Method for producing organic polymers

Abstract

To provide a hydrolyzable silyl group-containing organic polymer which achieves both good curability and high restorability, and a method for producing the same.SOLUTION: An organic polymer (A) having a structure of formula (1) and a structure of formula (2) in the same molecule is produced by: preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule; forming the structure of formula (2) by hydrosilylation of the carbon-carbon unsaturated bond with a hydrolyzable silyl group-containing hydrosilane compound; and forming the structure of formula (1) by urethanization of the hydroxyl group with a compound having a hydrolyzable silyl group and an isocyanate group. -O-CO-NH-(CR12)m-SiR2aX3-a (1). -O-(CR32)n-SiR4bY3-b (2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an organic polymer having a hydrolyzable silyl group, and an organic polymer having a hydrolyzable silyl group, a curable composition containing the polymer, and a cured product thereof.

Background Art

[0002] An organic polymer having a silicon atom with a hydroxyl group or a hydrolyzable group and capable of forming a siloxane bond (hereinafter referred to as a "hydrolyzable silyl group") is known as a moisture-reactive polymer and is included in many industrial products such as adhesives, sealing materials, coating materials, paints, adhesives, etc., and is used in a wide range of fields. As such a hydrolyzable silyl group-containing organic polymer, various polymers such as a polyoxyalkylene-based polymer, a saturated hydrocarbon-based polymer, and a (meth)acrylate-based copolymer as the main chain skeleton are known.

[0003] As a method for producing a hydrolyzable silyl group-containing organic polymer, for example, after synthesizing a polyoxyalkylene-based polymer having a hydroxyl group at the terminal by ring-opening polymerization of an epoxy compound, converting the hydroxyl group into a carbon-carbon double bond, and performing a hydrosilylation reaction between the carbon-carbon double bond and a silane compound to introduce a hydrolyzable silyl group into the polymer (see, for example, Patent Document 1).

[0004] As another production method, a method of introducing a hydrolyzable silyl group through a urethane bond by reacting a hydroxyl group of a polyoxyalkylene-based polymer with a hydrolyzable silyl group-containing isocyanate compound is also known (see, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] When hydrolyzable silyl group-containing organic polymers are used as sealants and in other applications, the cured product is often required to exhibit high resilience. Furthermore, organotin compounds are known to be highly active as curing catalysts used to cure hydrolyzable silyl group-containing organic polymers. However, due to growing environmental concerns in recent years, the use of non-tin curing catalysts is recommended. Therefore, there is a need for hydrolyzable silyl group-containing organic polymers that can exhibit good curability even when using non-tin catalysts with relatively low activity. However, conventionally known hydrolyzable silyl group-containing organic polymers have made it difficult to achieve both high resilience and good curability.

[0007] In view of the above situation, the present invention aims to provide a hydrolyzable silyl group-containing organic polymer that achieves both good curability and high resilience, and a method for producing the same. [Means for solving the problem]

[0008] As a result of diligent research, the inventors of the present invention have produced an organic polymer having two specific structures containing hydrolyzable silyl groups within the same molecule, and have found that this hydrolyzable silyl group-containing organic polymer can achieve both good curability and high resilience, leading to the present invention.

[0009] In other words, the present invention relates to a method for producing an organic polymer (A) having a structure represented by the following formula (1) and a structure represented by the following formula (2) in the same molecule, -O-CO-NH-(CR 1 2) m -SiR 2 a X 3-a (1) -O-(CR 3 2) n-SiR 4 b Y 3-b (2) (In formula (1), R 1 represents, independently or differently, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 0, 1 or 2. m is an integer from 1 to 5.) In formula (2), R 3 represents, independently or differently, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R 4 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. b is 0, 1 or 2. n is an integer from 1 to 10.) A process for preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule, a step of hydrosilylating a hydrolyzable silyl group-containing hydrosilane compound to the carbon-carbon unsaturated bond to form the structure represented by the formula (2), and a step of urethanizing a compound having a hydrolyzable silyl group and an isocyanate group to the hydroxyl group to form the structure represented by the formula (1). The present invention relates to a method for producing an organic polymer (A). Preferably, the step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is a step of reacting an organic polymer having a hydroxyl group with a carbon-carbon unsaturated bond-containing halide to convert a part of the hydroxyl group into a carbon-carbon unsaturated bond-containing group.) Also preferably, the step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is a step of reacting a polymer having a hydroxyl group with a carbon-carbon unsaturated bond-containing epoxy compound.) Preferably, the organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is an organic polymer having a structure represented by formula (4) described below.) The present invention also relates to an organic polymer (A') having a structure represented by formula (3), which will be described later. In formula (3), m is preferably 1. Preferably, n is 3. Preferably, the polymer backbone of the organic polymer is a polyoxyalkylene polymer. The present invention also relates to a curable composition containing the organic polymer (A'). The curable composition may further contain an organic polymer (B) having one hydrolyzable silyl group per molecule. The curable composition may not contain an organotin compound. Furthermore, the present invention also relates to a cured product obtained by curing the curable composition. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a hydrolyzable silyl group-containing organic polymer that achieves both good curability and high resilience, and a method for producing the same. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described in detail below. [Organic polymer (A)] The manufacturing method according to this embodiment is a method for producing an organic polymer (A) having a hydrolyzable silyl group. The organic polymer (A) has a structure represented by the following formula (1) and a structure represented by the following formula (2) in the same molecule. -O-CO-NH-(CR 1 2) m -SiR 2 a X 3-a (1) -O-(CR 3 2) n -SiR 4 b Y 3-b (2)

[0012] In the structure represented by formula (1), the hydrolyzable silyl group (-SiR 2 a X 3-a) is bonded to the polymer skeleton via urethane bonds, and in the structure represented by formula (2), hydrolyzable silyl groups (-SiR 4 b Y 3-b ) is bonded to the polymer backbone via an oxygen atom. Organic polymer (A) uses different structures of hydrolyzable silyl groups as bonding groups that attach to the polymer backbone. This unique structure, possessing both high resilience and good curability within a single molecule, allows for both. An organic polymer (A) having both the structure of formula (1) and the structure of formula (2) within the same molecule can exhibit higher resilience than a mixture of an organic polymer having the structure of formula (1) and an organic polymer having the structure of formula (2).

[0013] In formula (1), R 1 R represents, either identical or different, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2. m is an integer from 1 to 5.

[0014] In formula (2), R 3 R represents, either identical or different, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 4 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. b is 0, 1, or 2. n is an integer from 1 to 10.

[0015] R 1 and R 3 Each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. If the hydrocarbon group has substituents, the substituents are not particularly limited, but examples include halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups. 1 and R 3Each of these is particularly preferably a hydrogen atom. 1 and R 3 They may be the same or they may be different. Also, multiple Rs 1 They may be the same or different from each other. Multiple R 3 They may be the same as each other, or they may be different.

[0016] R 2 and R 4 Each of these represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. If the hydrocarbon group has substituents, the substituents are not particularly limited, but examples include halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups. 2 and R 4 They may be the same or they may be different. Also, R 2 If multiple instances exist, they may be identical or different. 4 Even if there are multiple instances, they may be identical or different.

[0017] R 2 and R 4 Specific examples include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl groups; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl groups; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, toluyl, and 1-naphthyl groups; and aralkyl groups such as benzyl groups. Preferably, the alkyl groups are substituted or unsubstituted, more preferably methyl, ethyl, chloromethyl, or methoxymethyl groups, even more preferably methyl or methoxymethyl groups, and particularly preferably methyl groups.

[0018] X and Y represent a hydroxyl group or a hydrolyzable group, respectively. Examples of X and Y include hydroxyl groups, hydrogen, halogens, alkoxy groups, acyloxy groups, ketoxymate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. The aforementioned alkoxy groups may have substituents. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle, methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups are more preferred, and methoxy groups and ethoxy groups are even more preferred. A toxic group is particularly preferred. X and Y may be the same or different. Also, if there are multiple Xs, they may be the same or different. Similarly, if there are multiple Ys, they may be the same or different.

