Oxyalkylene polymer, its production method, curable composition, and cured product

Abstract

The present invention relates to an oxyalkylene polymer which comprises a polyoxyalkylene chain that contains an oxyethylene group, and a reactive silicon group that is bonded to the polyoxyalkylene chain via an organic group that contains one group represented by -C(=O)NH-, wherein: the number average molecular weight is from 3,000 to 150,000; the molecular weight distribution is 2.00 or less; the content of the oxyethylene groups is from 3% by mass to 90% by mass; and the number of the reactive silicon groups per one molecule is 0.5 or more.

Description

[Technical Field]

[0001] The present invention relates to an oxyalkylene polymer having a reactive silicon group, a method for producing the oxyalkylene polymer, a curable composition containing the oxyalkylene polymer, and a cured product of the curable composition. This application claims priority based on Japanese Patent Application No. 2020-205019 filed on December 10, 2020, and Japanese Patent Application No. 2021-107746 filed on June 29, 2021, the contents of which are incorporated herein by reference. [Background technology]

[0002] Oxyalkylene polymers having reactive silicon groups cure by hydrolysis to form flexible rubber-like cured products, which are used as curing components for sealing materials, adhesives, and the like. These applications require low viscosity, good workability, and good strength and elongation after curing. Depending on the area to be coated, the ability to cure sufficiently from the surface to the depths (deep curing) is also required.

[0003] Patent Document 1 describes an example of producing an oxyalkylene polymer having a reactive silicon group, which is suitable for use in sealants and adhesives. Specifically, the example describes a process in which a polyether polyol is reacted with a diisocyanate compound to produce a urethane prepolymer having an isocyanate group at its terminal, and a reactive silicon group is introduced into the resulting urethane prepolymer via a urea bond to produce a polymer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2001-31757 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the oxyalkylene polymer produced by the above method tends to have a high viscosity. The present invention provides an oxyalkylene polymer capable of realizing a curable composition that has low viscosity, good deep curing properties, and good strength and elongation of the cured product, a method for producing the same, and a curable composition containing the oxyalkylene polymer and a cured product thereof. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] An oxyalkylene polymer having a polyoxyalkylene chain containing an oxyethylene group and a reactive silicon group represented by the following formula (1) bonded to the polyoxyalkylene chain via an organic group containing one group represented by the following formula (i), wherein the number average molecular weight is 3,000 to 150,000, the molecular weight distribution is 2.00 or less, the content of the oxyethylene group is 3 to 90 mass%, and the number of the reactive silicon groups per molecule is 0.5 or more. -C(=O)NH- (i) -SiX a R 3-a (1) In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer of 1 to 3; when a is 1, R may be the same or different from each other; and when a is 2 or 3, X may be the same or different from each other. [2] An oxyalkylene polymer of [1] that does not contain a urea bond. [3] A curable composition comprising the oxyalkylene polymer of [1] or [2]. [4] The curable composition according to [3], wherein the content of the oxyalkylene polymer is 5 to 90% by mass based on the total mass of the curable composition. [5] The curable composition of [3] or [4], further comprising a plasticizer. [6] The curable composition according to [5], wherein the content of the plasticizer is 1 to 350 parts by mass per 100 parts by mass of the oxyalkylene polymer. [7] The curable composition according to any one of [3] to [6], which is for use as a sealant or adhesive. [8] A cured product of the curable composition according to any one of [3] to [7] above. [9] A method for producing an oxyalkylene polymer, comprising reacting a precursor polymer having a polyoxyalkylene chain containing an oxyethylene group and an active hydrogen-containing group bonded to the polyoxyalkylene chain, the precursor polymer having a number average molecular weight of 3,000 to 150,000, a molecular weight distribution of 2.00 or less, and a content of the oxyethylene group of 3 to 90 mass %, with a compound represented by the following formula (2) so that the number of reactive silicon groups represented by the following formula (1) per molecule is 0.5 or more, to obtain an oxyalkylene polymer: -SiX a R 3-a (1) In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer of 1 to 3; when a is 1, R may be the same or different from each other; and when a is 2 or 3, X may be the same or different from each other. O=C=NQ 1 -SiX a R 3-a (2) In the formula (2), Q 1 is a divalent organic group having 1 to 20 carbon atoms, and R, X, and a are the same as in the formula (1).

[10] The method of [9], wherein the precursor polymer has a total degree of unsaturation of 0.1 meq / g or less.

[11] The method according to [9] or

[10] , wherein the precursor polymer is produced by polymerizing a cyclic ether containing ethylene oxide as an initiator in the presence of a double metal cyanide complex.

[12] The production method according to [9] or

[10] , wherein a cyclic ether is polymerized using an initiator in the presence of a double metal cyanide complex, and then ethylene oxide is polymerized in the presence of an alkali metal hydroxide to produce the precursor polymer. [Effects of the Invention]

[0007] According to the present invention, an oxyalkylene polymer capable of realizing a curable composition having low viscosity, good deep curing properties, and good strength and elongation of the cured product, a method for producing the same, and a curable composition containing the oxyalkylene polymer and a cured product thereof are obtained. DETAILED DESCRIPTION OF THE INVENTION

[0008] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed by "to" means that the numerical values before and after "to" are the lower and upper limits of the numerical range. "Polymer" means a material having a number average molecular weight of 1,000 or greater. "Oxyalkylene polymer" means a polymer having a polyoxyalkylene chain formed from cyclic ether-based units. The "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, and a sulfanyl group. The term "active hydrogen" refers to a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from the hydroxyl group of water. The "initiator" is a compound having the above active hydrogen.

[0009] The number-average molecular weight (hereinafter referred to as "Mn") and weight-average molecular weight (hereinafter referred to as "Mw") of a polymer are polystyrene-equivalent molecular weights obtained by GPC measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is the ratio of Mw to Mn (hereinafter referred to as "Mw / Mn"). The total degree of unsaturation of the polymer is a value measured by iodine value titration in accordance with JIS K1557-3:2007.

[0010] The content of oxyethylene groups in the oxyalkylene polymer is 1 It can be measured by H-NMR. The number of reactive silicon groups per polymer molecule is 1 It can be measured by the H-NMR internal standard method. The number of groups represented by -C(=O)NH- (hereinafter also referred to as "group (i)") per polymer molecule can be measured using GPC, NMR, etc. after dissociating urethane bonds and urea bonds, for example, by the analytical methods described in JP 2000-227430 A and JP 2001-141726 A. The number of groups (i) per molecule can be calculated from the number of groups (i) obtained by this method and the number average molecular weight of the polymer.

[0011] <Oxyalkylene polymer> The oxyalkylene polymer of this embodiment (hereinafter also referred to as "polymer A") has a polyoxyalkylene chain containing an oxyethylene group and a reactive silicon group represented by the following formula (1) (hereinafter also simply referred to as "reactive silicon group"). The reactive silicon group is bonded to the polyoxyalkylene chain via an organic group (hereinafter also referred to as "organic group A"), which contains one group (i) represented by the following formula (i): -C(=O)NH- (i)

[0012] -SiX a R 3-a (1) In formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain a hydrolyzable group. R includes hydrocarbon groups, halohydrocarbon groups, and triorganosiloxy groups.

