Curable composition, cured product, and method for manufacturing a curable composition

Abstract

The present invention provides a curable composition that yields a cured product with good tensile strength, a cured product of the curable composition, and a method for manufacturing the curable composition. [Solution] A curable composition comprising polymer A and polymer B, wherein polymer A is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups not having a divalent organic group represented by -C(=O)NH-, and the terminal groups having at least one group selected from the group consisting of a specific reactive silicon group, an unsaturated group, and a hydroxyl group, and having a silylation rate of 85 to 100 mol%, and polymer B is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups having at least one group selected from the group consisting of a specific reactive silicon group, an isocyanate group, an amino group, and a hydroxyl group, and having a specific organic group.

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a cured product, and a method for producing a curable composition. [Background technology]

[0002] Polymers having at least one reactive silicon group in a single molecule are known to have the property of crosslinking even at room temperature through the formation of siloxane bonds accompanied by hydrolysis reactions of the reactive silicon group due to moisture, etc., resulting in a rubbery cured product.

[0003] Among these polymers having reactive silicon groups, polymers with a main chain skeleton consisting of oxyalkylene polymers, saturated hydrocarbon polymers, alkyl acrylate polymers, and alkyl methacrylate polymers are already produced industrially and are widely used in applications such as sealants, adhesives, and paints. When curable compositions containing these polymers having reactive silicon groups are used in the above applications, the tensile strength of the cured product is required. Cured products with excellent tensile strength are less prone to fracture.

[0004] Patent Document 1 discloses a curable composition containing, in a specific proportion, an oxyalkylene polymer having three or more terminal groups in one molecule and a specific reactive silicon group with a number average molecular weight of 6000 or more per terminal group, and an oxyalkylene polymer having two or more terminal groups in one molecule and having an average of more than 0.5 and 1.0 trialkoxysilyl groups per terminal group. For example, Example 1 of Patent Document 1 describes a curable composition containing an oxyalkylene polymer having three terminal groups in one molecule, a number average molecular weight of 8000 per terminal group, and a methyldimethoxylyl group, and an oxyalkylene polymer having two terminal groups in one molecule and having a urethane bond and a trimethoxysilyl group. It is disclosed that the cured product of the above curable composition exhibits excellent curing speed, resilience of the cured product, conformability to the adherend, and elongation. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2020 / 066551 [Overview of the project] [Problems that the invention aims to solve]

[0006] When the inventors of this application manufactured a cured product using the curable composition described in Patent Document 1, they found that it had a problem of inferior tensile strength.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a curable composition that yields a cured product with good tensile strength, a cured product of the curable composition, and a method for manufacturing the curable composition. [Means for solving the problem]

[0008] The present invention is as follows [1] to [9]. [1] A curable composition comprising polymer A and polymer B, The polymer A is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups not having a divalent organic group represented by -C(=O)NH-, and the terminal groups having at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group represented by the following formula 1, and having a silylation rate of 85 to 100 mol% calculated by the following formula f1. The polymer B is a curable composition having two or more terminal groups in one molecule, and each terminal group has at least one group selected from the group consisting of a reactive silicon group represented by the following formula 1, an isocyanate group, an amino group, and a hydroxyl group, and is an oxyalkylene polymer having an organic group represented by the following formula i. -SiR a X 3-a formula 1 In the above formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms, which is an organic group other than a hydrolyzable group; X represents a hydroxyl group or a hydrolyzable group; and a is an integer of 0 to 2. When a is 2, R may be the same as or different from each other; when a is 0 or 1, X may be the same as or different from each other. The reactive silicon groups of the polymer A and the reactive silicon groups of the polymer B may be the same as or different from each other. ―C(=O)NH- formula (i) [Number] [2] The curable composition according to [1], wherein the number average molecular weight of the polymer A is 5,000 to 100,000. [3] The curable composition according to [1] or [2], wherein the reactive silicon group of the polymer A is a reactive silicon group represented by the following formula (3). -O-R 11 -SiR 12 a2 X 2 3-a2 Formula (3) In the above formula (3), R 11 is a linear alkylene group having 1 to 20 carbon atoms, and R 12 , X 2 , and a2 are the same as R, X, and a in the above formula (1), respectively. When a2 is 2, R 12 may be the same as or different from each other; when a2 is 0 or 1, X 2 may be the same as or different from each other. [4] The curable composition according to any one of [1] to [3], wherein the number average molecular weight of the polymer B is 3,000 to 50,000. [5] The curable composition according to any one of [1] to [4], further comprising a curing catalyst, and the content of the curing catalyst is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total content of the polymer A and the polymer B. [6] The curable composition according to any one of [1] to [5], wherein the curing catalyst is a non-tin catalyst. [7] A cured product of the curable composition according to any one of [1] to [6]. A method for producing a curable composition according to any one of items [8][1] to [6], Polymer A is obtained by reacting an unsaturated group-containing oxyalkylene polymer with a silylating agent in the presence of a group 8 metal catalyst and a co-catalyst containing either or both of a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond at the α-carbon position. A method for producing a curable composition, comprising mixing polymer A and polymer B. [9] The method for producing the curable composition according to [8], wherein the amount of silylating agent added is 0.85 to 1.50 molar times the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a curable composition that yields a cured product with good tensile strength, a cured product of the curable composition, and a method for producing the curable composition. [Modes for carrying out the invention]

[0010] The meanings and definitions of terms used in this specification are as follows: A numerical range represented by "~" means a range of numbers whose lower and upper limits are the numbers before and after the "~". The "units" that make up oxyalkylene polymers refer to atomic groups directly formed by the polymerization of alkylene oxide monomers. Oxyalkylene polymers are polymers consisting of a main chain containing polyoxyalkylene chains and terminal groups. In oxyalkylene polymers, the "main chain" refers to the portion (polyoxyalkylene chain) that includes residues obtained by removing active hydrogen from the initiator and repeating units based on alkylene oxide. In oxyalkylene polymers, the "end group" refers to the group of oxygen atoms in the polyoxyalkylene chain that is closest to the end of the molecule. However, if the group of oxygen atoms includes an initiator residue, it is not considered an end group but rather part of the main chain. An "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group, carboxyl group, amino group, monovalent functional group obtained by removing one hydrogen atom from a primary amine, hydrazide group, and sulfanyl group, all of which are bonded to a carbon atom. "Active hydrogen" refers to hydrogen atoms based on the active hydrogen-containing group described above, and hydrogen atoms based on the hydroxyl group of water. An "unsaturated group" refers to a carbon-carbon double bond or a carbon-carbon triple bond. Carbon-carbon double bonds and carbon-carbon triple bonds may be located at the ends of the molecule or elsewhere.

[0011] The number of terminal groups in an oxyalkylene polymer is the same as the number of active hydrogen atoms in the initiator, as will be discussed later. The "degree of unsaturation" can be measured according to the unsaturation measurement method (Wijs method). The degree of unsaturation indicates the proportion of carbon-carbon double bonds or carbon-carbon triple bonds in the polymer.

[0012] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC with tetrahydrofuran as the eluent, with calibration curves created using polystyrene polymers of known molecular weight. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0013] The silylation rate can be measured by NMR analysis. A "silylation agent" refers to a compound having a functional group that reacts with a hydroxyl group, an unsaturated group, an isocyanate group, or an amino group, and a reactive silicon group.

[0014] ≪Curable composition≫ The curable composition of this embodiment comprises polymer A and polymer B described below. Polymer A is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups not having a divalent organic group represented by -C(=O)NH-, but having at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group represented by formula 1 described below, and having a silylation rate of 85 to 100 mol% calculated by the following formula f1. Polymer B is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups having at least one group selected from the group consisting of a reactive silicon group, an isocyanate group, an amino group, and a hydroxyl group represented by formula 1 described below, and having an organic group represented by formula i described below.

[0015] (Reactive silicon group) Reactive silicon groups have hydroxyl groups or hydrolyzable groups bonded to silicon atoms and can crosslink by forming siloxane bonds. The reaction that forms siloxane bonds is accelerated by a curing catalyst. The reactive silicon groups in polymers A and B are represented by formula 1 below. -SiR a X 3-a formula 1

[0016] In Formula 1 above, R is a monovalent organic group having 1 to 20 carbon atoms, and represents an organic group other than a hydrolyzable group. R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0017] R is preferably at least one group selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, α-chloroalkyl groups, and triorganosiloxy groups. More preferably, R is at least one group selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, benzyl groups, α-chloromethyl groups, trimethylsiloxy groups, triethylsiloxy groups, and triphenylsiloxy groups. A methyl group or an ethyl group is preferred because of the good curability and stability of the curable composition containing polymers A and B. An α-chloromethyl group is preferred because of the fast curing rate of the cured product. A methyl group is particularly preferred because it is readily available.

