-nitrophenoxide), tantalum pentakis (p- methyl phenoxide), and the like. These may be used alone or in combination.

As the hydroxycarboxylic acid ester, both α-hydroxylcarboxylic acid ester and β-hydroxylcarboxylic acid ester can be used, and α-hydroxylcarboxylic acid ester is more preferable.
Examples of the α-hydroxylcarboxylic acid ester include methyl hydroxyacetate, ethyl hydroxyacetate, benzyl hydroxyacetate, butyl hydroxyacetate, sec-butyl hydroxyacetate, tert-butyl hydroxyacetate, hexyl hydroxyacetate, propyl hydroxyacetate, hydroxy Isopropyl acetate, heptyl hydroxyacetate, isoamyl hydroxyacetate, 3-methylpentyl hydroxyacetate, 2-methylpentyl hydroxyacetate, 1-methylpentyl hydroxyacetate, octyl hydroxyacetate, nonyl hydroxyacetate, decyl hydroxyacetate, dodecyl hydroxyacetate, hydroxyacetic acid Hydroxyacetic acid alkyl esters such as stearyl; hydroxyacetic acid aryls such as hydroxyacetic acid phenyl and hydroxyacetic acid benzyl Esters: methyl lactate, ethyl lactate, benzyl lactate, butyl lactate, sec-butyl lactate, tert-butyl lactate, hexyl lactate, propyl lactate, isopropyl lactate, heptyl lactate, isoamyl lactate, 3-methylpentyl lactate, 2-methyl lactate Lactic acid alkyl esters such as pentyl, 1-methylpentyl lactate, octyl lactate, nonyl lactate, decyl lactate, dodecyl lactate, hexadecyl lactate, stearyl lactate; lactate aryl esters such as phenyl lactate and benzyl lactate; 2-hydroxylbutyric acid Methyl, ethyl 2-hydroxybutyrate, benzyl 2-hydroxybutyrate, butyl 2-hydroxybutyrate, sec-butyl 2-hydroxybutyrate, tert-butyl 2-hydroxybutyrate, hexyl 2-hydroxybutyrate, 2-hydroxybutyrate pro Pills, isopropyl 2-hydroxybutyrate, heptyl 2-hydroxybutyrate, isoamyl 2-hydroxybutyrate, 2-methylpentyl 2-hydroxybutyrate, 2-methylpentyl 2-hydroxybutyrate, 2-methylpentyl 2-hydroxybutyrate, 2-hydroxyl 2-hydroxylbutyric acid alkyl esters such as octyl butyrate, nonyl 2-hydroxylbutyrate, decyl 2-hydroxylbutyrate, dodecyl 2-hydroxylbutyrate, hexadecyl 2-hydroxylbutyrate, stearyl 2-hydroxylbutyrate; phenyl 2-hydroxylbutyrate, 2 2-arylbutyric acid aryl esters such as benzyl hydroxylbutyrate; methyl 2-hydroxyvalerate, ethyl 2-hydroxyvalerate, benzyl 2-hydroxyvalerate, butyric 2-hydroxyvalerate Sec-butyl 2-hydroxyvalerate, tert-butyl 2-hydroxyvalerate, hexyl 2-hydroxyvalerate, propyl 2-hydroxyvalerate, isopropyl 2-hydroxyvalerate, heptyl 2-hydroxyvalerate, 2- Isoamyl hydroxyvalerate, 2-methylpentyl 2-hydroxyvalerate, 2-methylpentyl 2-hydroxyvalerate, 2-methylpentyl 2-hydroxyvalerate, octyl 2-hydroxyvalerate, nonyl 2-hydroxyvalerate, 2 2-hydroxyvalerate alkyl esters such as decyl hydroxyvalerate, dodecyl 2-hydroxyvalerate, hexadecyl 2-hydroxyvalerate, stearyl 2-hydroxyvalerate; phenyl 2-hydroxyvalerate, 2-hydroxyvalerate 2-hydroxy licorice like benzyl Aryl esters; methyl 3-methyl-2-hydroxyvalerate, ethyl 3-methyl-2-hydroxyvalerate, benzyl 3-methyl-2-hydroxyvalerate, butyl 3-methyl-2-hydroxyvalerate, 3- Sec-butyl methyl-2-hydroxyvalerate, tert-butyl 3-methyl-2-hydroxyvalerate, hexyl 3-methyl-2-hydroxyvalerate, propyl 3-methyl-2-hydroxyvalerate, 3-methyl Isopropyl-2-hydroxyvalerate, heptyl 3-methyl-2-hydroxyvalerate, isoamyl 3-methyl-2-hydroxyvalerate, 3-methylpentyl 3-methyl-2-hydroxyvalerate, 3-methyl-2- 2-methylpentyl hydroxyvalerate, 1-methylpentyl 3-methyl-2-hydroxyvalerate, 3-methyl-2 -Octyl hydroxyvalerate, nonyl 3-methyl-2-hydroxyvalerate, decyl 3-methyl-2-hydroxyvalerate, dodecyl 3-methyl-2-hydroxyvalerate, hexadecyl 3-methyl-2-hydroxyvalerate, 3-methyl-2-hydroxyvalerate alkyl esters such as stearyl 3-methyl-2-hydroxyvalerate; phenyl 