[0013] R is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group, or a triorganosiloxy group. It is more preferably at least one group selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, and a triphenylsiloxy group. From the viewpoints of good curability of the polymer having a reactive silicon group and good stability of the curable composition, a methyl group or an ethyl group is preferred. From the viewpoint of a fast curing rate of the cured product, a 1-chloromethyl group is preferred. A methyl group is particularly preferred from the viewpoint of easy availability.

[0014] In formula (1), X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, which is a group that can react with water to form a silanol group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group. X is preferably an alkoxy group because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, it quickly forms a siloxane bond, making it easier to form a crosslinked structure in the cured product, and the physical properties of the cured product are better.

[0015] In formula (1), a represents an integer of 1 to 3. When a is 1, R may be the same or different from each other. When a is 2 or more, X may be the same or different from each other. a is preferably 2 or 3, and 2 is more preferred.

[0016] Examples of the reactive silicon group represented by formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a diisopropoxymethylsilyl group, a chloromethyldimethoxysilyl group, and a chloromethyldiethoxysilyl group. In terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a dimethoxymethylsilyl group and a trimethoxysilyl group are more preferred.

[0017] The number of reactive silicon groups per molecule of polymer A is 0.5 or more, preferably 0.8 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.2 to 4.0. When the number is at least the lower limit of the above range, excellent deep curing is achieved, and when the number is no more than the upper limit, excellent elongation properties of the cured product are achieved.

[0018] The polyoxyalkylene chain consists of cyclic ether-based units. Examples of the cyclic ether include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide; and cyclic ethers other than alkylene oxides such as tetrahydrofuran. As the cyclic ether, alkylene oxides are preferred.

[0019] The polyoxyalkylene chain of polymer A is a copolymer chain having a unit based on ethylene oxide (oxyethylene group) and another unit based on a cyclic ether other than ethylene oxide. The copolymer chain may be a block copolymer chain, a random copolymer chain, or a combination thereof. The other units are preferably units based on alkylene oxide (oxyalkylene groups), and more preferably units based on propylene oxide (oxypropylene groups). In one aspect of the present invention, the polyoxyalkylene chain of polymer A preferably contains only oxyethylene groups and oxypropylene groups. The polyoxyalkylene chain of polymer A is preferably, for example, a random copolymer chain containing an oxyethylene group and an oxypropylene group, a block copolymer chain having a block chain composed of an oxypropylene group and a block chain composed of an oxyethylene group, or a molecular chain having a random copolymer chain containing an oxyethylene group and an oxypropylene group and a block chain composed of an oxyethylene group. The polyoxyalkylene chain of polymer A preferably has an oxyethylene group at least at the end on the reactive silicon group side. For example, when the polymer A has a block chain consisting of an oxyethylene group, the block chain preferably has the block chain at least at the end on the reactive silicon group side of the polyoxyalkylene chain.

[0020] The content of oxyethylene groups (hereinafter also referred to as "EO content") is 3 to 90 mass%, preferably 4 to 85 mass%, and more preferably 6 to 80 mass%, relative to the total mass of polymer A. When it is at least the lower limit of the above range, excellent deep curing properties are achieved, and when it is at most the upper limit, viscosity can be easily reduced.

[0021] In polymer A, organic group A present between the polyoxyalkylene chain and the reactive silicon group is an organic group derived from compound 2 described below, which is used to introduce a reactive silicon group into an oxyalkylene polymer (precursor polymer) that does not have a reactive silicon group. Organic group A contains one group (i) represented by the following formula (i): -C(=O)NH- (i) The group (i) is a divalent group derived from an isocyanate group contained in the compound 2. When the compound 2 contains one isocyanate group, the organic group A contains one group (i). The group (i) preferably forms a urethane bond (-OC(=O)NH-, where -O- represents the oxygen atom at the terminal of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one urethane bond exists between the polyoxyalkylene chain and the reactive silicon group in the polymer A. It is preferable that the polymer A does not contain a urea bond (-NH-C(=O)NH-). When the compound 2 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polymer A is the same as the number of groups (i) per molecule. In the organic group A, a divalent organic group Q is formed between the group (i) and the reactive silicon group. 1 It is preferable that Q is interposed. 1 is preferably a divalent hydrocarbon group, more preferably an alkylene group having 1 to 20 carbon atoms. 1 A preferred embodiment of this will be explained later in relation to formula (2).

[0022] The Mn of polymer A is 3,000 to 150,000, preferably 4,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 8,000 to 60,000. When it is at least the lower limit of the above range, the elongation of the cured product is excellent, and when it is no more than the upper limit, the viscosity can be easily reduced.

[0023] The Mw / Mn of polymer A is 2.00 or less, preferably 1.50 or less, more preferably 1.45 or less, and even more preferably 1.40 or less. When it is below the upper limit, the viscosity is easily reduced. Furthermore, the elongation properties of the cured product are easily improved. The lower limit is not particularly limited. For example, it is 1.00 or more, and preferably 1.01 or more. The above lower and upper limits can be combined arbitrarily. For example, the Mw / Mn of polymer A is preferably 1.00 or more and 2.00 or less, more preferably 1.00 or more and 1.50 or less, even more preferably 1.01 or more and 1.45 or less, and particularly preferably 1.01 or more and 1.40 or less.

[0024] The viscosity of polymer A at 25° C. is preferably 0.1 to 50.0 Pa·s, more preferably 0.3 to 40.0 Pa·s, even more preferably 0.8 to 35.0 Pa·s, and most preferably 1.0 to 25.0 Pa·s. If it is within this range, workability will be superior.

[0025] <Method for producing oxyalkylene polymer> Polymer A can be produced by reacting a precursor polymer (hereinafter also referred to as "precursor polymer B") having a polyoxyalkylene chain containing an oxyethylene group and an active hydrogen-containing group bonded to the polyoxyalkylene chain with a compound represented by the following formula (2) (hereinafter also referred to as "compound 2").

[0026] The precursor polymer B can be produced by polymerizing an initiator and a cyclic ether containing ethylene oxide in the presence of a ring-opening polymerization catalyst. The number of active hydrogens in the initiator is preferably 1 to 8, more preferably 1 to 6, and even more preferably 2 to 4. It is preferable to select the number depending on the number of reactive silicon groups per molecule of the polymer A to be obtained. The initiator may be used alone or in combination of two or more kinds.

[0027] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and low-molecular-weight polyoxypropylene glycol. Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, and low-molecular-weight polyoxypropylenetriol. Examples of initiators having four or more hydroxyl groups include pentaerythritol, sucrose, sorbitol, dipentaerythritol, trehalose, and diglycerin.