[0019] In formula (1), a and in formula (2), b represent 0, 1, or 2, respectively. Preferably, they are 0 or 1. In particular, from the viewpoint of curability, storage stability, and resilience, it is preferable that a is 1 and b is 0.

[0020] In formula (1) above, m represents an integer from 1 to 5. An integer from 1 to 3 is preferred, and 1 or 3 is more preferred. From the viewpoint of curability, m is most preferably 1.

[0021] In formula (2) above, n represents an integer from 1 to 10. An integer from 1 to 5 is preferred, an integer from 1 to 3 is more preferred, and 2 or 3 is even more preferred. From a manufacturing standpoint, n is most preferably 3.

[0022] The hydrolyzable silyl group in organic polymer (A) is -SiR in formula (1) above. 2 a X 3-a The group represented by and -SiR in formula (2) 4 b Y 3-bThe group is represented by .Specific examples of the hydrolyzable silyl group include, for example, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, etc. There may be only one type of hydrolyzable silyl group, or two or more types may coexist.

[0023] The ratio of the structure of formula (1) to the structure of formula (2) contained in the organic polymer (A) can be appropriately set by those skilled in the art, and the curability and resilience can be adjusted by changing the ratio. The ratio is not particularly limited, but it is preferably 10:90 to 90:10 in molar ratio, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30.

[0024] The manufacturing method according to this embodiment includes at least the following steps (I) to (III). Step (I): Step to prepare an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. Step (II): A step in which a hydrolyzable silyl group-containing hydrosilane compound is hydrosilylated to the carbon-carbon unsaturated bond to form the structure represented by formula (2). Step (III): A step of urethane-forming the hydroxyl group with a compound containing a hydrolyzable silyl group and an isocyanate group to form the structure represented by formula (1).

[0025] The preferred order for carrying out steps (I) to (III) is step (I), step (II), and step (III), but the order is also acceptable: step (I), step (III), and step (II). Each step will be explained below.

[0026] [Process (I)] Step (I) is a step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. The method for obtaining the polymer is not particularly limited, but it is preferable to obtain an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule from an organic polymer (E) having a hydroxyl group.

[0027] (Hydroxygroup-containing organic polymer (E)) The organic polymer has a polymer skeleton composed of multiple repeating units. The polymer skeleton of the organic polymer may be linear or branched. The position where the hydroxyl group is attached to the polymer skeleton is not particularly limited, but it is preferably at the end of the polymer skeleton.

[0028] There are no particular restrictions on the polymer skeleton of the aforementioned organic polymer, and various polymer skeletons can be used. Specific examples of polymer skeletons include, for example, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, copolymers of isoprene or butadiene with acrylonitrile and / or styrene, etc., copolymers of polybutadiene, isoprene or butadiene with acrylonitrile and styrene, etc., and polyolefin polymers of these materials. Examples of organic polymers include saturated hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenation of a composite; polyester polymers; vinyl polymers such as (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as ethyl (meth)acrylate and butyl (meth)acrylate, and polymers obtained by radical polymerization of monomers such as (meth)acrylic acid monomers, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the aforementioned polymers; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. The above polymers may be mixed in block form, graft form, etc. Among these, saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance, with polyoxyalkylene polymers being more preferred and polyoxypropylene being particularly preferred.

[0029] The organic polymer may be a polymer having one type of polymer skeleton, or a mixture of two or more polymers having different polymer skeletons. Furthermore, the mixture may be a mixture of polymers manufactured separately, or a mixture manufactured simultaneously to achieve any desired mixed composition.

[0030] The number-average molecular weight of the organic polymer is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 3,000 to 30,000 in terms of polystyrene-based molecular weight in GPC. A number-average molecular weight of 3,000 or more is desirable in terms of manufacturing cost because the relative amount of hydrolyzable silyl groups to the entire polymer is within an appropriate range. Furthermore, a number-average molecular weight of 100,000 or less makes it easier to achieve a desirable viscosity in terms of workability. The number-average molecular weight can be determined in terms of polystyrene-based molecular weight by GPC measurement.

[0031] The molecular weight distribution (Mw / Mn) of the organic polymer is not particularly limited, but a narrow range is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving the durability and mechanical properties such as elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and weight average molecular weight obtained in polystyrene equivalent by GPC measurement.

[0032] Next, a method for producing an organic polymer (E) having a hydroxyl group will be described. (Polyoxyalkylene polymers) The polymer backbone of the hydroxyl group-containing organic polymer (E) is a polyoxyalkylene polymer. In this case, the polymer can be produced by polymerizing an epoxy compound onto a hydroxyl group-containing initiator using conventionally known methods. This yields a hydroxyl-terminated polyoxyalkylene polymer. While there are no particular limitations on the specific polymerization method, a polymerization method using a complex metal cyanide catalyst such as a zinc hexacyanocobaltate grime complex is preferred because it yields a polymer with a small molecular weight distribution (Mw / Mn).

[0033] The initiator having a hydroxyl group is not particularly limited, but examples include organic compounds having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight polyoxypropylene monoalkyl ether.

[0034] The epoxy compound is not particularly limited, but examples include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

[0035] ((meth)acrylic acid ester polymer) When the polymer skeleton of the hydroxyl group-containing organic polymer (E) is a (meth)acrylic acid ester polymer, methods for producing the hydroxyl group-containing organic polymer include (I) copolymerizing a compound having a polymerizable unsaturated group and a hydroxyl group (for example, 2-hydroxyethyl acrylate) with a monomer having a (meth)acrylic structure to obtain a polymer, and (II) polymerizing a monomer having a (meth)acrylic structure by a living radical polymerization method such as atom transfer radical polymerization to obtain a polymer, and then introducing a hydroxyl group at any position (preferably at the end of the molecular chain) in the obtained polymer.

[0036] (Saturated hydrocarbon polymers) When the polymer backbone of the hydroxyl group-containing organic polymer (E) is a saturated hydrocarbon polymer, a method for producing the hydroxyl group-containing organic polymer includes a method in which an olefin compound having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, and isobutylene, is polymerized as the main monomer to obtain a polymer, and then a hydroxyl group is introduced at any position (preferably at the end of the molecular chain) of the obtained polymer.

[0037] [Process (Ia)] According to one aspect of this embodiment, step (I) may be a step in which an organic polymer (E) having hydroxyl groups is reacted with a carbon-carbon unsaturated bond-containing halide to convert a portion of the hydroxyl groups into carbon-carbon unsaturated bond-containing groups, thereby obtaining an organic polymer (F) having both hydroxyl groups and carbon-carbon unsaturated bonds in the same molecule. Step (I) according to this aspect will also be referred to as step (Ia) below.

[0038] (Reaction with alkali metal salts) In converting some of the hydroxyl groups in an organic polymer into carbon-carbon unsaturated bond-containing groups, it is preferable to first react the hydroxyl group-containing organic polymer (E) with an alkali metal salt to convert some of the hydroxyl groups into metal oxy groups. Alternatively, a complex metal cyanide catalyst can be used instead of the alkali metal salt. Through these steps, a metal oxy group-containing organic polymer is formed.

[0039] The alkali metal salt is not particularly limited, but examples include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide, etc. Easy handling From a solubility standpoint, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and sodium tert-butoxide being more preferred. Sodium methoxide is particularly preferred in terms of availability, and sodium tert-butoxide is particularly preferred in terms of reactivity. The alkali metal salt may be used in the reaction in a dissolved state in the solvent.

[0040] The amount of alkali metal salt used is not particularly limited, but it is preferable that the molar ratio to the hydroxyl groups of the organic polymer (E) is less than 1, more preferably 0.9 or less, even more preferably 0.8 or less, and particularly preferably 0.7 or less, so that some of the hydroxyl groups remain unreacted. The molar ratio is preferably 0.1 or more, more preferably 0.2 or more, and particularly preferably 0.3 or more.

[0041] To efficiently carry out the reaction that converts the hydroxyl groups of the organic polymer (E) to metal oxy groups, it is preferable to remove water and any other substances containing hydroxyl groups from the reaction system beforehand. Known methods can be used for this removal, such as heating evaporation, vacuum defloration, spray vaporization, thin-film evaporation, and azeotropic defloration.