3-methyl-2-hydroxyvalerate, benzyl 3-methyl-2-hydroxyvalerate, etc. 3-methyl-2-hydroxyvaleric acid aryl esters; methyl 2-hydroxyhexylate, ethyl 2-hydroxyhexylate, benzyl 2-hydroxyhexylate, butyl 2-hydroxyhexylate, sec-butyl 2-hydroxyhexylate, Tert-butyl 2-hydroxyhexylate, 2-hydroxy Hexyl xylate, propyl 2-hydroxyhexylate, isopropyl 2-hydroxyhexylate, heptyl 2-hydroxyhexylate, isoamyl 2-hydroxyhexylate, 3-methylpentyl 2-hydroxyhexylate, 2-hydroxyhexylate 2- Methylpentyl, 1-methylpentyl 2-hydroxyhexylate, octyl 2-hydroxyhexylate, nonyl 2-hydroxyhexylate, decyl 2-hydroxyhexylate, dodecyl 2-hydroxyhexylate, hexadecyl 2-hydroxyhexylate, 2- 2-hydroxyhexylic acid alkyl esters such as stearyl hydroxyhexylate; 2-hydroxyhexyl acid aryl esters such as phenyl 2-hydroxyhexylate and benzyl 2-hydroxyhexylate Methyl leucine, ethyl leucine, benzyl leucine, butyl leucine, sec-butyl leucine, tert-butyl leucine, hexyl leucine, propyl leucine, isopropyl leucine, heptyl leucine, isoamyl leucine, leucine Leucic acid alkyl esters such as 3-methylpentyl acid, 2-methylpentyl leucine, 1-methylpentyl leucine, octyl leucine, nonyl leucine, decyl leucine, dodecyl leucine, hexadecyl leucine, stearyl leucine Leucic acid aryl esters such as phenyl leucine and benzyl leucine; dimethyl malate, diethyl malate, dibenzyl malate, dibutyl malate, di-sec-butyl malate, malic acid Ditert-butyl, dihexyl malate, dipropyl malate, diisopropyl malate, diheptyl malate, diisoamyl malate, di-3-methylpentyl malate, di-2-methylpentyl malate, di-1-methylpentyl malate Dioctyl malate, dinonyl malate, didecyl malate, didodecyl malate, malate dialkyl esters such as distearyl malate; diphenyl malate, malate diaryl esters such as dibenzyl malate; trimethyl citrate, Triethyl citrate, tribenzyl citrate, tributyl citrate, tri-sec-butyl citrate, tri-tert-butyl citrate, trihexyl citrate, tripropyl citrate, trisopropyl citrate, triheptyl citrate, citrate Quench such as Soamyl, Tri 3-methylpentyl citrate, Tri 2-methylpentyl citrate, Tri 1-methylpentyl citrate, Trioctyl citrate, Trinonyl citrate, Tridecyl citrate, Tridodecyl citrate, Tristearyl citrate Acid trialkyl esters; citric acid triaryl esters such as triphenyl citrate, tribenzyl citrate; trimethyl isocitrate, triethyl isocitrate, tribenzyl isocitrate, tributyl isocitrate, trisec-butyl isocitrate, tricitrate tricitrate tert-butyl, trihexyl isocitrate, tripropyl isocitrate, trisopropyl isocitrate, triheptyl isocitrate, trisoamyl isocitrate, tri-3-methylpentyl isocitrate Isocitrate trialkyl esters such as tri-2-methylpentyl isocitrate, tri-1-methylpentyl isocitrate, trioctyl isocitrate, trinonyl isocitrate, tridecyl isocitrate, tridodecyl isocitrate, tristearyl isocitrate; , Isocitrate triaryl esters such as tribenzyl isocitrate; dimethyl tartrate, diethyl tartrate, dibenzyl tartrate, dibutyl tartrate, disec-butyl tartrate, ditert-butyl tartrate, dihexyl tartrate, dipropyl tartrate, diisopropyl tartrate, tartaric acid Diheptyl, diisoamyl tartrate, di-3-methylpentyl tartrate, di-2-methylpentyl tartrate, di-1-methylpentyl tartrate, dioctyl tartrate, dinonyl tartrate, Examples include dialkyl tartrate such as didecyl tartrate, didodecyl tartrate, dihexadecyl tartrate and distearyl tartrate; diaryl tartrate such as diphenyl tartrate and dibenzyl tartrate. These may be used alone or in combination. Among these, lactic acid ester, malic acid ester, and citrate ester are preferable, and ethyl lactate, diethyl malate, and triethyl citrate are more preferable from the viewpoint of availability and catalytic activity.