[0028] The cyclic ether is selected depending on the structural units of the polyoxyalkylene chains of the precursor polymer B and polymer A to be obtained. The cyclic ether contains at least ethylene oxide. The content of oxyethylene groups relative to the total mass of precursor polymer B is from 3 to 90 mass %, preferably from 4 to 85 mass %, and more preferably from 6 to 80 mass %. The units other than the oxyethylene group are preferably oxyalkylene groups, more preferably oxypropylene groups. In one aspect of the present invention, the polyoxyalkylene chain of the precursor polymer B preferably contains only oxyethylene groups and oxypropylene groups.

[0029] Examples of the ring-opening polymerization catalyst include composite metal cyanide complexes and alkali metal hydroxides (potassium hydroxide, etc.). It is preferable to use a composite metal cyanide complex, since the molecular weight distribution of the precursor polymer B is likely to be narrow and the total degree of unsaturation of the precursor polymer B is likely to be small. The composite metal cyanide complex may be a known compound, such as those disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Application Laid-Open No. 2004-269776, Japanese Patent Application Laid-Open No. 2005-15786, International Publication No. 2013 / 065802, or Japanese Patent Application Laid-Open No. 2015-010162. The composite metal cyanide complex is preferably a composite metal cyanide complex in which glyme or t-butyl alcohol is coordinated as an organic ligand to the catalyst skeleton. The catalyst skeleton is more preferably Zn3[Co(CN)6]2 (i.e., zinc hexacyanocobaltate complex). In particular, a composite metal cyanide complex using t-butyl alcohol as an organic ligand is preferred.

[0030] When the polyoxyalkylene chains of the precursor polymer B and the polymer A to be obtained are random copolymer chains, a method of producing the precursor polymer B is preferred, in which a cyclic ether containing ethylene oxide is polymerized with an initiator in the presence of a composite metal cyanide complex. For example, a method in which the precursor polymer B is obtained by reacting a mixture of ethylene oxide and propylene oxide with an initiator in the presence of a double metal cyanide complex is preferred.

[0031] When the polyoxyalkylene chains of the precursor polymer B and polymer A to be obtained have a block chain or random copolymer chain composed of an oxyalkylene group other than an oxyethylene group and a block chain composed of an oxyethylene group, a method of producing precursor polymer B by polymerizing a cyclic ether with an initiator in the presence of a composite metal cyanide complex, and further polymerizing ethylene oxide in the presence of an alkali metal hydroxide is preferred. For example, a method of obtaining the precursor polymer B by polymerizing propylene oxide with an initiator in the presence of a double metal cyanide complex, and then polymerizing ethylene oxide in the presence of an alkali metal hydroxide is preferred. Alternatively, a preferred method is to react a mixture of ethylene oxide and propylene oxide with an initiator in the presence of a double metal cyanide complex, and then polymerize the ethylene oxide in the presence of an alkali metal hydroxide to obtain a precursor polymer B. In the precursor polymer B, it is preferable that an oxyethylene group is present at least at the end of the polyoxyalkylene chain on the reactive silicon group side, since this will result in better deep curing properties.

[0032] The Mn of the precursor polymer B is 3,000 to 150,000, preferably 4,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 8,000 to 60,000. It is preferable to set it depending on the Mn of the polymer A to be obtained. The Mw / Mn of precursor polymer B is preferably set so that the Mw / Mn of polymer A is 2.00 or less. For example, the Mw / Mn of precursor polymer B is preferably 1.50 or less, more preferably 1.45 or less, and even more preferably 1.40 or less. The lower limit is not particularly limited. For example, it is 1.00 or more, and preferably 1.01 or more. The above lower and upper limits can be combined arbitrarily. For example, the Mw / Mn of precursor polymer B is preferably 1.00 or more and 2.00 or less, more preferably 1.00 or more and 1.50 or less, even more preferably 1.01 or more and 1.45 or less, and particularly preferably 1.01 or more and 1.40 or less. The total degree of unsaturation of the precursor polymer B is preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, even more preferably 0.03 meq / g or less, and most preferably 0.01 meq / g or less. When it is below the upper limit, excellent deep curing properties are achieved. The lower limit is not particularly limited. For example, it is preferably 0.0001 meq / g or more. The total degree of unsaturation of the precursor polymer B is preferably 0.0001 to 0.1 meq / g, more preferably 0.0001 to 0.05 meq / g, even more preferably 0.0001 to 0.03 meq / g, and most preferably 0.0001 to 0.01 meq / g.

[0033] The compound 2 to be reacted with the precursor polymer B is represented by the following formula (2). O=C=NQ 1-SiX a R 3-a (2) In formula (2), R, X, and a are the same as R, X, and a in formula (1), including preferred embodiments thereof. Q 1 is a divalent organic group having 1 to 20 carbon atoms. 1 is preferably a divalent hydrocarbon group, more preferably an alkylene group. 1 The number of carbon atoms is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8.

[0034] Examples of compound 2 include isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, isocyanate methylmethyldimethoxysilane, 1-isocyanate propylmethyldimethoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propylmethyldimethoxysilane, and 3-isocyanate propyltriethoxysilane. In that the curable composition has excellent deep curing properties in the cured product, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 1-isocyanatepropylmethyldimethoxysilane, and 3-isocyanatepropyltriethoxysilane are preferred.

[0035] The active hydrogen of the precursor polymer B reacts with the isocyanate group of the compound 2, thereby introducing a reactive silicon group into the precursor polymer B. When the active hydrogen-containing group of the precursor polymer B is a hydroxyl group, the polyoxyalkylene chain (-(R 1 O) n -, R 1 represents an alkylene group, and n represents the number of moles of oxyalkylene groups. 1 A polymer A having a reactive silicon group bonded via -(R 1 O) n -C(=O)NH-Q 1 -SiX a R 3-a A linked structure represented by the following formula is formed.

[0036] The reaction of precursor polymer B with compound 2 can be carried out by a known method. When the active hydrogen-containing group of precursor polymer B is a hydroxyl group, a known urethanization catalyst may be used in the reaction (urethanization reaction) of precursor polymer B with compound 2. Examples of the urethanization catalyst include organotin compounds, bismuth compounds, metal organic alkoxides, complexes containing metals other than tin, organic amines, and composite metal cyanide complex catalysts having organic ligands. Preferred urethanization catalysts are dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin bisisooctylthioglycol, and bismuth octoate. The molar ratio of the total number of isocyanate groups in compound 2 to the total number of active hydrogens in precursor polymer B is preferably set according to the number of reactive silicon groups per molecule of the target polymer A. Compound 2 is reacted so that the number of reactive silicon groups per molecule of the target polymer A is at least 0.5. For example, when the active hydrogen-containing group of precursor polymer B is a hydroxyl group, NCO / OH, which represents the molar ratio of the total number of isocyanate groups (NCO) of compound 2 to the total number of active hydrogens of precursor polymer B, is preferably 0.5 to 1.2, more preferably 0.6 to 1.1, and even more preferably 0.8 to 1.0. When the ratio is equal to or greater than the lower limit of the above range, the strength of the cured product is excellent, and when the ratio is equal to or less than the upper limit of the above range, the elongation of the cured product is excellent.

