Method for producing organic polymer

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, sealants, coating materials, paints, and adhesives, 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 are known as the main chain skeleton.

[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, the hydroxyl group is converted into a carbon-carbon double bond, and a hydrosilylation reaction between the carbon-carbon double bond and a silane compound is carried out 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 via 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

Summary of the Invention

Problems to be Solved by the Invention

[0006] When a hydrolyzable silyl group-containing organic polymer is used for sealing materials or the like, its cured product is often required to exhibit high resilience. In addition, as a curing catalyst used to cure a hydrolyzable silyl group-containing organic polymer, an organotin compound is known to be highly active. However, due to the increasing environmental concerns in recent years, the use of non-tin-based curing catalysts is recommended. Therefore, there is a need for a hydrolyzable silyl group-containing organic polymer that can exhibit good curability even when using a non-tin-based catalyst with relatively low activity. However, it has been difficult for conventionally known hydrolyzable silyl group-containing organic polymers to achieve both high resilience and good curability.

[0007] In view of the above situation, an object of the present invention is to provide a hydrolyzable silyl group-containing organic polymer and a method for producing the same, which achieve both good curability and high resilience.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found that by producing an organic polymer having two specific structures as structures containing hydrolyzable silyl groups in the same molecule, the hydrolyzable silyl group-containing organic polymer can achieve both good curability and high resilience, leading to the present invention.

[0009] That is, the present invention is 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 of 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 of 1 to 10.) A method for producing an organic polymer (A) comprising: a step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule; a step of subjecting the carbon-carbon unsaturated bond to a hydrosilylation reaction with a hydrosilane compound containing a hydrolyzable silyl group to form the structure represented by formula (2); and a step of subjecting the hydroxyl group to a urethanization reaction with a compound having a hydrolyzable silyl group and an isocyanate group to form the structure represented by formula (1). 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 halide containing a carbon-carbon unsaturated bond to convert a part of the hydroxyl group into a group containing a carbon-carbon unsaturated bond. 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 an epoxy compound containing a carbon-carbon unsaturated bond. 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 the following formula (3). In the formula (3), preferably, m is 1. Preferably, n is 3. Preferably, the polymer skeleton of the organic polymer is a polyoxyalkylene-based polymer. Furthermore, 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 in one 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] Hereinafter, embodiments of the present invention will be described in detail. [Organic Polymer (A)] The production method according to the present embodiment is a method for producing an organic polymer (A) having a hydrolyzable silyl group. The organic polymer (A) has, in the same molecule, a structure represented by the following formula (1) and a structure represented by the following formula (2). -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 the formula (1), the hydrolyzable silyl group (-SiR 2 a X 3-a) is bonded to the polymer backbone via a urethane bond. In the structure represented by the formula (2), the hydrolyzable silyl group (-SiR 4 b Y 3-b ) is bonded to the polymer backbone via an oxygen atom. The organic polymer (A) has different structures as the bonding groups through which the hydrolyzable silyl groups are bonded to the polymer backbone in the same molecule, and due to such a specific structure, high resilience and good curability can be achieved simultaneously. The organic polymer (A) having the structures of the formula (1) and the formula (2) in the same molecule can exhibit higher resilience than a mixture of the organic polymer having the structure of the formula (1) and the organic polymer having the structure of the formula (2).

[0013] In the 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 of 1 to 5.

[0014] In the 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 of 1 to 10.

[0015] R 1 and R 3 each represent 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, still more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro group, alkoxy groups such as methoxy group, and amino groups such as N,N-diethylamino group. R 1 and R 3is particularly preferably a hydrogen atom in each case. R 1 and R 3 may be the same or different. Also, a plurality of R 1 may be the same as or different from each other. A plurality of R 3 may also be the same as or different from each other.

[0016] R 2 and R 4 each represent 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, still more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro group, alkoxy groups such as methoxy group, and amino groups such as N,N-diethylamino group. R 2 and R 4 may be the same or different. Also, when there are a plurality of R 2 , they may be the same or different. When there are a plurality of R 4 , they may also be the same or different.

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

[0018] X and Y each represent a hydroxyl group or a hydrolyzable group. Examples of X and Y include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group, etc. The above-mentioned alkoxy group and the like may have a substituent. An alkoxy group is preferable because of its mild hydrolyzability and ease of handling, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferable, a methoxy group and an ethoxy group are even more preferable, and a methoxy group is particularly preferable. X and Y may be the same or different. Also, when a plurality of Xs exist, they may be the same or different. Similarly, when a plurality of Ys exist, they may be the same or different.

[0019] a in the formula (1) and b in the formula (2) each represent 0, 1, or 2. Preferably they are 0 or 1. In particular, from the viewpoints of curability, storage stability, and resilience, a is preferably 1 and b is preferably 0.

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

[0021] n in the formula (2) represents an integer of 1 to 10. An integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 2 or 3 is even more preferable. From the viewpoint of production, n is most preferably 3.

[0022] The hydrolyzable silyl group possessed by the organic polymer (A) is the group represented by -SiR in the formula (1) 2 a X 3-a and the group represented by -SiR in the formula (2) 4 b Y 3-bIt is a group represented by the following. 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, and the like. The hydrolyzable silyl group may be only one kind, or two or more kinds may coexist.

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

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

[0025] The order of carrying out steps (I) to (III) is preferably in the order of step (I), step (II), and step (III), but may also be in the order of step (I), step (III), and step (II). Hereinafter, each step will be described.

[0026] [Step (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] (Organic polymer (E) containing a hydroxyl group) The organic polymer has a polymer backbone composed of a plurality of repeating units. The polymer backbone of the organic polymer may be linear or branched. The position where the hydroxyl group binds to the polymer backbone is not particularly limited, but it is preferably at the end of the polymer backbone.