[0018] In Formula 1 above, X represents a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, ethoxy group, or isopropoxy group, with methoxy or ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are quickly formed, making it easy to form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0019] In the above formula 1, a is an integer between 0 and 2. When a is 2, R may be the same or different from each other. When a is 1 or less, X may be the same or different from each other. Since a lower crosslinking density due to siloxane bonds leads to a decrease in the modulus of the cured product, a is preferably 1 or less.

[0020] Examples of the reactive silicon group represented by Formula 1 above include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. From the viewpoint of high activity and good curability, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group is more preferred.

[0021] The reactive silicon groups in polymer A and polymer B may be the same or different. If polymer A has multiple reactive silicon groups, these multiple reactive silicon groups may be the same or different.

[0022] The reactive silicon group in polymer A is preferably a reactive silicon group represented by the following formula 3. -OR 11 -SiR 12 a2 X 2 3-a2 formula 3

[0023] R 12 , X 2 a2 is the same as R, X, and a in Equation 1 above, respectively. R 11 R is a straight-chain alkylene group having 1 to 20 carbon atoms. 11 The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 11 If the alkylene group is a straight chain, the curing rate of the curable composition containing polymers A and B tends to improve. Furthermore, if the number of carbon atoms is within the above range, the curing rate tends to improve even further.

[0024] <Polymer A> Polymer A is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups not having a divalent organic group represented by -C(=O)NH-, but having at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group represented by the above formula 1, and having a silylation rate of 85 to 100 mol% calculated by the following formula f1.

[0025]

number

[0026] Polymer A is a polymer consisting of a main chain and terminal groups. The main chain of polymer A includes a polyoxyalkylene chain consisting of residues obtained by removing active hydrogen from an initiator and repeating units based on one or more alkylene oxides (hereinafter, repeating units based on alkylene oxides are simply referred to as "alkylene oxide units"). Preferably, the main chain of polymer A consists of residues obtained by removing active hydrogen from an initiator and a polyoxyalkylene chain consisting of one or more alkylene oxide units.

[0027] When a polyoxyalkylene chain has two or more types of alkylene oxide units, these alkylene oxide units may form block polymers or random polymers.

[0028] Examples of polyoxyalkylene chains include polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of ethylene oxide units, polymer chains consisting of propylene oxide units, polymer chains consisting of butylene oxide units, polymer chains consisting of tetramethylene oxide units, polymer chains consisting of ethylene oxide units and propylene oxide units, and polymer chains consisting of propylene oxide units and butylene oxide units. Polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of propylene oxide units, and polymer chains consisting of ethylene oxide units and propylene oxide units are preferred, with polymer chains consisting of propylene oxide units being particularly preferred. Furthermore, when polymer A has polymer chains containing ethylene oxide units, the content of ethylene oxide units relative to the total mass of polymer A is preferably 0.1 to 30% by mass, and more preferably 10 to 20% by mass. When the ethylene oxide unit content in polymer A is above the lower limit, it is preferable that the curing process is faster, and when it is below the upper limit, it is preferable that the viscosity can be easily reduced. When polymer A has a polymerization chain having ethylene oxide units and propylene oxide units, or a polymerization chain consisting of ethylene oxide units and propylene oxide units, the ethylene oxide unit content relative to the total mass of polymer A is preferably 0.1 to 30% by mass, and more preferably 10 to 20% by mass. When the ethylene oxide unit content in polymer A is above the lower limit, it is preferable that the curing process is faster, and when it is below the upper limit, it is preferable that the viscosity can be easily reduced. When polymer A has a polymerization chain having ethylene oxide units and propylene oxide units, the propylene oxide unit content relative to the total mass of polymer A is preferably 50 to 99.9% by mass, and more preferably 70 to 90% by mass.

[0029] Polymer A has two or more terminal groups per molecule. The number of terminal groups is preferably 2 to 8, and more preferably 2 to 6, as this results in higher tensile strength, modulus, and elongation of the cured product. Each terminal group of polymer A has at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group represented by the above formula 1. Each terminal group may be the same or different from the others.

[0030] The silylation rate of polymer A is 85 to 100 mol%, more preferably 88 to 100 mol%, and even more preferably 90 to 100 mol%. When the silylation rate is above the lower limit, a good cured product with high modulus can be obtained. As a result, the resulting cured product has excellent tensile strength.

[0031] Polymer A may have multiple reactive silicon groups and multiple unsaturated groups per terminal group. Furthermore, the terminal groups of polymer A may have both reactive silicon groups and unsaturated groups.

[0032] When polymer A has multiple reactive silicon groups per terminal group, it is preferable that at least one terminal group has a group represented by the following formula 2.

[0033] [ka]

[0034] In equation 2 above, R 2 , R 3 Each of these independently represents a divalent organic group having 1 to 6 carbon atoms and lacking a carbon-carbon unsaturated bond. The organic group may contain heteroatoms. Examples of heteroatoms include oxygen, nitrogen, and sulfur atoms.

[0035] R 2 , R 3 Examples include -CH2-, -C2H4-, -C3H6-, -C4H8-, and -C5H 10 -, -C6H 12Examples include -, -C(CH3)2-, -CH2O-, -CH2-O-CH2-, -CH2-O-CH2-O-CH2-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CH=N-, and -CH=NN=CH-. R 2 -CH2-O-CH2-, -CH2O-, and -CH2- are preferred, and -CH2-O-CH2- is more preferred. R 3 -CH2- and -C2H4- are preferred, and -CH2- is more preferred.

[0036] R in equation 2 above 4 , R 5 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of branched alkyl groups include isopropyl group, s-butyl group, t-butyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-propylbutyl group, 3-methylbutyl group, 3-ethylbutyl group, 3-propylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-propylpentyl group, 3-methylpentyl group, 3-ethylpentyl group, 3-propylpentyl group, 4-methylpentyl group, 4-ethylpentyl group, 4-propylpentyl group, 2-methylhexyl group, 2-ethylhexyl group, 2-propylhexyl group, 3-methylhexyl group, 3-ethylhexyl group, 3-propylhexyl group, 4-methylhexyl group, 4-ethylhexyl group, 4-propylhexyl group, 5-methylhexyl group, 5-ethylhexyl group, and 5-propylhexyl group. R 4 , R 5 Each of these is independently preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0037] In the above formula 2, n represents an integer from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5, and even more preferably 1.

[0038] R 1 , X 1 a1 is the same as R, X, and a in Equation 1 above.

[0039] The average number of reactive silicon groups per terminal group of polymer A is preferably 0.85 to 4.00, more preferably 0.88 to 3.00, and even more preferably 0.90 to 1.00. If the number is above the lower limit of the above range, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained. As a result, the resulting cured product has excellent tensile strength.

[0040] The average number of unsaturated groups per terminal group of polymer A is preferably 0 to 0.30, more preferably 0 to 0.20, and even more preferably 0 to 0.15. The average number of hydroxyl groups per terminal group of polymer A is preferably 0.10 or less, more preferably 0.05 or less, and even more preferably 0.

[0041] The average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is preferably 0.85 to 4.40, more preferably 0.90 to 2.00, and even more preferably 0.95 to 1.50.

[0042] The average number of reactive silicon groups per molecule of polymer A is preferably 1.70 to 8.00, more preferably 1.75 to 6.00, and even more preferably 1.80 to 6.00. If the number is above the lower limit of the above range, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0043] The average number of unsaturated groups per molecule of polymer A is preferably 0 to 1.80, more preferably 0 to 1.20, and even more preferably 0 to 0.90. The average number of hydroxyl groups per molecule of polymer A is preferably 0.60 or less, more preferably 0.30 or less, and even more preferably 0.

[0044] The Mn content of polymer A is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 15,000 to 60,000, and particularly preferably 25,000 to 60,000. If it is above the lower limit, the elongation properties of the cured product will be better. If it is below the upper limit, the viscosity will be low and the workability will be good.