[0037] The method of reacting precursor polymer B with compound 2 to produce polymer A is preferred because it does not produce impurities having unsaturated groups as by-products. It is also preferred because it requires fewer production steps. The total unsaturation degree of polymer A obtained by this method is equal to or less than the total unsaturation degree of precursor polymer B. Specifically, the total unsaturation degree of polymer A is preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, even more preferably 0.03 meq / g or less, and most preferably 0.01 meq / g or less. When the total unsaturation degree is equal to or less than the upper limit, the strength of the cured product is superior. The lower limit is not particularly limited. For example, 0.0001 meq / g or more is preferred. The total unsaturation degree of polymer A is preferably 0.0001 to 0.1 meq / g, more preferably 0.0001 to 0.05 meq / g, even more preferably 0.0001 to 0.03 meq / g, and most preferably 0.0001 to 0.01 meq / g.

[0038] ≪Curable composition / cured product≫ The curable composition of the present embodiment contains a polymer A. It is preferable that the curable composition further contains one or more plasticizers. The curable composition may contain one type of polymer A, or two or more types. When two or more types of polymer A are used, the preferred ranges of Mn, EO content, number of reactive silicon groups per molecule, Mw / Mn, and viscosity of the polymer A are the preferred ranges for each polymer. The content of polymer A relative to the total mass of the curable composition is preferably 5 to 90 mass%, more preferably 10 to 60 mass%, and even more preferably 15 to 50 mass%. When the content is at least the lower limit of the above range, the modulus of the cured product of the curable composition tends to be in a good range, and when it is at most the upper limit, the elongation of the cured product of the curable composition tends to be good.

[0039] The plasticizer may contain a polymer (having an Mn of 1,000 or more) that does not have a reactive silicon group. Examples of the polymer include a (meth)acrylate polymer and an oxyalkylene polymer. Examples of the (meth)acrylate polymer include a polymer or copolymer of a monomer containing a (meth)acrylate, such as methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, or stearyl (meth)acrylate. "(Meth)acrylate" refers to either or both of an acrylate and a methacrylate. Examples of commercially available (meth)acrylate polymers include ARUFON (registered trademark) UP-1000, ARUFON UP-1110, and ARUFON UP-1171 (all manufactured by Toagosei Co., Ltd.). ARUFON (registered trademark) UP-1171 is preferred as the (meth)acrylate polymer.

[0040] Examples of the oxyalkylene polymer used as a plasticizer include polyoxyalkylene polyols and derivatives of the polyoxyalkylene polyols in which the hydroxyl groups are converted to esters or ethers. The polyoxyalkylene polyol has a polyoxyalkylene chain and a hydroxyl group. For example, the precursor polymer B can be used as the polyoxyalkylene polyol. The number of hydroxyl groups in one molecule of the polyoxyalkylene polyol is preferably 2 or 3. The polyoxyalkylene chain of the polyoxyalkylene polyol preferably contains an oxyethylene group, and more preferably contains an oxyethylene group and an oxypropylene group. When the polyoxyalkylene chain contains an oxyethylene group and an oxypropylene group, it may be a random copolymer chain, a block copolymer chain, or a combination thereof. The content of oxyethylene groups relative to the total mass of the oxyalkylene polymer used as a plasticizer is preferably from 3 to 90 mass %, more preferably from 4 to 85 mass %, and even more preferably from 6 to 80 mass %. The Mn of the oxyalkylene polymer used as a plasticizer is preferably 3,000 to 150,000, more preferably 4,000 to 100,000, further preferably 5,000 to 80,000, and most preferably 8,000 to 60,000. As the plasticizer, commercially available oxyalkylene polymers may be used, such as Preminol (registered trademark) S3011, Preminol S4012, and Preminol S4013F (all manufactured by AGC Inc.).

[0041] The plasticizer may contain one or more low-molecular-weight plasticizers (Mn or formula weight less than 1,000). Examples of low-molecular-weight plasticizers include phthalate ester compounds such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, and diisononyl phthalate; aliphatic carboxylic acid ester compounds such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, and 1,2-cyclohexanedicarboxylic acid-diisononyl ester; alcohol ester compounds such as pentaerythritol ester; phosphate ester compounds such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxy stearate; chlorinated paraffin; and polyester-based plasticizers such as polyesters obtained by reacting dibasic acids with dihydric alcohols. As the low molecular weight plasticizer, phthalate compounds such as diisononyl phthalate, and aliphatic carboxylic acid ester compounds such as diisononyl 1,2-cyclohexanedicarboxylic acid ester are preferred.

[0042] When the curable composition contains a plasticizer, the content of the plasticizer is preferably 1 to 350 parts by mass, more preferably 2 to 300 parts by mass, even more preferably 3 to 200 parts by mass, and particularly preferably 5 to 120 parts by mass, relative to 100 parts by mass of polymer A. When the content is at least the lower limit of the above range, the viscosity of the curable composition becomes lower and workability becomes better, and when the content is at most the upper limit, bleeding out is less likely in a cured product of the curable composition.

[0043] The curable composition may contain one or more other components that do not fall under either the polymer A or the plasticizer. Other components include additives according to the application of the curable composition, such as fillers, thixotropy-imparting agents, antioxidants, UV absorbers, light stabilizers, dehydrating agents, adhesion-imparting agents, amine compounds, modulus regulators, oxygen-curing compounds, photocuring compounds, and curing catalysts.Other components include those described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, Japanese Patent Application Laid-Open No. 2014-88481, Japanese Patent Application Laid-Open No. 2015-10162, Japanese Patent Application Laid-Open No. 2015-105293, Japanese Patent Application Laid-Open No. 2017-039728, and Japanese Patent Application Laid-Open No. 2017-214541, and can be used in combination without limitation.

[0044] The curable composition can be obtained by adding optional components to polymer A and mixing them. The curable composition may be a one-component type in which all ingredients are mixed in advance, stored in a sealed container, and cured by moisture in the air after application. Alternatively, a two-component type may be used in which a base composition containing at least a component having a reactive silicon group and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and base composition are mixed and cured before use. The one-component curable composition preferably does not contain water. It is preferable to dehydrate and dry the blended components containing water in advance, or to dehydrate them by applying a reduced pressure during blending and kneading. In the two-component curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components in advance. In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0045] Suitable applications of the curable composition include sealants (for example, elastic sealants for construction, sealants for double glazing, anti-rust and waterproof sealants for glass edges, sealants for the backside of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), electrical insulating materials (insulating coating materials for electric wires and cables), adhesives, and potting materials.

[0046] The curable composition of this embodiment has excellent deep section curing properties. For example, in the deep section curing test described in the Examples below, the composition can achieve deep section curing properties such that the thickness of the cured portion after 3 days is 7 mm or more and the thickness of the cured portion after 7 days is 12 mm or more. Preferably, the composition can achieve deep section curing properties such that the thickness of the cured portion after 3 days is 8 mm or more and the thickness of the cured portion after 7 days is 13 mm or more. The upper limit is not particularly limited. An example of the upper limit of the thickness of the cured portion after 3 days is 55 mm. An example of the upper limit of the thickness of the cured portion after 7 days is 55 mm. Preferably, the thickness of the cured portion after 3 days is 7 to 55 mm and the thickness of the cured portion after 7 days is 12 to 55 mm, and more preferably, the thickness of the cured portion after 3 days is 8 to 55 mm and the thickness of the cured portion after 7 days is 13 to 55 mm.