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

[0029] The organic polymer may be a polymer having one type of polymer backbone, or a mixture of two or more types of polymers having different polymer backbones. Further, for the mixture, it may be a mixture of polymers produced separately, or a mixture produced simultaneously with an arbitrary mixing 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 still more preferably 3,000 to 30,000 in terms of polystyrene equivalent molecular weight in GPC. When the number average molecular weight is 3,000 or more, the relative amount of the hydrolyzable silyl group with respect to the whole polymer is in an appropriate range, which is desirable from the viewpoint of production cost. Further, when the number average molecular weight is 100,000 or less, it is easy to achieve a desirable viscosity from the viewpoint of workability. The number average molecular weight can be determined in terms of polystyrene by GPC measurement.

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

[0032] Next, a method for producing the organic polymer (E) having a hydroxyl group will be described. (Polyoxyalkylene polymer) When the polymer skeleton of the hydroxyl group-containing organic polymer (E) is a polyoxyalkylene polymer the polymer can be produced by polymerizing an epoxy compound with a hydroxyl group-containing initiator by a conventionally known method. Thereby, a hydroxyl group-terminated polyoxyalkylene polymer can be obtained. The specific polymerization method is not particularly limited, but a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable because a polymer having a small molecular weight distribution (Mw / Mn) can be obtained.

[0033] The initiator having a hydroxyl group is not particularly limited, and examples thereof 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, and examples thereof 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)acrylate polymer) When the polymer skeleton of the hydroxyl group-containing organic polymer (E) is a (meth)acrylate polymer, examples of the method for producing the hydroxyl group-containing organic polymer include (I) a method of 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) a method of 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 the molecular chain end) in the obtained polymer.

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

[0037] [Step (Ia)] According to one aspect of the present embodiment, step (I) can be a step of reacting an organic polymer (E) 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, thereby obtaining an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. Step (I) according to this aspect is also referred to as step (Ia) below.

[0038] (Reaction with an alkali metal salt) When converting a part of the hydroxyl groups of the organic polymer into carbon-carbon unsaturated bond-containing groups, first, it is preferable to allow an alkali metal salt to act on the hydroxyl group-containing organic polymer (E) to convert a part of the hydroxyl groups of the organic polymer into metal oxy groups. Further, instead of the alkali metal salt, a double metal cyanide complex catalyst can also be used. Thus, a metal oxy group-containing organic polymer is formed.

[0039] The alkali metal salt is not particularly limited, and examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide, etc. From the viewpoints of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide are preferable, and sodium methoxide and sodium tert-butoxide are more preferable. In terms of availability, sodium methoxide is particularly preferable, and in terms of reactivity, sodium tert-butoxide is particularly preferable. The alkali metal salt may be used in the reaction in a state dissolved in a solvent.

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

[0041] In order to efficiently proceed the reaction of converting the hydroxyl group of the organic polymer (E) into a metal oxy group, it is preferable to previously remove moisture and substances having hydroxyl groups other than the organic polymer from the reaction system. For the removal, known methods may be used, for example, heating evaporation, devolatilization under reduced pressure, spray vaporization, thin film evaporation, azeotropic devolatilization, etc. can be used.

[0042] The temperature when the alkali metal salt acts can be appropriately set by those skilled in the art, but it is preferably 50°C or higher and 150°C or lower, and more preferably 110°C or higher and 145°C or lower. The time when the alkali metal salt acts is preferably 10 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less.

[0043] (Reaction with the carbon-carbon unsaturated bond-containing halide (G1)) By reacting the metal oxy group-containing organic polymer with the 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 by a substitution reaction of the halogen to form an ether bond. Thereby, an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule can be formed.

[0044] The 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 is the R described above for formula (2).3 It 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 into the organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule, which is obtained by reacting the halide (G1), the structure represented by the formula (2) can be formed.

[0045] Specific examples of the carbon-carbon unsaturated bond-containing halide (G1) are not particularly limited, and include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide, etc. From the viewpoint of ease of handling, allyl chloride and methallyl chloride are preferred.

[0046] The addition amount of the carbon-carbon unsaturated bond-containing halide (G1) is not particularly limited, but the molar ratio of the organic halide (G1) to the metal oxy group of the organic polymer is preferably 0.7 or more, more preferably 1.0 or more. Also, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

[0047] When reacting the carbon-carbon unsaturated bond-containing halide (G1 ) with the metal oxy group-containing organic polymer, the temperature is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower. The reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

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

[0049] (Reaction with an alkali metal salt) When reacting an organic polymer (E) having a hydroxyl group with an epoxy compound containing a carbon-carbon unsaturated bond, first, it is preferable to convert the hydroxyl group of the hydroxyl group-containing organic polymer (E) to a metal oxy group by reacting an alkali metal salt therewith. Further, instead of the alkali metal salt, a double metal cyanide complex catalyst can also be used. Thus, 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 the alkali metal salt used, which will be described below.

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

[0051] (Reaction with an epoxy compound (G2) containing a carbon-carbon unsaturated bond) When an epoxy compound (G2) containing a carbon-carbon unsaturated bond is allowed to act on the metal oxy group-containing organic polymer, the epoxy compound (G2) containing a carbon-carbon unsaturated bond reacts with the metal oxy group by a ring-opening addition reaction of the epoxy group to form an ether bond, and a structure containing a carbon-carbon unsaturated bond and a hydroxyl group can be introduced into the organic polymer. Thereby, an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule can be obtained. In the above ring-opening addition reaction, by adjusting the amount of the epoxy compound (G2) containing a carbon-carbon unsaturated bond used and the reaction conditions with respect to the metal oxy group, one or more epoxy compounds (G2) can be added to one metal oxy group.

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

[0053]

Chemical formula

[0054] In formula (6), R 3 is the same as R 3 is the same as R 5 represents a direct bond or a divalent bonding group having 1 to 6 carbon atoms. n is an integer of 2 to 10.

[0055] R 5 R 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 or 2. 5 is preferably a direct bond or a methylene group, and most preferably a methylene group.

[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 monoxide, and 1,4-cyclopentadiene monoepoxide are preferred in terms of reaction activity, with allyl glycidyl ether being particularly preferred.