[0045] The molecular weight distribution of polymer A is preferably 1.80 or less. A smaller molecular weight distribution is preferable, more preferably 1.00 to 1.60, even more preferably 1.02 to 1.50, and particularly preferably 1.04 to 1.40, as this makes it easier to obtain good elongation properties and reduces viscosity, resulting in good workability.

[0046] The viscosity of polymer A at 25°C is preferably 1 to 50 Pa·s, more preferably 1 to 40 Pa·s, and even more preferably 1 to 30 Pa·s.

[0047] <Method for producing polymer A> The method for producing polymer A involves reacting an unsaturated group-containing oxyalkylene polymer (hereinafter simply referred to as "unsaturated group-containing oxyalkylene polymer") with a silylating agent. The unsaturated group-containing oxyalkylene polymer can be produced by converting the hydroxyl groups of an oxyalkylene polymer, whose terminal groups are hydroxyl groups, into groups having unsaturated groups.

[0048] (Method for producing oxyalkylene polymers with hydroxyl groups as terminal groups) Oxyalkylene polymers, whose terminal groups are hydroxyl groups, can be produced by polymerizing alkylene oxides on an initiator containing active hydrogen in the presence of a ring-opening polymerization catalyst.

[0049] The initiator has active hydrogen atoms. The number of active hydrogen atoms in the initiator is preferably two or more, more preferably two to eight, and even more preferably two to six. The number of active hydrogen atoms in the initiator is the same as the number of terminal groups in polymer A. Therefore, the initiator should be selected according to the number of terminal groups in polymers A and B. Initiating agents may be used individually or in combination of two or more.

[0050] The initiator preferably has a hydroxyl group as an active hydrogen-containing group. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripylene 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 polyoxypropylenetriols. Examples of initiators having four or more hydroxyl groups include pentaerythritol, sucrose, sorbitol, dipentaerythritol, trehalose, and diglycerin. Alternatively, a low molecular weight polymer obtained by polymerizing alkylene oxide with the above initiator in the presence of an alkali metal hydroxide may be used as the initiator.

[0051] The alkylene oxide is selected according to the constituent units of the polyoxyalkylene chain of polymer A. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. Among these, ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.

[0052] Examples of ring-opening polymerization catalysts include complex metal cyanide complexes and alkali metal hydroxides (such as potassium hydroxide). It is preferable to use a composite metal cyanide complex because the molecular weight distribution of oxyalkylene polymers with hydroxyl groups at the end tends to be small, and the total degree of unsaturation of oxyalkylene polymers with hydroxyl groups at the end tends to be small. The composite metal cyanide complex can be a conventionally known compound. For example, compounds and manufacturing methods disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Publication No. 2004-269776, Japanese Patent Publication No. 2005-15786, International Publication No. 2013 / 065802, and Japanese Patent Publication No. 2015-010162 can be used. The composite metal cyanide complex is preferably one in which glyme or t-butyl alcohol is coordinated as an organic ligand to the catalytic skeleton. The catalytic skeleton is more preferably Zn3[Co(CN)6]2 (i.e., a zinc hexacyanocobaltate complex). In particular, composite metal cyanide complexes using t-butyl alcohol as the organic ligand are preferred.

[0053] When the polyoxyalkylene chain of polymer A is a random copolymer chain, a preferred method is to produce an oxyalkylene polymer having hydroxyl groups as terminal groups by polymerizing an alkylene oxide containing propylene oxide as an initiator in the presence of a complex metal cyanide complex. For example, a preferred method involves reacting an initiator with a mixture of ethylene oxide and propylene oxide in the presence of a complex metal cyanide to obtain an oxyalkylene polymer having hydroxyl groups as terminal groups.

[0054] When the polyoxyalkylene chain of polymer A has a block chain or random copolymer chain consisting of oxyalkylene groups and a block chain consisting of oxyethylene groups, a preferred method is to produce an oxyalkylene polymer having hydroxyl groups as terminal groups by polymerizing alkylene oxide as an initiator in the presence of a complex metal cyanide complex, and then polymerizing ethylene oxide in the presence of an alkali metal hydroxide. For example, a preferred method involves polymerizing propylene oxide as an initiator in the presence of a complex metal cyanide, and then polymerizing ethylene oxide in the presence of an alkali metal hydroxide to obtain an oxyalkylene polymer whose terminal groups are hydroxyl groups. Alternatively, a preferred method involves reacting an initiator with a mixture of ethylene oxide and propylene oxide in the presence of a complex metal cyanide, and then polymerizing the ethylene oxide in the presence of an alkali metal hydroxide to obtain an oxyalkylene polymer having hydroxyl groups as terminal groups. In oxyalkylene polymers whose terminal groups are hydroxyl groups, the presence of an oxyethylene group at least at the reactive silicon group end of the polyoxyalkylene chain is preferable because it improves deep curing properties.

[0055] The manganese (Mn) of the oxyalkylene polymer whose terminal group is a hydroxyl group is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 15,000 to 60,000, and particularly preferably 25,000 to 60,000. It is preferable to set the manganese depending on the Mn of polymer A and polymer B.

[0056] The Mw / Mn ratio of an oxyalkylene polymer whose terminal group is a hydroxyl group is preferably 1.80 or less, more preferably 1.00 to 1.60, even more preferably 1.02 to 1.50, and particularly preferably 1.04 to 1.40.

[0057] The total unsaturation of oxyalkylene polymers whose terminal groups are hydroxyl groups 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 above upper limit, the deep curing performance is excellent. The lower limit is not particularly limited. For example, 0.0001 meq / g or more is preferred. The total unsaturation of oxyalkylene polymers whose terminal groups are hydroxyl groups 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.

[0058] Polymerization can be carried out in a continuous or batch manner, but it is preferable to carry it out in a batch manner. The polymerization temperature is preferably 30 to 180°C, more preferably 70 to 160°C, and even more preferably 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. It is preferable to supply the alkylene oxide to the reactor at a rate that maintains the above reaction temperature. The reaction atmosphere should preferably be one that is less susceptible to moisture contamination, and an inert gas atmosphere such as nitrogen is more preferable.

[0059] (Method for producing unsaturated group-containing oxyalkylene polymers) Methods for converting the hydroxyl group of an oxyalkylene polymer having a hydroxyl group at its end to a group having an unsaturated group include: a method in which an alkali metal salt is reacted with an oxyalkylene polymer having a hydroxyl group at its end, followed by a reaction with a halogenated hydrocarbon compound having a carbon-carbon double bond (Method 1); a method in which an alkali metal salt is reacted with an epoxy compound having a carbon-carbon double bond, followed by another reaction with an alkali metal salt, followed by a reaction with a halogenated hydrocarbon compound having a carbon-carbon double bond (Method 2); or a method in which an alkali metal salt is reacted with an alkali metal salt, followed by a reaction with a halogenated hydrocarbon compound having a carbon-carbon triple bond (Method 3).

[0060] If the average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is 1.0 or less, adopt Method 1 above. If the average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is greater than 1.0, adopt Method 2 or Method 3 above. If the average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is greater than 1.0 and the reactive silicon groups possessed by polymer A are reactive silicon groups represented by Formula 3 above, adopt Method 2 above.

[0061] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the standpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, with sodium methoxide and potassium ethoxide being more preferred. Sodium methoxide is particularly preferred from the standpoint of availability. Alkali metal salts may also be used in a dissolved state in a solvent.

[0062] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred.

[0063] In Method 1 and Method 2 described above, when producing polymer A having a reactive silicon group represented by Formula 3, it is preferable to use a linear halogenated hydrocarbon compound containing a carbon-carbon double bond. Preferred linear halogenated hydrocarbon compounds containing a carbon-carbon double bond include vinyl chloride, allyl chloride, vinyl bromide, allyl bromide, vinyl iodide, and allyl iodide. Two or more halogenated hydrocarbon compounds having a carbon-carbon double bond may be used in combination.

[0064] Examples of halogenated hydrocarbon compounds containing a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentine, 1,4-dichloro-2-butyne, 5-chloro-1-pentine, 6-chloro-1-hexine, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo- Examples include 2-octyne, 1-bromo-2-pentine, 1,4-dibromo-2-butine, 5-bromo-1-pentine, 6-bromo-1-hexine, propargyl iodide, 1-iodo-2-butine, 4-iodo-1-butine, 1-iodo-2-octyne, 1-iodo-2-pentine, 1,4-diiodo-2-butine, 5-iodo-1-pentine, and 6-iodo-1-hexine. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred. Two or more halogenated hydrocarbon compounds having a carbon-carbon triple bond may be used in combination.