  Examples of the β-hydroxylcarboxylic acid ester include methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, benzyl 3-hydroxypropionate, butyl 3-hydroxypropionate, sec-butyl 3-hydroxypropionate, Tert-butyl hydroxypropionate, hexyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, heptyl 3-hydroxypropionate, soamyl 3-hydroxypropionate, 3-hydroxypropionic acid 3 -Methylpentyl, 3-methylpentyl 3-hydroxypropionate, 1-methylpentyl 3-hydroxypropionate, octyl 3-hydroxypropionate, noni-3-hydroxypropionate 3-hydroxypropionic acid alkyl esters such as 3-decyl 3-hydroxypropionate, dodecyl 3-hydroxypropionate, stearyl 3-hydroxypropionate; 3 such as phenyl 3-hydroxypropionate, benzyl 3-hydroxypropionate -Hydroxypropionic acid aryl esters; methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate, benzyl 3-hydroxybutyrate, butyl 3-hydroxybutyrate, sec-butyl 3-hydroxybutyrate, tert-butyl 3-hydroxybutyrate, 3- Hexyl hydroxybutyrate, propyl 3-hydroxybutyrate, sopropyl 3-hydroxybutyrate, heptyl 3-hydroxybutyrate, soamyl amyl 3-hydroxybutyrate, 3-methylpentyl 3-hydroxybutyrate, 3-methylbutyric acid 3-hydroxybutyric acid alkyl esters such as tilpentyl, 1-methylpentyl 3-hydroxybutyrate, octyl 3-hydroxybutyrate, nonyl 3-hydroxybutyrate, decyl 3-hydroxybutyrate, dodecyl 3-hydroxybutyrate, stearyl 3-hydroxybutyrate 3-hydroxybutyric acid aryl esters such as phenyl 3-hydroxybutyrate and benzyl 3-hydroxybutyrate; methyl 3-hydroxyvalerate, ethyl 3-hydroxyvalerate, benzyl 3-hydroxyvalerate, butyl 3-hydroxyvalerate Sec-butyl 3-hydroxyvalerate, tert-butyl 3-hydroxyvalerate, hexyl 3-hydroxyvalerate, propyl 3-hydroxyvalerate, propyl 3-hydroxyvalerate, heptyl 3-hydroxyvalerate, 3- Hydroxyvalerate Mill, 3-methylpentyl 3-hydroxyvalerate, 3-methylpentyl 3-hydroxyvalerate, 1-methylpentyl 3-hydroxyvalerate, octyl 3-hydroxyvalerate, nonyl 3-hydroxyvalerate, 3-hydroxyvalerate 3-hydroxyvaleric alkyl esters such as decyl herbate, 3-hydroxydodecyl valerate, stearyl 3-hydroxyvalerate; aryl 3-hydroxyvalerates such as phenyl 3-hydroxyvalerate, benzyl 3-hydroxyvalerate Esters; methyl 3-hydroxyhexanoate, ethyl 3-hydroxyhexanoate, benzyl 3-hydroxyhexanoate, butyl 3-hydroxyhexanoate, sec-butyl 3-hydroxyhexanoate, tert-butyl 3-hydroxyhexanoate, 3 -To hydroxyhexanoic acid Sil, 3-hydroxyhexanoic acid propyl, 3-hydroxyhexanoic acid sopropyl, 3-hydroxyhexanoic acid heptyl, 3-hydroxyhexanoic acid soamyl, 3-hydroxyhexanoic acid 3-methylpentyl, 3-hydroxyhexanoic acid 3-methylpentyl, 3-hydroxyhexyl such as 1-methylpentyl 3-hydroxyhexanoate, octyl 3-hydroxyhexanoate, nonyl 3-hydroxyhexanoate, decyl 3-hydroxyhexanoate, dodecyl 3-hydroxyhexanoate, stearyl 3-hydroxyhexanoate Hexanoic acid alkyl esters; 3-hydroxyhexanoic acid aryl esters such as phenyl 3-hydroxyhexanoate and benzyl 3-hydroxyhexanoate; methyl 3-hydroxyisobutyrate, ethyl 3-hydroxyisobutyrate Chill, benzyl 3-hydroxyisobutyrate, butyl 3-hydroxyisobutyrate, sec-butyl 3-hydroxyisobutyrate, tert-butyl 3-hydroxyisobutyrate, hexyl 3-hydroxyisobutyrate, propyl 3-hydroxyisobutyrate, 3 -Sopropyl hydroxyisobutyrate, heptyl 3-hydroxyisobutyrate, soamyl amyl 3-hydroxyisobutyrate, 3-methylpentyl 3-hydroxyisobutyrate, 3-methylpentyl 3-hydroxyisobutyrate, 1-methylpentyl 3-hydroxyisobutyrate, 3-hydroxyisobutyric acid alkyl esters such as octyl 3-hydroxyisobutyrate, nonyl 3-hydroxyisobutyrate, decyl 3-hydroxyisobutyrate, dodecyl 3-hydroxyisobutyrate, stearyl 3-hydroxyisobutyrate; Butyric acid fe , 3-hydroxyisobutyric aryl esters such as benzyl 3-hydroxyisobutyrate; methyl 3-hydroxyisovalerate, ethyl 3-hydroxyisovalerate, benzyl 3-hydroxyisovalerate, 3-hydroxyisovaleric acid Butyl, sec-butyl 3-hydroxyisovalerate, tert-butyl 3-hydroxyisovalerate, hexyl 3-hydroxyisovalerate, propyl 3-hydroxyisovalerate, sopropyl 3-hydroxyisovalerate, 3-hydroxy Heptyl isovalerate, soamyl amyl 3-hydroxyisovalerate, 3-methylpentyl 3-hydroxyisovalerate, 3-methylpentyl 3-hydroxyisovalerate, 1-methylpentyl 3-hydroxyisovalerate, 3-hydroxyiso Octyl valerate, nonyl 3-hydroxyisovalerate 3-hydroxyisovaleric acid alkyl esters such as decyl 3-hydroxyisovalerate, dodecyl 3-hydroxyisovalerate, stearyl 3-hydroxyisovalerate; phenyl 3-hydroxyisovalerate, 3-hydroxyisovaleric acid 3-hydroxyisovaleric acid aryl esters such as benzyl; methyl 3-hydroxyoctylate, ethyl 3-hydroxyoctylate, benzyl 3-hydroxyoctylate, butyl 3-hydroxyoctylate, sec-butyl 3-hydroxyoctylate Tert-butyl 3-hydroxyoctylate, hexyl 3-hydroxyoctylate, propyl 3-hydroxyoctylate, propyl 3-hydroxyoctylate, heptyl 3-hydroxyoctylate, soamyl 3-hydroxyoctylate, 3-hydroxy 3-methylpentyl thiooctylate, 3-methylpentyl 3-hydroxyoctylate, 1-methylpentyl 3-hydroxyoctylate, octyl 3-hydroxyoctylate, nonyl 3-hydroxyoctylate, decyl 3-hydroxyoctylate, 3- 3-hydroxyoctyl acid alkyl esters such as dodecyl hydroxyoctylate and stearyl 3-hydroxyoctylate; 3-hydroxyoctylate aryl esters such as phenyl 3-hydroxyoctylate and benzyl 3-hydroxyoctylate; Hydroxy 2- (hydroxymethyl) methyl acrylate, 3-hydroxy 2- (hydroxymethyl) ethyl acrylate, 3-hydroxy 2- (hydroxymethyl) acrylate benzyl, 3-hydroxy 2- (hydroxymethyl) a Butyl yllate, sec-butyl 3-hydroxy-2- (hydroxymethyl) acrylate, tert-butyl 3-hydroxy-2- (hydroxymethyl) acrylate, hexyl 3-hydroxy-2- (hydroxymethyl) acrylate, 3- Hydroxy 2- (hydroxymethyl) propyl acrylate, 3-hydroxy 2- (hydroxymethyl) sopropyl acrylate, 3-hydroxy 2- (hydroxymethyl) heptyl acrylate, soamyl 3-hydroxy 2- (hydroxymethyl) acrylate, 3-hydroxypentyl 3-hydroxy-2- (hydroxymethyl) acrylate, 3-methylpentyl 3-hydroxy-2- (hydroxymethyl) acrylate, 1-methylpentyl 3-hydroxy-2- (hydroxymethyl) acrylate, 3- Hydroxy 2- (hydride 2- (hydroxymethyl) acrylic acid (xymethyl) acrylate, nonyl 3-hydroxy-2- (hydroxymethyl) acrylate, decyl 3-hydroxy-2- (hydroxymethyl) acrylate, dodecyl 3-hydroxy-2- (hydroxymethyl) acrylate 3-hydroxy 2- (hydroxymethyl) acrylic acid alkyl esters such as stearyl of 3-hydroxy 2- (hydroxymethyl) acrylate; phenyl 3-hydroxy 2- (hydroxymethyl) acrylate, 3-hydroxy 2- ( And 3-hydroxy 2- (hydroxymethyl) acrylic acid aryl esters such as hydroxymethyl) benzyl acrylate. These may be used alone or in combination.