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

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

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

[0060] The reaction with the alkali metal salt and the reaction with the epoxy compound (G2) may be repeatedly carried out a plurality of times in order to increase the introduction rate of the carbon-carbon unsaturated bond into the organic polymer. When these reactions are repeatedly carried out a plurality of times, the reactants (alkali metal salt or epoxy compound (G2)) used in each step may be the same as or different from each other.

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

[0062] [Chemical formula]

[0063] In formula (4), R 3 and R 5 are the same as the respective groups described above for the above formula (6). d is an integer of 1 to 10. n is an integer of 2 to 10.

[0064] [Step (II)] Step (II) is a step of hydrosilylating a carbon-carbon unsaturated bond of the organic polymer with a hydrosilane compound containing a hydrolyzable silyl group to introduce the structure represented by the formula (2) into the organic polymer. Step (II) is preferably carried out after Step (I). In this case, Step (II) is carried out on the organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule obtained in Step (I). Thereby, an organic polymer having a hydroxyl group and a hydrolyzable silyl group (the structure of the formula (2)) in the same molecule can be obtained.

[0065] Specific examples of the hydrolyzable silyl group-containing hydrosilane compound include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, 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-trifluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoropropyl)dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane, diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate)methylsilane; isopropenylsilanes (acetone-eliminating type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, (methoxymethyl)diisopropenyloxysilane, etc.

[0066] The amount of the hydrolyzable silyl group-containing hydrosilane compound used may be appropriately set in consideration of the amount of carbon-carbon unsaturated bonds in the organic polymer and the number of hydrolyzable silyl groups to be introduced as intended.

[0067] For the hydrosilylation reaction, for the purpose of promoting the reaction, it is preferably carried out in the presence of a hydrosilylation catalyst. As the hydrosilylation catalyst, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, etc., and their complexes, etc. can be used. Specifically, those in which platinum is supported on a carrier such as alumina, silica, carbon black, etc.; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, ketones, etc.; platinum-olefin complexes [for example, Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [for example, Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [for example, Ph(PPh3)4, Pt(PBu3)4]; platinum-phosphite complexes [for example, Pt{P(OPh)3}4], etc. can be mentioned. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complexes are preferred.

[0068] The hydrosilylation reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the organic polymer, the hydrosilane compound, and the hydrosilylation catalyst, and also for easily realizing the temperature control of the reaction system and the addition of the hydrosilylation catalyst, an organic solvent may be added and the reaction may be carried out.

[0069] The temperature during the hydrosilylation reaction is not particularly limited and can be appropriately set by those skilled in the art. However, for the purpose of reducing the viscosity of the reaction system or improving the reactivity, heating conditions are preferred. Specifically, it is more preferably 50°C to 150°C, and even more preferably 70°C to 120°C. The reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, and more preferably 3 hours or less.

[0070] [Step (III)] Step (III) is a step of subjecting the hydroxyl groups of the organic polymer to a urethanization reaction with a compound having a hydrolyzable silyl group and an isocyanate group (hereinafter also referred to as a silyl group-containing isocyanate compound) to introduce the structure represented by the above formula (1) into the organic polymer. Step (III) is preferably carried out after Step (II). In this case, Step (III) is carried out on the organic polymer having a hydroxyl group and a hydrolyzable silyl group in the same molecule obtained in Step (II). Thereby, the organic polymer (A) is obtained.

[0071] The silyl group-containing isocyanate compound is a compound having an isocyanate group capable of undergoing a urethanization reaction with the hydroxyl group of the 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 formula (7) 1 、R 2 、X, a, and m are the same as those described above for formula (1).

[0072] Specific examples of the silyl group-containing isocyanate compound include, for example, (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxymethylsilane, (3-isocyanatopropyl)triethoxysilane, (3-isocyanatopropyl)diethoxymethylsilane, (isocyanatomethyl)trimethoxysilane, (isocyanatomethyl)triethoxysilane, (isocyanatomethyl)dimethoxymethylsilane, (isocyanatomethyl)diethoxymethylsilane, and the like. The silyl group-containing isocyanate compound may be used alone or in combination of two or more.

[0073] The amount of the silyl group-containing isocyanate compound used is based on the hydroxyl group of the organic polymer It can be appropriately determined in consideration of the amount and the amount of the target hydrolyzable silyl group to be introduced, and is not particularly limited. 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 with respect to the hydroxyl group of the organic polymer.

[0074] By subjecting the isocyanate group of the silyl group-containing isocyanate compound to a urethanization reaction with respect to the hydroxyl group of the organic polymer to form a urethane bond, the structure represented by the formula (1) can be introduced into the organic polymer.

[0075] The urethanization reaction may be carried out without using a urethanization catalyst, but may also be carried out in the presence of a urethanization catalyst for the purpose of improving the reaction rate or the reaction ratio. As such a urethanization catalyst, for example, a conventionally known urethanization catalyst such as the catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963 can be used. Specifically, base catalysts such as organotin compounds, bismuth compounds, and organic amines can be mentioned, but are not limited thereto.

[0076] As the urethanization catalyst, an organotin compound is preferred because of its high activity. Specifically, tin octylate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutyl maleate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyldistannoxane, 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, dioctyltin diversatate, etc. may be mentioned. Further, a urethanization catalyst having low activity with respect to the hydrolyzable silyl group is preferred, and from this viewpoint, an organotin compound containing a sulfur atom is preferred. Among them, dibutyltin bis(isononyl-3-mercaptopropionate), dibutyltin bis(isooctyl mercaptopropionate), and dibutyltin bis(isooctyl thioglycolate) are particularly preferred.

[0077] As the urethanization catalyst, an organic bismuth compound is preferred in terms of good activity and maintaining good storage stability of the hydrolyzable silyl group-containing organic polymer. Bismuth-containing catalysts include, for example, catalysts having the trade names Borchi(R) Kat 22, Borchi(R) Kat 24, Borchi(R) Kat 320, Borchi(R) Kat 315EU, Borchi(R) Kat VP 0243, Borchi(R) Kat VP 0244 manufactured by Borchers GmbH, bismuth(III) 2-ethylhexanoate 2-ethylhexanoate solution (Bi: 25%), bismuth(III) 2-ethylhexanoate, 70 - 75% manufactured by Fujifilm Wako Pure Chemical Corporation Examples include xylenes (~24% Bi) and PURATREM (99.99+% -Bi), but are not particularly limited as long as they can promote the urethanization reaction.