[0065] Examples of epoxy compounds having a carbon-carbon double bond include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide. Allyl glycidyl ether is preferred.

[0066] As epoxy compounds having a carbon-carbon double bond, compounds represented by the following formula 4 are preferred.

[0067] [ka] R in formula 4 above 2 , R 5 This is R in equation 2 above. 2 , R 5 It is the same as this.

[0068] (Method for introducing reactive silicon groups) The introduction of reactive silicon groups involves reacting an unsaturated group-containing oxyalkylene polymer with a silylation agent (silylation reaction). The silylation reaction is preferably carried out in the presence of a group 8 metal catalyst.

[0069] (Silylaters) Examples of silylation agents include compounds having both a group that can react with the carbon-carbon double bond of an unsaturated group-containing oxyalkylene polymer to form a bond (e.g., a sulfanyl group) and a reactive silicon group represented by the above formula 1, and hydrosilane compounds (e.g., HSiR a X 3-a Examples include (where R, X, and a are the same as in Formula 1 above). Specifically, examples include trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diisopropoxymethylsilane, (α-chloromethyl)dimethoxysilane, and (α-chloromethyl)diethoxysilane. Trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred from the viewpoint of high activity and good curability, and dimethoxymethylsilane or trimethoxysilane are more preferred.

[0070] In the production of polymer A, the amount of silylating agent added is preferably 0.85 to 1.50 molar times, more preferably 0.95 to 1.45 molar times, and even more preferably 1.00 to 1.40 molar times, relative to the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer.

[0071] (Group 8 metal catalyst) A Group 8 metal catalyst is a catalyst containing a metal from Group 8 of the short-period periodic table. The Group 8 metal is preferably at least one metal selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum; more preferably at least one metal selected from the group consisting of ruthenium, palladium, and platinum; and even more preferably platinum. Group 8 metal catalysts can be used as elemental metals, metal salts, or complexes with organic compounds. Specifically, preferred materials include, for example, elemental platinum, platinum metal on a support such as alumina, silica, or carbon black, complexes of chloroplatinic acid with ligands such as alcohols, aldehydes, or ketones, platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2], platinum-acetylacetonate complexes [Pt(C5H7O2)2], platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4], platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4], platinum-phosphine complexes [Pt{P(OPh)3}4], and platinum complexes such as these.

[0072] These Group 8 metal catalysts may be used individually or in combination of two or more. Chloroplatinic acid, platinum olefin complexes, platinum-acetylacetonate complexes, and platinum-vinylsiloxane complexes are preferred due to their high reaction activity. Specifically, a solution of hexachloroplatinic acid hexahydrate and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is preferred.

[0073] There are no particular restrictions on the amount of Group 8 metal catalyst used, but the amount of Group 8 metal catalyst used relative to the unsaturated group-containing oxyalkylene polymer is preferably 1.0 to 20 ppm by mass, and more preferably 1.5 to 10 ppm by mass. If the amount of Group 8 metal catalyst used is above the lower limit, the silylation reaction proceeds sufficiently, and if it is below the upper limit, it is preferable from a cost perspective.

[0074] It is known that even when a silylation reaction is carried out using an excess amount of silylating agent relative to the number of moles of carbon-carbon double bonds at the molecular ends of an unsaturated group-containing oxyalkylene polymer, the silylation rate will not reach 100 mol%. This is thought to be because, during the silylation reaction, the carbon-carbon double bonds at the molecular ends of the unsaturated group-containing oxyalkylene polymer are transferred to the interior of the molecule, and these transferred carbon-carbon double bonds do not react with the silylating agent. In this case, the upper limit of the silylation rate is less than 85 mol%. To achieve a silylation rate of 85 mol% or more, it is preferable to use the following co-catalyst. By using a co-catalyst, the silylation rate can be achieved to 85 mol% or more.

[0075] <Auxiliary catalyst> The co-catalyst preferably contains either or both a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond. In this specification, a carboxylic acid compound means a compound having a carboxyl group and its derivatives. Examples of derivatives include esters and carboxylic anhydrides. One type of carboxylic acid compound having a carbon-carbon triple bond may be used alone or two or more types may be used in combination. One type of carboxylic acid compound having a carbon-carbon double bond may be used alone or two or more types may be used in combination. The co-catalyst may contain either a carboxylic acid compound having a carbon-carbon triple bond or a carboxylic acid compound having a carbon-carbon double bond, and it is preferable to contain both a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond.

[0076] (Carboxylic acid compounds containing a carbon-carbon triple bond) Examples of carboxylic acid compounds having a carbon-carbon triple bond include monocarboxylic acids having a carbon-carbon triple bond, dicarboxylic acids having a carbon-carbon triple bond, carboxylic anhydrides having a carbon-carbon triple bond, and esters having a carbon-carbon triple bond.

[0077] Monocarboxylic acids having a carbon-carbon triple bond are compounds in which a hydrogen atom bonded to a carbon in a hydrocarbon compound having a carbon-carbon triple bond is replaced by a carboxyl group. A dicarboxylic acid having a carbon-carbon triple bond is a compound in which two hydrogen atoms bonded to the carbon in a hydrocarbon compound having a carbon-carbon triple bond are replaced by carboxyl groups. A carboxylic anhydride having a carbon-carbon triple bond is a compound obtained by the dehydration condensation of two carboxyl groups of a carboxylic acid having the carbon-carbon triple bond, a compound obtained by the dehydration condensation of a carboxyl group of a carboxylic acid having the carbon-carbon triple bond and a carboxyl group of a carboxylic acid not having a carbon-carbon triple bond, or a compound obtained by the dehydration condensation of two carboxyl groups within one molecule of a dicarboxylic acid having a carbon-carbon triple bond. Esters having a carbon-carbon triple bond are compounds in which a hydrogen atom in the carboxyl group of a carboxylic acid having a carbon-carbon triple bond is replaced with a monovalent hydrocarbon group. A monovalent saturated hydrocarbon group is preferred as the monovalent hydrocarbon group, and examples include linear or branched alkyl groups and cycloalkyl groups. Among these, methyl groups and ethyl groups are preferred.

[0078] Examples of hydrocarbon compounds having a carbon-carbon triple bond include compounds having a carbon-carbon triple bond in which at least one of the carbon-carbon single bonds in a saturated hydrocarbon compound is replaced by a carbon-carbon triple bond. Examples of saturated hydrocarbon compounds include linear or branched alkanes. Hydrogen atoms in the compounds having a carbon-carbon triple bond may be replaced by substituents. Examples of substituents include aromatic groups and hydroxyl groups.

[0079] The carbon number of the carboxylic acid compound having a carbon-carbon triple bond is preferably 3 to 17, more preferably 3 to 10, and particularly preferably 4 to 10. The carbon number of the monocarboxylic acid compound having a carbon-carbon triple bond is preferably 3 to 17, more preferably 3 to 10. The carbon number of the dicarboxylic acid having a carbon-carbon triple bond is preferably 4 to 10. The carbon number of the carboxylic anhydride having a carbon-carbon triple bond is preferably 4 to 10. The carbon number of the ester having a carbon-carbon triple bond is preferably 4 to 17, more preferably 4 to 10.

[0080] The number of carbon-carbon triple bonds in one molecule of the carboxylic acid compound having the carbon-carbon triple bond is preferably one or two, and more preferably one.

[0081] As carboxylic acid compounds having a carbon-carbon triple bond, carboxylic acid compounds having a carbon-carbon triple bond at the α-position are preferred. Examples of carboxylic acid compounds having a carbon-carbon triple bond at the α-position include monocarboxylic acids having a carbon-carbon triple bond at the α-position, dicarboxylic acids having a carbon-carbon triple bond at the α-position, carboxylic anhydrides having a carbon-carbon triple bond at the α-position, or esters having a carbon-carbon triple bond at the α-position. Monocarboxylic acids and esters having a carbon-carbon triple bond at the α-position are preferred, and monocarboxylic acids having a carbon-carbon triple bond at the α-position are more preferred. In the case of dicarboxylic acids, there are dicarboxylic acids having carbon-carbon triple bonds at both α-positions and dicarboxylic acids having a carbon-carbon triple bond at only one α-position, but dicarboxylic acids having carbon-carbon triple bonds at both α-positions are preferred.