[0042] The temperature for reacting with the alkali metal salt can be set appropriately by those skilled in the art, but is preferably 50°C to 150°C, and more preferably 110°C to 145°C. The reaction time for the alkali metal salt is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0043] (Reaction with carbon-carbon unsaturated bond-containing halide (G1)) By reacting the aforementioned metal oxy group-containing organic polymer with a carbon-carbon unsaturated bond-containing halide (G1), the metal oxy group of the organic polymer can be converted into a carbon-carbon unsaturated bond-containing group. The halide (G1) reacts with the metal oxy group through a halogen substitution reaction to form an ether bond. This can result in the formation of an organic polymer (F) having both a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule.

[0044] A carbon-carbon unsaturated bond-containing halide (G1) can be represented by the following formula (5). Z-(CR 3 2) n-2 -C(R 3 )=CR 3 2(5) In formula (5), R 3 The R mentioned above applies to equation (2).3 This is the same as above. n is an integer from 2 to 10. Z represents a halogen atom. When a hydrolyzable silyl group is introduced in step (II) to an organic polymer (F) obtained by reacting the halide (G1) and having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule, the structure represented by formula (2) above can be formed.

[0045] Specific examples of carbon-carbon unsaturated bond-containing halides (G1) are not particularly limited, but include vinyl chloride, allyl chloride, methyl chloride, vinyl bromide, allyl bromide, methyl bromide, vinyl iodide, allyl iodide, and methyl iodide. Allyl chloride and methyl chloride are preferred due to their ease of handling.

[0046] There are no particular restrictions on the amount of carbon-carbon unsaturated bond-containing halide (G1) added, but the molar ratio of the organic halide (G1) to the metal oxy groups of the organic polymer is preferably 0.7 or higher, and more preferably 1.0 or higher. Furthermore, this molar ratio is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0047] For metal oxy group-containing organic polymers, carbon-carbon unsaturated bond-containing halogens (G1 The temperature during the reaction is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0048] [Process (Ib)] According to another aspect of this embodiment, step (I) may be a step of reacting an organic polymer (E) having a hydroxyl group with an epoxy compound containing a carbon-carbon unsaturated bond to obtain an organic polymer (F) having both a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. Step (I) according to this other aspect will also be referred to as step (Ib) below.

[0049] (Reaction with alkali metal salts) When reacting an organic polymer (E) containing hydroxyl groups with an epoxy compound containing carbon-carbon unsaturated bonds, it is preferable to first react the hydroxyl group-containing organic polymer (E) with an alkali metal salt to convert the hydroxyl groups of the organic polymer into metal oxy groups. Alternatively, a complex metal cyanide catalyst can be used instead of the alkali metal salt. Through this process, a metal oxy group-containing organic polymer is formed. The details are the same as those described in detail for step (Ia), except for the amount of alkali metal salt used, which will be explained next.

[0050] In step (Ib), it is not necessary to leave some of the hydroxyl groups unreacted, so the amount of alkali metal salt used is not particularly limited, but the molar ratio to the hydroxyl groups of the organic polymer (E) is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and even more preferably 0.8 or more. The molar ratio is preferably 1.2 or less, and more preferably 1.1 or less.

[0051] (Reaction with a carbon-carbon unsaturated bond-containing epoxy compound (G2)) When a carbon-carbon unsaturated bond-containing epoxy compound (G2) is reacted with the metal oxy group-containing organic polymer, the carbon-carbon unsaturated bond-containing epoxy compound (G2) reacts with the metal oxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing a carbon-carbon unsaturated bond and a hydroxyl group into the organic polymer. This yields an organic polymer (F) having both a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. In the ring-opening addition reaction, by adjusting the amount of carbon-carbon unsaturated bond-containing epoxy compound (G2) used relative to the metal oxy group and the reaction conditions, one or more epoxy compounds (G2) can be added to a single metal oxy group.

[0052] A carbon-carbon unsaturated bond-containing epoxy compound (G2) can be represented by the following formula (6).

[0053] [ka]

[0054] In formula (6), R 3 The R mentioned above applies to equation (2). 3 It is the same as R 5 represents a direct bond or a divalent bonding group with 1 to 6 carbon atoms. n is an integer from 2 to 10.

[0055] R 5 This may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. 5 As for the bonding, direct bonding or a methylene group is preferred, with a methylene group being the most preferred.

[0056] Specific examples of the carbon-carbon unsaturated bond-containing epoxy compound (G2) are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide are preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.

[0057] The amount of carbon-carbon unsaturated bond-containing epoxy compound (G2) added can be any amount, taking into consideration the amount of carbon-carbon unsaturated bond introduced into the polymer and its reactivity. In particular, the molar ratio of epoxy compound (G2) to hydroxyl groups of the organic polymer (E) is preferably 0.2 or higher, more preferably 0.5 or higher. Furthermore, this molar ratio is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0058] The reaction temperature when reacting a metaloxy group-containing organic polymer with a carbon-carbon unsaturated bond-containing epoxy compound (G2) is preferably 60°C to 150°C, and more preferably 110°C to 140°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0059] As described above, when a metal-oxygen group-containing organic polymer is reacted with a carbon-carbon unsaturated bond-containing epoxy compound (G2), a new metal-oxygen group is generated by ring-opening of the epoxy group. By reacting this metal-oxygen group with a protic solvent, the metal-oxygen group is converted to a hydroxyl group, and an organic polymer (F) having both a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is formed. The protic solvent is not particularly limited, but examples include alcohols such as methanol and ethanol; carboxylic acids such as formic acid and acetic acid; nitromethane, water, etc. Due to their ease of handling, methanol, ethanol, and water are particularly preferred.

[0060] The reactions with alkali metal salts and epoxy compounds (G2) may be repeated multiple times to increase the rate of carbon-carbon unsaturated bond introduction into the organic polymer. When these reactions are repeated multiple times, the reagents used in each step (alkali metal salts or epoxy compounds (G2)) may be the same or different.

[0061] In step (Ib), by using the carbon-carbon unsaturated bond-containing epoxy compound (G2) represented by formula (6), an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule can be obtained, which has the structure represented by the following formula (4).

[0062] [ka]

[0063] In formula (4), R 3 and R 5 The bases are the same as those described above for equation (6). d is an integer from 1 to 10. n is an integer from 2 to 10.

[0064] [Process (II)] Step (II) is a step in which a hydrolyzable silyl group-containing hydrosilane compound is hydrosilylated to the carbon-carbon unsaturated bond of the organic polymer to introduce the structure represented by formula (2) into the organic polymer. It is preferable to carry out step (II) after step (I). In this case, step (II) is carried out on the organic polymer (F) obtained in step (I) which has a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. This yields an organic polymer having a hydroxyl group and a hydrolyzable silyl group (structure of formula (2)) in the same molecule.

[0065] Specific examples of the hydrolyzable silyl group-containing hydrosilane compounds include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane Lan, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trifluor (Propropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-triph Examples include alkoxysilanes such as [dimethoxysilyloxy]dimethylsilane ([orolhopropyl]dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone-free type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0066] The amount of hydrolyzable silyl group-containing hydrosilane compound used should be appropriately determined considering the amount of carbon-carbon unsaturated bonds in the organic polymer and the desired number of hydrolyzable silyl groups to be introduced.

[0067] Hydrosilylation reactions are preferably carried out in the presence of a hydrosilylation catalyst to accelerate the reaction. Suitable hydrosilylation catalysts include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as their complexes. Specifically, examples include platinum supported on a carrier such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid with alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [e.g., Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphine complexes [e.g., Pt{P(OPh)3}4]. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complexes are preferred.

[0068] Hydrosilylation reactions can be carried out without the use of solvents, but organic solvents may be added to ensure uniform dissolution of the organic polymer, hydrosilane compound, and hydrosilylation catalyst, and to facilitate temperature control of the reaction system and addition of the hydrosilylation catalyst.

