Moisture curable composition

Abstract

The present invention addresses the problem of providing a moisture curable composition which is excellent in terms of transparency, adhesiveness, and weather resistance and / or a moisture curable composition which is capable of forming a cured product that is excellent in terms of transparency, adhesiveness, and weather resistance. The present invention provides, as a solution, a moisture curable composition which contains: a crosslinkable silyl group-containing polyoxyalkylene-based organic polymer (A) that has an average of 1.3 or more crosslinkable silyl groups in each molecule and a number average molecular weight of 20,000 or more; a crosslinkable silyl group-containing vinyl-based organic polymer (B); and silica (C).

Description

Moisture-curable curable composition

[0001] The present invention relates to a moisture-curable composition. More specifically, the present invention relates to a moisture-curable composition having excellent transparency, adhesiveness, and weather resistance and / or a moisture-curable composition capable of forming a cured product having excellent transparency, adhesiveness, and weather resistance.

[0002] Moisture-curable compositions that crosslink and cure at room temperature due to moisture in the air or added water are widely used in adhesives, sealants, coating materials, etc., due to their properties, etc. Such moisture-curable compositions and the cured products obtained by curing them are required to have properties such as adhesion and weather resistance, and further properties such as transparency, and have been the subject of much research to date.

[0003] Patent Document 1 discloses a sealant composition containing 100 parts by weight of a polymer (A) having a hydrolyzable silyl group in its molecule and whose main chain skeleton is a polyalkylene ether or a (meth)acrylic acid ester polymer, 0.1 to 5 parts by weight of a silicone surfactant (B) containing a hydroxyl group in its molecule, 40 to 100 parts by weight of calcium carbonate (C) having an average particle size of 0.01 μm or more and surface-treated with a fatty acid, resin acid, or fatty acid ester surface treatment agent, and 0.5 to 15 parts by weight of a curing catalyst (D). Patent Document 2 discloses a curable resin composition containing 0.05 to 100 parts by weight of a polyphenylene ether compound (B) having a number-average molecular weight of 200 to 10,000, per 100 parts by weight of a curable resin (A) having a crosslinkable silicon group in its molecule. Patent Document 3 discloses a moisture-curable adhesive composition containing (1) a polyoxypropylene-modified silicone resin containing an acrylic polymer having a silicon atom-containing functional group, (2) the curing agent of (1) above, (3) hydrophobic finely powdered silica, and (4) a silane coupling agent having an amino group.

[0004] JP 2012-56982 A JP 2015-196729 A JP 2000-38560 A

[0005] Previously known moisture-curable compositions have not provided a cured product obtained by curing that has a good balance of transparency, adhesiveness, and weather resistance.

[0006] The problem to be solved by the present invention is to provide a moisture-curable composition having excellent transparency, adhesion, and weather resistance, and / or a moisture-curable composition capable of forming a cured product having excellent transparency, adhesion, and weather resistance.

[0007] The present inventors conducted extensive research to solve the above-mentioned problems, and as a result, discovered that a moisture-curable composition having a specific composition can solve the above-mentioned problems, thereby completing the present invention. Specifically, the present invention is as follows: [Item 1] A moisture-curable composition comprising a crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) containing an average of 1.3 or more crosslinkable silyl groups per molecule and having a number-average molecular weight of 20,000 or more, a crosslinkable silyl group-containing vinyl organic polymer (B), and silica (C). [Item 2] The moisture-curable composition according to Item 1, wherein the crosslinkable silyl group-containing vinyl organic polymer (B) contains an average of 1.0 to 1.5 crosslinkable silyl groups at molecular terminals and has a weight-average molecular weight of 1,000 to 7,000. [Item 3] The moisture-curable composition according to Item 1 or 2, wherein the silica (C) is hydrophobic fumed silica or hydrophilic fumed silica. [Item 4] The moisture-curable curable composition according to any one of Items 1 to 3, wherein the crosslinkable silyl group-containing vinyl organic polymer (B) comprises a crosslinkable silyl group-containing (meth)acrylic polymer. [Item 5] The moisture-curable curable composition according to any one of Items 1 to 4, wherein the content of the crosslinkable silyl group-containing vinyl organic polymer (B) is 10 parts by mass or more and 45 parts by mass or less per 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A). [Item 6] The moisture-curable curable composition according to any one of Items 1 to 5, further comprising a vinyl organic polymer (D) that does not contain a crosslinkable silyl group. [Item 7] The moisture-curable curable composition according to Item 6, wherein the sum of the content of the crosslinkable silyl group-containing vinyl organic polymer (B) and the content of the vinyl organic polymer (D) not containing a crosslinkable silyl group is 20 parts by mass or more and 55 parts by mass or less per 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A). [Item 8] The moisture-curable curable composition according to any one of Items 1 to 7, comprising a moisture-curable polymer (E) other than the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) and the crosslinkable silyl group-containing vinyl organic polymer (B). [Item 9] A sealant comprising the moisture-curable curable composition according to any one of Items 1 to 8. [Item 10] An adhesive comprising the moisture-curable curable composition according to any one of Items 1 to 8.

[0008] According to the present invention, it is possible to provide a moisture-curable composition having excellent transparency, adhesiveness, and weather resistance and / or a moisture-curable composition capable of forming a cured product having excellent transparency, adhesiveness, and weather resistance.

[0009] {Moisture-Curable Curable Composition} The moisture-curable curable composition of the present invention contains a crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) containing an average of 1.3 or more crosslinkable silyl groups per molecule and having a number average molecular weight of 20,000 or more, a crosslinkable silyl group-containing vinyl organic polymer (B), and silica (C). The moisture-curable curable composition of the present invention may further contain one or more of the following: a vinyl organic polymer (D) not having a crosslinkable silyl group in the molecule; a moisture-curable polymer (E) other than component (A) and component (B); a light stabilizer, an ultraviolet absorber, an antioxidant, a diluent, a moisture absorber, an adhesion promoter, a curing catalyst, or other components (F). The moisture-curable curable composition of the present invention will be described in detail below, but these are shown by way of example only, and it goes without saying that various modifications are possible as long as they do not deviate from the technical concept of the present invention.

[0010] [Component (A)] Component (A) constituting the moisture-curable curable composition of the present invention is a crosslinkable silyl group-containing polyoxyalkylene organic polymer in which the main chain of the organic polymer is composed of polyoxyalkylene, the polymer contains an average of 1.3 or more crosslinkable silyl groups per molecule, and the number average molecular weight is 20,000 or more.

[0011] <Crosslinkable Silyl Group> The crosslinkable silyl group of the crosslinkable silyl group-containing polyoxyalkylene polymer has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a group that can be crosslinked by forming a siloxane bond. As the crosslinkable silyl group, for example, a group represented by structural formula (1) is preferable. -Si(R １１ ) ３－ａ１ X １１ ａ１ ...(1) In structural formula (1), R １１represents a hydrocarbon group having 1 to 20 carbon atoms, 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, R １１ ３ SiO-(R １１ is the same as above), or a triorganosiloxy group represented by the formula -CH ２ OR １１ Group (R １１ is the same as above). １１ is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen, -OR １２ , -NR １３ R １４ , -N=R １５ , -SR １６ (R １２ , R １３ , R １４ , R １６ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; R １５ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not have a substituent. ), a perfluoroalkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a cyano group. １１ is preferably a methyl group. １１ When there are two or more R １１ may be the same or different. １１ represents a hydroxyl group or a hydrolyzable group, and X １１ If there are two or more X １１ may be the same or different, and a1 is an integer of 0, 1, 2, or 3. In consideration of curability, in order to obtain a moisture-curable curable composition having a sufficient curing rate, a1 in structural formula (1) is preferably 2 or more.

[0012] One to three hydrolyzable groups or hydroxyl groups can be bonded to one silicon atom. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group may be one or two or more.

[0013] X １１ The hydrolyzable group represented by the formula (I) is not particularly limited as long as it is other than a fluorine atom. Examples include a hydrogen atom, a halogen atom (chlorine atom, bromine atom, iodine 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, a halogen 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 preferred, and an alkoxy group, a halogen atom, an amide group, and an aminooxy group are more preferred. From the viewpoint of mild hydrolysis and easy handling, an alkoxy group is particularly preferred. The number of carbon atoms in the alkoxy group is not particularly limited, but is 1 or more carbon atoms, for example, 12 or less, preferably 6 or less. The fewer the carbon atoms in the alkoxy group, the higher the reactivity, and the higher the carbon number, the lower the reactivity, in the order of methoxy group > ethoxy group > propoxy group. The alkoxy group can be selected depending on the purpose and application, but a methoxy group or an ethoxy group is usually used.

[0014] Specific examples of the crosslinkable silyl group include trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl groups [—Si(OR) ３ ], dialkoxysilyl groups such as methyldimethoxysilyl group and methyldiethoxysilyl group [—SiR １ (OR) ２ ]. When increasing reactivity, a trimethoxysilyl group is suitable, and when suppressing reactivity, a dialkoxysilyl group is suitable. Here, R may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably any of a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of the adhesiveness, weather resistance, and mechanical properties (elongation) of the resulting moisture-curable curable composition and / or the cured product thereof, the crosslinkable silyl group is preferably a methyldimethoxysilyl group. One type of crosslinkable silyl group may be used, or two or more types may be used in combination.

[0015] The crosslinkable silyl group may be present at the end of the main chain and / or the end of the side chain of the polyoxyalkylene organic polymer molecular chain. In particular, it is preferable that the crosslinkable silyl group is present only at the end of the main chain of the polyoxyalkylene organic polymer molecular chain. In this case, the effective network length of the polyoxyalkylene organic polymer component contained in the finally formed cured product is increased, thereby exhibiting excellent properties in terms of adhesion, weather resistance, mechanical strength, etc. Furthermore, multiple crosslinkable silyl groups represented by structural formula (1) may be linked to each other.

[0016] In the moisture-curable curable composition of the present invention, the crosslinkable silyl group-containing polyoxyalkylene organic polymer, which is component (A), contains an average of 1.3 or more crosslinkable silyl groups per molecule. Furthermore, the crosslinkable silyl groups can be, for example, an average of 5 or less, preferably 3 or less, more preferably 2 or less per molecule. If the average number of crosslinkable silyl groups contained per molecule is less than 1.3, the curability may be insufficient, and problems may arise in terms of adhesion and weather resistance. If the average number of crosslinkable silyl groups contained per molecule exceeds 5, the production may be difficult, and the curability may be too high, resulting in reduced storage stability and handling.