[0082] Preferred monocarboxylic acids having a carbon-carbon triple bond at the α-carbon position include phenylpropiolic acid, propiolic acid, 2-butic acid, 2-heptic acid, 2-methyl-3-butic acid, 2-hydroxy-3-butic acid, and 3-butic acid, with phenylpropiolic acid being more preferred. Examples of dicarboxylic acids having a carbon-carbon triple bond at the α-carbon position include acetylenedicarboxylic acid. Examples of carboxylic anhydrides having a carbon-carbon triple bond at the α-carbon position include propiolic anhydride. Examples of esters having a carbon-carbon triple bond at the α-carbon position include methyl phenylpropiolate. If a carboxylic acid compound having a carbon-carbon triple bond at the α-carbon position has two or more triple bonds in one molecule, it may also have carbon-carbon triple bonds at positions other than the α-carbon.

[0083] (Carboxylic acid compounds having a carbon-carbon double bond) Examples of carboxylic acid compounds having a carbon-carbon double bond include monocarboxylic acids having a carbon-carbon double bond, dicarboxylic acids having a carbon-carbon double bond, carboxylic anhydrides having a carbon-carbon double bond, and esters having a carbon-carbon double bond. In the case of a carboxylic acid compound having both a carbon-carbon triple bond and a carbon-carbon double bond in one molecule, it is considered a carboxylic acid compound having a carbon-carbon triple bond. That is, in this specification, "carboxylic acid compound having a carbon-carbon double bond" is a carboxylic acid compound that has a carbon-carbon double bond and does not have a carbon-carbon triple bond.

[0084] Monocarboxylic acids having a carbon-carbon double bond are compounds in which a hydrogen atom bonded to the carbon in a hydrocarbon compound having a carbon-carbon double bond is replaced by a carboxyl group. A dicarboxylic acid having a carbon-carbon double bond is a compound in which two hydrogen atoms bonded to the carbon in a hydrocarbon compound having a carbon-carbon double bond are replaced by carboxyl groups. A carboxylic anhydride having a carbon-carbon double bond is a compound obtained by the dehydration condensation of the carboxyl groups of two carboxylic acids having carbon-carbon double bonds, a compound obtained by the dehydration condensation of the carboxyl group of a carboxylic acid having a carbon-carbon double bond and the carboxyl group of a carboxylic acid without a carbon-carbon double bond, or a compound obtained by the dehydration condensation of two carboxyl groups within one molecule of a dicarboxylic acid having a carbon-carbon double bond. Esters having a carbon-carbon double bond are compounds in which a hydrogen atom in the carboxyl group of a monocarboxylic acid having a carbon-carbon double bond is replaced with a monovalent hydrocarbon group. A monovalent saturated hydrocarbon group is preferred as the monovalent hydrocarbon group, and examples include linear or branched alkyl groups and cycloalkyl groups. Among these, methyl groups and ethyl groups are preferred.

[0085] Examples of hydrocarbon compounds having a carbon-carbon double bond include compounds having a carbon-carbon double bond in which at least one of the carbon-carbon single bonds in a saturated hydrocarbon compound is replaced by a carbon-carbon double bond. Examples of saturated hydrocarbon compounds include straight-chain or branched alkanes and cycloalkanes. The hydrogen atoms in the compounds having a carbon-carbon double bond may be replaced by substituents. Examples of substituents include aromatic groups and hydroxyl groups.

[0086] The carbon number of the carboxylic acid compound having a carbon-carbon double bond is preferably 3 to 18, more preferably 4 to 18, and even more preferably 4 to 10. The "carbon number" of the carboxylic acid compound having a carbon-carbon double bond refers to the carbon number of the main chain, not the carbon number of the branched chain. The "main chain" refers to the longest molecular chain containing the double bond. For example, in the case of methacrylic acid, the carbon number of the methyl group is not included, and the carbon number of the main chain containing the double bond is counted as 3.

[0087] The number of double bonds in a single molecule of the carboxylic acid compound having a carbon-carbon double bond is preferably one or two, and more preferably one.

[0088] As carboxylic acid compounds having a carbon-carbon double bond, carboxylic acid compounds having a carbon-carbon double bond at the α-position are preferred. Examples of carboxylic acid compounds having a carbon-carbon double bond at the α-position include monocarboxylic acids having a carbon-carbon double bond at the α-position, dicarboxylic acids having a carbon-carbon double bond at the α-position, carboxylic anhydrides having a carbon-carbon double bond at the α-position, or esters having a carbon-carbon double bond at the α-position. Monocarboxylic acids having a carbon-carbon double bond at the α-position and esters having a carbon-carbon double bond at the α-position are preferred, and monocarboxylic acids having a carbon-carbon double bond at the α-position are more preferred. In the case of dicarboxylic acids, there are dicarboxylic acids having carbon-carbon double bonds at both α-positions and dicarboxylic acids having a carbon-carbon double bond at only one α-position, but dicarboxylic acids having carbon-carbon double bonds at both α-positions are preferred.

[0089] Preferred monocarboxylic acids having a carbon-carbon double bond at the α-carbon position include acrylic acid, methacrylic acid, 3-methyl-2-hexenoic acid, 2-hexenoic acid, crotonic acid, sorbic acid, 2-nonenic acid, 2-decenoic acid, 2-heptadecenoic acid, and 2-octadecenoic acid, with crotonic acid being more preferred. Ethyl crotonic acid is preferred as an ester having a carbon-carbon double bond at the α-carbon position. Maleic acid is preferred as a dicarboxylic acid having a carbon-carbon double bond at the α-carbon position. Maleic anhydride is preferred as a carboxylic acid carboxylic acid halide having a carbon-carbon double bond at the α-carbon position. Crotonic acid chloride is an example of a carboxylic acid halide having a carbon-carbon double bond at the α-carbon position. If a carboxylic acid compound having a carbon-carbon double bond at the α-carbon position has two or more double bonds in one molecule, it may also have carbon-carbon double bonds at positions other than the α-carbon.

[0090] (Silane compounds) It is preferable to further include a silane compound represented by the following formula 2a as a co-catalyst. Including a silane compound tends to improve the silylation rate. HSiR 13 3 type 2a

[0091] In the above formula 2a, R 13 R is a monovalent organic group having 1 to 20 carbon atoms, and represents an organic group other than a hydrolyzable group. 13 They may be the same or different from each other.

[0092] R 13 It is preferable that it is at least one selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups. It is more preferable that it is at least one selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, and benzyl groups. A methyl group or an ethyl group is preferred, and an ethyl group is particularly preferred. Also, R 13 It is preferable that they are the same.

[0093] Examples of the silane compound include trimethylsilane, triethylsilane, triisopropylsilane, triphenylsilane, dimethylethylsilane, and dimethylphenylsilane, with triethylsilane being preferred. When the above-mentioned silane compound is included as a co-catalyst, any combination of a carboxylic acid compound having a carbon-carbon triple bond and the silane compound, a carboxylic acid compound having a carbon-carbon double bond and the silane compound, or a carboxylic acid compound having a carbon-carbon triple bond, a carboxylic acid compound having a carbon-carbon double bond and the above-mentioned silane compound may be used, and it is preferable that the carboxylic acid compound having a carbon-carbon triple bond, a carboxylic acid compound having a carbon-carbon double bond and the silane compound are included.

[0094] When a carboxylic acid compound having a carbon-carbon triple bond is included as a co-catalyst, the molar ratio of the carboxylic acid compound having a carbon-carbon triple bond to the group 8 metal catalyst is preferably 0.01 to 25, more preferably 0.05 to 20, and particularly preferably 0.1 to 10. If the ratio is above the lower limit, the silylation rate is further improved. If the ratio is below the upper limit, the amount of acid in the solution is suppressed, and viscosity is suppressed.

[0095] When a carboxylic acid compound having a carbon-carbon double bond is included as a co-catalyst, the amount of carboxylic acid compound having a carbon-carbon double bond used is preferably 0.1 to 10 moles, and more preferably 0.5 to 5 moles, per mole of unsaturated groups in the unsaturated oxyalkylene polymer. If the amount is above the lower limit, the silylation rate is further improved. If the amount is below the upper limit, the amount of acid in the solution is suppressed, and the thickening of the composition containing polymer A is suppressed.