[0069] The temperature during the hydrosilylation reaction is not particularly limited and can be set appropriately by those skilled in the art, but heating conditions are preferred in order to lower the viscosity of the reaction system and improve reactivity. Specifically, 50°C to 150°C is more preferred, and 70°C to 120°C is even more preferred. The reaction time can also be set appropriately, but it is preferable to adjust the reaction time along with the temperature conditions to prevent unintended condensation reactions between polymers from proceeding. Specifically, the reaction time is preferably 30 minutes to 5 hours, and more preferably 3 hours or less.

[0070] [Process (III)] Step (III) is a step in which a compound having a hydrolyzable silyl group and an isocyanate group (hereinafter also referred to as a silyl group-containing isocyanate compound) reacts with the hydroxyl group of the organic polymer to introduce the structure represented by formula (1) into the organic polymer. It is preferable to carry out step (III) after step (II). In this case, step (III) is carried out on an organic polymer having the hydroxyl group and hydrolyzable silyl group obtained in step (II) in the same molecule. This yields organic polymer (A).

[0071] The silyl group-containing isocyanate compound is a compound having an isocyanate group capable of urethane reaction with hydroxyl groups of an organic polymer and a hydrolyzable silyl group in the same molecule. The silyl group-containing isocyanate compound can be represented by the following formula (7). OCN-(CR 1 2) m -SiR 2 a X 3-a (7) R in equation (7) 1 , R 2 X, a, and m are the same as those described above for equation (1).

[0072] Specific examples of the silyl group-containing isocyanate compounds include, for example, (3-isocyanate propyl)trimethoxysilane, (3-isocyanate propyl)dimethoxymethylsilane, (3-isocyanate propyl)triethoxysilane, (3-isocyanate propyl)diethoxymethylsilane, (isocyanate methyl)trimethoxysilane, (isocyanate methyl)triethoxysilane, (isocyanate methyl)dimethoxymethylsilane, and (isocyanate methyl)diethoxymethylsilane. One type of silyl group-containing isocyanate compound may be used alone, or two or more types may be used in combination.

[0073] The amount of the silyl group-containing isocyanate compound used is the amount of the hydroxyl group of the organic polymer. The amount can be appropriately determined considering the quantity and the amount of hydrolyzable silyl groups to be introduced, and is not particularly limited, but for example, it is preferably 0.1 to 10 molar times, more preferably 0.3 to 5 molar times, and even more preferably 0.5 to 3 molar times relative to the hydroxyl groups of the organic polymer.

[0074] The structure represented by formula (1) can be introduced into the organic polymer by causing a urethane reaction between the hydroxyl groups of the organic polymer and the isocyanate groups of a silyl group-containing isocyanate compound to form a urethane bond.

[0075] The urethane reaction may be carried out without a urethane catalyst, but it may also be carried out in the presence of a urethane catalyst to improve the reaction rate or reaction efficiency. Such urethane catalysts include, for example, those listed in *Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963*, and other conventionally known urethane catalysts. Specifically, examples include, but are not limited to, organotin compounds, bismuth compounds, and base catalysts such as organic amines.

[0076] As a urethane catalyst, organotin compounds are preferred due to their high activity. Specifically, examples include tin octylate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl malate, dibutyltin dibutyl malate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyldistanoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis(o-phenylphenoxide), dibutyltin oxide, dibutyltin bis(triethoxysilicate), dibutyltin distearate, dibutyltin bis(isononyl-3-mercaptopropionate), dibutyltin bis(isooctyl mercaptopropionate), dibutyltin bis(isooctyl thioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin diversate. Furthermore, urethane catalysts with low activity towards hydrolyzable silyl groups are preferred, and from this viewpoint, organotin compounds containing sulfur atoms are preferred, among which dibutylsutunbis(isononyl-3-mercaptopropionate), dibutylsutunbis(isooctyl mercaptopropionate), and dibutylsutunbis(isooctyl thioglycolate) are particularly preferred.

[0077] As a urethane catalyst, an organic bismuth compound is preferred because it exhibits good activity and maintains good storage stability of the hydrolyzable silyl group-containing organic polymer. Examples of bismuth-containing catalysts include Borchi(R) Kat 22, Borchi(R) Kat 24, Borchi(R) Kat 320, Borchi(R) Kat 315EU, and Borchi(R) Kat VP, all manufactured by Borchers GmbH. Catalyst containing 0243, Borchi(R) Kat VP 0244, trade name bismuth(III) 2-ethylhexanoate solution (Bi:25%), bismuth(III) 2-ethylhexanoate, 70-75% Examples include xylenes (~24% Bi) (99.99+%-Bi) and PURATREM, but the substance is not particularly limited as long as it promotes the urethane reaction.

[0078] The amount of urethane catalyst added can be appropriately determined by those skilled in the art, but from the viewpoint of reaction activity, 1 to 1000 ppm and more preferably 10 to 100 ppm per 100 parts by weight of the organic polymer is preferred. Within this range, sufficient reaction activity can be obtained, and the physical properties of the hydrolyzable silyl group-containing organic polymer produced can be well maintained.

[0079] The urethane formation reaction can be carried out without using a solvent, but an organic solvent may be added to uniformly dissolve the organic polymer, the silyl group-containing isocyanate compound, and the urethane formation catalyst, and to facilitate temperature control of the reaction system and addition of the urethane formation catalyst.

[0080] When using organic solvents, there are no particular limitations on the type, and they can be selected as appropriate. Examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cyclooctane, cyclodecane, cyclododecane, and petroleum ether; aliphatic halogenated hydrocarbons such as dichloroethane and chloroform; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and isopropylbenzene; aromatic halogenated hydrocarbons such as chlorobenzene and chlorotoluene; and ether solvents such as tetrahydrofuran (THF) and tetrahydropyran (THP). One type of organic solvent may be used, or two or more types may be used in combination.

[0081] The temperature during the urethane formation reaction can be set appropriately by those skilled in the art, but it is preferably 50°C to 120°C, and more preferably 70°C to 100°C. The reaction time can also be set appropriately, but it is preferable to adjust the reaction time along with the temperature conditions to prevent unintended condensation reactions between polymers. Specifically, the reaction time is preferably 15 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0082] By carrying out steps (I) to (III) described above, an organic polymer (A) having the structure represented by formula (1) and the structure represented by formula (2) in the same molecule can be produced.

[0083] [Organic polymer (A')] If an organic polymer having the structure represented by formula (4) is obtained by carrying out step (I) as step (I), then by subsequently carrying out steps (II) and (III), an organic polymer (A') having the structure represented by the following formula (3) can be produced. This organic polymer (A') corresponds to organic polymer (A) and is a novel polymer that has not been previously reported.

[0084] [ka]

[0085] In formula (3), R 1 , R 2 , R 3 , R 4 , R 5 X, Y, a, b, d, m, and n are the same as those described above. The structure represented by formula (3) includes both the structure represented by formula (1) and the structure represented by formula (2). In this way, the positions in which the structure of formula (1) and the structure of formula (2) are introduced in organic polymer (A') are controlled, and each end of organic polymer (A') may have the structure of formula (1). Therefore, organic polymer (A') can exhibit particularly good curability among organic polymers (A).

[0086] The details of the polymer skeleton of organic polymer (A'), its number-average molecular weight, and the range of its molecular weight distribution are the same as those of hydroxyl group-containing organic polymer (E), so they are omitted from this description.

[0087] (Curable composition) The organic polymer (A') has a hydrolyzable silyl group, and a curable composition containing this polymer can be formed. In this curable composition, only one type of organic polymer (A') may be used, or two or more types may be used in combination.

[0088] (Organic polymer (B)) The curable composition according to this embodiment may contain, together with the organic polymer (A'), an organic polymer (B) having one hydrolyzable silyl group per molecule. By incorporating the organic polymer (B) having one hydrolyzable silyl group per molecule, the modulus of the cured product obtained by curing the curable composition can be reduced, and the physical properties can be adjusted to be suitable for sealing material applications. The organic polymer (B) may be used alone or in combination of two or more types. Furthermore, the hydrolyzable silyl group of organic polymer (B) may be the same as or different from the hydrolyzable silyl group of organic polymer (A').