[0017] <Number Average Molecular Weight> In the moisture-curable curable composition of the present invention, the crosslinkable silyl group-containing polyoxyalkylene organic polymer, component (A), may be linear or branched, and its number average molecular weight is 20,000 or more in terms of polystyrene measured by GPC. The number average molecular weight can be, for example, 100,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less. If the number average molecular weight is less than 20,000, the adhesiveness decreases, while if the number average molecular weight exceeds 100,000, the viscosity becomes high, which may cause problems in terms of workability. The molecular weight distribution of the crosslinkable silyl group-containing polyoxyalkylene organic polymer, component (A), is not particularly limited, and can be 2 or less, preferably 1.6 or less.

[0018] <Main Chain> The polyoxyalkylene polymer constituting the main chain of the crosslinkable silyl group-containing polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by structural formula (2): -R ２１ -O-...(2) In structural formula (2), R ２１ 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 a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by structural formula (2) include: 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 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.

[0019] 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 components obtained by reacting an aromatic polyisocyanate such as toluene (tolylene) diisocyanate or diphenylmethane diisocyanate, or an aliphatic polyisocyanate such as isophorone diisocyanate with a polyoxyalkylene polymer having a hydroxyl group. The polyoxyalkylene polymer having a crosslinkable silyl group may be used alone or in combination of two or more types.

[0020] The synthesis method of the polyoxyalkylene polymer is not particularly limited. For example, polymerization of alkylene oxide using an alkali catalyst such as KOH, polymerization of alkylene oxide using a double metal cyanide complex catalyst, etc. By the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a number average molecular weight of 20,000 or more and a Mw / Mn ratio of 1.6 or less, and a narrow molecular weight distribution, can be obtained.

[0021] A functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group is introduced into the molecule of the obtained polyoxyalkylene polymer as needed, and a compound having a functional group reactive with the functional group and a crosslinkable silyl group is reacted with the introduced functional group, thereby obtaining a polyoxyalkylene polymer having a crosslinkable silyl group by a "polymer reaction method."

[0022] A specific example of the polymer reaction method is a method in which an unsaturated group-containing polyoxyalkylene polymer is subjected to hydrosilylation or mercapto conversion with a hydrosilane having a crosslinkable silyl group or a mercapto compound having a crosslinkable silyl group to obtain a polyoxyalkylene polymer having a crosslinkable silyl group. The unsaturated group-containing polyoxyalkylene polymer can be 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 is reactive with the functional group. Other specific examples of the polymer reaction method include a method in which a polyoxyalkylene polymer having a terminal hydroxyl group is reacted with a compound having an isocyanate group and a crosslinkable silyl group, and a method in which a polyoxyalkylene polymer having a terminal isocyanate group is reacted with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silyl group. The use of an isocyanate compound makes it easy to obtain a polyoxyalkylene polymer having a crosslinkable silyl group.

[0023] <Content of Component (A)> The content of component (A) "a crosslinkable silyl group-containing polyoxyalkylene organic polymer containing an average of 1.3 or more crosslinkable silyl groups per molecule and having a number average molecular weight of 20,000 or more" in the moisture-curable curable composition is not particularly limited. The content can be, for example, 30.0% by mass or more, preferably 40.0% by mass or more, and more preferably 50.0% by mass or more, and can be, for example, 90.0% by mass or less, preferably 80.0% by mass or less, and more preferably 75.0% by mass or less, based on 100% by mass of the total amount of the moisture-curable curable composition.

[0024] [Component (B)] Component (B) constituting the moisture-curable composition of the present invention is a crosslinkable silyl group-containing vinyl organic polymer.

[0025] <Crosslinkable silyl group> The crosslinkable silyl group of the crosslinkable silyl group-containing vinyl organic polymer is the same as the crosslinkable silyl group described in <Crosslinkable silyl group> of [Component (A)] above. Note that the crosslinkable silyl group of Component (A) and the crosslinkable silyl group of Component (B) may be the same or different.

[0026] In the moisture-curable curable composition of the present invention, the average number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing vinyl organic polymer, which is component (B), is not particularly limited. For example, it can be an average of 0.1 or more, preferably an average of 0.12 or more, more preferably an average of 0.15 or more, and for example, it can be an average of 3.0 or less, preferably 2.0 or less, more preferably 1.5 or less. The crosslinkable silyl group-containing vinyl organic polymer, which is component (B), preferably includes one containing an average of 0.1 to 1.5 crosslinkable silyl groups at the molecular terminal.

[0027] <Weight Average Molecular Weight> In the moisture-curable curable composition of the present invention, the crosslinkable silyl group-containing vinyl organic polymer, component (B), may be linear or branched, and its weight average molecular weight is not particularly limited. The weight average molecular weight, as calculated in polystyrene terms by GPC, can be, for example, 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and can be, for example, 30,000 or less, preferably 10,000 or less, more preferably 7,000 or less, and even more preferably 5,000 or less. The crosslinkable silyl group-containing vinyl organic polymer, component (B), preferably has a weight average molecular weight of 1,000 or more and 7,000 or less. The molecular weight distribution of the crosslinkable silyl group-containing vinyl organic polymer, component (B), is not particularly limited, and is preferably 2.0 or less, particularly 1.6 or less.

[0028] <Main Chain> The vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited, as long as it is a vinyl organic polymer that is an addition polymer of a vinyl monomer containing a carbon-carbon unsaturated bond. Examples of vinyl organic polymers include (meth)acrylic polymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene polymers, isobutylene-isoprene copolymers, polychloroprene polymers, polyisoprene polymers, isoprene and / or butadiene-acrylonitrile and / or styrene copolymers, polybutadiene polymers, and hydrogenated polymers of diene polymers; dilyl phthalate polymers; and the like. The vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer may be used alone or in combination of two or more. Among these, the vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer preferably contains a (meth)acrylic polymer and / or a hydrocarbon polymer, and more preferably contains a (meth)acrylic polymer.

[0029] ((Meth)acrylic polymer) The (meth)acrylic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited as long as it is a (meth)acrylic polymer obtained by polymerizing a monomer component containing a (meth)acrylate monomer. The (meth)acrylate monomer is not particularly limited as long as it is a monomer having a (meth)acryloyl group. Examples include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate; alicyclic (meth)acrylates; aromatic (meth)acrylates; oxygen-containing (meth)acrylates such as 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate; silyl group-containing (meth)acrylates such as 3-(methacryloyloxypropyl)trimethoxysilane and 3-(methacryloyloxypropyl)dimethoxymethylsilane; (meth)acrylic acid; and fluorine-containing (meth)acrylates. One type of (meth)acrylate monomer may be used alone, or two or more types may be used in combination. Examples of monomers other than (meth)acrylate-based monomers that may be contained in the monomer component containing a (meth)acrylate-based monomer include styrene, maleic anhydride, vinyl acetate, etc. The monomers other than (meth)acrylate-based monomers may be used alone or in combination of two or more.

[0030] In the present invention, the (meth)acrylic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer includes (i) a (meth)acrylic polymer composed of a (meth)acrylate monomer, (ii) a (meth)acrylic polymer obtained by combining one or more alkyl (meth)acrylate monomers with, if necessary, a (meth)acrylate monomer other than the alkyl (meth)acrylate monomer, and the like. By using a silyl group-containing (meth)acrylate monomer in combination as the (meth)acrylate monomer, the number of silicon groups in the (meth)acrylic polymer can be controlled. From the viewpoint of adhesiveness, etc., a methacrylate polymer containing a methacrylate monomer is preferred as the (meth)acrylate monomer. From the viewpoint of reducing viscosity, imparting flexibility, imparting tackiness, etc., a (meth)acrylate polymer containing an appropriate amount of an acrylate monomer is preferred. In this specification, (meth)acrylate means acrylate and / or methacrylate.

[0031] The method for producing the (meth)acrylic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited. For example, a radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a polymerization initiator is used to copolymerize predetermined monomer units, and a controlled radical polymerization method in which a reactive silyl group can be introduced into a controlled position such as a terminal.

[0032] Polymers obtained by free radical polymerization are usually (meth)acrylic acid ester-based polymers having a high viscosity and a broad molecular weight distribution, generally with a molecular weight distribution value of 2 or more.

[0033] Polymerization by free radical polymerization may be any of solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. In the case of solution polymerization, the organic solvent used in the polymerization is not particularly limited. Examples include one or more of cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol. Polymerization by free radical polymerization may be any of batch polymerization, semi-continuous polymerization, and continuous polymerization. In the present invention, continuous bulk polymerization using, for example, a stirred tank reactor is particularly preferred because of its excellent productivity.

[0034] The polymerization temperature in the free radical polymerization method is not particularly limited and can be, for example, 150°C or higher, preferably 200°C or higher, more preferably 220°C or higher, and can be, for example, 330°C or lower, preferably 300°C or lower, more preferably 290°C or lower.

[0035] As the radical polymerization initiator, peroxides such as diisopropyl peroxydicarbonate, t-butyl peroxypivalate, benzoyl peroxide, lauroyl peroxide, and di-t-butyl peroxide, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and inorganic peroxides such as ammonium persulfate and potassium persulfate can be used. Chain transfer agents such as alcohols and mercaptan compounds may also be used, but are preferably not used because they lead to a decrease in weather resistance.

[0036] A (meth)acrylic acid ester polymer obtained by polymerization using a free radical polymerization method is preferred because it tends to have excellent weather resistance even if it has a low weight average molecular weight of 500 to 3,000.

[0037] The polymer obtained by controlled radical polymerization is a (meth)acrylic acid ester-based polymer having a narrow molecular weight distribution and low viscosity, and a high proportion of which has crosslinkable functional groups at the molecular terminals. Examples of controlled radical polymerization include free radical polymerization using a chain transfer agent having a specific functional group and living radical polymerization. Living radical polymerization methods such as reversible addition-fragmentation chain transfer (RAFT) polymerization and radical polymerization using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferred. Reactions using thiol compounds having reactive silyl groups and reactions using thiol compounds and metallocene compounds having reactive silyl groups are also suitable.

[0038] A method for producing a crosslinkable silyl group-containing vinyl organic polymer using a reaction of a thiol compound having a reactive silyl group and a metallocene compound includes, for example, using a polymerization catalyst represented by the structural formula (3): and a crosslinkable silyl group-containing thiol compound, and polymerizing an acrylic monomer having a polymerizable unsaturated bond in the presence of this catalyst.