  The reaction conditions for reacting the metal alkoxide with the hydroxycarboxylic acid ester are not particularly limited, but the reaction is performed at a reaction temperature of −20 ° C. to 120 ° C., preferably 0 ° C. to 80 ° C. for 5 minutes to 100 hours. Is preferred. If it is carried out below -20 ° C, the reaction takes a long time and the production efficiency is poor. If the temperature exceeds 120 ° C., side reactions may occur, which is not preferable.

  (B) The usage-amount of a component is 0.1-20 mass parts with respect to 100 mass parts of (A) component, 0.5-10 mass parts is more preferable, About 2-8 mass parts is especially preferable. . When the blending amount of component (B) is below this range, a practical curing rate may not be obtained, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (B) exceeds this range, the pot life tends to be too short and the workability tends to deteriorate.

  In the present invention, the above-described metal compound is used as a curing catalyst, but other curing catalysts can be used in combination to the extent that the effects of the present invention are not reduced. Other curing catalysts include, for example, carboxylic acid metal salts such as tin 2-ethylhexanoate, tin versatate, bismuth 2-ethylhexanoate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyl Tin bis (2-ethylhexanoate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (Tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide) ), Dibutenyl tin Tetravalent organotin compounds such as oxides, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester Is mentioned. However, the toxicity of the resulting curable composition may increase depending on the amount of the organotin compound added.

  A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride Examples include fillers such as resin organic microballoons, PVC powder, PMMA powder, and the like; fibrous fillers such as asbestos, glass fibers, and filaments. When using a filler, the usage-amount is preferable 1-250 mass parts with respect to 100 mass parts of polymer of (A) component, More preferably, it is 10-200 mass parts.

  As described in JP-A No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, sealed in a bag made of an airtight material, and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved particularly when a one-component composition is used.

  Further, when obtaining a highly transparent composition, as described in JP-A-11-302527, polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as fillers. Further, as described in JP-A-2000-38560, a composition having high transparency can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler. Obtainable. The surface of silicon dioxide fine powder is generally a silanol group (-SiOH), and (-SiO-hydrophobic group) is generated by reacting organosilanide or alcohol with this silanol group. What is made is hydrophobic silica. Specifically, dimethyl siloxane, hexamethyldisilazane, dimethyl dichloro sealing material, remethoxy octyl sealing material, limethyl silane, and the like are reactively bonded to silanol groups present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.

  When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and if used in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the organic polymer (A) having a crosslinkable silicon group. Favorable results are obtained. In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in a range of 5 to 200 parts by mass with respect to 100 parts by mass of the organic polymer (A) having a crosslinkable silicon group, preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

  In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  An adhesiveness imparting agent can be added to the composition of the present invention. Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; Methyldimethoxy sealing material, Limethoxysilane, Methyldi Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product will be high, and if it is too low, the adhesiveness will be lowered. Therefore, 0.1 to 100 parts by mass of the polymer having all crosslinkable silicon groups. It is preferable to add 15 parts by mass, and more preferably 0.5 to 10 parts by mass.

  A tackifier can be added to the composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resins, xylene-phenolic resins, cyclohexane. Pentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9) Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin and the like. These may be used alone or in combination of two or more. Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifying resins may be used alone or in combination of two or more.

  The tackifying resin is preferably used in an amount of 5 to 1,000 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the (A) organic polymer.

  A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

  Of these polymer plasticizers, those compatible with the polymer of component (A) are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, it is measured by molecular weight distribution (Mw / Mn) GPC method (polystyrene conversion).

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

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

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

You may add the compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by a hydrolysis as needed to the curable composition of this invention. This compound has the effect of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mention | raise | lifted. In addition, derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, which generate a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029 Examples thereof include a compound of a polyhydric alcohol having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol, or sorbitol, which generates a silicon compound that generates R3SiOH such as trimethylsilanol by hydrolysis.

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

  The compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis is 0.1-20 mass parts with respect to 100 mass parts of organic polymers (A) which have a crosslinkable silicon group, Preferably it is 0. Used in the range of 5 to 10 parts by mass.

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

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

  A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. A photocurable substance is a substance that undergoes a chemical change in its molecular structure in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toa Gosei Kagaku Kogyo Co., Ltd.) Polyvinylcinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group and polyvinyl alcohol esterified with cinnamic acid. Many polyvinyl cinnamate derivatives are exemplified. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect. The photo-curing substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) having a crosslinkable silicon group. When the amount is less than 1 part by mass, there is no effect of increasing the weather resistance, and when the amount is more than 20 parts by mass, the cured product tends to be too hard and tends to crack.

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

  An antioxidant (antiaging agent) can be used in the composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.); Manufactured by Denka Kogyo Co., Ltd.); hindered amines shown by Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Corporation) A system light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a crosslinkable silicon group. Part by mass.

  A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer may be used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a crosslinkable silicon group. Part by mass. Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.); MARKLA-57, LA-62, LA-67, LA-63 (all above) Asahi Denka Kogyo Co., Ltd.); light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Co., Ltd.).

  An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a crosslinkable silicon group. Part by mass. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  An epoxy resin can be added to the composition of the present invention. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies Resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins. The use ratio of these epoxy resins and (A) the organic polymer having a crosslinkable silicon group is in the range of (A) / epoxy resin = 100/1 to 1/100 in terms of mass ratio. When the ratio of (A) / epoxy resin is less than 1/100, the effect of improving the impact strength and toughness of the cured epoxy resin is difficult to obtain, and the ratio of (A) / epoxy resin exceeds 100/1. And the intensity | strength of organic type polymer cured material will become inadequate. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The component (A) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the intensity | strength of the hardened | cured material of (A) component, it is good to use 1-200 mass parts of epoxy resins with respect to 100 mass parts of (A) component, More preferably, 5-100 mass parts is used. .

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

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

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

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

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

  To the curable composition of the present invention, a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added. The said flame retardant may be used independently and may be used together 2 or more types.

  The flame retardant is preferably used in the range of 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the component (A).

  In the composition of the present invention, a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketone solvents, ether solvents, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. In the case of using a solvent, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. These solvents may be used alone or in combination of two or more.

  However, when the amount of the solvent is large, toxicity to the human body may be increased, and volume shrinkage of the cured product may be observed. Accordingly, the blending amount of the solvent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and substantially contains the solvent with respect to 100 parts by mass of the organic polymer of the component (A). Most preferably not.

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

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

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is of a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a crosslinkable silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl By adding an alkoxysilane compound such as methyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane, the storage stability is further improved.

  The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 100 parts by weight of (A) organic polymer having a crosslinkable silicon group. The range of 0.5-10 mass parts is preferable.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.

  Moreover, in the preparation method of the curable composition of this invention, it is suitable to include the ageing | curing | ripening process which age | cures the composition containing the said component (A) and (B) at predetermined temperature on sealing conditions. The storage stability can be further improved by the aging step. Here, aging means transesterification of (A) a part of the hydrolyzable group of the organic polymer and (B) a part of the alkoxyl group of the metal compound. It is preferable to reach the state of chemical equilibrium by the aging.

  Although there is no restriction | limiting in particular in the reaction temperature conditions in the said aging process, It is preferable to make it react at 30 to 100 degreeC, 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 aging step may be performed on the composition containing at least the components (A) and (B), and the timing and number of aging steps are not limited and may be appropriately determined. For example, when preparing a curable composition comprising components (A) and (B), a mixture containing components (A) and (B) may be aged at a predetermined temperature. In addition to components (A) and (B), when other compounding substances are blended, the aging step may be performed on the composition containing components (A), (B) and other compounding substances, You may add another compounding substance, after performing an aging process with respect to the composition containing a component (A) and (B). Moreover, after the aging process of the composition containing at least components (A) and (B), a part or all of the remaining compounding substances may be blended, and the aging process may be further performed. Moreover, you may age | cure | ripen at the predetermined temperature further with respect to the composition which mix | blended all the compounding substances.