[0089] Organic polymer (B) may have the structure represented by formula (1) above, or it may have the structure represented by formula (2) above, with respect to organic polymer (A). Furthermore, a structure that does not correspond to either the structure of formula (1) or the structure of formula (2) may contain a hydrolyzable silyl group.

[0090] The polymer skeleton of organic polymer (B) can be the same as that of the hydroxyl group-containing organic polymer (E) described above, with polyoxyalkylene polymers being preferred and polyoxypropylene being particularly preferred.

[0091] When the polymer backbone of organic polymer (B) is a polyoxyalkylene polymer, such organic polymer (B) can be produced, for example, by polymerizing an epoxy compound in the presence of an initiator having only one hydroxyl group per molecule, followed by a one-step or two-step reaction to introduce a hydrolyzable silyl group. This method allows for the production of a polyoxyalkylene polymer having a hydrolyzable silyl group at one of its ends.

[0092] With regard to the number-average molecular weight or molecular weight distribution of organic polymer (B), the above description can be applied to hydroxyl group-containing organic polymer (E).

[0093] The mixing ratio of organic polymer (A') and organic polymer (B) is not particularly limited, but is preferably 99:1 to 50:50 by weight, more preferably 95:5 to 60:40, and even more preferably 90:10 to 70:30.

[0094] (curing catalyst) The curable composition according to this embodiment preferably contains a curing catalyst for the purpose of promoting the reaction of hydrolysis and condensation of hydrolyzable silyl groups, i.e., the curing reaction.

[0095] Conventional known curing catalysts can be used, specifically organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc.

[0096] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), and dibutyltin oxide in silicate form. Examples include reaction products with compound, reaction products of dibutyltin oxide and phthalate esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), and reaction products of dioctyltin oxide and silicate compounds. Due to the growing environmental concerns in recent years, dioctyltin compounds are preferred. However, since organic polymer (A') may exhibit rapid curing, the curable composition according to this embodiment may not contain an organotin compound and may contain a curing catalyst (especially an amine compound, etc.) that is generally considered to have lower activity than an organotin compound. Even if the curable composition according to this embodiment contains an amine compound, it can still exhibit good curability.

[0097] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. Various metals can be combined with the following carboxylic acids as carboxylate groups.

[0098] Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butyl biguanide, 1-o-tolyl biguanide, and 1-phenyl biguanide; and ketimine compounds.

[0099] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0100] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxy titanium bis (ethylacetoacetate), aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0101] Other curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0102] The curing catalyst may be used in combination with two or more different catalysts. For example, using the aforementioned amine compound and carboxylic acid in combination may improve reactivity.

[0103] Furthermore, since the organic polymer (A') has a highly active hydrolyzable silyl group, it is possible to reduce the amount of curing catalyst, use a less active curing catalyst, or use aminosilane, an amino group-containing silane coupling agent, as the curing catalyst. Since aminosilane is usually added as an adhesion promoter, when aminosilane is used as the curing catalyst, a curable composition can be prepared without using the commonly used curing catalyst. For this reason, it is preferable not to add other curing catalysts. In particular, when m in the structure represented by formula (1) is 1, or when the hydrolyzable silyl group includes a trimethoxysilyl group or a methoxymethyldimethoxysilyl group, excellent curability is exhibited even when aminosilane is used alone as the curing catalyst.

[0104] Specific examples of the aminosilane mentioned above include γ-aminopropyltrimethoxysilane, γ- Minopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane Examples include amino group-containing silanes such as γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; and ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine. Only one type of aminosilane may be used, or two or more types may be used in combination.

[0105] The amount of curing catalyst to be added is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of organic polymer (A'). If the amount of curing catalyst is less than 0.001 parts by weight, the reaction rate may be insufficient. On the other hand, if the amount of curing catalyst exceeds 20 parts by weight, the reaction rate is too fast, which tends to shorten the usable time of the composition, resulting in poor workability and poor storage stability. Furthermore, some curing catalysts may seep out onto the surface of the cured product or contaminate the surface of the cured product after the curable composition has cured. In such cases, by using an amount of curing catalyst of 0.01 to 3.0 parts by weight, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0106] The curable composition according to this embodiment may also contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents. Furthermore, the curable composition according to this embodiment may contain various additives as needed to adjust the properties of the composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0107] (Filler) Various fillers can be incorporated into the curable composition according to this embodiment. Examples of fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, settling silica, crystalline silica, fused silica, anhydrous silicic acid, hydrated silicic acid, carbon black, ferric oxide, aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fibers, and filaments.

[0108] The amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of organic polymer (A').

[0109] Organic balloons and inorganic balloons may be added to reduce the weight (lower specific gravity) of the composition. A balloon is a spherical, hollow-bodied material. Materials for these balloons include inorganic materials such as glass, shirasu (volcanic ash), and silica, as well as organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0110] The amount of balloon used is preferably 0.1 to 100 parts by weight, and more preferably 1 to 20 parts by weight, per 100 parts by weight of organic polymer (A').

[0111] (Adhesion-enhancing agent) Adhesion-imparting agents may be added to the curable composition according to this embodiment. As adhesion-imparting agents, silane coupling agents and reaction products of silane coupling agents may be added. Specific examples of silane coupling agents include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; as well as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-iso Examples include isocyanate group-containing silanes such as cyanate-propylmethyldimethoxysilane, α-isocyanate-methyltrimethoxysilane, and α-isocyanate-methyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The above adhesion-imparting agents may be used individually or in combination of two or more types.

[0112] The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A').

[0113] (Plasticizer) A plasticizer may be added to the curable composition according to this embodiment. Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkyl sulfonate phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

[0114] Furthermore, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc. Plasticizers may be used alone or in combination of two or more types.

[0115] The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of organic polymer (A').

[0116] (Solvents, diluents) A solvent or diluent may be added to the curable composition according to this embodiment. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc., can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher, due to concerns about air pollution when the composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more.

[0117] (Drip prevention agent) The curable composition according to this embodiment may contain, if necessary, an anti-sagging agent to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used individually or in combination of two or more. The amount of anti-slip agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of organic polymer (A').

[0118] (Antioxidant) The curable composition according to this embodiment may contain an antioxidant (anti-aging agent). Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731. The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of organic polymer (A').

[0119] (Light stabilizer) A light stabilizer can be used in the curable composition according to this embodiment. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, but hindered amine-based compounds are particularly preferred. The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of organic polymer (A').

[0120] (UV absorber) A UV absorber can be used in the curable composition according to this embodiment. Using a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate compounds, but benzotriazole-based compounds are particularly preferred, and examples include commercially available products such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, and Tinuvin B75 (all manufactured by BASF). The amount of UV absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of organic polymer (A').

[0121] (Property modifier) The curable composition according to this embodiment may contain a property modifier to adjust the tensile properties of the resulting cured product as needed. The property modifier is not particularly limited, but examples include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using the above property modifier, the hardness of the curable composition according to this embodiment can be increased or decreased, resulting in increased elongation at break. The above property modifiers may be used alone or in combination of two or more.

[0122] In particular, compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis have the effect of reducing the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are especially preferred. Examples of compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and produce silane monool upon hydrolysis.

[0123] The amount of property modifier used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of organic polymer (A').

[0124] (Adhesive-forming resin) The curable composition according to this embodiment may contain a tackifying resin to enhance adhesion to the substrate or as needed. There are no particular restrictions on the tackifying resin; commonly used resins can be used.

[0125] Specific examples include terpene resins, aromatically modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, 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, styrene block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used individually or in combination of two or more types.

[0126] The amount of tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, per 100 parts by weight of organic polymer (A').

[0127] (Compounds containing epoxy groups) In the curable composition according to this embodiment, compounds containing epoxy groups can be used. Using compounds with epoxy groups can improve the resilience of the cured product. Examples of compounds with epoxy groups include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (EP Examples include epoxy octyl stearate and epoxy butyl stearate. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of organic polymer (A').