[0047] The curable composition of this embodiment tends to have a low viscosity and is therefore easy to work with. For example, the viscosity of the curable composition at 25°C can be 0.1 to 1000 Pa s, preferably 1.0 to 500 Pa s, and more preferably 1.0 to 200 Pa s. A viscosity within this range provides excellent workability when used as, for example, a sealant or adhesive.

[0048] The cured product of the curable composition of this embodiment has excellent strength. For example, the maximum cohesive strength (Tmax) in the tensile test described in the Examples below is 0.50 N / mm 2 or more, preferably 1.00N / mm 2 Within the above range, the strength as a sealant or adhesive is excellent. The upper limit is not particularly limited. The upper limit is 5.00 N / mm 2 Examples of Tmax are 0.50 to 5.00 N / mm 2 is preferable, and 1.00 to 5.00 N / mm2 is more preferred.

[0049] The cured product of the curable composition of this embodiment has excellent elongation properties. For example, a maximum elongation (E) of 50% or more, preferably 60% or more, can be achieved in the tensile test described in the Examples below. When the maximum elongation (E) is equal to or greater than the lower limit, the product exhibits excellent elongation properties, for example, as a sealant or adhesive. The upper limit is not particularly limited. An example of the upper limit is 300%. E is preferably 50 to 300%, more preferably 60 to 300%. [Example]

[0050] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0051] <Measurement method> [Mn and Mw / Mn of polymer] Using an HLC-8220GPC (product name of Tosoh Corporation), a TSKgel SupermultiporeHZ-M (product name of Tosoh Corporation) column, and tetrahydrofuran as the solvent, the sample pump was set at 0.350 mL / min, the reference pump at 0.350 mL / min, the detector temperature at 40°C, and the collection time from 6 to 15 minutes. Mw, Mn, and Mw / Mn were determined by analyzing the peaks that appeared from 6 to 11 minutes into the collection time.

[0052] [Number of hydroxyl groups in precursor polymer] The number of hydroxyl groups in one molecule of the precursor polymer was measured by esterifying the hydroxyl groups with a pyridine solution of phthalic anhydride and titrating them with a sodium hydroxide (NaOH) solution (in accordance with JIS K1557:2007).

[0053] [viscosity] The viscosity of the oxyalkylene polymer A was measured at a measurement temperature of 25°C using an E-type viscometer VISCOMETER TV-22 (product name of Toki Sangyo Co., Ltd.). The viscosity of the curable composition was measured using a Brookfield viscometer VISCOMETER TV-25H (product name of Toki Sangyo) at a measurement temperature of 25°C after rotating at 10 rpm for 1 minute.

[0054] [others] The total degree of unsaturation of precursor polymer B, the content of oxyethylene groups in the polymer, and the number of reactive silicon groups and the number of groups represented by -C(=O)NH- per molecule of polymer A were measured by the methods described above.

[0055] <Evaluation method> [Deep section hardening test] The curable composition to be measured was filled into a polyethylene tube with a diameter of 24 mm and a height of 55 mm in an atmosphere at a temperature of 23°C and a relative humidity of 50%, taking care to avoid the formation of bubbles. The curable composition that protruded from the open end of the tube was scraped off with a spatula to flatten the surface, yielding a test specimen. The obtained test specimen was left standing in the same atmosphere with the surface of the curable composition level, and after 1 day, 3 days, and 7 days, the extent of curing of the curable composition from the surface toward the interior was examined. Specifically, the cured surface layer (cured portion) of the curable composition was peeled off, the uncured portion was removed, and the thickness of the cured portion (unit: mm) was measured using a vernier caliper. The thicker the cured portion, the better the deep curability.

[0056] [Tensile test (M50, Tmax, E)] The curable composition to be measured was filled into a 2 mm thick mold and cured for 7 days in an atmosphere at a temperature of 23°C and a relative humidity of 50%, and then further cured for 7 days in an atmosphere at a temperature of 50°C and a relative humidity of 65°C. The resulting cured product was punched out using a dumbbell mold to obtain a test specimen. The obtained test specimens were subjected to a tensile test at a tensile speed of 500 mm / min, and the stress at 50% elongation (M50, unit: N / mm 2 ), maximum cohesive strength (Tmax, unit: N / mm 2 The tensile properties of the specimen were measured, including elongation at maximum point (E, unit: %).

[0057] (Production Example 1: Production of Precursor Polymer B1) A pressure-resistant reactor equipped with a stirrer and a nitrogen inlet tube was charged with a slurry containing a zinc hexacyanocobaltate-glyme complex (hereinafter referred to as "Gly-DMC catalyst") and polyoxypropylene triol (hereinafter referred to as "initiator A") having an Mn of 3000 and obtained by polymerizing propylene oxide (hereinafter referred to as "PO") using glycerin as an initiator, to prepare a reaction solution. The amount of the slurry added was such that the metal concentration of the Gly-DMC catalyst in the reaction solution would be 46 ppm by mass. Next, the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, and the reaction solution was heated with stirring, and PO was supplied into the pressure-resistant reactor at 135°C to react so that the PO had the desired molecular weight. Next, after confirming that the temperature rise of the reaction liquid had stopped, the reaction liquid was cooled to 120° C. Next, 48% by mass of KOH catalyst was added to the resulting reaction liquid so that the active ingredient concentration was 0.3% by mass, and then the mixture was dehydrated to form an alcoholate, and then ethylene oxide (hereinafter also referred to as “EO”) was supplied to the pressure-resistant reactor so as to achieve the target content and reacted. After the internal pressure stopped changing and the reaction was confirmed to be complete, the catalyst was neutralized and removed using a synthetic adsorbent (Kyowado 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain Precursor Polymer B1. The number of hydroxyl groups per molecule, Mn, Mw / Mn, EO content, and total unsaturation degree of the obtained precursor polymer are shown in Table 1 (the same applies hereinafter).

[0058] (Production Example 2: Production of Precursor Polymer B2) A slurry containing zinc hexacyanocobaltate-tert-butyl alcohol complex (hereinafter referred to as "TBA-DMC catalyst") and initiator A were charged to form a reaction liquid in the same pressure-resistant reactor as in Production Example 1. The amount of the slurry charged was such that the metal concentration of the TBA-DMC catalyst was 46 ppm by mass. Next, after replacing the atmosphere inside the pressure-resistant reactor with nitrogen, the reaction solution was heated with stirring, and a mixture of PO and EO was supplied to the pressure-resistant reactor at 135°C and reacted to reach the target molecular weight, thereby obtaining precursor polymer B2 (PO / EO mass ratio 80 / 20).

[0059] (Production Example 3: Production of Precursor Polymer B3) In Production Example 2, initiator A was changed to polyoxyethyleneoxypropylenetriol with an Mn of 3400 obtained by polymerizing a mixture with a PO / EO mass ratio of 35 / 65 using glycerin as an initiator, and the PO / EO ratio of the PO and EO mixture was changed so that the PO / EO mass ratio of the resulting precursor polymer was 35 / 65. Otherwise, precursor polymer B3 was obtained in the same manner as in Production Example 2.