  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 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 analyzer / analyzer: Alliance (Waters), 2410 differential refraction detector (Waters), 996 multi-wavelength detector (Waters), Milleniam data processor (Waters)
Column: Plgel GUARD + 5 μm Mixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by PolymerLab)
・ Flow rate: 1 mL / min ・ Measurement temperature: 40 ° C.

2) Storage stability test and curability (TFT) test The prepared curable composition was allowed to stand in an environment at 23 ° C. for 24 hours, and the viscosity and the curing time were measured. The condition was referred to as initial, and the measured viscosity was defined as initial viscosity. The viscosity was measured with a BS type rotational viscometer (rotor No. 7-10 rotation) (measurement temperature 23 ° C.). As for the curing time, the touch drying time (TFT) was measured in an environment of 23 ° C. and RH 50% in accordance with JIS A 1439 5.19.
Next, the sample was left in a 50 ° C. environment for a predetermined period (1, 2, 4 weeks). And it left still for 3 hours in 23 degreeC environment, and measured the viscosity and hardening time. The measured viscosity was defined as the storage viscosity for each predetermined period. Furthermore, the viscosity increase rate of each predetermined period was obtained by dividing the storage viscosity of each predetermined period by the initial viscosity.

3) Adhesive strength test 0.2 g of the curable composition was uniformly applied on the adherend and immediately bonded to an area of 25 mm × 25 mm. After pasting, measurement was performed according to the tensile shear bond 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 50% relative humidity. As the adherend, hard vinyl chloride, polycarbonate, mild steel plate, anodized aluminum were used.

(Synthesis Example 1)
Propylene glycol was used as an initiator, and propylene oxide was reacted in the presence of the synthesized zinc hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene diol having a number average molecular weight of 25,000 and Mw / Mn = 1.3. A methanol solution of sodium methoxide (NaOMe) was added to the polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by degassing under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added to react with trimethoxysilane, and the polystyrene-reduced number average molecular weight is about 26000, and 1.5 terminal trioxyls per molecule. A polyoxypropylene polymer M1 having a methoxysilyl group was obtained.

(Synthesis Example 2)
Propylene glycol was used as an initiator, and propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene diol having a number average molecular weight of 13,000 and Mw / Mn = 1.3. A methanol solution of sodium methoxide (NaOMe) was added to the polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by degassing under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added, and trimethoxysilane is reacted. The number average molecular weight in terms of polystyrene is about 14,000, and 1.5 terminal trioxyls per molecule. A polyoxypropylene polymer M2 having a methoxysilyl group was obtained.

(Synthesis Example 3)
Using glycerin as an initiator, propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene diol having a number average molecular weight of 13,000 and Mw / Mn = 1.3. A methanol solution of sodium methoxide (NaOMe) was added to the polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by degassing under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. 50 parts by mass of toluene is added to 100 parts by mass of the obtained allyl group-terminated polyoxypropylene, 3.41 parts by mass of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and further 8.25 parts by mass of mercaptopropyl. Trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was heated to 80 ° C. and reacted for 3 hours. After completion of the reaction, toluene and unreacted substances are removed by heating under reduced pressure, and the polyoxypropylene polymer M3 having a polystyrene-equivalent number average molecular weight of about 15000 and 2.7 terminal trimethoxysilyl groups per molecule is obtained. Got.

(Synthesis Example 4)
30.00 g of n-butylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, followed by acryloxypropyltrimethoxysilane (trade name: 96.12 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added. The mixture was stirred at room temperature for 24 hours to obtain a silylating agent. Subsequently, 100 parts by mass of polyoxypropylene diol having a number average molecular weight of 10,000 (trade name: Preminol 4010, manufactured by Asahi Glass Co., Ltd.), m-xylene diisocyanate (trade name: Takenate 500, manufactured by Mitsui Chemicals, Inc.) 3.75 Part by mass was placed under a nitrogen atmosphere. A urethane prepolymer was obtained by reacting at 90 ° C. for 3 hours with stirring and mixing. To 100 parts by mass of the obtained urethane prepolymer, 5.92 parts by mass of the previously obtained silylating agent was added, heated to 80 ° C., and reacted for 3 hours. Check the appearance of a peak attributed to urea groups near disappearance 1660 cm ^-1 of the peak caused by FT-IR isocyanate group near 2250 cm ^-1, it was confirmed that the polymer of interest was synthesized. A polyoxypropylene polymer M4 having a polystyrene-reduced number average molecular weight of about 11,000 and 2.0 terminal trimethoxysilyl groups per molecule was obtained.

(Synthesis Example 5)
In a flask, 40 parts by mass of ethyl acetate as a solvent, 59 parts by mass of methyl methacrylate, 25 parts by mass of 2-ethylhexyl methacrylate, 22 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by mass of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Next, 8 parts by mass of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by mass of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. The number average molecular weight in terms of polystyrene was 5000, and Mw / Mn = 1.6, and an acrylate polymer A1 having an average of 2.0 trimethoxysilyl groups per molecule was obtained.

(Synthesis Example 6)
36.7 parts by mass of ethyl acetate was placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, and heated to 80 ° C. In another container, 66 parts by weight of methyl methacrylate, 13 parts by weight of stearyl methacrylate, 6 parts by weight of n-butyl acrylate, 5.4 parts by weight of methacryloxypropyltrimethoxysilane, 7.6 parts by weight of mercaptopropyltrimethoxysilane, AIBN2. Mix 6 parts by mass, add it dropwise over 3 hours, react for 6 hours at 80 ° C., polystyrene equivalent number average molecular weight is 6000, and Mw / Mn = 1.6, and average 2 per molecule An acrylate polymer A2 having 0.0 trimethoxysilyl groups was obtained.

(Synthesis Example 7)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 10 parts by mass of toluene, 70 parts by mass of methyl methacrylate, 30 parts by mass of 2-ethylhexyl methacrylate, 15.2 parts by mass of acryloxymethyltrimethoxysilane Part, 5.5 parts by mass of methyl 2-bromoisobutyrate, 4.3 parts by mass of CuBr as a transition metal catalyst, 0.2 parts by mass of Cu, and N, N, N ′, N ″, N ′ as a ligand '-Pentamethylenediethylenetriamine 2.8 parts by mass The contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. After the reaction for 12 hours, the temperature of the reaction product was returned to room temperature, and 20 parts by mass of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, and dehydrated methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) The reaction product is purified by precipitation, and the number average molecular weight is 6000 in terms of polystyrene, Mw / Mn = 1.1, and an acrylic ester polymer having an average of 2.0 trimethoxysilyl groups per molecule. A3 was obtained.