[0128] (light curing substance) A photocurable substance can be used in the curable composition according to this embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many types of compounds of this kind are known, including organic monomers, oligomers, resins, or compositions containing them. Typical examples include unsaturated acrylic compounds, vinyl polycinnamates, or azidized resins, which are monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups.

[0129] The amount of photocurable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A').

[0130] (oxygen curing substance) The curable composition according to this embodiment can use oxygen-curable substances. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing stickiness on the surface and the adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; butadiene, chloroprene Examples include liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes, obtained by polymerizing or copolymerizing diene compounds such as isoprene and 1,3-pentadiene. These may be used individually or in combination of two or more.

[0131] The amount of oxygen-curable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A'). As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0132] (Epoxy resin) An epoxy resin can be used in combination with the curable composition according to this embodiment. Compositions with added epoxy resin are particularly preferred as adhesives, especially adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins or novolac type epoxy resins.

[0133] The ratio of epoxy resin to organic polymer (A') used is preferably in the range of organic polymer (A') / epoxy resin = 100 / 1 to 1 / 100 by weight. If the ratio of organic polymer (A') / epoxy resin is less than 1 / 100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the epoxy resin cured product, and if the ratio of organic polymer (A') / epoxy resin exceeds 100 / 1, the strength of the polymer cured product becomes insufficient.

[0134] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to this embodiment. There are no particular restrictions on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be used.

[0135] When using a curing agent for epoxy resin, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

[0136] <<Preparation of Curable Composition>> The curable composition according to this embodiment can be prepared as a one-component type in which all components are pre-mixed and sealed for storage, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which components such as a curing catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and these components are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

[0137] When the curable composition is a one-component type, all components are pre-mixed. Therefore, it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them during mixing by reducing pressure. Furthermore, storage stability can be further improved by adding alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane in addition to the dehydration and drying method.

[0138] <Application> The curable composition according to this embodiment can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., a waterproofing material, a waterproof coating material, a molding material, a vibration damping material, a soundproofing material, a foaming material, a paint, or a spray material. The cured product obtained by curing the curable composition according to this embodiment has excellent flexibility and adhesion, and can therefore be suitably used as a sealing material or an adhesive.

[0139] Furthermore, the curable composition according to this embodiment is used for electrical and electronic component materials such as back-surface sealing materials for solar cells, electrical and electronic component and device insulating coatings such as wire and cable insulating coatings, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray sealants, crack repair materials, tile adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealing materials, dental impression materials, food packaging materials, and sealants for joints of exterior materials such as sizing boards. It can be used in a wide variety of applications, including adhesives, coatings, anti-slip coatings, cushioning materials, primers, conductive materials for electromagnetic shielding, thermally conductive materials, hot-melt materials, potting agents for electrical and electronic applications, films, gaskets, concrete reinforcement materials, temporary adhesives, various molding materials, and liquid sealants used in rust prevention and waterproofing of wired glass and laminated glass edges (cut sections), as well as in automotive parts, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical components, and various machine parts. Taking automobiles as an example, it can be used in a wide variety of applications, such as adhesive attachment of plastic covers, trims, flanges, bumpers, window mounting, interior components, and exterior components. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin molded products, either alone or with the help of a primer, it can also be used as various types of sealing and adhesive compositions. Furthermore, the curable composition according to this embodiment can be used as an adhesive for interior panels, exterior panels, tile, stone, ceiling finishes, floor finishes, wall finishes, vehicle panels, electrical / electronic / precision equipment assembly, adhesives for bonding leather, textiles, fabrics, paper, boards, and rubber, post-reactive crosslinking pressure-sensitive adhesives, direct glazing sealants, double-glazed glass sealants, SSG method sealants, working joint sealants for buildings, and materials for civil engineering and bridges. In addition, it can be used as an adhesive material such as adhesive tape or adhesive sheet. [Examples]

[0140] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The number-average molecular weight in the examples is the GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8220GPC Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0141] (Synthesis Example 1) Using a polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate grime complex catalyst to obtain branched polyoxypropylene (E-1) with a number-average molecular weight of 23,300 and hydroxyl groups at the terminals. 0.60 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of the obtained polymer (E-1). After removing the methanol by vacuum distillation, 0.69 molar equivalents of allyl chloride were added to the hydroxyl groups of polymer (E-1), and the reaction was carried out at 130°C for 1 hour, after which the allyl chloride was removed by vacuum distillation. The obtained unpurified polyoxypropylene was dissolved in n-hexane, and aluminum silicate (Kyoward R700SEN-S, manufactured by Kyowa Chemical Co., Ltd.) was mixed and stirred to adsorb the metal salts in the polymer onto the aluminum silicate. After removing the aluminum silicate by filtration, the hexane was removed from the obtained hexane solution by vacuum distillation. Through the above steps, polyoxypropylene (F-1) having carbon-carbon unsaturated bonds (allyl groups) and hydroxyl groups was obtained. Next, at 90°C, 50 ppm of platinum divinyldisiloxane complex (a solution of isopropanol equivalent to 3% by weight of platinum) and 0.87 parts by weight of trimethoxysilane were added to 100 parts by weight of polymer (F-1) to carry out a hydrosilylation reaction with the allyl groups of polymer (F-1) to form the structure represented by formula (2). The reaction was carried out at 90°C until the allyl groups were completely consumed, and then the volatile components were removed by distillation. Next, at 90°C, 30 ppm of bismuth(III) 2-ethylhexanoic acid solution (Bi: 25%) and 0.95 molar equivalents of (isocyanate methyl)dimethoxymethylsilane were added per 100 parts by weight of the polymer to carry out a urethane reaction on the hydroxyl groups of the polymer, forming the structure represented by formula (1). Based on the above, a branched polyoxypropylene (A-1) having the structure represented by formula (1) and the structure represented by formula (2) in the same molecule was obtained.

[0142] (Synthesis Example 2) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain polyoxypropylene (E-2) with a number-average molecular weight of 27,900 and hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide was added to the hydroxyl groups of polymer (E-2) as a 28% methanol solution. After removing the methanol by vacuum distillation at 140°C, 1.5 molar equivalents of allyl glycidyl ether were added to the hydroxyl groups of polymer (E-2) and the reaction was carried out at 140°C for 2 hours. Subsequently, 3.0 molar equivalents of methanol were added to the hydroxyl groups of polymer (E-2) at 80°C to convert the terminal sodium alkoxide groups to hydroxyl groups. The obtained unpurified polyoxypropylene was dissolved in n-hexane, and aluminum silicate (Kyowa Chemical Co., Ltd., Kyoward R700SEN-S) was mixed and stirred to adsorb the metal salts in the polymer onto the aluminum silicate. After removing the aluminum silicate by filtration, the hexane was removed from the obtained hexane solution by vacuum distillation. As a result, polyoxypropylene (F-2) having a carbon-carbon unsaturated bond (allyl group) and a hydroxyl group in one terminal site was obtained. The polymer (F-2) has the structure represented by formula (4). Next, at 65°C, 50 ppm of platinum divinyldisiloxane complex (a solution of isopropanol equivalent to 3% by weight of platinum) and 1.3 parts by weight of trimethoxysilane were added to 100 parts by weight of polymer (F-2) to carry out a hydrosilylation reaction with the allyl groups of polymer (F-2) to form the structure represented by formula (2). The reaction was carried out at 85°C until the trimethoxysilane was completely consumed, and then the volatile components were removed by distillation. Next, at 90°C, 30 ppm of bismuth(III) 2-ethylhexanoic acid solution (Bi: 25%) and 0.95 molar equivalents of (isocyanate methyl)dimethoxymethylsilane were added per 100 parts by weight of the polymer to carry out a urethane reaction on the hydroxyl groups of the polymer, forming the structure represented by formula (1). Based on the above, a polyoxypropylene (A-2) having the structure represented by formula (1) and the structure represented by formula (2) in the same molecule was obtained. The polymer (A-2) has the structure represented by formula (3).