[0060] (Production Example 4: Production of Precursor Polymer B4) In Production Example 2, initiator A was changed to polyoxyethyleneoxypropylenetriol with an Mn of 3400 obtained by polymerizing a mixture with a PO / EO mass ratio of 20 / 80 using glycerin as an initiator, and the PO / EO ratio of the PO and EO mixture was changed so that the PO / EO mass ratio of the resulting precursor polymer was 20 / 80. Otherwise, precursor polymer B4 was obtained in the same manner as in Production Example 2.

[0061] (Production Example 5: Production of Precursor Polymer B5) In Production Example 2, precursor polymer B5 was obtained in the same manner as in Production Example 2, except that initiator A was changed to polyoxypropylene diol having an Mn of 3000 in which PO was polymerized using dipropylene glycol as an initiator.

[0062] (Production Example 6: Production of Precursor Polymer B6) The target Mn was changed in Production Example 2. Otherwise, a precursor polymer B6 was obtained in the same manner as in Production Example 2.

[0063] (Production Example 7: Production of Precursor Polymer B7) In Production Example 1, the target molecular weight was changed, and the amounts of PO and EO supplied were changed so that the PO / EO mass ratio of the resulting precursor polymer was 80 / 20. Otherwise, Precursor Polymer B7 was obtained in the same manner as in Production Example 1.

[0064] (Production Example 8: Production of Precursor Polymer B8) In Production Example 1, the target molecular weight was changed, and the amounts of PO and EO supplied were changed so that the PO / EO mass ratio of the resulting precursor polymer was 80 / 20. Otherwise, a precursor polymer B8 was obtained in the same manner as in Production Example 1.

[0065] (Production Example 9: Production of Precursor Polymer B'9 (Comparative Example)) In Production Example 2, initiator A was changed to polyoxypropylenetriol with an Mn of 1000, which was prepared by polymerizing PO using glycerin as an initiator, and PO was supplied to the pressure-resistant reactor instead of a mixture of PO and EO, and reacted to achieve the target molecular weight. Precursor polymer B'9 was obtained in the same manner as in Production Example 2.

[0066] (Production Example 10: Production of Precursor Polymer B'10 (Comparative Example)) In Production Example 2, initiator A was changed to polyoxyethylene triol with an Mn of 3000, which was prepared by polymerizing EO using glycerin as an initiator, and EO was supplied to the pressure-resistant reactor instead of a mixture of PO and EO, and the reaction was carried out to achieve the target molecular weight. A precursor polymer B'10 was obtained in the same manner as in Production Example 2.

[0067] (Production Example 11: Production of Precursor Polymer B'11 (Comparative Example)) The target molecular weight was changed in Production Example 2. Otherwise, a precursor polymer B'11 was obtained in the same manner as in Production Example 2.

[0068] (Production Example 12: Production of Precursor Polymer B12) In Production Example 2, initiator A was changed to a polyoxypropylene polyol having a molecular weight of 1,000 in which PO was polymerized using sorbitol as an initiator, the target molecular weight was changed, and the PO / EO ratio of the mixture of PO and EO was changed so that the PO / EO mass ratio of the resulting precursor polymer was 95 / 5. Otherwise, a precursor polymer B12 was obtained in the same manner as in Production Example 2.

[0069] [Table 1]

[0070] (Example 1: Production of Polymer A1) The reactor containing Precursor Polymer B1 was purged with nitrogen gas. While maintaining the internal temperature at 50°C, 3-isocyanatopropyltrimethoxysilane was added to adjust the NCO / OH (molar ratio) to 0.97. Dioctyltin bisisooctylthioglycol (Neostan U-860: Nitto Kasei Co., Ltd. product name) was then added as a catalyst. The temperature was then raised to 80°C and stirred while maintaining the temperature at 80°C. Analysis was performed using a Fourier transform infrared spectrophotometer, and the reaction was continued until the completion of the reaction between the hydroxyl group and the isocyanate group was confirmed, yielding Polymer A1. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803: Shin-Etsu Chemical Co., Ltd. product name) was added as a storage stabilizer per 100 parts by mass of Precursor Polymer B1 to obtain a mixture containing Polymer A1. The number of reactive silicon groups per molecule, the number of groups i(-C(=O)NH-) per molecule, Mn, Mw / Mn, EO content, and viscosity of the obtained polymer A1 are shown in Table 2 (the same applies hereinafter).

[0071] (Example 1-1: Preparation of curable composition) A curable composition was prepared by mixing 100 parts by mass of a mixture containing polymer A1 with additive 1 shown in Table 3. The formulations shown in Table 3 are values (unit: parts by mass) relative to 100 parts by mass of the mixture containing polymer A (the same applies hereinafter). The viscosity of the obtained curable composition, the results of the deep curing test, and the measurement results of M50, Tmax and E of the cured product are shown in Table 4 (the same applies hereinafter).

[0072] (Example 1-2: Preparation of curable composition) In Example 1-1, Additive 1 was changed to Additive 8. Otherwise, a curable composition was produced in the same manner as in Example 1-1.

[0073] (Example 2: Preparation of Polymer A2-1 and Curable Composition) A mixture and a curable composition containing the polymer A2-1 were produced in the same manner as in Example 1, except that the precursor polymer B1 in Example 1 was changed to the same mass of the precursor polymer B2.

[0074] (Example 3: Preparation of Polymer A2-2 and Curable Composition) A mixture containing polymer A2-2 was obtained in the same manner as in Example 2, except that 3-isocyanatepropyltrimethoxysilane was changed to 3-isocyanatepropylmethyldimethoxysilane. 100 parts by mass of the mixture containing polymer A2-2 and additive 2 shown in Table 3 were mixed to prepare a curable composition.

[0075] (Example 4: Preparation of polymer A2-3 and curable composition) A mixture containing polymer A2-3 was obtained in the same manner as in Example 2, except that 3-isocyanatepropyltrimethoxysilane was changed to 1-isocyanatepropylmethyldimethoxysilane. 100 parts by mass of the mixture containing polymer A2-3 and additive 1 shown in Table 3 were mixed to prepare a curable composition.

[0076] (Examples 5 to 9: Preparation of Polymers A3 to A7 and Curable Compositions) In Example 1, the precursor polymer B1 was changed to the same mass of precursor polymers B3 to B7, except that the procedure was the same as in Example 1 to obtain a mixture containing polymers A3 to A7. 100 parts by mass of each of the mixtures containing polymers A3 to A7 and additive 1 shown in Table 3 were mixed to prepare curable compositions.