[0039] In structural formula (3), M is a metal selected from the group consisting of metals of groups 4, 5, and 14 of the periodic table, chromium, ruthenium, and palladium. Examples of M include titanium, zirconium, chromium, ruthenium, vanadium, palladium, and tin. In structural formula (3), R ３１ and R ３２ are each independently at least one group selected from the group consisting of an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a silicon-containing group which may have a substituent, or a hydrogen atom or a single bond. ３１ and R ３２may combine to bond two 5-membered rings in the compound represented by structural formula (3). In structural formula (3), b1 and b2 each independently represent an integer of 1 to 4, X represents a hydrocarbon group in which at least a portion of the hydrogen atoms may be substituted with halogen atoms or a halogen atom, and n represents an integer of 0 or the valence of the metal M minus 2.

[0040] Examples of the metallocene compound represented by structural formula (3) include dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophenyl-1-yl, and dicyclopentadiene-Ti-bis-2,6-difluorophenyl. -1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyr-1-yl)-phenyl-1- titanocene compounds such as dicyclopentadienyl-Zr-dichloride, dicyclopentadiene-Zr-bisphenyl, dicyclopentadiene-Zr-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadiene-Zr-bis-2,5,6-trifluorophenyl-1-yl, dicyclopentadiene-Zr-bis-2,6-di ... zirconocene compounds such as ene-Zr-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6-difluorophenyl-1-yl, and dimethylcyclopentadienyl-Zr-bis-2,6-difluoro-3-(pyr-1-yl)-phenyl-1-yl;Examples of the metallocene compounds include dicyclopentadienyl V-chloride, bismethylcyclopentadienyl V-chloride, bispentamethylcyclopentadienyl V-chloride, dicyclopentadienyl Ru-chloride, and dicyclopentadienyl Cr-chloride. The metallocene compounds can be used alone or in combination of two or more.

[0041] The metallocene compound can be used in a normal catalytic amount, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, and for example, 1.0 part by mass or less, preferably 0.01 part by mass or less, relative to 100 parts by mass of the acrylic monomer to be polymerized.

[0042] Examples of the crosslinkable silyl group-containing thiol compound used together with the metallocene compound represented by the structural formula (3) include those represented by the structural formula (4): HS-R ４１ In the structural formula (4), R ４１ is a group having a crosslinkable silyl group. Examples of the crosslinkable silyl group include the same crosslinkable silyl groups as those described in [Component (A)]. In particular, at least one crosslinkable silyl group selected from the group consisting of a hydroxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a chlorosilyl group, and a bromosilyl group is preferred.

[0043] Examples of the compound represented by structural formula (4) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmonomethyldimethoxysilane, 3-mercaptopropylmonophenyldimethoxysilane, 3-mercaptopropyldimethylmonomethoxysilane, 3-mercaptopropylmonomethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 3-mercaptobutyltrimethoxysilane, etc. The crosslinkable silyl group-containing thiol compounds can be used alone or in combination of two or more.

[0044] The amount of the crosslinkable silyl group-containing thiol compound used can be appropriately set in consideration of the properties of the polymer to be obtained. Increasing the amount of the crosslinkable silyl group-containing thiol compound used in the reaction system increases the polymerization rate per unit time and the ultimate polymerization rate. On the other hand, increasing the amount of the metallocene compound used increases the polymerization rate per unit time, but does not have a significant effect on the ultimate polymerization rate.

[0045] The amount of metallocene compound used has almost no effect on the molecular weight of the resulting polymer, but the reaction does not proceed effectively without the use of a metallocene compound. Increasing the amount of thiol compound used increases the polymerization rate. From these trends, it is believed that in the catalyst used to produce component (B) of the present invention, the metallocene compound acts as an activating catalyst throughout the reaction, while the thiol compound exerts a polymerization initiation effect (acts as a polymerization initiation species). It is believed that the amount of crosslinkable silyl group-containing thiol compound used in the catalyst used to prepare component (B) of the present invention is a limiting factor for the molecular weight and polymerization rate.

[0046] The amount of the crosslinkable silyl group-containing thiol compound used can be appropriately set in consideration of the molecular weight of the polymer to be obtained, the polymerization rate, etc. In order to smoothly proceed with the reaction and prevent the reaction from going out of control, the metallocene compound and the crosslinkable silyl group-containing thiol compound can be used at a molar ratio (metallocene compound:crosslinkable silyl group-containing thiol compound) in the range of, for example, 100:1 to 1:50,000, preferably 10:1 to 1:10,000.

[0047] The crosslinkable silyl group-containing thiol compound can be used by (i) adding the entire amount at the start of the reaction, (ii) adding the crosslinkable silyl group-containing thiol compound first and reacting for a desired time, and then additionally adding the crosslinkable silyl group-containing thiol compound, or (iii) additionally adding both the crosslinkable silyl group-containing thiol compound and the acrylic monomer, etc. In this way, the additional addition of the crosslinkable silyl group-containing thiol compound, or the additional addition of the crosslinkable silyl group-containing thiol compound and the acrylic monomer, can improve the polymerization rate.

[0048] A metallocene compound represented by structural formula (3) and a crosslinkable silyl group-containing thiol compound represented by structural formula (4) are used as polymerization catalysts, and an acrylic monomer having a polymerizable unsaturated bond is polymerized in the presence of the catalyst to obtain a crosslinkable silyl group-containing vinyl organic polymer, which has at least one terminal a residue (-S-R) in which a hydrogen atom has been eliminated from the crosslinkable silyl group-containing thiol compound used as the catalyst. ３３ ) is bonded. ３３ is a group having a crosslinkable silyl group.

[0049] In the present invention, a metallocene compound represented by structural formula (3) and a crosslinkable silyl group-containing thiol compound represented by structural formula (4) are used as polymerization catalysts, and when an acrylic monomer having a polymerizable unsaturated bond is polymerized in the presence of this catalyst, in addition to the crosslinkable silyl group-containing thiol compound, it is also possible to use in combination: alkyl thiol compounds having no functional groups other than thiol groups, such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan, tertiary dodecyl mercaptan, normal dodecyl mercaptan, and octyl mercaptan; aromatic thiol compounds having no functional groups other than thiol groups, such as phenyl mercaptan and benzyl mercaptan; thiol compounds having functional groups other than thiol groups, such as β-mercaptopropionic acid, mercaptoethanol, and thiophenol; polyfunctional thiol compounds esterified with trithioglycerin, pentaerythritol, and β-mercaptopropionic acid; and polymeric thiols having active thiol groups, such as polysulfide polymers.

[0050] In the present invention, in addition to the metallocene compound and the crosslinkable silyl group-containing thiol compound, sulfide compounds such as disulfide compounds, trisulfide compounds, and tetrasulfide compounds can be used for the purpose of adjusting the polymerization rate and degree of polymerization. Examples of disulfide compounds, trisulfide compounds, and tetrasulfide compounds that can be used as polymerization modifiers include diethyl trisulfide, dibutyl tetrasulfide, diphenyl disulfide, bis(2-hydroxyethyl) disulfide, bis(4-hydroxybutyl) tetrasulfide, bis(3-hydroxypropyl) trisulfide, bis(3-carboxypropyl) trisulfide, bis(3-carboxypropyl) tetrasulfide, bis(3-propyltrimethoxysilane) disulfide, and bis(3-propyltriethoxysilane) tetrasulfide. The sulfide compounds can be used alone or in combination of two or more. Such a sulfide compound can be used in the polymerization of the present invention to an extent that it does not deactivate the polymerization. Specifically, it can be used in an amount of, for example, 50 parts by mass or less, preferably 20 parts by mass or less, per 100 parts by mass of the acrylic monomer to be polymerized.

[0051] (Hydrocarbon Polymer) The hydrocarbon polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited as long as it is a hydrocarbon polymer formed by polymerizing a monomer component containing a hydrocarbon monomer. As the hydrocarbon polymer, saturated hydrocarbon polymers are preferred. Examples of hydrocarbon monomers include olefin monomers having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, and isobutylene; diene monomers, such as butadiene and isoprene; and the like. One type of hydrocarbon monomer may be used alone, or two or more types may be used in combination. Of these, isobutylene polymers and hydrogenated polybutadiene polymers are preferred, with isobutylene polymers being particularly preferred, in terms of ease of introducing functional groups to the terminals, ease of controlling the molecular weight, and ease of increasing the number of terminal functional groups.

[0052] Various polymerization methods are available for synthesizing saturated hydrocarbon polymers. In particular, various living polymerizations have been developed. Saturated hydrocarbon polymers, particularly isobutylene polymers, can be easily produced by inifer polymerization, discovered by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed., 1997, Vol. 15, p. 2843). This polymerization method allows for the polymerization of polymers with molecular weights of approximately 500 to 100,000 with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced to the molecular ends. Examples of methods for producing saturated hydrocarbon polymers having crosslinkable silyl groups include cationic polymerization, which uses a combination of an organic halogen compound that generates stable carbocations and a Friedel-Crafts acid catalyst as a polymerization initiator. One example is the method disclosed in Japanese Patent Publication No. 4-69659.

[0053] <Specific Examples of Component (B)> Specific examples of the crosslinkable silyl group-containing vinyl organic polymer, which is component (B), include a crosslinkable silyl group-containing (meth)acrylic polymer. The crosslinkable silyl group-containing (meth)acrylic polymer has, for example, a crosslinkable silyl group and a main chain represented by the structural formula (5): -CH ２ -C(R ５１ ) (COOR ５２ )-...(5) (wherein, R ５１ is a hydrogen atom or a methyl group, R ５２ represents an alkyl group having 1 to 5 carbon atoms), and a (meth)acrylate monomer unit represented by structural formula (6); ２ -C(R ６１ ) (COOR ６２ )-...(6) (wherein, R ６１ is the R ５１ is the same as R ６２ In structural formula (5), R represents an alkyl group having 6 or more carbon atoms. ５２Examples of R include alkyl groups having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. ５２ may be the same or different. ６２ Examples of R include long-chain alkyl groups having 6 or more carbon atoms, typically 7 to 30 carbon atoms, and preferably 8 to 20 carbon atoms, such as 2-ethylhexyl, lauryl, and stearyl groups. ６２ may be the same or different from each other.