[0078] The addition amount of the urethanization catalyst can be appropriately set by those skilled in the art. From the viewpoint of reaction activity, 1 to 1000 ppm, preferably 10 to 100 ppm, is preferable with respect to 100 parts by weight of the organic polymer. In this range, in addition to obtaining sufficient reaction activity, the physical properties of the produced hydrolyzable silyl group-containing organic polymer can be maintained well.

[0079] The urethanization reaction can be carried out without using a solvent. However, for the purpose of uniformly dissolving the organic polymer, the silyl group-containing isocyanate compound, and the urethanization catalyst, and also for easily realizing the temperature control of the reaction system and the addition of the urethanization catalyst, it may be carried out by adding an organic solvent.

[0080] When using an organic solvent, its type is not particularly limited and can be appropriately selected. For example, 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, ether solvents such as tetrahydrofuran (THF) and tetrahydropyran (THP), etc. can be mentioned. Only one type of organic solvent may be used, or two or more types may be used in combination.

[0081] The temperature during the urethanization reaction can be appropriately set by those skilled in the art, but it is preferably 50°C or higher and 120°C or lower, more preferably 70°C or higher and 100°C or lower. The reaction time can also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 15 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

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

[0083] [Organic polymer (A’)] When the step (Ib) is carried out as the step (I) to obtain an organic polymer having the structure represented by the formula (4), subsequently, by carrying out the steps (II) and (III), an organic polymer (A’) having the structure represented by the following formula (3) can be produced. The organic polymer (A’) corresponds to the organic polymer (A) and is a novel polymer not reported conventionally.

[0084] [Chemical formula]

[0085] In the 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 the formula (3) includes both the structure represented by the formula (1) and the structure represented by the formula (2). Thus, in the organic polymer (A’), the positions where the structures of the formula (1) and the formula (2) are introduced are controlled, and each terminal of the organic polymer (A’) can have the structure of the formula (1). Therefore, the organic polymer (A’) can exhibit particularly good curability among the organic polymers (A).

[0086] Details of the polymer backbone of the organic polymer (A’), the number average molecular weight, and the range of the molecular weight distribution are the same as those of the hydroxyl group-containing organic polymer (E), and thus the description is omitted.

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

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

[0089] The organic polymer (B) may have a structure represented by the above formula (1) described for the organic polymer (A), or may have a structure represented by the formula (2). Further, among the structures not corresponding to either the structure of the formula (1) or the structure of the formula (2), those containing a hydrolyzable silyl group may be used.

[0090] Examples of the polymer skeleton of the organic polymer (B) include the same as the polymer skeleton of the above-described hydroxyl group-containing organic polymer (E), and a polyoxyalkylene-based polymer is preferable, and polyoxypropylene is particularly preferable.

[0091] When the polymer skeleton of the organic polymer (B) is a polyoxyalkylene-based polymer, such an organic polymer (B) can be produced, for example, by polymerizing an epoxy compound in the presence of an initiator having only one hydroxyl group in one molecule and then performing one-step or two-step or more reactions for introducing a hydrolyzable silyl group. According to this method, a polyoxyalkylene-based polymer having a hydrolyzable silyl group at one end can be produced.

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

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

[0094] (Curing catalyst) The curable composition according to the present embodiment preferably contains a curing catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl group, that is, the curing reaction.

[0095] As the curing catalyst, conventionally known ones can be used. Specifically, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. can be used.

[0096] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), the reaction product of dibutyltin oxide and a silicate compound, the reaction product of dibutyltin oxide and a phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), the reaction product of dioctyltin oxide and a silicate compound, etc. Due to the increasing environmental concerns in recent years, dioctyltin compounds are preferred. However, since the organic polymer (A') can exhibit rapid curability, the curable composition according to the present embodiment does not contain an organotin compound and can contain a curing catalyst (particularly, an amine-based compound, etc.) that is generally less active than an organotin compound. Even if the curable composition according to the present embodiment contains an amine-based compound, it can exhibit good curability. ​

[0097] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, etc. As the carboxylic acid group, various metals can be combined with the following carboxylic acids.

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

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

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

[0101] As other curing catalysts, fluoride anion-containing compounds, photoacid generators, and photobase generators can also be used.

[0102] The curing catalyst may be used in combination of two or more different catalysts. For example, by using the above-mentioned amine compound and carboxylic acid in combination, there may be an effect of improving the reactivity.

[0103] In addition, since the organic polymer (A') has a highly active hydrolyzable silyl group, it is possible to reduce the amount of the curing catalyst, use a curing catalyst with low activity, or use aminosilane, which is 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 that does not use the usually used curing catalyst can be prepared. Therefore, it is preferable not to add other curing catalysts. In particular, when m in the structure represented by the formula (1) is 1, or when the hydrolyzable silyl group contains a trimethoxysilyl group or a methoxymethyldimethoxysilyl group, excellent curability is exhibited even when only aminosilane is used as the curing catalyst.

[0104] Specific examples of the aminosilane include γ-aminopropyltrimethoxysilane, γ-a Aminosilanes such as 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, 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, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; ketimine type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine and the like. Only one type of aminosilane may be used, or two or more types may be used in combination.

[0105] As the compounding amount of the curing catalyst, 0.001 to 20 parts by weight is preferable, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable with respect to 100 parts by weight of the organic polymer (A’). If the compounding amount of the curing catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, if the compounding amount of the curing catalyst exceeds 20 parts by weight, the reaction rate is too fast, so the usable time of the composition becomes short, resulting in poor workability or poor storage stability. Furthermore, in some cases, after the curable composition has cured, it may ooze out onto the surface of the cured product or contaminate the surface of the cured product. In such a case, by setting the usage amount of the curing catalyst to 0.01 to 3.0 parts by weight, the surface state of the cured product can be kept good while ensuring curability.