[0077] Example 10: Preparation of Polymer A'1 (Comparative Example) and Curable Composition In this example, a comparative polymer was prepared in which reactive silyl groups were attached to the polyoxyalkylene chain via urethane and urea bonds. The TDI used in this example is tolylene diisocyanate, and "TDI-80" is a mixture of 2,4-TDI / 2,6-TDI = 80 / 20 (mass ratio) (product name, manufactured by Nippon Polyurethane Co., Ltd.). 2EHA is 2-ethylhexyl acrylate, and KBM602 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) is N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane. First, precursor polymer B1 was placed in a pressure reactor, heated to 110°C, and vacuum dehydrated. The reactor was then purged with nitrogen and cooled to 80°C. TDI-80 and dibutyltin dilaurate (DBTDL) were then added and reacted for 7 hours. After confirming by titration that the NCO content had reached 1.18, the mixture was cooled to room temperature to obtain a prepolymer having urethane bonds. The molar ratio (NCO / OH) of the total number of isocyanate groups of TDI to the total number of hydroxyl groups of the precursor polymer B1 used was 2. Next, in accordance with Example 3 described in JP-A-11-100427, the prepolymer was cooled to 50°C and mixed at a ratio (parts by mass) of 2EHA:KBM602 = 184:206. 25 parts by mass of the mixture, which had been kept at 60°C for 5 days, was added and reacted at 50°C for 1 hour under a nitrogen atmosphere. After confirming the disappearance of the isocyanate peak using a Fourier transform infrared spectrophotometer, the mixture was cooled to room temperature to obtain Polymer A'1. 100 parts by mass of Polymer A'1 and Additive 1 shown in Table 3 were mixed to produce a curable composition. The obtained curable composition had high viscosity and poor workability, so further investigation was not performed.

[0078] Example 11: Preparation of Polymer A'8 (Comparative Example) and Curable Composition In Example 10, the precursor polymer B1 was changed to the same mass of precursor polymer B8. Otherwise, the procedure was the same as in Example 10 to obtain polymer A'8. 100 parts by mass of Polymer A'8 and Additive 1 shown in Table 3 were mixed to prepare a curable composition.

[0079] (Examples 12 to 14: Preparation of Polymers A'9 to A'11 (Comparative Examples) and Curable Compositions) In Example 1, the precursor polymer B1 was changed to the same mass of precursor polymers B'9 to B'11, and otherwise the same procedure as in Example 1 was repeated to obtain a mixture containing polymers A'9 to A'11. The polymer A'10 obtained in Example 13 was a solid at 25° C., and it was impossible to measure the viscosity, so no further investigation was carried out. In Examples 12 and 14, 100 parts by mass of the mixture containing polymer A'9 or A'11 and additive 1 shown in Table 3 were mixed together to prepare curable compositions.

[0080] Example 15: Preparation of polymer A16 and curable composition In Example 1, the precursor polymer B1 was changed to the same mass of precursor polymer B12. Otherwise, a mixture and a curable composition containing polymer A16 were produced in the same manner as in Example 1.

[0081] <Other ingredients> The additives listed in Table 3 are as follows: Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. CCR: White gloss CCR colloidal calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. R-820: Titanium oxide, product name of Ishihara Sangyo Kaisha. Balloon 81GCA: Organic balloon, product name of Matsumoto Oil & Fat Co., Ltd. Printex30: Carbon black, Orion Engineered Carbons product name. CML35: Calcium oxide, Shiraishi Kogyo Co., Ltd. product name. DINP: Diisononyl phthalate. UP-1171: ARUFON UP-1171, an acrylic polymer with Mw 3,000, manufactured by Toagosei Co., Ltd. Polymer C1: Polypropylene glycol (EO-free) with Mn of 10,000. DINCH: 1,2-cyclohexanedicarboxylic acid-diisononyl ester. Polymer B1: Precursor polymer B1 obtained in Production Example 1. Sanso Cizer EPS: 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, product name of New Japan Chemical Co., Ltd. Disparlon #6500: Hydrogenated castor oil-based thixotropic agent, product name of Kusumoto Chemicals. IRGANOX 1010: Hindered phenolic antioxidant, product name of BASF. TINUVIN 326: Benzotriazole-based UV absorber, product name of BASF. TINUVIN 765: Tertiary amine-containing hindered amine light stabilizer, product name of BASF. LA-63P: Adeka STAB LA-63P, ADEKA product name. KBM-1003: Vinyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-403: 3-glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd. Farmin CS: Coconutamine, Kao product name. DEAPA: 3-diethylaminopropylamine, manufactured by Tokyo Chemical Industry Co., Ltd. TMP-3TMS: Tristrimethylsilyl derivative of trimethylolpropane. Tung oil: Air oxidation curing compound, manufactured by Kimura Company. M-309: Aronix M-309, a product name of Toagosei Co., Ltd. U-810: Dioctyl tin catalyst, product name of Nitto Kasei Co., Ltd. U-220H: Dibutyltin catalyst, product name of Nitto Kasei Co., Ltd. DBTDL: Dibutyltin dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd. TC750: Titanium diisopropoxybis(ethyl acetoacetate), Orgatix TC750, product name of Matsumoto Fine Chemical Co., Ltd. Neodecanoic acid: manufactured by Strem Chemicals. Catalyst composition: A composition obtained by mixing 4 parts by mass of a mixture of Stanoct (stannous octoate, product name of Yoshitomi Pharmaceutical Co., Ltd.) and laurylamine (reagent, product of Junsei Chemical Co., Ltd.) in a mass ratio of 6:1, 6 parts by mass of Sanso Cizer DINP (diisononyl phthalate, product name of New Japan Chemical Co., Ltd.), 15 parts by mass of Whiten SB (heavy calcium carbonate, product name of Shiraishi Calcium Industry Co., Ltd.), and 5 parts by mass of Glomax LL (calcined kaolin, product name of Takehara Chemical Industry Co., Ltd.).

[0082] [Table 2]

[0083] [Table 3]

[0084] [Table 4]

[0085] The curable compositions of Examples 1-1, 1-2, 2 to 9, and 15 had low viscosity, good workability, and excellent deep curing properties, and the cured products had high Tmax and E values and were excellent in strength and elongation. In Examples 1-1, 1-2, 2 to 9, and 15, the additives can be changed to Additives 1 to 16 shown in Table 3, and the same effects can be obtained.

[0086] (Reference Example 1: Production of Polymer A12) The reactor containing Precursor Polymer B1 was purged with nitrogen gas, and while maintaining the internal temperature at 50°C, 3-isocyanatepropyltrimethoxysilane was added so that the NCO / OH (molar ratio) was 0.97, and bismuth octylate (Nikka Otics-Bismuth 25%, manufactured by Nippon Chemical Industry Co., Ltd.) was added as a catalyst. The temperature was then raised to 80°C and stirred while maintaining the temperature at 80°C. The amount of the catalyst added was 0.0010 parts by mass relative to Precursor Polymer B1 (100 parts by mass). After 5 hours, the disappearance of the isocyanate peak was confirmed using a Fourier transform infrared spectrophotometer, and the mixture was then cooled to room temperature to obtain Polymer A12.