[0143] (Comparative Synthesis Example 1) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain polyoxypropylene (E-3) with a number-average molecular weight of 15,000 and hydroxyl groups at both ends. To 100 parts by weight of polymer (E-3), 30 ppm of bismuth(III) 2-ethylhexanoic acid solution (Bi: 25%) and 0.95 molar equivalents of (isocyanate methyl)dimethoxymethylsilane were added relative to the hydroxyl groups of the polymer, and a urethane reaction was carried out on the hydroxyl groups of the polymer to form the structure represented by formula (1). Based on the above, polyoxypropylene (C-1) having the structure represented by formula (1) was obtained.

[0144] (Comparative Synthesis Example 2) In Synthesis Example 1, 1.1 molar equivalents of sodium methoxide were added to the hydroxyl groups of polymer (E-1) as a 28% methanol solution. After removing the methanol by vacuum distillation, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of polymer (E-1) and the reaction was carried out at 130°C for 1.5 hours, after which the allyl chloride was removed by vacuum distillation. The resulting unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and the water was removed by centrifugation. The metal salts in the polymer were removed by vacuum distillation of the hexane from the resulting hexane solution. Thus, polyoxypropylene (F-3) having carbon-carbon unsaturated bonds (allyl groups) at the ends was obtained. Next, at 90°C, 50 ppm of platinum divinyldisiloxane complex (a solution of isopropanol equivalent to 3% by weight of platinum) and 1.35 parts by weight of trimethoxysilane were added to 100 parts by weight of polymer (F-3) to carry out a hydrosilylation reaction with the allyl groups of polymer (F-3) to form the structure represented by formula (2). The reaction was carried out at 90°C until the trimethoxysilane was completely consumed, and then the volatile components were removed by distillation. Based on the above, a branched polyoxypropylene (C-2) having the structure represented by formula (2) was obtained.

[0145] (Comparative Synthesis Example 3) In Synthesis Example 2, 1.0 molar equivalent of sodium methoxide was added to the hydroxyl groups of polymer (E-2) as a 28% methanol solution. After removing the methanol by vacuum distillation, 1.1 molar equivalents of allyl glycidyl ether were added to the hydroxyl groups of polymer (E-2) and the reaction was carried out at 140°C for 3 hours. Furthermore, 1.22 molar equivalents of allyl chloride were added to the hydroxyl groups of polymer (E-2) and the reaction was carried out at 130°C for 1 hour, after which the allyl chloride was removed by distillation. Subsequently, 0.30 molar equivalents of sodium methoxide were added to the hydroxyl groups of polymer (E-2) as a 28% methanol solution. After removing the methanol by vacuum distillation at 130°C, 0.79 molar equivalents of allyl chloride were added to the hydroxyl groups of polymer (E-2) and the reaction was carried out at 130°C for 2 hours, after which the allyl chloride was removed by distillation. Subsequently, 0.2 molar equivalents of sodium methoxide were added to the hydroxyl groups of polymer (E-2) as a 28% methanol solution. After removing the methanol by vacuum distillation at 130°C, 0.3 molar equivalents of allyl chloride were added to the hydroxyl groups of polymer (E-2) and the reaction was carried out at 130°C for 2 hours, after which the allyl chloride was removed by distillation. The obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, then the water was removed by centrifugation, and the metal salts in the polymer were removed by distilling off the hexane from the resulting hexane solution under reduced pressure. This process yielded polyoxypropylene (F-4) having multiple carbon-carbon unsaturated bonds (allyl groups) per terminal site. Next, at 90°C, 50 ppm of platinum divinyldisiloxane complex (a solution of isopropanol equivalent to 3% by weight of platinum) and 1.92 parts by weight of trimethoxysilane were added to 100 parts by weight of polymer (F-4) to carry out a hydrosilylation reaction with the allyl groups of polymer (F-4) to form the structure represented by formula (2). The reaction was carried out at 90°C until the trimethoxysilane was completely consumed, and then the volatile components were removed by distillation. Based on the above, we obtained polyoxypropylene (C-3) having multiple structures represented by formula (2) at each terminal site.

[0146] (Reference example 1) Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (E-4) with a number-average molecular weight of 7800 and a hydroxyl group at one end. Next, at 90°C, 30 ppm of bismuth(III) 2-ethylhexanoic acid solution (Bi: 25%) and 0.95 molar equivalents of (isocyanate methyl)dimethoxymethylsilane were added to 100 parts by weight of polymer (E-4) to carry out a urethane reaction on the hydroxyl groups of the polymer. As a result, polyoxypropylene (B-1) having an alkoxysilyl group at one end was obtained.

[0147] (Reference example 2) At 90°C, 30 ppm of bismuth(III) 2-ethylhexanoic acid solution (Bi: 25%) and 0.95 molar equivalents of (3-isocyanatetopropyl)trimethoxysilane were added to 100 parts by weight of polymer (E-4) obtained in Reference Example 1 to carry out a urethane reaction on the hydroxyl groups of the polymer. As a result, polyoxypropylene (B-2) having an alkoxysilyl group at one end was obtained.

[0148] (Reference example 3) In Reference Example 1, 0.75 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (E-4) as a 28% methanol solution. After removing the methanol by vacuum distillation, 1.1 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer (E-4) and the reaction was carried out at 130°C for 1 hour, after which the allyl chloride was removed by vacuum distillation. Subsequently, 0.47 molar equivalents of sodium methoxide were added to the hydroxyl groups of the polymer (E-4) as a 28% methanol solution. After removing the methanol by vacuum distillation at 130°C, 2.1 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer (E-4) and the reaction was carried out at 130°C for 2 hours, after which the allyl chloride was removed by vacuum distillation. The resulting unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and the water was removed by centrifugation. The metal salts in the polymer were removed by vacuum distillation of the hexane from the resulting hexane solution. Therefore, polyoxypropylene (F-5) having a carbon-carbon unsaturated bond (allyl group) at one end. I obtained it. Next, at 90°C, 50 ppm of platinum divinyldisiloxane complex (a solution of isopropanol equivalent to 3% by weight of platinum) and 2.07 parts by weight of trimethoxysilane were added to 100 parts by weight of polymer (F-5) to carry out a hydrosilylation reaction of the allyl groups of polymer (F-5). The reaction was carried out at 90°C until the trimethoxysilane was completely consumed, and then the volatile components were removed by distillation. As a result, polyoxypropylene (B-3) having a trimethoxysilyl group at one end was obtained.

[0149] (Example 1, Comparative Examples 1-3) For every 100 parts by weight of the polymers listed in Table 1, add 90 parts by weight of DINP (J-Plus Co., Ltd.: diisononyl phthalate), 160 parts by weight of Shirotsuya CCR (Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate), and Whiten 54 parts by weight of SB (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), 5 parts by weight of Typeque R820 (titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd.), 2 parts by weight of Disparon 6500 (fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.), 1 part by weight of Tinuvin 770 (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, manufactured by BASF), and 1 part by weight of Tinuvin 326 (2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, were mixed together, and then 2 parts by weight of A-171 (vinyltrimethoxysilane, manufactured by Momentive), the amount (parts by weight) of A-1120 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, manufactured by Momentive) as listed in Table 1, and the amount (parts by weight) of DBU (diazabicycloundecene) as listed in Table 1 were added and mixed. A-1120 (the aminosilane) and DBU (the amine compound) promote the condensation of hydrolyzable silyl groups and accelerate the curing of the polymer.

[0150] (Leather stretching time) The obtained composition was filled into a mold approximately 5 mm thick using a spatula. The time it took to smooth the surface was defined as the curing start time, and the time it took for the evaluation composition to no longer adhere to the spatula after touching the surface was defined as the skinning time. The curing time was measured in each table. The results are shown in the respective tables.

[0151] (Dumbbell tensile properties) The obtained composition was filled into a mold and cured at 23°C and 50% RH for 3 days, and then at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched out into a No. 3 dumbbell shape, and a tensile strength test was performed at 23°C and 50% RH to measure the modulus at 50% or 100% elongation, the strength at fracture, and the elongation. The measurements were performed using a Shimadzu Autograph (AGS-J) at a tensile speed of 200 mm / min. The results are shown in the respective tables.