[0054] In the main chain, the total amount of the (meth)acrylate monomer units represented by structural formula (5) and the (meth)acrylate monomer units represented by structural formula (6) is more than 50% by mass, preferably 70% by mass or more, based on 100% by mass of the total amount of the main chain. The abundance ratio of the (meth)acrylate monomer units represented by structural formula (5) and the (meth)acrylate monomer units represented by structural formula (6) is preferably 95:5 to 40:60, more preferably 90:10 to 60:40, by mass ratio.

[0055] <Content of Component (B)> The content of component (B) “crosslinkable silyl group-containing vinyl organic polymer” in the moisture-curable curable composition is not particularly limited. It can be, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and can be, for example, 45 parts by mass or less, preferably 40 parts by mass or less, relative to 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A).

[0056] [Component (C)] Component (C) constituting the moisture-curable curable composition of the present invention is silica. Examples of silica include one or more selected from the group consisting of fumed silica, wet silica, precipitated silica, crystalline silica, fused silica, calcined silica, pulverized silica, amorphous silica, quartz, silicic acid anhydride, hydrous silicic acid, and colloidal silica. The silica may be surface-treated with an organosilicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organosilazane compound, a low-molecular-weight siloxane compound, or a diorganocyclopolysiloxane compound, or a coupling agent (silane coupling agent, titanium coupling agent, etc.). Either hydrophilic or hydrophobic silica can be used as the silica. One type of silica may be used alone, or two or more types may be used in combination.

[0057] In the present invention, from the viewpoint of the effect of improving thixotropy and the strength of the cured product of the moisture-curable curable composition, it is preferable to use fumed silica as component (C). Fumed silica is silica produced by flame hydrolysis, which is composed of amorphous, approximately spherical, and few-pore primary particles. Fumed silica can be produced by hydrolyzing silicon tetrachloride as a raw material in a flame of oxygen and hydrogen. Fumed silica differs from wet silica produced by a wet method such as precipitation silica, and is also called "dry silica" or "vapor-phase silica."

[0058] Examples of fumed silica include hydrophilic fumed silica and hydrophobic fumed silica. Hydrophobic fumed silica is obtained by subjecting fumed silica particles to hydrophobic treatment, in which silanol groups on the surface of the fumed silica are reacted with a surface treatment agent having a functional group, such as an organosilicon compound or silicone oil, to chemically fix the surface treatment agent to the surface of the fumed silica particles. On the other hand, hydrophilic fumed silica is fumed silica that has not been subjected to such surface treatment, and has silanol groups on the surface of the fumed silica particles. In the present invention, either hydrophilic fumed silica or hydrophobic fumed silica can be used as the fumed silica. One type of fumed silica may be used alone, or two or more types may be used in combination.

[0059] <Hydrophobic fumed silica> The surface treatment agent used in producing hydrophobic fumed silica is not particularly limited, as long as it is a compound that can make the surface of fumed silica particles hydrophobic.For example, it can be one or more selected from the group consisting of polysiloxane compounds such as dimethyldichlorosilane, polydimethylsiloxane, organohydrogenpolysiloxane; silazane compounds such as hexamethyldisilazane; silane compounds such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, octyltrichlorosilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris(methoxyethoxy)silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and chloropropyltrimethoxysilane; etc. For example, the amount can be 5 parts by mass or more and 75 parts by mass or less per 100 parts by mass of fumed silica.

[0060] The method for treating fumed silica with a surface treatment agent is not particularly limited. For example, untreated fumed silica and a surface treatment agent can be placed in a mechanical mixer or fluidized bed sealed at atmospheric pressure, and mixed at room temperature or by heating, if necessary, in the presence of an inert gas. If necessary, a catalyst can be used to promote the treatment. After the mixing, the mixture can be dried to obtain hydrophobic fumed silica.

[0061] <Average primary particle size> The average primary particle size of silica (C) is not particularly limited. For example, it can be 5 nm or more, preferably 6 nm or more, more preferably 7 nm or more, and for example, it can be 40 nm or less, preferably 30 nm or less, more preferably 20 nm or less. The average primary particle size of silica may be measured using a particle size distribution meter or may be measured by image analysis of images taken with a scanning electron microscope. When using a commercially available product, the catalog value can be used.

[0062] <Specific Surface Area> The specific surface area of ​​silica (C) is not particularly limited. ２ / g or more, preferably 70m ２ / g or more, more preferably 90m ２ / g or more, for example, 400m ２ / g or less, preferably 380m ２ / g or less, more preferably 350m ２ The specific surface area of ​​silica may be measured by the BET method, or when a commercially available product is used, the value listed in the catalog may be used.

[0063] <Commercially Available Products of Component (C)> Silica (C) may be a commercially available product. Examples of commercially available hydrophilic silica include one or more types selected from the group consisting of the AEROSIL series (OX50, 50, 90G, 130, 150, 200, 300, 380, etc.) manufactured by Nippon Aloesil Co., Ltd., the CAB-O-SIL series (MS-5, MS-7, etc.) manufactured by Cabot Corporation, the Reolosil series (QS-09, QS-10, QS-102, QS-103, QS-20, QS-30, Q40, etc.) manufactured by Tokuyama Corporation, and the Nipsil series (LP, etc.) manufactured by Tosoh Silica Corporation.

[0064] Among commercially available hydrophobic silica products, for example, one or more types selected from the group consisting of the AEROSIL series (R927, R974, R976, R976S, RX50, NAX50, NX90G, NX130, RX200, RX300, R812, R202, R504, R805, R711, etc.) manufactured by Nippon Aloesil Co., Ltd., and the Reolosil series (MT-10, DM-10, DM-20S, DM-30, DM-30S, KS-20SC, HG-09, HM-20L, HM-30S, DZ-30ST, PM-09, PM-20, X-20, X-30, etc.) manufactured by Tokuyama Corporation may be mentioned.

[0065] <Content of Component (C)> The content of silica as component (C) in the moisture-curable curable composition of the present invention is not particularly limited. It can be, for example, 5 parts by mass or more, preferably 7 parts by mass or more, and more preferably 10 parts by mass or more, and can be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of component (A) in the moisture-curable curable composition.

[0066] [Component (D)] The moisture-curable composition of the present invention may further contain a vinyl organic polymer (D) containing no crosslinkable silyl groups as component (D). The vinyl organic polymer (D) containing no crosslinkable silyl groups functions as a plasticizer for the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A).

[0067] The vinyl organic polymer constituting the main chain of the vinyl organic polymer not containing a crosslinkable silyl group is not particularly limited as long as it is a vinyl organic polymer that is an addition polymer of a vinyl monomer containing a carbon-carbon unsaturated bond. Examples of the vinyl organic polymer include polystyrene polymers such as poly-α-methylstyrene and polystyrene; ethylene-propylene copolymers; polybutadiene polymers; butadiene-acrylonitrile copolymers; polybutene polymers; hydrogenated polybutadiene polymers; hydrogenated polyisoprene polymers, polyisobutylene polymers; isobutylene-isoprene copolymers; polychloroprene polymers; polyisoprene polymers; isoprene and / or butadiene-acrylonitrile and / or styrene copolymers; hydrocarbon oligomers such as process oil; halogenated hydrocarbons such as chlorinated paraffin; (meth)acrylic acid ester polymers, hydroxyl group-containing (meth)acrylic polymers, carboxyl group-containing (meth)acrylic polymers, epoxy group-containing (meth)acrylic polymers; and dilyl phthalate polymers. The vinyl organic polymer not containing a crosslinkable silyl group may be used alone or in combination of two or more. Among these, the vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer more preferably contains a (meth)acrylic polymer.

[0068] <(Meth)acrylic Polymer> The (meth)acrylic polymer constituting the main chain of the vinyl organic polymer not containing a crosslinkable silyl group is not particularly limited as long as it is a (meth)acrylic polymer obtained by polymerizing a monomer component containing a (meth)acrylate monomer. The (meth)acrylate monomer is not particularly limited as long as it is a monomer having a (meth)acryloyl group. Examples include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate; alicyclic (meth)acrylates; aromatic (meth)acrylates; oxygen-containing (meth)acrylates such as 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate; silyl group-containing (meth)acrylates such as 3-(methacryloyloxypropyl)trimethoxysilane and 3-(methacryloyloxypropyl)dimethoxymethylsilane; (meth)acrylic acid; and fluorine-containing (meth)acrylates. One type of (meth)acrylate monomer may be used alone, or two or more types may be used in combination. Examples of monomers other than (meth)acrylate-based monomers that may be contained in the monomer component containing a (meth)acrylate-based monomer include styrene, maleic anhydride, vinyl acetate, etc. The monomers other than (meth)acrylate-based monomers may be used alone or in combination of two or more.

[0069] In the present invention, examples of the (meth)acrylic polymer constituting the main chain of the vinyl organic polymer not containing a crosslinkable silyl group include (i) a (meth)acrylic polymer composed of a (meth)acrylate monomer, (ii) a (meth)acrylic polymer containing one or more alkyl (meth)acrylate monomers and, if necessary, a (meth)acrylate monomer other than the alkyl (meth)acrylate monomer in combination, etc. From the viewpoints of reducing viscosity, imparting flexibility, imparting tackiness, etc., a (meth)acrylate polymer containing an appropriate amount of an acrylate monomer is preferred.

[0070] There are no particular limitations on the method for producing a (meth)acrylic polymer constituting a vinyl organic polymer that does not contain a crosslinkable silyl group. For example, a radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which predetermined monomer units are copolymerized using a polymerization initiator. Polymers obtained by free radical polymerization methods using an azo compound, peroxide, or the like as a polymerization initiator generally have a large molecular weight distribution value of 2 or more and high viscosity.

[0071] <Content of component (D)> The content of component (D) "vinyl organic polymer not containing a crosslinkable silyl group" in the moisture-curable curable composition of the present invention is not particularly limited. It can be, for example, 45 parts by mass or less, preferably 30 parts by mass or less, relative to 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A). The moisture-curable curable composition of the present invention may or may not contain a vinyl organic polymer (D) not containing a crosslinkable silyl group. In the moisture-curable curable composition of the present invention, the sum of the content of the crosslinkable silyl group-containing vinyl organic polymer (B) and the content of the vinyl organic polymer (D) not containing a crosslinkable silyl group, relative to 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A), can be, for example, 20 parts by mass or more, preferably 22 parts by mass or more, and for example, 60 parts by mass or less, preferably 55 parts by mass or less, more preferably 50 parts by mass or less.