(Synthesis Example 8)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 66 parts by mass of methyl methacrylate, 15 parts by mass of stearyl methacrylate, 13 parts by mass of n-butyl methacrylate, 20 parts by mass of methacryloxypropyltrimethoxysilane Then, 5.7 parts by mass of synthesized 2-phenylpropyl-2-dithiobenzoate and 1.7 parts by mass of AIBN were charged, and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. Heating and cooling were performed for 8 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. After the reaction, the temperature of the reaction product is returned to room temperature, the number average molecular weight is 8000 in terms of polystyrene, and Mw / Mn = 1.1 and acrylic acid having an average of 3.7 trimethoxysilyl groups per molecule An ester polymer A4 was obtained.

(Synthesis Example 9)
As shown in Table 1, 2.83 g (9.97 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, followed by 1.17 g of ethyl lactate. (9.97 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.40 g of a clear pale yellow liquid T-1.

(Synthesis Example 10)
As shown in Table 1, 2.40 g (8.43 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, followed by DL-diethyl malate. 1.60 g (8.43 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.49 g of a clear pale yellow liquid T-2.

(Synthesis Example 11)
As shown in Table 1, 2.61 g (9.18 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, followed by DL-diethyl malate. 1.39 g (11.02 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.44 g of a clear pale yellow liquid T-3.

(Synthesis Example 12)
As shown in Table 1, 2.22 g (7.81 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, followed by DL-diethyl malate. 1.78 g (6.25 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.56 g of a transparent light yellow liquid T-4.

(Synthesis Example 13)
As shown in Table 1, 1.71 g (6.02 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, followed by DL-diethyl malate. 2.29 g (12.03 mmol) was added. The mixture was reacted at 70 ° C. for 7 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 4.00 g of a clear pale yellow liquid T-5.

(Synthesis Example 14)
As shown in Table 1, 2.25 g (7.92 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, followed by triethyl citrate 1. 75 g (6.33 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.62 g of a clear pale yellow liquid T-6.

(Synthesis Example 15)
As shown in Table 1, 2.03 g (7.14 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, followed by triethyl citrate 1. 97 g (7.14 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.57 g of a clear pale yellow liquid T-7.

(Synthesis Example 16)
As shown in Table 1, 1.85 g (6.51 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, followed by triethyl citrate. 15 g (7.81 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 3.53 g of a clear pale yellow liquid T-8.

(Synthesis Example 17)
As shown in Table 1, 1.36 g (4.79 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, followed by triethyl citrate. 64 g (9.58 mmol) was added. The mixture was reacted at 70 ° C. for 7 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 4.00 g of a clear pale yellow liquid T-9.

(Synthesis Example 18)
As shown in Table 1, 2.20 g (7.74 mmol) of titanium tetraisopropoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, followed by DL-diethyl malate. 0.73 g (3.87 mmol) and triethyl citrate 3.87 g (3.87 mmol) were added. The mixture was reacted at 70 ° C. for 7 hours, and isopropyl alcohol was removed from the mixture under reduced pressure to obtain 4.00 g of a clear pale yellow liquid T-10.

(Synthesis Example 19)
As shown in Table 1, 1.90 g (11.05 mmol) of titanium tetramethoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, and 2.10 g of DL-diethyl malate was added. (11.05 mmol) was added. The mixture was reacted at 50 ° C. for 2 hours, and methanol was removed from the mixture under reduced pressure to obtain 3.34 g of a clear pale yellow liquid T-11.

(Synthesis Example 20)
As shown in Table 1, 2.56 g (7.52 mmol) of titanium tetra-t-butoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, and DL-diethyl malate 1. 43 g (7.52 mmol) was added. The mixture was reacted at 30 ° C. for 2 hours, and t-butanol was removed from the mixture under reduced pressure to obtain 3.54 g of a clear light yellow liquid T-12.

(Synthesis Example 21)
Take 1.00 g (5.27 mmol) of titanium tetrachloride with a syringe so that the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube is not exposed to the atmosphere, followed by 3.93 g (521) of dodecanol. .09 mmol) and 2.56 g (25.31 mmol) of triethylamine were added dropwise and reacted. After the reaction, filtration was performed to obtain titanium tetradodecoxide. As shown in Table 1, 3.22 g (4.08 mmol) of the previously obtained titanium tetradodecoxide was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, and DL-apple 0.78 g (4.08 mmol) of diethyl acid was added. The mixture was reacted at 70 ° C. for 2 hours to obtain 4.00 g of a clear pale yellow liquid T-13.

In Table 1, the compounding quantity of each compounding substance is shown by g. (B) Component x and (B) component y are x and y in the formula (7) when T-1 to T-13 obtained in Synthesis Examples 9 to 21 are represented by the formula (7). Is shown respectively.
Details of each compound used in Synthesis Examples 1 to 21 are as follows.
n-Butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Stearyl methacrylate (trade name: Light Ester S, manufactured by Kyoeisha Co., Ltd.)
Methyl methacrylate (trade name: Light Ester M, manufactured by Kyoeisha Co., Ltd.)
2-ethylhexyl methacrylate (trade name: Light Ester EH, manufactured by Kyoeisha Co., Ltd.)
n-Butyl methacrylate (trade name: Light Ester MB, manufactured by Kyoeisha Co., Ltd.)
Mercaptopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
AIBN: 2,2′-azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.)
THF (tetrahydrofuran, manufactured by Wako Pure Chemical Industries, Ltd.)
Ethyl acetate (Wako Pure Chemical Industries, Ltd.)
Preminol 4010: manufactured by Asahi Glass Co., Ltd., polyoxypropylene diol methacryloxypropyltrimethoxysilane having a number average molecular weight of 10,000 (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.)
Dehydrated methanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Methyl 2-bromoisobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CuBr (manufactured by Tokyo Chemical Industry Co., Ltd.)
Cu (manufactured by Tokyo Chemical Industry Co., Ltd.)
N, N, N ′, N ″, N ″ -pentamethylenediethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ruthenocene dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
Allyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
m-Xylene diisocyanate (trade name: Takenate 500, manufactured by Mitsui Chemicals, Inc.)
Titanium tetra-t-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
Titanium tetramethoxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
Titanium tetraisopropoxide (trade name: Olgatyx TA-10, manufactured by Matsumoto Fine Chemical Co., Ltd.)
Titanium tetrachloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
Dodecanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Example 1
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.40 parts by mass of T-1 obtained in Synthesis Example 9 was added, and deaerated and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 2)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.49 parts by mass of T-2 obtained in Synthesis Example 10 was added, and deaerated and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 3)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.44 parts by mass of T-3 obtained in Synthesis Example 11 was added, and deaerated and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