[0087] (Reference Example 2: Production of Polymer A13) Polymer A13 was obtained in the same manner as in Reference Example 1, except that Precursor Polymer B1 was changed to the same mass of Precursor Polymer B'9 and the amount of catalyst bismuth octylate (Nikka Otics-Bismuth 25%, manufactured by Nippon Chemical Industry Co., Ltd.) added was 0.0025 parts by mass relative to Precursor Polymer B'9 (100 parts by mass). Note that, as with Polymer A12, it was confirmed after 5 hours that the isocyanate peak had disappeared using a Fourier transform infrared spectrophotometer.

[0088] (Storage stability) Polymers A12 and A13 obtained in Reference Examples 1 and 2 were allowed to stand at 70°C for 7 days, and the rate of increase in viscosity after standing relative to the viscosity before standing (thickening rate) was measured. The thickening rate is an index showing storage stability; the lower the thickening rate, the better the storage stability of the polymer, and a thickening rate of 200% or less indicates good storage stability. The thickening rate of polymer A12 obtained in Reference Example 1 was 36%, and the thickening rate of polymer A13 obtained in Reference Example 2 was 700%. Polymer A13 had a higher thickening rate and poorer storage stability than polymer A12.

[0089] (Reference Example 3: Production of Polymer A14) In Reference Example 1, the amount of catalyst bismuth octylate (Nikka Otics-Bismuth 25%, manufactured by Nippon Chemical Industry Co., Ltd.) added was changed to 0.0050 parts by mass relative to Precursor Polymer B1 (100 parts by mass). Otherwise, a polymer A14 was obtained in the same manner as in Reference Example 1.

[0090] (Reference Example 4: Production of Polymer A15) In Reference Example 2, the amount of catalyst bismuth octylate (Nikka Otics-Bismuth 25%, manufactured by Nippon Chemical Industry Co., Ltd.) added was changed to 0.0050 parts by mass relative to Precursor Polymer B'9 (100 parts by mass). Otherwise, a polymer A15 was obtained in the same manner as in Reference Example 2.

[0091] (Reaction time) In Reference Examples 3 and 4, the reaction time was the time from adding the catalyst to confirming the completion of the reaction between the hydroxyl groups and the isocyanate groups. In Reference Example 3, it was 30 minutes. In Reference Example 4, it was 60 minutes. When the same amount of catalyst was added to Precursor Polymer B1 or Precursor Polymer B'9, the reaction between the hydroxyl groups and the isocyanate groups proceeded more quickly in Precursor Polymer B1 than in Precursor Polymer B'9.

Claims

1. An oxyalkylene polymer having a polyoxyalkylene chain containing an oxyethylene group and a reactive silicon group represented by the following formula (1) bonded to the polyoxyalkylene chain via an organic group containing one group represented by the following formula (i), wherein the number average molecular weight is 3,000 to 150,000, the molecular weight distribution is 2.00 or less, the content of the oxyethylene group is 3 to 90 mass%, and the number of the reactive silicon groups per molecule is 0.5 or more, and the number of the reactive silicon groups per molecule of the oxyalkylene polymer is the same as the number of groups represented by the following formula (i) per molecule. -C(=O)NH- (i) -SiX ａ R ３－ａ (1) In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer of 1 to 3; when a is 1, R may be the same or different from one another; and when a is 2 or 3, X may be the same or different from one another.

2. 2. The oxyalkylene polymer according to claim 1, which does not contain a urea bond.

3. A curable composition comprising the oxyalkylene polymer according to claim 1 or 2.

4. The curable composition according to claim 3, wherein the content of the oxyalkylene polymer is 5 to 90% by mass based on the total mass of the curable composition.

5. The curable composition according to claim 3 or 4, further comprising a plasticizer.

6. The curable composition according to claim 5, wherein the content of the plasticizer is 1 to 350 parts by mass per 100 parts by mass of the oxyalkylene polymer.

7. The curable composition according to any one of claims 3 to 6, which is used as a sealant or adhesive.

8. A cured product of the curable composition according to any one of claims 3 to 7.

9. A method for producing an oxyalkylene polymer, comprising reacting a precursor polymer having a polyoxyalkylene chain containing an oxyethylene group and an active hydrogen-containing group bonded to the polyoxyalkylene chain, the precursor polymer having a number average molecular weight of 3,000 to 150,000, a molecular weight distribution of 2.00 or less, and an oxyethylene group content of 3 to 90 mass %, with a compound represented by the following formula (2) so that the number of reactive silicon groups represented by the following formula (1) per molecule is 0.5 or more, and wherein the number of reactive silicon groups per molecule of the oxyalkylene polymer is the same as the number of groups represented by the following formula (i) per molecule. -SiX ａ R ３－ａ (1) In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer of 1 to 3; when a is 1, R may be the same or different from one another; and when a is 2 or 3, X may be the same or different from one another. O=C=N-Q １ -SiX ａ R ３－ａ (2) In the formula (2), Q １ is a divalent organic group having 1 to 20 carbon atoms, and R, X, and a are the same as in formula (1).

10. The process according to claim 9, wherein the precursor polymer has a total unsaturation level of 0.1 meq / g or less.

11. A method for producing an oxyalkylene polymer, comprising reacting a precursor polymer having a polyoxyalkylene chain containing an oxyethylene group and an active hydrogen-containing group bonded to the polyoxyalkylene chain, wherein the precursor polymer has a number average molecular weight of 3,000 to 150,000, a molecular weight distribution of 2.00 or less, and a content of the oxyethylene group of 3 to 90 mass %, with a compound represented by the following formula (2) so that the number of reactive silicon groups represented by the following formula (1) per molecule is 0.5 or more, wherein the precursor polymer is produced by polymerizing a cyclic ether containing ethylene oxide as an initiator in the presence of a composite metal cyanide complex. -SiX a R 3-a (1) In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer of 1 to 3; when a is 1, R may be the same or different from one another; and when a is 2 or 3, X may be the same or different from one another. O=C=N-Q 1 -SiX a R 3-a (2) In the formula (2), Q 1 is a divalent organic group having 1 to 20 carbon atoms, and R, X, and a are the same as those in the formula (1).

12. A method for producing an oxyalkylene polymer, comprising reacting a precursor polymer having a polyoxyalkylene chain containing an oxyethylene group and an active hydrogen-containing group bonded to the polyoxyalkylene chain, wherein the precursor polymer has a number average molecular weight of 3,000 to 150,000, a molecular weight distribution of 2.00 or less, and a content of the oxyethylene group of 3 to 90 mass %, with a compound represented by the following formula (2) so that the number of reactive silicon groups represented by the following formula (1) per molecule is 0.5 or more, wherein the method for producing an oxyalkylene polymer comprises polymerizing a cyclic ether with an initiator in the presence of a composite metal cyanide complex, and further polymerizing ethylene oxide in the presence of an alkali metal hydroxide to produce the precursor polymer. -SiX a R 3-a (1) In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer of 1 to 3; when a is 1, R may be the same or different from one another; and when a is 2 or 3, X may be the same or different from one another. O=C=N-Q 1 -SiX a R 3-a (2) In the formula (2), Q 1 is a divalent organic group having 1 to 20 carbon atoms, and R, X, and a are the same as those in the formula (1).

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