[0072] [Component (E)] The moisture-curable composition of the present invention may contain, as component (E), a moisture-curable polymer (E) other than the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) and the crosslinkable silyl group-containing vinyl organic polymer (B). Examples of the moisture-curing polymer (E) include crosslinkable silyl group-containing polymers that are neither the component (A) nor the component (B), and have a main chain skeleton other than a polysiloxane polymer (e.g., crosslinkable silyl group-containing polyoxyalkylene polymers containing an average of less than 1.3 crosslinkable silyl groups per molecule, crosslinkable silyl group-containing polyoxyalkylene polymers having a number average molecular weight of less than 20,000, crosslinkable silyl group-containing polyester polymers, crosslinkable silyl group-containing polyurethane polymers, crosslinkable silyl group-containing polysulfide polymers, crosslinkable silyl group-containing polyamide polymers, crosslinkable silyl group-containing polycarbonate polymers, crosslinkable silyl group-containing diallyl phthalate polymers, etc.); moisture-curing urethane resins; moisture-curing cyanoacrylate resins; and the like. The moisture-curing polymer (E) may be used alone or in combination of two or more.

[0073] When the moisture-curable polymer (E) is a crosslinkable silyl group-containing polymer, the crosslinkable silyl group may be the same as that described for the component (A). When the moisture-curable polymer (E) is a crosslinkable silyl group-containing polymer, the main chain skeleton is not particularly limited as long as it is a polymer other than a vinyl organic polymer and other than a polysiloxane polymer.

[0074] A moisture-curing urethane resin is a resin that has a urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with moisture in the air or on an adherend to crosslink and cure. The moisture-curing urethane resin may contain one or more isocyanate groups per molecule. In particular, it is preferable for the resin to have isocyanate groups at both ends of the main chain of the molecule.

[0075] Moisture-curable urethane resins can be obtained by reacting a polyol compound having two or more hydroxyl groups per molecule with a polyisocyanate compound having two or more isocyanate groups per molecule, and optionally with a chain extender. The reaction between the polyol compound and the polyisocyanate compound is typically carried out under conditions that result in an excess of isocyanate groups. For example, the molar ratio of hydroxyl groups (OH) in the polyol compound to isocyanate groups (NCO) in the polyisocyanate compound is [NCO] / [OH] = 2.0 to 2.5. The isocyanate group content of the moisture-curable urethane resin is not particularly limited. For example, it is 0.1% by mass or more, preferably 0.3% by mass or more, and 15.0% by mass or less, preferably 10.0% by mass or less. A urethane catalyst or organic solvent can also be used to synthesize the moisture-curable urethane resin.

[0076] Examples of moisture-curable cyanoacrylate resins include reactive resin compositions containing α-cyano(meth)acrylate. Moisture-curable cyanoacrylate resins exhibit high curability and strong adhesive properties even in the presence of trace amounts of moisture adsorbed on the surface of an adherend or in the air.

[0077] The content of component (E) "a moisture-curable polymer other than the crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) and the crosslinkable silyl group-containing vinyl organic polymer (B)" in the moisture-curable curable composition is not particularly limited. For example, it can be contained in an amount of 50.0 parts by mass or less, preferably 40.0 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0078] [Component (F)] The moisture-curable curable composition of the present invention may contain, as necessary, other components (F) as component (F) in addition to the components (A), (B), (C), (D), and (E). Examples of other components (F) include plasticizers other than the components (B) and (D), light stabilizers, ultraviolet absorbers, antioxidants, diluents, moisture absorbers, adhesion promoters, curing catalysts, thixotropy-imparting agents (anti-sagging agents), colorants, antioxidants, tackifiers, flame retardants, mildew inhibitors, and fillers other than the component (C). One type of other component (F) may be used alone, or two or more types may be used in combination.

[0079] <Plasticizer Other Than Component (B)> The moisture-curable curable composition of the present invention may contain a plasticizer other than component (B). The plasticizer other than component (B) is used for the purposes of improving the elongation properties of the cured product of the moisture-curable curable composition and promoting a low modulus. Examples of plasticizers other than component (B) include phthalate ester compounds such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diisononyl phthalate, and diisoundecyl phthalate; aliphatic dibasic acid ester compounds such as dioctyl adipate, isodecyl succinate, dioctyl sebacate, and dibutyl adipate; alicyclic dibasic acid ester compounds such as diisononyl 1,2-cyclohexanedicarboxylate (DINCH), dimethyl 1,2-cyclohexanedicarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di(n-butyl) 1,2-cyclohexanedicarboxylate, di(2-ethylhexyl) 1,2-cyclohexanedicarboxylate, and diisodecyl 1,2-cyclohexanedicarboxylate; glycol ester compounds such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and pentaerythritol ester; and fatty acid esters such as butyl oleate and methyl acetylricinoleate. ester compounds; phosphate ester compounds such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributyl phosphate, and tricresyl phosphate; epoxy-based plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxy benzyl stearate; polyester-based plasticizers such as polyester compounds of dibasic acids and dihydric alcohols; polyether-based plasticizers such as polypropylene glycol derivatives and polyethylene glycol derivatives; polyoxyethylene alkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl methyl ether, tetraethylene glycol diethyl ether, and polyoxyethylene dimethyl ether; and the like.The plasticizers other than the component (B) may be used singly or in combination of two or more.

[0080] The content of the plasticizer other than component (B) in the moisture-curable curable composition is not particularly limited, and may be, for example, 35.0 parts by mass or less, preferably 30.0 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0081] <Light Stabilizer> The moisture-curable curable composition of the present invention may contain a light stabilizer. The light stabilizer is used for the purpose of improving the weather resistance of a cured product of the moisture-curable curable composition, etc. Examples of the light stabilizer include benzotriazole-based light stabilizers, benzophenone-based light stabilizers, hindered amine-based light stabilizers, nickel-based light stabilizers, and benzoate-based light stabilizers. For example, benzotriazole-based light stabilizers such as 2-(3,5-di-t-amyl-2'hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, and 2-[2-hydroxy-3,5-di(1,1-dimethylbenzyl)]-2H-benzotriazole; benzophenone-based light stabilizers such as 2-hydroxy-4-(octyloxy)benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, 2-hydroxy-4-n-dodecyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, dimethyl succinate / 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene(2,2,6,6-tetramethyl-4-piperidyl)imino], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1H,3H,5H)trione, Examples of the light stabilizer include hindered amine-based light stabilizers such as this(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione; nickel-based light stabilizers such as [2,2'-thio-bis(4-t-octylphenolate)]-2-ethylhexylamine-nickel(II), nickel dibutyldithiocarbamate, and [2',2'-thio-bis(4-t-octylphenolate)]n-butylamine-nickel; and benzoate-based light stabilizers such as 2,4-di-t-butylphenyl-3,5'-di-t-butyl-4'-hydroxybenzoate. These light stabilizers may be used alone or in combination of two or more.

[0082] The content of the light stabilizer in the moisture-curable curable composition is not particularly limited, and may be, for example, 5.0 parts by mass or less, preferably 4.0 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0083] <Ultraviolet Absorber> The moisture-curable curable composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is used to prevent ultraviolet degradation of the moisture-curable curable composition and improve weather resistance. Examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, salicylate-based, substituted tolyl-based, and metal chelate-based ultraviolet absorbers. Examples of the ultraviolet absorber include 2,4-di-t-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and a reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300. benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-6-(straight-chain and branched-chain dodecyl)-4-methylphenol; triazine-based ultraviolet absorbers such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol; benzophenone-based ultraviolet absorbers such as octabenzone; benzoate-based ultraviolet absorbers such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate; etc. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

[0084] The content of the ultraviolet absorber in the moisture-curable curable composition is not particularly limited, and may be, for example, 10.0 parts by mass or less, preferably 5.0 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0085] <Antioxidant> The moisture-curable curable composition of the present invention may contain an antioxidant. The antioxidant is used for the purpose of suppressing oxidation of the moisture-curable curable composition and improving weather resistance and heat resistance, etc. Examples of the antioxidant include hindered phenol-based, hindered amine-based, phenol-based, organic sulfur-based, and organic phosphorus-based antioxidants. Of these, hindered phenol-based and / or hindered amine-based antioxidants are preferred. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0086] Examples of hindered phenol antioxidants include pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propioamide], 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoate C ７ -C ９Side chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexane-t-butyl-4-a,a',a''-(mesitylene-2,4,6-tolyl)tri-p-cresol, calcium diethyl bis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate], 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-t- butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, reaction products of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, tris(2,4-di-t-butylphenyl)phosphite, and the like.

[0087] Examples of the hindered amine antioxidant include N,N',N'',N'''-tetrakis-(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine / 1,3,5-triazine / N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine / N-(2,2,6,6-tetramethyl-4-piperidyl) Polycondensation polymer of 2,2,6,6-tetramethyl-1-octyloxy)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl)decanediate methyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane (70%) - polypropylene (30%), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4 -piperidyl) sebacate, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, and the like.

[0088] The content of the antioxidant in the moisture-curable curable composition is not particularly limited, and may be, for example, 10.0 parts by mass or less, preferably 5.0 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0089] <Moisture absorbent> The moisture-curable curable composition of the present invention may contain a moisture absorbent. The moisture absorbent is used for the purpose of improving the storage stability of the moisture-curable curable composition by absorbing moisture in the moisture-curable curable composition. Examples of moisture absorbents include inorganic moisture absorbents such as zeolite, calcium oxide, magnesium oxide, and zinc oxide; and silane compound moisture absorbents such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane. One type of moisture absorbent may be used alone, or two or more types may be used in combination.

[0090] The content of the moisture absorbent in the moisture-curable composition is not particularly limited, and may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable composition.