[0106] In the curable composition according to this embodiment, as other additives, a silicon compound, an adhesion-imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a physical property modifier, a tackifying resin, a compound containing an epoxy group, a photocurable substance, an oxygen-curable substance, a surface property improver, an epoxy resin, other resins, a flame retardant, and a foaming agent may be added. Further, in the curable composition according to this embodiment, various additives may be added as necessary for the purpose of adjusting various physical properties of the composition or the cured product. Examples of such additives include, for example, a curability modifier, a radical inhibitor, a metal deactivator, an ozone degradation inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, a fungicide, and the like.

[0107] (Filler) Various fillers can be blended in the curable composition according to this embodiment. Examples of the filler include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic anhydride, hydrous silicic acid, carbon black, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, and filament.

[0108] The amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the organic polymer (A’).

[0109] For the purpose of reducing the weight (lowering the specific gravity) of the composition, organic balloons or inorganic balloons may be added. The balloon is a spherical filler with a hollow interior. Examples of the material for this balloon include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0110] The amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the organic polymer (A’).

[0111] (Adhesion promoter) An adhesion promoter can be added to the curable composition according to this embodiment. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be added. Specific examples of the silane coupling agent 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; isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, and α-isocyanatomethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The above adhesion imparting agent may be used alone or in combination of two or more kinds.

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

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

[0114] In addition, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and derivatives obtained by converting the hydroxy groups of these polyether polyols into ester groups, ether groups, etc., such as polyethers; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. The plasticizer may be used alone or in combination of two or more.

[0115] The amount of the 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 with respect to 100 parts by weight of the organic polymer (A').

[0116] (Solvent, diluent) A solvent or diluent can be added to the curable composition according to this embodiment. The solvent and diluent are not particularly limited, and aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc. can be used. When using a solvent or diluent, due to the problem of air pollution when the composition is used indoors, 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. The above solvent or diluent may be used alone or in combination of two or more.

[0117] (Anti-sagging agent) An anti-sagging agent may be added to the curable composition according to this embodiment as needed to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more. The amount of the anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A').

[0118] (Antioxidant) An antioxidant (anti-aging agent) can be used in the curable composition according to this embodiment. Using an antioxidant can enhance the weather resistance of the cured product. Examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A'), and more preferably 0.2 to 5 parts by weight.

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

[0120] (Ultraviolet absorber) In the curable composition according to this embodiment, an ultraviolet absorber can be used. Using an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, etc., and the benzotriazole-based is particularly preferred. Examples include Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, Tinuvin B75 (all manufactured by BASF). The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the organic polymer (A').

[0121] (Physical property modifier) To the curable composition according to this embodiment, a physical property modifier for adjusting the tensile properties of the cured product generated as necessary may be added. The physical property modifier is not particularly limited. For example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane, phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates such as tris(trimethylsilyl) borate, tris(triethylsilyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, the hardness when the curable composition according to this embodiment is cured can be increased, or conversely, the hardness can be decreased and the elongation at break can be increased. The above physical property modifier may be used alone or in combination of two or more.

[0122] In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an effect of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. A compound that generates trimethylsilanol is particularly preferred. Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, etc. and generate silane monoalcohol by hydrolysis.

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

[0124] (Adhesion - imparting resin) In the curable composition according to this embodiment, an adhesion-imparting resin can be added for the purpose of enhancing the adhesiveness and close adhesiveness to a substrate, or as otherwise required. There is no particular limitation on the adhesion-imparting resin, and those commonly used can be employed.

[0125] Specific examples include terpene resins, aromatic-modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin-based resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene-based resins, styrene copolymer resins, styrene-based block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5-C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.

[0126] The amount of the adhesion-imparting 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 with respect to 100 parts by weight of the organic polymer (A').

[0127] (Compound containing an epoxy group) In the curable composition according to this embodiment, a compound containing an epoxy group can be used. When a compound having an epoxy group is used, the restorability of the cured product can be enhanced. Examples of the compound having an epoxy group include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown by epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-P S), epoxy octyl stearate, epoxy butyl stearate, and the like can be mentioned. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the organic polymer (A').

[0128] (Photo-curable substance) A photo-curable substance can be used in the curable composition according to this embodiment. When a photo-curable substance is used, a film of the photo-curable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many such compounds are known, such as organic monomers, oligomers, resins, or compositions containing them. Representative examples include monomers, oligomers having one to several acrylic or methacrylic unsaturated groups, or mixtures thereof, unsaturated acrylic compounds, vinyl polycinnamates, or azide resins.

[0129] The amount of the photo-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A').

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

[0131] The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A'). As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photo-curable substance.

[0132] (Epoxy resin) An epoxy resin can be used in combination with the curable composition according to this embodiment. The composition added with an epoxy resin is particularly preferable as an adhesive, especially an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A type epoxy resins or novolak type epoxy resins.

[0133] The usage ratio of the epoxy resin and the organic polymer (A') is preferably in the range of 100 / 1 to 1 / 100 by weight ratio of organic polymer (A') / epoxy resin. When 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 cured epoxy resin, and when the ratio of organic polymer (A') / epoxy resin exceeds 100 / 1, the strength of the cured polymer becomes insufficient.

[0134] When adding an epoxy resin, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to this embodiment. There is no particular limitation on the epoxy resin curing agent that can be used, and generally used epoxy resin curing agents can be used.

[0135] When using a curing agent for the epoxy resin, the usage amount is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the 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 the compounding components are pre-compounded and sealed for storage and cured by moisture in the air after construction, or as a two-component type in which a curing catalyst, a filler, a plasticizer, water and other components are separately compounded as a curing agent and the compounded material and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferable.

[0137] When the curable composition is of the one-component type, since all the compounding components are pre-compounded, it is preferable to dehydrate and dry in advance the compounding components containing moisture before use, or to dehydrate them by reducing the pressure during compounding and kneading. In addition to the dehydration drying method, the storage stability can be further improved by adding alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0138] <Use> The curable composition according to this embodiment can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproof material, a waterproof coating material, a mold release agent, a vibration-proof material, a vibration damping material, a sound-proof material, a foaming material, a paint, and a spraying material. The cured product obtained by curing the curable composition according to this embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealing material or an adhesive.