Example 4
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.56 parts by mass of T-4 obtained in Synthesis Example 12 was added and degassed and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 5)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.05 parts by mass of T-5 obtained in Synthesis Example 13 was added and degassed and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 6)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.62 parts by mass of T-6 obtained in Synthesis Example 14 was added, and deaerated and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 7)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.57 parts by mass of T-7 obtained in Synthesis Example 15 was added and deaerated and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 8)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 3.53 parts by mass of T-8 obtained in Synthesis Example 16 was added and deaerated and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

Example 9
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.00 parts by mass of T-9 obtained in Synthesis Example 17 was added and degassed and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 10)
As shown in Table 2, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.00 parts by mass of T-10 obtained in Synthesis Example 18 was added and degassed and stirred to obtain a curable composition. Table 4 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 11)
As shown in Table 3, 70 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, 20 parts by mass of the polyoxypropylene polymer M3 obtained in Synthesis Example 3, and the acrylic obtained in Synthesis Example 6 10 parts by weight of acid ester polymer A2 was placed in a 300 mL flask equipped with a weighed stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours. It returned to room temperature. 10.00 parts by mass of T-1 obtained in Synthesis Example 9 was added and deaerated and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 12)
As shown in Table 3, 60 parts by mass of the polyoxypropylene polymer M4 obtained in Synthesis Example 4 and 40 parts by mass of the acrylate polymer A2 obtained in Synthesis Example 6, a weighing stirrer, a thermometer, The flask was placed in a 300 mL flask equipped with a nitrogen inlet, a monomer charging tube and a water-cooled condenser, heated to 100 ° C., deaerated and stirred for 3 hours, and returned to room temperature. 20.00 parts by mass of T-5 obtained in Synthesis Example 13 was added and deaerated and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 13)
As shown in Table 3, 10 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1 and 20 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2 were obtained in Synthesis Example 3. 10 parts by mass of the polyoxypropylene polymer M3, 10 parts by mass of the polyoxypropylene polymer M4 obtained in Synthesis Example 4 and 50 parts by mass of the acrylate polymer A2 obtained in Synthesis Example 7 were weighed out. The flask was placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C., degassed and stirred for 3 hours, and returned to room temperature. 1.00 part by mass of T-10 obtained in Synthesis Example 18 was added, and deaerated and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 14)
As shown in Table 3, 70 parts by mass of the polyoxypropylene polymer M3 obtained in Synthesis Example 3 and 10 parts by mass of the acrylate polymer A2 obtained in Synthesis Example 6 were obtained in Synthesis Example 8. 20 parts by mass of acid ester polymer A4, weighed and stirred, thermometer, nitrogen inlet, monomer charging tube and 300 mL flask equipped with water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 15.00 parts by mass of T-10 obtained in Synthesis Example 18 was added, and deaerated and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 15)
As shown in Table 3, 70 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1 and 30 parts by mass of the acrylate polymer A2 obtained in Synthesis Example 6, a weighing stirrer, a thermometer, The flask was placed in a 300 mL flask equipped with a nitrogen inlet, a monomer charging tube and a water-cooled condenser, heated to 100 ° C., deaerated and stirred for 3 hours, and returned to room temperature. 3.34 parts by mass of T-11 obtained in Synthesis Example 19 was added and degassed and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 16)
As shown in Table 3, 70 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1 and 30 parts by mass of the acrylate polymer A2 obtained in Synthesis Example 6, a weighing stirrer, a thermometer, The flask was placed in a 300 mL flask equipped with a nitrogen inlet, a monomer charging tube and a water-cooled condenser, heated to 100 ° C., deaerated and stirred for 3 hours, and returned to room temperature. 3.54 parts by mass of T-11 obtained in Synthesis Example 20 was added and deaerated and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 17)
As shown in Table 3, 70 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1 and 30 parts by mass of the acrylate polymer A2 obtained in Synthesis Example 6, a weighing stirrer, a thermometer, The flask was placed in a 300 mL flask equipped with a nitrogen inlet, a monomer charging tube and a water-cooled condenser, heated to 100 ° C., deaerated and stirred for 3 hours, and returned to room temperature. 4.01 parts by mass of T-11 obtained in Synthesis Example 21 was added and degassed and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 18)
As shown in Table 3, 100 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1 was placed in a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. The mixture was heated to 100 ° C., degassed and stirred for 3 hours, and returned to room temperature. 4.05 parts by mass of T-5 obtained in Synthesis Example 13 was added and degassed and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Comparative Example 1)
As shown in Table 3, 70 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1 and 30 parts by mass of the acrylic ester polymer A1 obtained in Synthesis Example 5, a weighed stirrer, a thermometer, The flask was placed in a 300 mL flask equipped with a nitrogen inlet, a monomer charging tube and a water-cooled condenser, heated to 100 ° C., deaerated and stirred for 3 hours, and returned to room temperature. ORGATIXX TC-750 (titanium diisopropoxybis (ethylacetoacetate), manufactured by Matsumoto Fine Chemical Co., Ltd.) was added at 4.00 parts by mass, and deaerated and stirred to obtain a curable composition. Table 5 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

  In Table 2 and Table 3, the compounding quantity of each compounding substance is shown by g.

  As can be seen from Tables 4 and 5, the curable composition of the present invention has a lower viscosity increase rate after storage stability test than the curable composition of Comparative Example 1 using a conventional titanium catalyst, and good storage. Shows stability. In addition, the curable composition of the present invention also showed good results in adhesiveness.

(Synthesis Example 22)
As shown in Table 6, 1.00 g (40.60 mmol) of mono-sec-butoxyaluminum diisopropylate was obtained with a syringe so that the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser tube was not exposed to the atmosphere. Then, 4.80 g (40.60 mmol) of ethyl lactate was dropped and reacted. Reaction was carried out at 70 ° C. for 2 hours to obtain 14.80 g of a transparent light yellow liquid Al-1.

(Synthesis Example 23)
As shown in Table 6, 10.00 g (40.83 mmol) of aluminum sec-butylate was taken with a syringe so that the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube was not exposed to the atmosphere. Then, 10.83 g (81.20 mmol) of ethyl lactate was dropped and reacted. The reaction was carried out at 70 ° C. for 2 hours to obtain 20.83 g of transparent light yellow liquid Al-2.

(Synthesis Example 24)
As shown in Table 6, 10.00 g (40.83 mmol) of aluminum sec-butylate was taken with a syringe so that the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube was not exposed to the atmosphere. Then, 16.24 g (137.49 mmol) of ethyl lactate was dropped and reacted. The reaction was carried out at 70 ° C. for 2 hours to obtain 26.24 g of a transparent light yellow liquid Al-3.