[0091] <Adhesion imparting agent> The moisture-curable curable composition of the present invention may contain an adhesion imparting agent. The adhesion imparting agent is used for the purpose of improving the adhesion of the moisture-curable curable composition and accelerating curing. Examples of the adhesion imparting agent include a compound represented by the following structural formula (7): Si(R ７１ ) ４－ａ５ X ７１ ａ５ ...(7) (In structural formula (7), R ７１ represents a hydrocarbon group having 1 to 20 carbon atoms, 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, R ７２ ３ SiO-(R ７２ is R ７１ a triorganosiloxy group represented by the formula (same as above), or —CH ２ OR ７３ Group (R ７３ is R７１ (same as R ７１ is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen, -OR ７４ , -NR ７５ R ７６ , -N=R ７７ , -SR ７８ (R ７４ , R ７５ , R ７６ , R ７８ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; R ７７ represents a hydrocarbon group having 1 to 20 carbon atoms, which may or may not have a divalent substituent, and represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a perfluoroalkyl group having 1 to 20 carbon atoms, a glycidyl group, an isocyanate group, or a cyano group. ７１ When there are two or more R ７１ may be the same or different. ７１ represents a hydroxyl group or a hydrolyzable group (such as a halogen group or an alkoxy group having 1 to 6 carbon atoms), and X ７１ If there are two or more X ７１ may be the same or different, and a5 is an integer of 0, 1, 2, or 3.

[0092] Examples of adhesion promoters include 3-aminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane), 3-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane), 3-aminopropylmethyldimethoxysilane (3-aminopropylmethyldimethoxysilane), 3-aminopropylmethyldiethoxysilane (3-aminopropylmethyldiethoxysilane), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(β-aminoethyl)-3-aminopropyltriethoxysilane, N- Isocyanurate silanes such as (2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane, and tris(3-trimethoxysilylpropyl)isocyanurate; N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3- amino group-containing silanes such as alkoxysilanes containing a secondary amino group and / or a tertiary amino group, such as N-ethyl-3-aminoisobutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)- ... Epoxy group-containing silanes such as ethyltrimethoxysilane, 4-oxiranylbutyltrimethoxysilane, and 8-oxiranyloctyltrimethoxysilane; mercapto group-containing silanes such as alkoxysilanes containing a mercapto group, such as 2-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane;Silanes containing vinyl-type unsaturated groups, such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloyloxypropyltrimethoxysilane, and acryloyloxypropylmethyldimethoxysilane; chlorine atom-containing silanes, such as 3-chloropropyltrimethoxysilane; 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, isocyanate-containing silanes such as (isocyanatemethyl)triethoxysilane and (isocyanatemethyl)diethoxymethylsilane; hydrosilanes such as methyldimethoxysilane, trimethoxysilane and methyldiethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane and tetra-t-butoxysilane; and the like. One type of adhesion promoter may be used alone, or two or more types may be used in combination.

[0093] The content of the adhesion promoter in the moisture-curable curable composition is not particularly limited, and may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0094] <Curing Catalyst> The moisture-curable composition of the present invention may contain a curing catalyst. The curing catalyst is a catalyst for the moisture-curing reaction of the crosslinkable silyl group, and is used for the purpose of accelerating the curing of the moisture-curable composition.Examples of the curing catalyst include tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanoate (dioctyltin diversatate), dioctyltin oxide, and reaction products of dibutyltin oxide with phthalate esters; tin dioctylate, tin dinaphthenate, tin distearate, tin dineodecanoate (tin diversatate), and the like. organic tin compounds such as divalent tin compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate, titanium chelates, and the like; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, and the like; reaction products of bismuth salts such as bismuth-tris(2-ethylhexoate) and bismuth-tris(neodecanoate) with organic carboxylic acids or organic amines, and the like; chelate compounds such as zirconium tetraacetylacetonate, and the like; organic lead compounds such as lead octoate, and the like; organic iron compounds such as iron naphthenate, and the like; organic vanadium compounds; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidinium Examples of the curing catalyst include amine compounds such as amine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), or their salts with carboxylic acids, etc.; low-molecular-weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; acidic phosphoric acid compounds; compounds having a fluorosilyl group; and boron halide compounds. Of these curing catalysts, organotin compounds and / or titanium compounds are preferred.The curing catalyst may be used alone or in combination of two or more.

[0095] Examples of organic tin compounds include tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanoate (dioctyltin diversatate), dioctyltin oxide, and reaction products of dibutyltin oxide with phthalic acid esters; and divalent tin compounds such as tin dioctylate, tin dinaphthenate, tin distearate, and tin dineodecanoate (tin diversatate). One type of organic tin compound may be used alone, or two or more types may be used in combination.

[0096] Examples of titanium-based compounds include one or more selected from the group consisting of titanium chelates represented by structural formula (8) and titanium chelates represented by structural formula (9). In structural formula (8), n6 R ８１ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4 to n6 R ８２ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4 to n6 R ８３ and 4-n6 R ８４ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; and n6 is 0, 1, 2, or 3.

[0097] In structural formula (9), R ９１ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and two R ９２ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and two R ９３ and two R ９４ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The titanium-based compounds may be used alone or in combination of two or more.

[0098] Examples of titanium chelates represented by structural formula (8) or structural formula (9) include titanium dimethoxide bis(ethylacetoacetate), titanium diethoxide bis(ethylacetoacetate), titanium diisopropoxide bis(ethylacetoacetate), titanium diisopropoxide bis(methylacetoacetate), titanium diisopropoxide bis(t-butylacetoacetate), titanium diisopropoxide bis(methyl-3-oxo-4 ,4-dimethylhexanoate), titanium diisopropoxide bis(ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium di-n-butoxide bis(ethyl acetoacetate), titanium diisobutoxide bis(ethyl acetoacetate), titanium di-t-butoxide bis(ethyl acetoacetate), titanium di-2-ethylhexoxide bis(ethyl acetoacetate), titanium bis(1-methoxy-2-propoxide) bis (ethyl acetoacetate), titanium bis(3-oxo-2-butoxide) bis(ethyl acetoacetate), titanium bis(3-diethylaminopropoxide) bis(ethyl acetoacetate), titanium triisopropoxide(ethyl acetoacetate), titanium triisopropoxide(allyl acetoacetate), titanium triisopropoxide(methacryloxyethyl acetoacetate), 1,2-dioxyethane titanium bis(ethyl acetoacetate acetate), 1,3-dioxypropane titanium bis(ethyl acetoacetate), 2,4-dioxypentane titanium bis(ethyl acetoacetate), 2,4-dimethyl-2,4-dioxypentane titanium bis(ethyl acetoacetate), titanium tetrakis(ethyl acetoacetate), titanium bis(trimethylsiloxy)bis(ethyl acetoacetate), titanium bis(trimethylsiloxy)bis(acetylacetonate), etc. Among these, titanium diethoxide bis(ethyl acetoacetate), titanium diisopropoxide bis(ethyl acetoacetate), titanium dibutoxide bis(ethyl acetoacetate), etc. are mentioned, with titanium diisopropoxide bis(ethyl acetoacetate) being more preferred.The titanium chelates may be used alone or in combination of two or more.

[0099] Examples of chelating agents capable of forming chelating ligands for titanium chelates include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, 2-methacryloxyethyl acetoacetate, methyl 3-oxo-4,4-dimethylhexanoate, and ethyl 3-oxo-4,4,4-trifluorobutanoate, with methyl acetoacetate and ethyl acetoacetate being preferred, and ethyl acetoacetate being more preferred. When two or more chelating ligands are present, the respective chelating ligands may be the same or different.

[0100] In addition to the organotin compound and / or titanium compound, the moisture-curable composition of the present invention can also use other curing catalysts in combination to the extent that the effects of the present invention are not impaired. Examples of other curing catalysts include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. Examples of silanol condensation catalysts include dialkyltin oxides such as stannous octoate, dimethyltin oxide, dibutyltin oxide, and dioctyltin oxide; reaction products of dibutyltin oxide and phthalic acid esters; titanate esters such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic lead acids such as lead octoate and lead naphthenate; organic bismuth acids such as bismuth octoate, bismuth neodecanoate, and bismuth rosinate; and other acidic and basic catalysts known as silanol condensation catalysts. However, depending on the amount of organotin compound added, the toxicity of the resulting moisture-curable curable composition may increase. The silanol condensation catalyst may be used alone or in combination of two or more.

[0101] Among these curing catalysts, organometallic compounds or combinations of organometallic compounds and amine compounds are preferred in terms of curability.Furthermore, dibutyltin maleate, reaction products of dibutyltin oxide and phthalic acid ester, dibutyltin diacetylacetonate, dioctyltin dineodecanoate, and reaction products of dioctyltin oxide and alkoxysilane are preferred in terms of fast curing speed.Similarly, titanium compounds may also be used.

[0102] The content of the curing catalyst in the moisture-curable curable composition is not particularly limited, and may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0103] <Thixotropy-imparting agent (sagging prevention agent)> The moisture-curable curable composition of the present invention may contain a thixotropy-imparting agent (sagging prevention agent). The thixotropy-imparting agent is used for the purpose of adjusting the thixotropy of the moisture-curable curable composition and preventing sagging during application. Examples of the thixotropy-imparting agent include light calcium carbonate, magnesium carbonate, diatomaceous earth, precipitated silica, silicic anhydride, hydrated silicic acid, calcium silicate, silica, titanium dioxide, clay, calcined clay, talc, slate powder, mica, kaolin, zeolite, carbon black (ketjen black, acetylene black, furnace black, channel black, thermal black, etc.), sepiolite, polymer powders ((meth)acrylic acid ester-based, polystyrene-based, polyvinyl chloride-based, polyethylene-based, modified polyester polyol-based, rubber-based, etc.), and benzophenone-based. Examples of the thixotropic agent include thixotropic agents such as thixotropic cellulose, ...

[0104] The volume average particle size of the thixotropy-imparting agent is not particularly limited and can be, for example, 20 μm or less, preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 0.1 μm or less, and can be, for example, 0.005 μm or more.

[0105] <Diluent> The moisture-curable curable composition of the present invention may contain a diluent. The diluent is used for the purpose of adjusting the physical properties, such as the viscosity, of the moisture-curable curable composition. Examples of diluents include saturated hydrocarbon solvents such as normal paraffin and isoparaffin; α-olefin derivatives such as Linearene Dimer (trade name manufactured by Idemitsu Kosan Co., Ltd.); aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, and diacetone alcohol; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate; citrate ester solvents such as acetyl triethyl citrate, acetyl tributyl citrate, and triethyl citrate; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. One type of diluent may be used alone, or two or more types may be used in combination.

[0106] The flash point of the diluent is not particularly limited. In consideration of the safety of the moisture-curable curable composition, the flash point of the diluent is desirably higher than 60°C. The boiling point of the diluent is not particularly limited. In order to suppress volatile substances from the moisture-curable curable composition, the boiling point of the diluent is preferably higher than 100°C.