[0139] In addition, the curable composition according to this embodiment can be used in various applications such as electrical and electronic component materials such as back surface encapsulants for solar cells, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulation materials for electrical appliances and devices, acoustic insulation materials, elastic adhesives, binders, contact adhesives, spray sealants, crack repair materials, adhesives for tiling, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, anti-slip coatings, cushioning materials, primers, conductive materials for electromagnetic wave shielding, heat conductive materials, hot melt materials, potting agents for electrical and electronics, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and anti-rust and waterproof sealants for wire mesh glass and the end faces (cut parts) of laminated glass, automotive parts, large vehicle parts such as trucks and buses, parts for train vehicles, aircraft parts, ship parts, electrical machine parts, and various mechanical parts. Taking an automobile as an example, it can be used in a variety of ways such as adhesive attachment of plastic covers, trims, flanges, bumpers, window attachments, interior members, and exterior parts. Furthermore, it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings, either alone or with the help of a primer, so it can also be used as various types of sealing compositions and adhesive compositions. In addition, the curable composition according to this embodiment can also be used as an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone cladding, an adhesive for ceiling finishing, an adhesive for floor finishing, an adhesive for wall finishing, an adhesive for vehicle panels, an adhesive for assembling electrical, electronic, and precision instruments, an adhesive for bonding leather, fiber products, fabrics, paper, boards, and rubber, a reactive post-crosslinking pressure-sensitive adhesive, a sealing material for direct glazing, a sealing material for laminated glass, a sealing material for the SSG method, or a sealing material for working joints of buildings, civil engineering, and bridge materials. Furthermore, it can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.

Examples

[0140] Examples are given below to explain the present invention in more detail, 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: HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GEL H type manufactured by Tosoh Corporation Solvent: THF Molecular weight: Polystyrene conversion Measurement temperature: 40 °C

[0141] (Synthesis Example 1) Using polyoxypropylene triol with a number average molecular weight of about 4,500 as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate glyme complex catalyst to obtain a branched polyoxypropylene (E-1) with a number average molecular weight of 23,300 and having a hydroxyl group at the terminal. 0.60 molar equivalent of sodium methoxide as a 28% methanol solution was added to the hydroxyl group of the obtained polymer (E-1). After methanol was distilled off under reduced pressure, 0.69 molar equivalent of allyl chloride was added to the hydroxyl group of the polymer (E-1) and reacted at 130 °C for 1 hour, and then allyl chloride was distilled off. The obtained unpurified polyoxypropylene was dissolved in n-hexane, and by mixing and stirring aluminum silicate (Kyoward R700SEN-S manufactured by Kyowa Chemical Industry Co., Ltd.), the metal salt in the polymer was adsorbed on the aluminum silicate, and then the aluminum silicate was removed by filtration, and hexane was distilled off under reduced pressure from the obtained hexane solution. Thus, polyoxypropylene (F-1) having a carbon-carbon unsaturated bond (allyl group) and a hydroxyl group was obtained. Next, at 90 °C, 50 ppm of a platinum divinyldisiloxane complex (a 3 wt% isopropanol solution in terms of platinum) and 0.87 parts by weight of trimethoxysilane were added to 100 parts by weight of the polymer (F-1), and a hydrosilylation reaction was carried out with respect to the allyl group of the polymer (F-1) to form the structure represented by the above formula (2). After reacting at 90 °C until the allyl group was completely consumed, volatile components were distilled off. Subsequently, at 90 °C, 30 ppm of bismuth(III) 2-ethylhexanoate 2-ethylhexanoate solution (Bi: 25%) and 0.95 molar equivalent of (isocyanatomethyl)dimethoxymethylsilane with respect to the hydroxyl groups of the polymer were added to 100 parts by weight of the polymer, and a urethanization reaction was carried out with respect to the hydroxyl groups of the polymer to form the structure represented by the above formula (1). Thus, a branched polyoxypropylene (A-1) having the structure represented by the above formula (1) and the structure represented by the above formula (2) in the same molecule was obtained.

[0142] (Synthesis Example 2) Using polyoxypropylene glycol having a number average molecular weight of about 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (E-2) having a number average molecular weight of 27,900 and hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide as a 28% methanol solution was added to the hydroxyl groups of the polymer (E-2). After distilling off methanol by vacuum distillation at 140 °C, 1.5 molar equivalents of allyl glycidyl ether were added to the hydroxyl groups of the polymer (E-2) and reacted at 140 °C for 2 hours. Then, at 80 °C, 3.0 molar equivalents of methanol were added to the hydroxyl groups of the polymer (E-2) to convert the terminal sodium alkoxide groups to hydroxyl groups. The obtained unpurified polyoxypropylene was dissolved in n-hexane, and by mixing and stirring aluminum silicate (Kyoward R700SEN-S manufactured by Kyowa Chemical Industry Co., Ltd.), the metal salts in the polymer were adsorbed onto the aluminum silicate, and then the aluminum silicate was removed by filtration, and hexane was distilled off under reduced pressure from the obtained hexane solution. Thus, 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 the above formula (4). Next, at 65°C, 50 ppm of a platinum divinyldisiloxane complex (an isopropanol solution containing 3% by weight of platinum) and 1.3 parts by weight of trimethoxysilane were added to 100 parts by weight of the polymer (F-2), and a hydrosilylation reaction was carried out with respect to the allyl groups possessed by the polymer (F-2) to form the structure represented by the above formula (2). After reacting at 85°C until trimethoxysilane was completely consumed, volatile components were distilled off. Subsequently, at 90°C, 30 ppm of bismuth(III) 2-ethylhexanoate 2-ethylhexanoate solution (Bi: 25%) and 0.95 molar equivalent of (isocyanatomethyl)dimethoxymethylsilane with respect to the hydroxyl groups possessed by the polymer were added to 100 parts by weight of the polymer, and a urethanization reaction was carried out with respect to the hydroxyl groups possessed by the polymer to form the structure represented by the above formula (1). Thus, polyoxypropylene (A-2) having the structure represented by the above formula (1) and the structure represented by the above formula (2) in the same molecule was obtained. The polymer (A-2) has the structure represented by the above formula (3).