[0152] (Recovery rate) The obtained composition was filled into a mold and cured at 23°C and 50% RH for 3 days, and then at 50°C for 4 days to produce a sheet-like hardened material with a thickness of approximately 3 mm. The sheet-like hardened material was punched out into a No. 7 dumbbell shape, and the dumbbell shape was stretched by 10 mm and fixed at both ends with clips. It was then left to stand at 23°C and 50% RH for 24 hours. After that, the clips were removed and the force that caused deformation was removed, and the dumbbell was left to stand on a smooth glass plate. After 24 hours, the extent to which it returned to its original shape was checked. The elongation of the dumbbell after 24 hours was denoted as X (mm), and the recovery rate was calculated as follows. The results are shown in the tables. Recovery rate (%) = (10 - X) ÷ 10 × 100

[0153] [Table 1]

[0154] As is clear from Table 1, the curable composition of Comparative Example 2, which contained polymer (C-2) having only the structure represented by formula (2), showed remarkably low curability in the presence of aminosilane (A-1120) and amine compound (DBU), and did not cure sufficiently. In contrast, the curable composition of Example 1, which contained polymer (A-1) having both the structure represented by formula (1) and the structure represented by formula (2) in the same molecule, showed good curability. Furthermore, the curable composition of Example 1 showed higher restorability compared to the curable composition of Comparative Example 1, which contained polymer (C-1) having only the structure represented by formula (1), and the curable composition of Comparative Example 3. Comparative Example 3 is a curable composition containing polymer (C-1) and polymer (C-2) in a ratio of the structure represented by formula (1) and the structure represented by formula (2) contained in polymer (A-1). In other words, a polymer having both the structure represented by formula (1) and the structure represented by formula (2) in the same molecule exhibits higher resilience than a mixture of a polymer having the structure represented by formula (1) and a polymer having the structure represented by formula (2).

[0155] (Example 2, Comparative Examples 1, 4, 5) For every 100 parts by weight of the polymers listed in Table 2, add 90 parts by weight of DINP (J-Plus Co., Ltd.: diisononyl phthalate), 160 parts by weight of Shirotsuya CCR (Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate), and Whiten 54 parts by weight of SB (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), 5 parts by weight of Typeque R820 (titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd.), 2 parts by weight of Disparon 6500 (fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.), 1 part by weight of Tinuvin 770 (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, manufactured by BASF), and 1 part by weight of Tinuvin 326 (2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, were mixed, and then 2 parts by weight of A-171 (vinyltrimethoxysilane, manufactured by Momentive) and 3 parts by weight of A-1120 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, manufactured by Momentive) were added and mixed.

[0156] [Table 2]

[0157] As is clear from Table 2, the curable composition of Comparative Example 4, which contains polymer (C-3) having only the structure represented by formula (2), showed remarkably low curability in the presence of aminosilane (A-1120) and did not cure sufficiently. In contrast, the curable composition of Example 2, which contains polymer (A-2) having both the structure represented by formula (1) and the structure represented by formula (2) in the same molecule, showed good curability. Furthermore, the curable composition of Example 2 showed higher resilience compared to the curable composition of Comparative Example 1, which contains polymer (C-1) having only the structure represented by formula (1), and the curable composition of Comparative Example 5. Comparative Example 5 is a curable composition containing polymer (C-1) and polymer (C-3) in a ratio of the structure represented by formula (1) and the structure represented by formula (2) contained in polymer (A-2). In other words, it can be seen that polymers having both the structure represented by formula (1) and the structure represented by formula (2) in the same molecule show higher resilience than a mixture of polymers having the structure represented by formula (1) and polymers having the structure represented by formula (2). Furthermore, Example 2 also showed higher curability than Comparative Example 5.

[0158] (Examples 3-5, Comparative Examples 6-8) For every 100 parts by weight of the polymers listed in Table 3, add 90 parts by weight of DINP (J-Plus Co., Ltd.: diisononyl phthalate), 160 parts by weight of Shirotsuya CCR (Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate), and Whiten 54 parts by weight of SB (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), 5 parts by weight of Typeque R820 (titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd.), 2 parts by weight of Disparon 6500 (fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.), 1 part by weight of Tinuvin 770 (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, manufactured by BASF), and 1 part by weight of Tinuvin 326 (2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, were mixed, and then 2 parts by weight of A-171 (vinyltrimethoxysilane, manufactured by Momentive) and 3 parts by weight of A-1120 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, manufactured by Momentive) were added and mixed.

[0159] [Table 3]

[0160] As is clear from Table 3, the curable compositions of Examples 3 to 5, in which polymers (B-1) to (B-3), each having a hydrolyzable silyl group at one end, were mixed with polymer (A-2), showed higher resilience compared to the curable compositions of Comparative Examples 6 to 8, in which polymers (B-1) to (B-3) were mixed with polymers (C-1) and (C-3). In other words, polymers having the structure represented by formula (1) and the structure represented by formula (2) in the same molecule show high resilience even when their modulus is reduced by using them in combination with polymers having a hydrolyzable silyl group at one end.

Claims

1. A method for producing an organic polymer (A) having a structure represented by the following formula (1) and a structure represented by the following formula (2) in the same molecule, -O-CO-NH-(CR １ ２ ) ｍ -SiR ２ ａ X ３－ａ (1) -O-(CR ３ ２ ) ｎ -SiR ４ ｂ Y ３－ｂ (2) (In formula (1), R １ R represents, either identical or different, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ２ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2. m is an integer from 1 to 5. In formula (2), R ３ R represents, either identical or different, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ (where represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; Y represents a hydroxyl group or a hydrolyzable group; b is 0, 1, or 2; n is an integer from 1 to 10) A process of reacting an alkali metal salt with a hydroxyl group-containing organic polymer (E) to convert the hydroxyl groups in the organic polymer (E) into metal oxy groups. The process involves reacting the obtained metaloxy group-containing organic polymer with a carbon-carbon unsaturated bond-containing epoxy compound (G2) to form an ether bond by a ring-opening addition reaction of the epoxy group, and then reacting the newly formed metaloxy group with a protic solvent to prepare an organic polymer (F) having both a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. A step of forming the structure represented by formula (2) by hydrosilylation reaction of a hydrolyzable silyl group-containing hydrosilane compound to the carbon-carbon unsaturated bond of an organic polymer (F), and A method for producing an organic polymer (A), comprising the step of urethane-forming the hydroxyl group of an organic polymer (F) with a compound having a hydrolyzable silyl group and an isocyanate group to form a structure represented by formula (1).

2. A method for producing the organic polymer (A) according to claim 1, wherein the organic polymer (F) having the hydroxyl group and carbon-carbon unsaturated bond in the same molecule is an organic polymer having a structure represented by the following formula (4). 【Chemistry 1】 (In formula (4), R ３ The same as above. R ５ (where represents a direct bond or a divalent bonding group with 1 to 6 carbon atoms. d is an integer from 1 to 10. n is an integer from 2 to 10.)

3. A method for producing the organic polymer (A) according to claim 1 or 2, wherein the organic polymer (A) has a structure represented by the following formula (3). 【Chemistry 2】 (In formula (3), R １ R represents, either identical or different, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ２ R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ３ R represents, either identical or different, a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ５ (where represents a direct bond or a divalent bond group having 1 to 6 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. Y represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2. b is 0, 1, or 2. d is an integer from 1 to 10. m is an integer from 1 to 5. n is an integer from 1 to 10.)

4. A method for producing an organic polymer (A) according to any one of claims 1 to 3, wherein m is 1.

5. A method for producing an organic polymer (A) according to any one of claims 1 to 4, wherein n is 3.

6. A method for producing an organic polymer (A) according to any one of claims 1 to 5, wherein the polymer skeleton of the organic polymer is a polyoxyalkylene polymer.

7. A method for producing an organic polymer (A) according to any one of claims 1 to 6, wherein the protic solvent is methanol, ethanol, or water.

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