[0107] The content of the diluent in the moisture-curable curable composition is not particularly limited, and may be, for example, 20 parts by mass or less, preferably 15 parts by mass or less, per 100 parts by mass of component (A) in the moisture-curable curable composition.

[0108] <Colorant> The moisture-curable curable composition of the present invention may contain a colorant. The colorant is used for the purpose of coloring the moisture-curable curable composition to a desired color tone, etc. Examples of the colorant include inorganic pigments such as carbon black, red iron oxide, titanium dioxide, and zinc oxide; organic pigments; dyes; etc. One type of colorant may be used alone, or two or more types may be used in combination.

[0109] <Antiaging Agent> The moisture-curable curable composition of the present invention may contain an antioxidant. The antioxidant is used for the purpose of preventing thermal degradation of the moisture-curable curable composition and improving its heat resistance, etc. Examples of the antioxidant include amine-ketone antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and a reaction product of diphenylamine and acetone; N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamido)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p aromatic secondary amine-based antioxidants such as N-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, and N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine; benzimidazole-based antioxidants such as 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts of 2-mercaptobenzimidazole; thiourea-based antioxidants such as 1,3-bis(dimethylaminopropyl)-2-thiourea and tributylthiourea; and phosphorous-based antioxidants such as tris(nonylphenyl)phosphite. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0110] <Tackifier> The moisture-curable curable composition of the present invention may contain a tackifier. The tackifier is used for the purpose of improving the adhesion of the moisture-curable curable composition and improving initial fixation, etc. Examples of tackifiers include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenating these, terpene-phenol resins obtained by copolymerizing a terpene compound with a phenol compound, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene resins, styrene copolymer resins, and petroleum resins (e.g., C ５ Hydrocarbon resin, C ９ Hydrocarbon resin, C ５ C ９ Examples of the tackifier include hydrocarbon copolymer resins, hydrogenated petroleum resins, dicyclopentadiene resins, etc. The tackifier may be used alone or in combination of two or more.

[0111] <Flame Retardant> The moisture-curable curable composition of the present invention may contain a flame retardant. The flame retardant is used for the purpose of improving the flame retardancy of the moisture-curable curable composition and a cured product thereof, for example. Examples of the flame retardant include phosphorus-based flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide-based flame retardants such as antimony trioxide; bromine-based flame retardants; chlorine-based flame retardants; and metal hydroxide-based flame retardants such as aluminum hydroxide and magnesium hydroxide. One type of flame retardant may be used alone, or two or more types may be used in combination.

[0112] [Form of Moisture-Curable Curable Composition] The form of the moisture-curable curable composition of the present invention is not particularly limited and can be appropriately determined depending on the application, constituent components, etc. For example, it can be a one-component moisture-curable curable composition containing at least component (A), component (B), and component (C). For example, it can be a two-component moisture-curable curable composition composed of a first part containing at least component (A) and component (B) and a second part containing at least a curing catalyst. In this case, the silica of component (C) may be contained in either or both of the first part and the second part. The moisture-curable curable composition of the present invention can be particularly suitably used as a one-component type.

[0113] The moisture-curable curable composition of the present invention may be a room-temperature curable type or a heat-curable type. For example, if it can be cured at room temperature (25°C) by moisture in the air, it can be a room-temperature curable moisture-curable curable composition. In this case, if necessary, curing may be accelerated by heating. For example, it can be a heat-curable room-temperature curable adhesive composition that is cured by adding moisture (water) to the moisture-curable curable composition and heating it.

[0114] [Method for producing moisture-curable curable composition] The method for producing the moisture-curable curable composition is not particularly limited. It can be produced by mixing component (A), component (B), component (C), and other component (D) in a container and degassing and stirring. When the moisture-curable curable composition is a one-component type, for example, it can be produced by taking predetermined amounts of component (A), component (B), component (C), and other component (D) used as needed, mixing them in a container, and degassing and stirring. The order of compounding component (A), component (B), component (C), and other component (D) used as needed is not particularly limited and can be determined appropriately. When the moisture-curable curable composition is a two-component type, for example, component (A) and component (B) are used as a first part, and the curing catalyst is used as a second part, and each is placed in a separate container, and component (C) and other component (D) are mixed into either the first part and / or the second part.

[0115] The mixing step is, for example, a step of preparing a moisture-curable curable composition by mixing components (A), (B), (C), and (D), which is used as needed, by a conventionally known method. The mixing step does not require the use of a completely sealable mixing device, and can be carried out in the presence of air. However, the use of a completely sealable mixing device is not excluded. In the manufacturing process, the moisture-curable curable composition of the present invention must undergo a container filling step in which the moisture-curable curable composition is filled into a sealed container. The filling method can be a conventionally known method and is not particularly limited.

[0116] The moisture-curable curable composition of the present invention is preferably stored in a sealed container to ensure storage stability, since the crosslinkable silyl groups cure through a crosslinking reaction caused by moisture in the air. The shape of the sealed container is not particularly limited as long as it can seal the moisture-curable curable composition, and may be selected depending on the application. Examples of the sealed container include a pail that can store 3 to 50 L of the moisture-curable curable composition, and a cartridge container or tube container that can store less than 1 L of the moisture-curable curable composition.

[0117] [Uses of Moisture-Curable Composition] The moisture-curable composition of the present invention is a moisture-curable composition excellent in transparency, adhesiveness, and weather resistance, and is capable of forming a cured product excellent in transparency, adhesiveness, and weather resistance. Therefore, it can be used for various applications, such as adhesives, sealants, pressure-sensitive adhesives, coating materials, potting materials, paints, putty materials, primers, etc. for buildings, automobiles, civil engineering, the electrical and electronic fields, households, etc. In particular, it can be suitably used as a sealant or adhesive.

[0118] {Sealant} The sealant of the present invention is a sealant containing the moisture-curable curable composition. The sealant of the present invention has excellent adhesion to various metals, various plastics, glass, ceramics, stone, wood materials, concrete, etc., and is used, for example, as a sealant for buildings, automobiles, civil engineering, the electrical and electronic fields, households, etc. The sealant of the present invention can be used, for example, as an elastic sealant for buildings, a sealant for double-glazing, a sealant for rust prevention and waterproofing of glass edges, a sealant for the back surface of solar cells, a sealant for outdoor construction of buildings, a sealant for indoor construction of buildings, a sealant for ships, a sealant for automobiles, a sealant for roads, a sealant for electrical and electronic devices, a sealant for household appliances, etc.

[0119] {Adhesive} The adhesive of the present invention is an adhesive comprising the moisture-curable curable composition. The adhesive of the present invention has excellent adhesion to various metals, various plastics, glass, ceramics, stone, wood materials, concrete, etc., and is used as an adhesive for these substrates. The adhesive of the present invention is used, for example, as an adhesive for structures, buildings, civil engineering, automobiles, electrical and electronic applications, household applications, etc. The adhesive of the present invention can be used, for example, as an adhesive for interior panels, adhesive for exterior panels, adhesive for stone veneer, adhesive for ceiling finishes, adhesive for floor finishes, adhesive for wall finishes, adhesive for vehicle panels, adhesive for assembling electrical, electronic, and precision equipment, adhesive for structures, etc.

[0120] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." The contents of each component in Tables 1 and 2 are all in parts by mass.

[0121] [Production of moisture-curable resin] <Synthesis Example 1> Using polyoxypropylene glycol as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polyoxypropylene (P-1) having hydroxyl groups at both ends, a number average molecular weight of 29,000, and a molecular weight distribution Mw / Mn = 1.25. A methanol solution of sodium methoxide was added to the obtained hydroxyl-terminated polyoxypropylene (P-1), and then allyl chloride was added to convert the terminal hydroxyl groups to allyl groups, thereby obtaining polyoxypropylene (Q-1) having allyl groups at its ends. A platinum divinyldisiloxane complex solution was added to polyoxypropylene (Q-1) having allyl groups at its ends, and dimethoxymethylsilane was then added dropwise with stirring to allow the mixture to react, thereby obtaining a crosslinkable silyl group-containing polyoxypropylene organic polymer A-1 having an average of 1.3 dimethoxymethylsilyl groups per molecule and a number average molecular weight of approximately 29,000.

[0122] Synthesis Example 2 In the same manner as in Synthesis Example 1, a polymer A-2 having an average of 1.5 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 26,000 was obtained.

[0123] Synthesis Example 3 In the same manner as in Synthesis Example 1, a polymer A-3 having an average of 1.6 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 21,000 was obtained.

[0124] Synthesis Example 4 In the same manner as in Synthesis Example 1, a polymer A-4 having an average of 1.7 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 29,000 was obtained.

[0125] Synthesis Example 5 Using ruthenocene dichloride as the metallocene compound metal catalyst, butyl acrylate was polymerized in the presence of 3-mercaptopropyltrimethoxysilane to obtain a crosslinkable silyl group-containing vinyl organic polymer (trimethoxysilane group-containing acrylic organic polymer) B-1 having one crosslinkable silyl group at the end, a weight-average molecular weight of approximately 4,500, and a glass transition temperature (Tg) of −60° C. The weight-average molecular weight was measured by gel permeation chromatography, and the glass transition temperature was measured by the TMA method.

[0126] Synthesis Example 6 A mixture of 20 parts by mass of methyl methacrylate, 47 parts by mass of butyl acrylate, 30 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of 3-methacryloxypropyltrimethoxysilane, and 1 part by mass of di-tertiarybutyl peroxide was supplied to a stirred tank reactor and polymerized by bulk polymerization at a reaction temperature of 235°C. Unreacted monomers were removed to obtain a crosslinkable silyl group-containing vinyl polymer (trimethoxysilane group-containing acrylic organic polymer) B-2 having 0.18 crosslinkable silyl groups at its terminals and a weight-average molecular weight of approximately 2,500. The weight-average molecular weight was measured by gel permeation chromatography.

[0127] Synthesis Example 7 In the same manner as in Synthesis Example 1, a polymer E-1 having an average of 1.6 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 9,000 was obtained.

[0128] Synthesis Example 8 In the same manner as in Synthesis Example 1, a polymer E-2 having an average of 1.5 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 11,000 was obtained.

[0129] Synthesis Example 9 In the same manner as in Synthesis Example 1, a polymer E-3 having an average of 1.0 terminal dimethoxymethylsilyl group per molecule and a number average molecular weight of about 8,000 was obtained.