[0096] When a silane compound represented by formula 2a is included as a co-catalyst, the molar ratio of the silane compound to the total of the carboxylic acid compounds having a carbon-carbon triple bond and the carboxylic acid compounds having a carbon-carbon double bond is preferably 0.05 to 20, and more preferably 0.1 to 10. If the ratio is above the lower limit of this range, the silylation rate is further improved. In addition, the amount of acid in the solution is suppressed, and viscosity is reduced.

[0097] It is preferable to stabilize the Group 8 metal catalyst and co-catalyst by dissolving and diluting them in various solvents, thereby facilitating the handling of the catalyst and co-catalyst. Preferred solvents include, for example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, and xylene, halogenated hydrocarbon compounds, alcohols, glycols, ethers, esters, ketones, nitriles, and amides. Among these, alcohols, ketones, nitriles, and amides are preferred, with isopropyl alcohol, acetone, N,N-dimethylformamide, and acetonitrile being more preferred, and acetonitrile being particularly preferred. The Group 8 metal catalyst and co-catalyst may be diluted in two or more solvents.

[0098] <Method for adding Group 8 metal catalysts, co-catalysts, and silylating agents> The method of adding the Group 8 metal catalyst, co-catalyst, and silylating agent in the silylation reaction, including the order of addition, is not particularly limited.

[0099] When a carboxylic acid compound having a carbon-carbon triple bond is included as a co-catalyst, the Group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon triple bond may be dissolved in the solvent to form colloidal particles of the Group 8 metal catalyst. This premix may then be added to the unsaturated group-containing oxyalkylene polymer, followed by the addition of a silylating agent to carry out the silylation reaction. Alternatively, the Group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon triple bond may each be added to a reaction solution containing an unsaturated group-containing organic polymer, followed by the addition of a silylating agent to carry out hydrosilylation. It is preferable to add the premix to the reaction solution because pre-forming colloidal particles of the Group 8 metal catalyst improves the dispersibility of the Group 8 metal catalyst and facilitates the silylation reaction.

[0100] If a carboxylic acid compound having a carbon-carbon double bond is included as a co-catalyst, the group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon double bond may be added to the unsaturated group-containing oxyalkylene polymer, and then a silylation agent may be added to carry out the silylation reaction.

[0101] When using a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond as co-catalysts, the carboxylic acid compound having a carbon-carbon double bond may be added to the unsaturated group-containing oxyalkylene polymer, a premix containing the above-mentioned Group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon triple bond may be added, and then a silylating agent may be added to carry out the silylation reaction. Alternatively, the Group 8 metal catalyst, the carboxylic acid compound having a carbon-carbon triple bond, and the carboxylic acid compound having a carbon-carbon double bond may each be added to a reaction solution containing an unsaturated group-containing organic polymer, and then a silylating agent may be added to carry out hydrosilylation.

[0102] If a silane compound is included as a co-catalyst, the silane compound may be added to the unsaturated group-containing oxyalkylene polymer, or it may be added to a premix containing the above-mentioned Group 8 metal catalyst and a carboxylic acid compound having a carbon-carbon triple bond.

[0103] (Reaction conditions) Silylation reactions can be carried out in a solvent-free system or in the presence of a solvent. Hydrocarbons, halogenated hydrocarbons, ethers, and esters can be used as solvents for silylation reactions, but heptane, hexane, cyclohexane, benzene, toluene, and xylene are preferred. If the unsaturated group-containing oxyalkylene polymer is a solid or a highly viscous liquid, it is preferable to use a solvent to reduce the viscosity of the reaction solution.

[0104] The gas phase of the reactor during the silylation reaction may consist only of inert gases such as nitrogen or helium, or it may also contain oxygen or other gases.

[0105] When oxygen is introduced into the gas phase, the hydrosilylation reaction can be carried out in the presence of an antioxidant to suppress oxidation of the reaction solvent. The antioxidant is not particularly limited, but phenolic antioxidants or amine antioxidants that have the function of radical chain inhibitors can be used. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetrakis{methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane, and 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane. Examples of amine-based antioxidants that can be used include phenyl-β-naphthylamine, α-naphthylamine, N,N'-di-sec-butyl-p-phenylenediamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine.

[0106] The reaction may be carried out in a continuous or batch manner, but it is preferable to carry it out in a batch manner. The reaction temperature is preferably 50 to 120°C, more preferably 50 to 110°C, and even more preferably 50 to 100°C. The reaction pressure is preferably 0.01 to 0.2 MPa, more preferably 0.01 to 0.15 MPa, and even more preferably 0.01 to 0.1 MPa.

[0107] <Polymer B> Polymer B is an oxyalkylene polymer having two or more terminal groups in one molecule, each terminal group having at least one group selected from the group consisting of a reactive silicon group, an isocyanate group, an amino group, and a hydroxyl group represented by the above formula 1, and having an organic group represented by the following formula i.

[0108] Polymer B is a polymer consisting of a main chain and terminal groups. The main chain of polymer B contains residues obtained by removing active hydrogen from an initiator and a polyoxyalkylene chain consisting of one or more alkylene oxide units. Preferably, the main chain of polymer B consists of residues obtained by removing active hydrogen from an initiator and a polyoxyalkylene chain consisting of one or more alkylene oxide units. The polyoxyalkylene chain is similar to that of polymer A.

[0109] Polymer B has two or more terminal groups per molecule. The number of terminal groups is preferably 2 to 8, and more preferably 2 to 6, as this results in higher tensile strength, modulus, and better elongation of the cured product. Each terminal group of polymer B has at least one group selected from the group consisting of a reactive silicon group, an isocyanate group, an amino group, and a hydroxyl group, as represented by the above formula 1. Each terminal group may be the same or different from the others.

[0110] Polymer B preferably contains 2 to 8 of the following organic groups (i), and more preferably 2 to 6 of them. -C(=O)NH- Equation (i) Organic group (i) is a divalent group derived from a urethane bond or a urea bond.

[0111] The organic group (i) preferably forms a urethane bond (-OC(=O)NH-, where -O- represents the oxygen atom at the end of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) exists between the polyoxyalkylene chain and the reactive silicon group in polymer B. When polymer B is produced by method (a) described below, polymer B with a high silylation rate is obtained. Furthermore, when produced by method (a), polymer B with a narrow molecular weight distribution is obtained. The viscosity of the polymer is suppressed, resulting in good workability. If the isocyanate silane compound represented by formula 3a described later contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polymer B will be the same as the number of groups (i) per molecule.

[0112] As a method for producing polymer B, using method (a) described later, that is, reacting an oxyalkylene polymer with hydroxyl groups at its terminals with an isocyanate silane compound represented by formula 3a described later, is preferable because it does not produce impurities with unsaturated groups as by-products. It is also preferable because it requires fewer manufacturing steps. The total degree of unsaturation of polymer B obtained by this method is less than or equal to the total degree of unsaturation of the oxyalkylene polymer with hydroxyl groups at its terminals. Specifically, the total degree of unsaturation of 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. The strength of the cured product is better when it is below the upper limit. The lower limit is not particularly limited. For example, 0.0001 meq / g or more is preferred. The total degree of unsaturation of 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.

[0113] The silylation rate of polymer B is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, and even more preferably 80 to 100 mol%. If the silylation rate is above the lower limit of the above value, a good cured product with high modulus can be obtained. Specifically, the silylation rate of polymer B is calculated as follows: Silylation rate (%) = 100 × number of reactive silicon groups / [number of reactive silicon groups + number of hydroxyl groups + number of isocyanate groups + number of active hydrogens in amino groups].

[0114] The average number of reactive silicon groups per terminal group of polymer B is preferably 0.50 to 2.00, more preferably 0.75 to 2.00, and even more preferably 0.80 to 1.00. If the number is above the lower limit of the above range, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0115] The average number of isocyanate groups per terminal group of polymer B is preferably 0 to 0.30, more preferably 0 to 0.20, and even more preferably 0 to 0.15. The average number of hydroxyl groups per terminal group of polymer B is preferably 0.10 or less, more preferably 0.05 or less, and even more preferably 0.

[0116] The average total number of reactive silicon groups, isocyanate groups, amino groups, and hydroxyl groups per terminal group of polymer B is preferably 0.50 to 2.00, more preferably 0.75 to 1.50, and even more preferably 0.90 to 1.00.