[0143] (Comparative Synthesis Example 1) Using polyoxypropylene glycol with a number average molecular weight of about 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (E-3) having a number average molecular weight of 15,000 and hydroxyl groups at both ends. To 100 parts by weight of the polymer (E-3), 30 ppm of bismuth(III) 2-ethylhexanoate 2-ethylhexanoate solution (Bi: 25%) and 0.95 molar equivalent of (isocyanatomethyl)dimethoxymethylsilane with respect to the hydroxyl groups possessed by the polymer were added, and a urethanization reaction was carried out with respect to the hydroxyl groups possessed by the polymer to form the structure represented by the above formula (1). Thus, polyoxypropylene (C-1) having the structure represented by the above formula (1) was obtained.

[0144] (Comparative Synthesis Example 2) 1.1 molar equivalents of sodium methoxide as a 28% methanol solution was added to the hydroxyl groups of the polymer (E-1) obtained in Synthesis Example 1. After methanol was distilled off under reduced pressure, 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (E-1), and the reaction was carried out at 130 °C for 1.5 hours. Then, allyl chloride was distilled off. The obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and then water was removed by centrifugation. Hexane was distilled off under reduced pressure from the obtained hexane solution to remove the metal salts in the polymer. Thus, polyoxypropylene (F-3) having a carbon-carbon unsaturated bond (allyl group) at the terminal was obtained. Next, at 90 °C, 50 ppm of a platinum divinyldisiloxane complex (an isopropanol solution containing 3% by weight of platinum) and 1.35 parts by weight of trimethoxysilane were added to 100 parts by weight of the polymer (F-3), and a hydrosilylation reaction was carried out with respect to the allyl groups possessed by the polymer (F-3) to form the structure represented by the above formula (2). After reacting until trimethoxysilane was completely consumed at 90 °C, volatile components were distilled off. Thus, a branched polyoxypropylene (C-2) having the structure represented by the above formula (2) was obtained.

[0145] (Comparative Synthesis Example 3) 1.0 molar equivalent of sodium methoxide as a 28% methanol solution was added to the hydroxyl groups of the polymer (E-2) obtained in Synthesis Example 2. After methanol was distilled off under reduced pressure, 1.1 molar equivalents of allyl glycidyl ether was added to the hydroxyl groups of the polymer (E-2), and the reaction was carried out at 140 °C for 3 hours. Further, 1.22 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (E-2), and the reaction was carried out at 130 °C for 1 hour. Then, allyl chloride was distilled off Thereafter, 0.30 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the polymer (E-2). After distilling off methanol by distillation under reduced pressure at 130°C, 0.79 molar equivalent of allyl chloride was added to the hydroxyl groups of the polymer (E-2), and the reaction was carried out at 130°C for 2 hours. Then, allyl chloride was distilled off. Thereafter, 0.2 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the polymer (E-2). After distilling off methanol by distillation under reduced pressure at 130°C, 0.3 molar equivalent of allyl chloride was added to the hydroxyl groups of the polymer (E-2), and the reaction was carried out at 130°C for 2 hours. Then, allyl chloride was distilled off. The obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and then water was removed by centrifugation. Hexane was distilled off from the obtained hexane solution under reduced pressure to remove metal salts in the polymer. Thus, polyoxypropylene (F-4) having a plurality of carbon-carbon unsaturated bonds (allyl groups) per one terminal site was obtained. Next, at 90°C, 50 ppm of a platinum divinyldisiloxane complex (an isopropanol solution containing 3% by weight of platinum) and 1.92 parts by weight of trimethoxysilane were added to 100 parts by weight of the polymer (F-4), and a hydrosilylation reaction was carried out with respect to the allyl groups possessed by the polymer (F-4) to form the structure represented by the formula (2). After reacting until trimethoxysilane was completely consumed at 90°C, volatile components were distilled off. Thus, polyoxypropylene (C-3) having a plurality of the structures represented by the formula (2) per one terminal site was obtained.

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

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

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

[0149] (Example 1, Comparative Examples 1 to 3) For a total of 100 parts by weight of the polymers shown in Table 1, 90 parts by weight of DINP (diisononyl phthalate, manufactured by J-Plus Corporation), 160 parts by weight of Hakuenka CCR (precipitated calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), and 54 parts by weight of SB (Shiraishi Calcium Co., Ltd.: heavy calcium carbonate), 5 parts by weight of Typec R820 (Ishihara Sangyo Kaisha, Ltd.: titanium oxide), 2 parts by weight of Disparlon 6500 (Kusumoto Chemical Co., Ltd.: fatty acid amide wax), 1 part by weight of Tinuvin 770 (BASF: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate), and 1 part by weight of Tinuvin 326 (BASF: 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole) were mixed, and 2 parts by weight of A-171 (Momentive: vinyltrimethoxysilane), the amount (parts by weight) of A-1120 (Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) shown in Table 1, and the amount (parts by weight) of DBU (diazabicycloundecene) shown in Table 1 were added and mixed. A-1120 (the aminosilane) and DBU (the amine compound) promote the condensation of the hydrolyzable silyl group, and promote the hardening of the polymer.

[0150] (Skinning time) The obtained composition was filled into a mold about 5 mm thick with a spatula, and the time when the surface was smoothed to a flat surface was defined as the curing start time, and the time when the evaluation composition no longer adhered to the spatula when the surface was touched with the spatula was defined as the skinning time, and the curing time was measured. The results are shown in each table.

[0151] (Dumbbell tensile physical properties) The obtained composition was filled into a mold and cured at 23°C and 50% RH for 3 days, and further cured at 50°C for 4 days to prepare a sheet-like cured product with a thickness of about 3 mm. The sheet-like cured product was punched into a No. 3 dumbbell shape, and a tensile strength test was performed at 23°C and 50% RH. The modulus at 50% or 100% elongation, the strength at break, and the elongation were measured. The measurement was carried out using an autograph (AGS-J) manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in each table.