(Synthesis Example 25)
As shown in Table 6, 1.00 g (40.60 mmol) of mono-sec-butoxyaluminum diisopropylate was obtained with a syringe so that the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser tube was not exposed to the atmosphere. Then, DL-diethyl malate 7.22 g (40.60 mmol) was dropped and reacted. The reaction was carried out at 70 ° C. for 2 hours to obtain 17.22 g of a transparent light yellow liquid Al-4.

(Synthesis Example 26)
As shown in Table 6, 1.00 g (40.60 mmol) of mono-sec-butoxyaluminum diisopropylate was obtained with a syringe so that the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser tube was not exposed to the atmosphere. Then, 11.22 g (40.60 mmol) of triethyl citrate was dropped and reacted. The reaction was carried out at 70 ° C. for 2 hours to obtain 21.22 g of a transparent light yellow liquid Al-5.

In Table 6, the compounding quantity of each compounding substance is shown by g. (B) Component x and (B) component y are x and y in the formula (7) when Al-1 to Al-5 obtained in Synthesis Examples 22 to 26 are represented by the formula (7). Is shown respectively.
Details of each compound used in Synthesis Examples 22 to 26 are as follows.
Mono sec-butoxyaluminum diisopropylate (trade name: AMD, manufactured by Kawaken Fine Chemical Co., Ltd.)
Aluminum sec-butyrate (trade name: ASBD, manufactured by Kawaken Fine Chemical Co., Ltd.)

(Example 19)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.97 parts by mass of Al-1 obtained in Synthesis Example 22 was added, deaerated and stirred, filled in a sealed container, and allowed to stand in an environment of 50 ° C. for 3 days to prepare a curable composition. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 20)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 5.77 parts by mass of Al-2 obtained in Synthesis Example 23 was added, deaerated and stirred, filled in a sealed container, and allowed to stand in an environment of 50 ° C. for 3 days to prepare a curable composition. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 21)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 6.35 parts by mass of Al-3 obtained in Synthesis Example 24 was added, deaerated and stirred, filled in a sealed container, and allowed to stand in an environment of 50 ° C. for 3 days to prepare a curable composition. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 22)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.77 parts by mass of Al-4 obtained in Synthesis Example 25 was added, deaerated and stirred, filled in a sealed container, and allowed to stand in an environment of 50 ° C. for 3 days to prepare a curable composition. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Example 23)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.61 parts by mass of Al-5 obtained in Synthesis Example 26 was added, deaerated and stirred, filled in a sealed container, and allowed to stand in an environment of 50 ° C. for 3 days to prepare a curable composition. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Comparative Example 2)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. 4.00 parts by mass of monosec-butoxyaluminum diisopropylate was added, deaerated and stirred, filled into a sealed container, and allowed to stand in an environment of 50 ° C. for 3 days to prepare a curable composition. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

(Comparative Example 3)
As shown in Table 7, 60 parts by mass of the polyoxypropylene polymer M1 obtained in Synthesis Example 1, 10 parts by mass of the polyoxypropylene polymer M2 obtained in Synthesis Example 2, and the acrylic obtained in Synthesis Example 5 30 parts by mass of acid ester polymer A1, put into a 300 mL flask equipped with a weighing stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, heated to 100 ° C. and degassed and stirred for 3 hours, It returned to room temperature. Add 10.00 parts by mass of aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum monoacetylacetonate bis (ethylacetoacetate)) The curable composition was prepared by allowing to stand. Table 8 shows the results of storage stability, curability (TFT), and adhesive strength test of the curable composition.

In Table 7, the compounding quantity of each compounding substance is shown by g.

  As is apparent from Table 8, the curable composition of the present invention has a lower viscosity increase rate after storage stability test than the curable compositions of Comparative Examples 2 and 3 using a conventional aluminum catalyst, and good storage stability. Showed sex. In addition, the curable composition of the present invention also showed good results in adhesiveness.

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

  The curable composition of the present invention comprises an adhesive, an adhesive for buildings, ships, automobiles, roads, etc., a sealing material, a mold preparation, a vibration damping material, a vibration damping material, a soundproof material, a foam material, a paint, and a spraying material. Can be used for etc. Since the hardened | cured material obtained by hardening | curing the curable composition of this invention is excellent in a softness | flexibility and adhesiveness, it is more preferable to use as an adhesive agent or a sealing material among these. Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, Can also be used.

Claims (11)

(A) an organic polymer having a hydrolyzable group bonded to a silicon atom, a crosslinkable silicon group that can be cross-linked by forming a siloxane bond by the action of moisture, and a main chain that is not polysiloxane; ) Metal compounds as curing catalysts,
A curable composition having adhesiveness containing
The metal compound (B) is a compound of one or more metals selected from the group consisting of metals other than tin, and a residue of α- or β-keto alcohol is bonded to the metal atom, A metal compound in which carbon is saturated carbon,
An adhesive curable composition comprising 0.1 to 20 parts by mass of the (B) metal compound with respect to 100 parts by mass of the (A) organic polymer.   2. The curable composition according to claim 1, wherein the metal compound (B) is a reaction product obtained by reacting at least a metal alkoxide and a hydroxycarboxylic acid ester.   The curable composition according to claim 2, wherein the hydroxycarboxylic acid ester is at least one selected from the group consisting of a lactic acid ester, a malic acid ester and a citric acid ester.   The curable composition according to claim 2 or 3, wherein the metal alkoxide is a metal alkoxide containing an alkoxide group having 1 to 12 carbon atoms.   The curable composition according to any one of claims 1 to 4, wherein the metal is at least one selected from the group consisting of titanium, aluminum, zirconium, niobium, vanadium and tantalum.   The main chain skeleton of the (A) organic polymer is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer. The curable composition of any one of Claims 1-5 characterized by these. The curable composition according to claim 1, wherein the crosslinkable silicon group is a group represented by the following formula (1).

(In the formula (1), R ¹ 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, or an aralkyl group having 7 to 20 carbon atoms. Yes, when two or more R ¹ are present, they may be the same or different, X represents a hydrolyzable group, and when two or more X are present, they are the same. A may be different or a is an integer of 1, 2 or 3.)   The curable composition according to claim 7, wherein X in the formula (1) is an alkoxy group.   The curable composition according to claim 7 or 8, wherein a in the formula (1) is 2 or 3.   10. The curable composition according to claim 9, wherein a in the formula (1) is 3.   The curable composition according to any one of claims 7 to 10, wherein at least a part of X in the formula (1) is a methoxy group.