[0117] The average number of reactive silicon groups per molecule of polymer B is preferably 1.50 to 8.00, more preferably 1.75 to 6.00, and even more preferably 1.80 to 6.00. If the number is above the lower limit of the above range, the crosslinking density due to siloxane bonds increases, and a good cured product with high modulus can be obtained.

[0118] The average number of isocyanate groups per molecule of polymer B is preferably 0 to 1.80, more preferably 0 to 1.20, and even more preferably 0 to 0.90 to 0. The average number of hydroxyl groups per molecule of polymer B is preferably 0.60 or less, more preferably 0.30 or less, and even more preferably 0.

[0119] The manganese content (Mn) of polymer B is preferably less than or equal to that of polymer A. The manganese content of polymer B is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, even more preferably 7,500 to 25,000, and particularly preferably 10,000 to 25,000. If it is above the lower limit, the elongation properties of the cured product are better. If it is below the upper limit, the viscosity is low and the workability is good.

[0120] The molecular weight distribution of polymer B is preferably 1.80 or less. A smaller molecular weight distribution is preferable, more preferably 1.00 to 1.60, even more preferably 1.02 to 1.50, and particularly preferably 1.04 to 1.40, as this makes it easier to obtain good spreadability and reduces viscosity, resulting in good workability.

[0121] The viscosity of polymer B at 25°C is preferably 1 to 40 Pa·s, more preferably 1 to 30 Pa·s, and even more preferably 1 to 20 Pa·s.

[0122] <Method for producing polymer B> Methods for producing polymer B include the following methods (a) and (b). Method (a): A method of converting a hydroxyl group of an oxyalkylene polymer having a hydroxyl group as a terminal group to a group having a reactive silicon group represented by formula 1, by reacting the hydroxyl group with a silylating agent having a functional group that can react with the hydroxyl group and a reactive silicon group represented by formula 1. Method (b): A method of converting the hydroxyl group of an oxyalkylene polymer having a hydroxyl group as a terminal group into a group having an isocyanate group, and then reacting it with a silylating agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by the above formula 1, thereby converting the hydroxyl group into a group having a reactive silicon group represented by the above formula 1.

[0123] In method (a), a silylating agent is reacted with an oxyalkylene polymer having a hydroxyl group as described above. It is preferable to use an isocyanate silane compound represented by the following formula 3a as the silylating agent. OCN-(CH2) n -SiR 20 a X 1 3-a ...Formula 3a -SiR in equation 3a above 20 a X 1 3-a This is the same as formula 1 above. n is an integer from 1 to 8, preferably from 1 to 3. The hydroxyl group of the oxyalkylene polymer, whose terminal group is a hydroxyl group, reacts with the above isocyanate silane compound, resulting in the hydroxyl group of the oxyalkylene polymer, whose terminal group is a hydroxyl group, becoming -OC(=O)NH-(CH2) n -SiR 20 a X 1 3-a Represented by a urethane bond (-OC(=O)NH-) and -SiR 20 a X 1 3-a It is converted to a terminal group having a . Examples of isocyanate silane compounds include 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, 3-isocyanate propylmethyldimethoxysilane, 3-isocyanate propylmethyldiethoxysilane, isocyanate methylmethyldimethoxysilane, and isocyanate methylmethyldiethoxysilane. As isocyanate silane compounds, 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-isocyanatetopropylmethyldimethoxysilane, isocyanatemethylmethyldimethoxysilane, and isocyanatemethyltrimethoxysilane are preferred due to their reactivity with oxyalkylene polymers having hydroxyl groups as terminal groups and their ease of handling.

[0124] A reactive silicon group is introduced into the oxyalkylene polymer, which has a hydroxyl group as its terminal group, by the reaction of the hydroxyl group of the oxyalkylene polymer, which has a hydroxyl group as its terminal group, with the isocyanate group of the isocyanate silane compound represented by formula 3a. When the active hydrogen-containing group of an oxyalkylene polymer whose terminal group is a hydroxyl group is a hydroxyl group, the polyoxyalkylene chain (-(R 50 O) m -, R 50 -(R 50 O) m -C(=O)NH-(CH2) n -SiR 20 a X 1 3-a A connected structure represented by is formed.

[0125] This reaction may be carried out in the presence of a urethane catalyst. The urethane catalyst is not particularly limited, and any known urethane catalyst can be used as appropriate. Examples include organotin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal catalysts such as bismuth compounds, and base catalysts such as organic amines. The reaction temperature is preferably 20 to 200°C, and more preferably 50 to 150°C. Furthermore, the urethane reaction is preferably carried out under an inert gas atmosphere. Nitrogen is preferred as the inert gas.

[0126] The molar ratio of the total number of isocyanate groups in the isocyanate-silane compound represented by formula 3a to the total number of active hydrogens in the oxyalkylene polymer whose terminal group is a hydroxyl group is preferably set according to the number of reactive silicon groups per molecule of the polymer A to be obtained. The isocyanate-silane compound represented by formula 3a is reacted such that at least 1.8 reactive silicon groups are obtained per molecule of polymer A. For example, when the active hydrogen-containing group of an oxyalkylene polymer whose terminal group is a hydroxyl group is a hydroxyl group, the molar ratio NCO / OH, which represents the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by formula 3a to the total number of active hydrogens of the oxyalkylene polymer whose terminal group is a hydroxyl group, is preferably 0.7 to 1.0, more preferably 0.8 to 1.0, and even more preferably 0.9 to 1.0. If the value is above the lower limit of the above range, the strength of the cured product is excellent, and if it is below the upper limit, the elongation of the cured product is excellent.

[0127] In method (b), a polyisocyanate compound is reacted with the hydroxyl group of an oxyalkylene polymer whose terminal group is a hydroxyl group to convert the hydroxyl group into a monovalent organic group containing an isocyanate group (hereinafter also referred to as the "isocyanate-containing group") which has a urethane bond (-OC(=O)NH-) on the end end that is bonded to the oxyalkylene polymer whose terminal group is a hydroxyl group. Then, the isocyanate-containing group is reacted with a silylation agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by the above formula 1 to obtain a terminal group that is a monovalent organic group (hereinafter also referred to as the "urethane-bonded and reactive silicon group-containing group") which has one or more urethane bonds (-OC(=O)NH-) and a silylation agent residue that has reacted with the isocyanate group. Hereinafter, the polyisocyanate compound described above will be a diisocyanate compound represented by formula 5 below, and the silylation agent having a functional group that can react with an isocyanate group and a reactive silicon group represented by formula 1 above will be a compound represented by formula 6 below, and method (b) will be described below, but will not be limited thereto.

[0128] OCN-R 30 -NCO...Formula 5 R in formula 5 above 30 This indicates a divalent organic group.

[0129] WR 40 -SiR 20 a X 1 3-a ...Formula 6 In the above formula 6, W is a functional group capable of reacting with a monovalent isocyanate group (a group having one or more active hydrogens), R 40 is a divalent organic group, -SiR 20 a X 1 3-a is the same as the above formula 3a.

[0130] As the oxyalkylene polymer having a hydroxyl group as the terminal group, the above-described oxyalkylene polymer having a hydroxyl group as the terminal group can be used. When the polyisocyanate compound represented by the above formula 5 is reacted with the hydroxyl group of the oxyalkylene polymer having a hydroxyl group as the terminal group, the isocyanate-containing group is -O-C(=O)NH-R 30 -NCO group. When the isocyanate-containing group is reacted with the silylating agent represented by the above formula 6, the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R 30 -NHC(=O)-W’-R 40 -SiR 20 a X 1 3-a (However, W’ is a divalent group obtained by removing one active hydrogen from W.) group. For example, when W is a hydroxyl group, the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R 30 -NHC(=O)-O-R 40 -SiR 20 a X 1 3-a group represented by. In this case, the urethane bond and the reactive silicon group-containing group have two urethane bonds. Further, for example, when W is an amino group (-NH2), the urethane bond and the reactive silicon group-containing group are -O-C(=O)NH-R 30 -NHC(=O)-NH-R 40 -SiR 20 a X 1 3-a group represented by.

[0131] R 30Preferably, the group is a divalent organic group having 2 to 20 carbon atoms, and examples include alkylene groups, cycloalkylene groups, bicycloalkylene groups, monocyclic or polycyclic divalent aromatic hydrocarbon groups, divalent groups obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, divalent groups obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes that may have alkyl groups as substituents and are bonded via an alkylene group, a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons that may have alkyl groups as substituents and are bonded via an alkylene group.