[0130] Synthesis Example 10 In the same manner as in Synthesis Example 1, a polymer E-4 having an average of 1.6 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 15,000 was obtained.

[0131] Synthesis Example 11 In the same manner as in Synthesis Example 1, a polymer E-5 having an average of 2.1 terminal dimethoxymethylsilyl groups per molecule and a number average molecular weight of about 16,000 was obtained.

[0132] [Constituents of moisture-curable curing composition] <Crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) containing an average of 1.3 or more crosslinkable silyl groups per molecule and having a number average molecular weight of 20,000 or more> A-1: ​​A crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 1, containing an average of 1.3 dimethoxymethylsilyl groups per molecule and having a number average molecular weight of approximately 29,000 A-2: A crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 2, containing an average of 1.5 dimethoxymethylsilyl groups per molecule and having a number average molecular weight of approximately 26,000 A-3: A crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 3, containing an average of 1.6 dimethoxymethylsilyl groups per molecule and having a number average molecular weight of approximately 21,000 A-4: A crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 4, containing an average of 1.7 dimethoxymethylsilyl groups per molecule and having a number average molecular weight of approximately 29,000.

[0133] <Crosslinkable silyl group-containing vinyl organic polymer (B)> B-1: A crosslinkable silyl group-containing vinyl polymer obtained in Synthesis Example 5, containing an average of 1.0 trimethoxysilyl group per molecule and having a weight-average molecular weight of about 4,500. B-2: A crosslinkable silyl group-containing vinyl polymer obtained in Synthesis Example 6, containing an average of 0.18 trimethoxysilyl groups per molecule and having a weight-average molecular weight of about 2,500.

[0134] <Silica (C)> C-1: Hydrophobic fumed silica C-2: Hydrophilic fumed silica

[0135] <Vinyl organic polymer (D) not containing a crosslinkable silyl group> D-1: (meth)acrylic organic polymer (weight average molecular weight 2,500)

[0136] <Moisture-curable polymers (E) other than component (A) and component (B)> E-1: a crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 7, containing an average of 1.6 dimethoxymethylsilyl groups per molecule and having a number-average molecular weight of approximately 9,000. E-2: a crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 8, containing an average of 1.5 dimethoxymethylsilyl groups per molecule and having a number-average molecular weight of approximately 11,000. E-3: a crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 9, containing an average of 1.0 dimethoxymethylsilyl group per molecule and having a number-average molecular weight of approximately 8,000. E-4: a crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 10, containing an average of 1.6 dimethoxymethylsilyl groups per molecule and having a number-average molecular weight of approximately 15,000. E-5: A crosslinkable silyl group-containing polyoxypropylene organic polymer obtained in Synthesis Example 11, containing an average of 2.1 dimethoxymethylsilyl groups per molecule and having a number average molecular weight of approximately 16,000.

[0137] <Other components (F)> F-1: Hindered amine light stabilizer F-2: Triazine ultraviolet absorber F-3: Hindered phenol antioxidant F-4: Silane moisture absorber F-5: Amino group-containing silane adhesion promoter F-6: Organotin curing catalyst

[0138] <Ingredients for preparing the comparative example> R-1: Phthalate ester plasticizer R-2: Polypropylene glycol plasticizer R-3: Calcium carbonate

[0139] [Evaluation of Moisture-Curable Curable Composition] <Transparency> The moisture-curable curable composition was poured to a thickness of 5 mm and cured, and the transparency was measured using a haze meter and evaluated according to the following criteria. In the present invention, A is pass and B is fail. (Evaluation criteria) A: Haze value is 20 or less B: Haze value is more than 20

[0140] <Adhesion> In accordance with "5.20 Tensile Adhesion Test" in "JIS A 1439 Test Methods for Sealant for Construction," a test for tensile adhesion after curing was carried out under the following conditions: Curing conditions: 23±2°C, (50±10)% RH for 14 days (pre-curing), 30±2°C for 14 days (post-curing) Adherend: Aluminum anodized film (A6063S) Primer: No primer was used, and the results were evaluated according to the following criteria. In the present invention, A is a pass, and B and C are fail. (Evaluation criteria) A: Maximum tensile stress 0.4 N / mm ２ or more, and elongation rate at maximum load is 300% or more B: Maximum tensile stress 0.4 N / mm ２ C: Maximum tensile stress 0.4 N / mm or more or elongation at maximum load 300% or more ２ and elongation rate at maximum load is less than 300%

[0141] <Weather resistance> The moisture-curable composition was poured to a thickness of 5 mm, cured, and then aged at 23±2°C and (50±10)% RH for 7 days. Then, accelerated exposure was performed using a metal weather meter under the following conditions: irradiance: 81 mW / cm ２ (300nm to 400nm), black panel temperature: 63°C, relative humidity in the test chamber during irradiation: 50% RH, irradiation time: 200 hours, exposure cycle: (irradiation + water spray) 2 minutes + (irradiation only) 118 minutes. The test was carried out under these conditions, and changes in the surface (crack state) were observed. The evaluation was carried out in accordance with JIS A 1439 5.21 Dynamic Weathering Test, and the evaluation was based on the QW value using the following criteria. The QW value is the Q value x the W value, where the Q value indicates an evaluation value for the amount of cracks and the W value indicates an evaluation value for the width of the cracks. In the present invention, A is a pass, and B and C are fail. (Evaluation criteria) A: QW value 0 to 5 B: QW value 6 to 15 C: QW value 16 to 25

[0142] <Overall Evaluation> An overall evaluation was made based on the evaluation of transparency, adhesion, and weather resistance. The overall evaluation was performed according to the following criteria. In the present invention, A is pass, and B and C are fail. (Evaluation criteria) A: The evaluation values ​​of transparency, adhesion, and weather resistance are all A. B: The evaluation values ​​of transparency, adhesion, and weather resistance include B, but do not include C. C: The evaluation values ​​of transparency, adhesion, and weather resistance include C.

[0143] [Example 1] A vessel equipped with a stirrer, thermometer, nitrogen inlet, component charging tube, and water-cooled condenser was charged with 100.0 parts by mass of A-1 as component (A), 25.0 parts by mass of B-1 as component (B), 15.0 parts by mass of C-1 as component (C), 2.0 parts by mass of F-1 as other components, 2.0 parts by mass of F-2, and 0.5 parts by mass of F-3, and the mixture was heated under reduced pressure and stirred to dehydrate the blended materials. Furthermore, 3.0 parts by mass of F-4, 1.3 parts by mass of F-5, and 1.0 part by mass of F-6 were added and stirred to prepare a moisture-curable curable composition. The resulting moisture-curable curable composition was evaluated for transparency, adhesion, and weather resistance. The results are shown in Table 1.

[0144] [Examples 2 to 12, Comparative Examples 1 to 9] Moisture-curable curable compositions were obtained in the same manner as in Example 1, except that the components shown in Table 1 or Table 2 were used in the amounts shown in Table 1 or Table 2, respectively. The resulting moisture-curable curable compositions were evaluated for transparency, adhesion, and weather resistance. The results are also shown in Table 1 or Table 2.

[0145]

[0146]

[0147] As shown in Table 1, the moisture-curable curable compositions of Examples 1 to 12 according to the present invention were excellent in the transparency evaluation, adhesion evaluation, and weather resistance evaluation. As shown in Table 2, Comparative Examples 1 to 4, which did not contain "a crosslinkable silyl group-containing polyoxyalkylene organic polymer (A) containing an average of 1.3 or more crosslinkable silyl groups per molecule and having a number average molecular weight of 20,000 or more," were rated B or C in adhesion evaluation. As shown in Table 2, Comparative Example 5, which contained a vinyl organic polymer not containing a crosslinkable silyl group instead of "a crosslinkable silyl group-containing vinyl organic polymer (B)," Comparative Example 6, which contained a phthalate ester compound, and Comparative Example 7, which contained a polypropylene glycol-based compound, all received a C in weather resistance evaluation. As shown in Table 2, Comparative Example 8, which did not contain "a crosslinkable silyl group-containing vinyl organic polymer (B)," received a C in weather resistance evaluation. As shown in Table 2, Comparative Example 9, which contained calcium carbonate instead of "silica (C)," received a B in transparency evaluation. From this, it can be seen that the moisture-curable curable composition of the present invention is excellent in transparency, adhesion, and weather resistance, and is a moisture-curable curable composition that can form a cured product that is excellent in transparency, adhesion, and weather resistance.

Claims

1. A moisture-curable curable composition containing a crosslinkable silyl group-containing polyoxyalkylene-based organic polymer (A) having an average of 1.3 or more crosslinkable silyl groups per molecule and a number average molecular weight of 20,000 or more, a crosslinkable silyl group-containing vinyl-based organic polymer (B), and silica (C).

2. The moisture-curable curable composition according to claim 1, wherein the crosslinkable silyl group-containing vinyl-based organic polymer (B) contains an average of 1.0 or more and 1.5 or less crosslinkable silyl groups at the molecular terminals and has a weight average molecular weight of 1,000 or more and 7,000 or less.

3. The moisture-curable curable composition according to claim 1 or 2, wherein the silica (C) is hydrophobic fumed silica or hydrophilic fumed silica.

4. The moisture-curable curable composition according to claim 1 or 2, wherein the crosslinkable silyl group-containing vinyl-based organic polymer (B) includes a crosslinkable silyl group-containing (meth)acrylic polymer.

5. The moisture-curable curable composition according to claim 1 or 2, wherein the content of the crosslinkable silyl group-containing vinyl-based organic polymer (B) is 10 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene-based organic polymer (A).

6. The moisture-curable curable composition according to claim 1 or 2, further containing a vinyl-based organic polymer (D) that does not contain a crosslinkable silyl group.

7. The moisture-curable curable composition according to claim 6, wherein the sum of the content of the crosslinkable silyl group-containing vinyl-based organic polymer (B) and the content of the vinyl-based organic polymer (D) that does not contain a crosslinkable silyl group is 20 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene-based organic polymer (A).

8. The moisture-curable curable composition according to claim 1 or 2, containing a moisture-curable polymer (E) other than the crosslinkable silyl group-containing polyoxyalkylene-based organic polymer (A) and other than the crosslinkable silyl group-containing vinyl-based organic polymer (B).

9. A sealing material containing the moisture-curable curable composition according to claim 1 or 2.

10. An adhesive containing the moisture-curable curable composition according to claim 1 or 2.

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