[0152] (Recovery rate) The obtained composition was filled into a mold and cured at 23°C and 50% RH for 3 days, and further cured at 50°C for 4 days to prepare a sheet-like cured product with a thickness of about 3 mm. The sheet-like cured product was punched into a No. 7 dumbbell shape, and both ends were fixed with clips in a state where the dumbbell shape was stretched by 10 mm. Then, it was left standing at 23°C and 50% RH for 24 hours in that state. After that, the clips were removed, and it was left standing on a smooth glass plate in a state where the deforming force was removed, and it was confirmed how much it had returned to its original shape after 24 hours. Taking the elongation of the dumbbell after 24 hours as X (mm), the recovery rate was calculated as follows. The results are shown in each table. Recovery rate (%) = (10 - X) ÷ 10 × 100

[0153] [Table 1]

[0154] As is clear from Table 1, the curable composition of Comparative Example 2 containing the polymer (C-2) having only the structure represented by the formula (2) had extremely low curability in the presence of aminosilane (A-1120) and amine compound (DBU), and did not cure sufficiently, whereas the curable composition of Example 1 containing the polymer (A-1) having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule showed good curability. Furthermore, the curable composition of Example 1 showed high restoration compared to the curable composition of Comparative Example 1 containing the polymer (C-1) having only the structure represented by the formula (1) and the curable composition of Comparative Example 3. Comparative Example 3 is a curable composition containing the polymer (C-1) and the polymer (C-2) in the content ratio of the structure represented by the formula (1) and the structure represented by the formula (2) contained in the polymer (A-1). That is, it is found that a polymer having a structure represented by the formula (1) and a structure represented by the formula (2) in the same molecule exhibits higher recovery than a mixture of a polymer having a structure represented by the formula (1) and a polymer having a structure represented by the formula (2).

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

[0156]

Table 2

[0157] As is clear from Table 2, the curable composition of Comparative Example 4 containing the polymer (C-3) having only the structure represented by the formula (2) had extremely low curability and did not cure sufficiently in the presence of aminosilane (A-1120), whereas the curable composition of Example 2 containing the polymer (A-2) having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule showed good curability. Further, the curable composition of Example 2 showed higher resilience than the curable composition of Comparative Example 1 containing the polymer (C-1) having only the structure represented by the formula (1) and the curable composition of Comparative Example 5. Comparative Example 5 is a curable composition containing the polymer (C-1) and the polymer (C-3) in terms of the content ratio of the structure represented by the formula (1) and the structure represented by the formula (2) contained in the polymer (A-2). That is, it can be seen that the polymer having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule shows higher resilience than the mixture of the polymer having the structure represented by the formula (1) and the polymer having the structure represented by the formula (2). Furthermore, Example 2 also showed higher curability than Comparative Example 5.

[0158] (Examples 3 to 5, Comparative Examples 6 to 8) Based on 100 parts by weight of the total polymers described in Table 3, 90 parts by weight of DINP (manufactured by J Plus Co., Ltd.: Diisononyl phthalate), 160 parts by weight of Blanc Fixe CCR (manufactured by Shiraishi Calcium Co., Ltd.: Precipitated calcium carbonate), 54 parts by weight of Whiton SB (manufactured by Shiraishi Calcium Co., Ltd.: Heavy calcium carbonate), 5 parts by weight of Ti-Paque R820 (manufactured by Ishihara Sangyo Co., Ltd.: Titanium oxide), 2 parts by weight of Disparlon 6500 (manufactured by Enomoto Chemical Co., Ltd.: Fatty acid amide wax), 1 part by weight of Tinuvin 770 (manufactured by BASF: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), and 1 part by weight of Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole) were mixed, and then 2 parts by weight of A-171 (manufactured by Momentive: Vinyltrimethoxysilane) and 3 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) 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) having a hydrolyzable silyl group at one end were mixed with polymer (A-2) showed higher resilience than 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). That is, it can be seen that the polymer having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule shows high resilience even when it is used in combination with a polymer having a hydrolyzable silyl group at one end to lower the modulus.

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, comprising the steps of: -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 are the same or different and each represents 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 of 1 to 5. In formula (2), R ３ are the same or different and each represents 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; and n is an integer from 1 to 10. preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule; a step of subjecting the carbon-carbon unsaturated bond to a hydrosilylation reaction with a hydrolyzable silyl group-containing hydrosilane compound to form a structure represented by formula (2); and and forming a structure represented by formula (1) by subjecting the hydroxyl group to a urethanization reaction with a compound having a hydrolyzable silyl group and an isocyanate group.

2. The method for producing an organic polymer (A) according to claim 1, wherein 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 groups into a carbon-carbon unsaturated bond-containing group.

3. The method for producing the organic polymer (A) according to claim 1, wherein 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.

4. The method for producing the organic polymer (A) according to claim 3, wherein 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 the following formula (4): 【Chemistry 1】 (In formula (4), R ３ is the same as above. ５ represents a direct bond or a divalent bonding group having 1 to 6 carbon atoms; d is an integer from 1 to 10; and n is an integer from 2 to 10.

5. An organic polymer (A') having a structure represented by the following formula (3): 【Chemistry 2】 (In formula (3), R １ are the same or different and each represents 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 are the same or different and each represents 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 represents a direct bond or a divalent bonding 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.

6. The organic polymer (A') according to claim 5, wherein m is 1.

7. The organic polymer (A') according to claim 5 or 6, wherein n is 3.

8. The organic polymer (A') according to any one of claims 5 to 7, wherein the polymer backbone of the organic polymer is a polyoxyalkylene polymer.

9. A curable composition comprising the organic polymer (A') according to any one of claims 5 to 8.

10. The curable composition according to claim 9 , further comprising an organic polymer (B) having one hydrolyzable silyl group in each molecule.

11. The curable composition according to claim 9 or 10, which does not contain an organotin compound.

12. A cured product obtained by curing the curable composition according to any one of claims 9 to 11.

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