[0132] Examples of diisocyanate compounds represented by the above formula 5 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing modified aromatic polyisocyanates (compounds that do not have isocyanate groups directly bonded to carbon atoms constituting the aromatic ring), aliphatic polyisocyanates and alicyclic polyisocyanates, as well as urethane modified products, biuret modified products, allophanate modified products, carbodiimide modified products and isocyanurate modified products obtained from the above polyisocyanates.

[0133] Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylene-polymethylene-polyisocyanate, 4,4'-diphenylmethane-diisocyanate, 2,4-tolylene-diisocyanate, and 2,6-tolylene-diisocyanate. Examples of non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethylxylylene diisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate). The polyisocyanate compound is preferably one having two isocyanate groups, and is preferably hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate, with tolylene diisocyanate being more preferred because it is easier to obtain the tensile strength of the cured product. One polyisocyanate compound may be used, or two or more may be used in combination.

[0134] Functional groups that can react with the isocyanate group represented by formula 6 and -SiX 1 a R 1 3-a In silylaters having R 40 Preferably, the group is a divalent organic group having 1 to 20 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms; more preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 12 carbon atoms; even more preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms; and particularly preferably, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms. W is preferably a group having one or two active hydrogen atoms, selected from a hydroxyl group, a carboxyl group, a sulfanyl group, an amino group, or an amino group in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms. Hydroxyl groups, sulfanyl groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are preferred, and hydroxyl groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are more preferred.

[0135] [Other ingredients] Examples of the other components mentioned above include polymers other than polymer A and polymer B, curable compounds, epoxy resin curing agents, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropic agents, stabilizers, adhesion modifiers, property modifiers, dehydrating agents, adhesion-improving resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in any combination without limitation from those conventionally known as described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, Japanese Patent Publication No. 2014-88481, Japanese Patent Publication No. 2015-10162, Japanese Patent Publication No. 2015-105293, Japanese Patent Publication No. 2017-039728, Japanese Patent Publication No. 2017-214541, etc. Two or more of each component may be used in combination.

[0136] <Curing catalyst> The curing catalyst acts as a catalyst in the formation of silanol bonds by promoting hydrolysis reactions at hydroxyl groups and hydrolyzable groups in reactive silicon groups, thereby curing the composition. Examples of curing catalysts include tin catalysts and non-tin catalysts, and non-tin catalysts are preferred from the viewpoint of their effect on living organisms as endocrine disruptors. Examples of tin catalysts include salts of tin with organic acids and alkyl tin catalysts. Examples of salts of tin with organic acids include tin octylate, tin naphthenate, tin laurate, tin felzaticate, and tin tris(2-ethylhexanoate). Examples of alkyl tin catalysts include dioctyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin phthalate, dibutyl tin dioctanoate, dibutyl tin bis(2-ethylhexanoate), dibutyl tin bis(methyl maleate), dibutyl tin bis(ethyl maleate), dibutyl tin bis(butyl maleate), dibutyl tin bis(octyl maleate), dibutyl tin bis(tridecyl maleate), dibutyl tin bis(benzyl maleate), dibutyl tin diacetate, and dioctyl tin bis Examples include (ethyl maleate), dioctyl tin bis(octyl maleate), dibutyl tin dimethyloxide, dibutyl tin bis(nonylphenoxide), dibutenyl tin oxide, dibutyl tin oxide, dibutyl tin bis(acetylacetonate), dioctyl tin bis(acetylacetonate), dibutyl tin bis(ethylacetoacetonate), reaction products of dibutyl tin oxide and silicate compounds, reaction products of dioctyl tin oxide and silicate compounds, and reaction products of dibutyl tin oxide and phthalate esters. Examples of non-tin catalysts include (i) aminosilanes, (ii) strong bases (DBU), (iii) compounds in which a silyl group has been introduced into a strong base compound, (iv) acid catalysts such as carboxylic acids of quaternary carbons, and (v) non-tin metal catalysts such as titanium-based, zirconium-based, and aluminum-based catalysts. (i) For aminosilanes, for example, those exemplified in Japanese Patent Application Publication No. 2022-80386 can be used. (ii) For strong bases (DBU), those exemplified in Japanese Patent Application Publication No. 2014-218584 can be used. (iii) For compounds in which a silyl group has been introduced into a strong base compound, for example, those exemplified in WO2022 / 186123 can be used. (iv) For acid catalysts such as carboxylic acids of quaternary carbons, for example, those exemplified in Japanese Patent Application No. 2006-550689 can be used. Also, (v) For non-tin metal catalysts such as titanium-based, zirconium-based, and aluminum-based catalysts, those exemplified in Japanese Patent No. 5225582 can be used. Non-tin catalysts not exemplified in these may also be used.

[0137] The curing catalyst content in the curable composition is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, even more preferably 0.1 to 1 part by mass, and particularly preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the total of polymer A and polymer B. Within this range, the curing reaction proceeds smoothly, localized heat generation and foaming during curing are less likely to occur, and a good cured product is easily obtained.

[0138] <Curable composition> The content of polymer A relative to the total mass of the curable composition is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass. If the content is below the upper limit of the above range, the tensile strength of the cured product will be superior and the elongation properties will be better. The content of polymer B relative to the total mass of the curable composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 3 to 30% by mass. If it is above the lower limit of the above range, the viscosity of the curable composition decreases and the elongation properties become better. If it is below the upper limit of the above range, the tensile strength of the cured product is better and the modulus is higher.

[0139] The total content of polymers A and B relative to the total mass of the curable composition is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass. When the content is above the lower limit of the above range, the curability is good, the cured product has excellent tensile strength, and the modulus is high.

[0140] The content of polymer A is preferably 1 to 99 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the total content of polymer A and polymer B. If the content is above the lower limit of the above range, the viscosity of the curable composition decreases and the tensile strength of the cured product is improved. If the content is below the upper limit of the above range, the tensile strength and modulus are improved.

[0141] The content of components other than polymer A and polymer B relative to the total mass of the curable composition is preferably 30 to 90% by mass, more preferably 40 to 90% by mass, and even more preferably 50 to 85% by mass.

[0142] The curable composition may be a one-component type in which all polymers and other components are pre-mixed and sealed for storage, and cured by moisture in the air after application. Alternatively, it may be a two-component type in which a main component composition containing at least a polymer having reactive silicon groups and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition and the main component composition are mixed before use. In the case of the two-component type, the "total mass of the curable composition" in the above-mentioned content of polymers A and B shall be read as the "total mass of the main component composition and the curing agent composition". It is preferable that the one-component curable composition does not contain water. It is preferable to dehydrate and dry any water-containing components beforehand, or to dehydrate them by reducing the pressure during mixing. In a two-component curable composition, the curing agent composition may contain water, and the main component composition is less likely to gel even if it contains a small amount of water. However, from the viewpoint of storage stability, it is preferable to dehydrate and dry the components beforehand. To improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main component composition.

[0143] ≪Method for producing a curable composition≫ The curable composition of this embodiment can be produced by mixing polymer A produced by the above-mentioned method for producing polymer A, polymer B produced by the above-mentioned method for producing polymer B, and the other components as needed.

[0144] ≪Cured product≫ The cured product of this embodiment is a cured product of the above-mentioned curable composition. The reactive silicon groups of polymer A and the reactive silicon groups of polymer B undergo a hydrolysis reaction due to moisture in the air, and the intermolecular condensation reaction of the silanols produced by the hydrolysis reaction gives a crosslinked cured product.

[0145] <Uses of curable compositions> Suitable applications for the curable composition of this embodiment include adhesives, sealing materials (e.g., elastic sealing materials for buildings, sealing materials for double-glazed windows, sealing materials for rust prevention and waterproofing of glass edges, back sealing materials for solar cells, sealing materials for buildings, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), and electrical insulating materials (insulating coatings for electric wires and cables). [Examples]

[0146] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0147] [Mn, Mw / Mn] A gel permeation chromatograph analyzer, model HLC-8420GPC (Tosoh Corporation), was used as the measurement device. A TSKgel SupermultiporeHZ-M column (Tosoh Corporation) was used, and tetrahydrofuran was used as the solvent. The sample pump was set to a flow rate of 0.350 mL / min, the reference pump to 0.350 mL / min, the detector temperature to 40°C, and the collection time to 6-15 minutes. Mn, Mw, and Mw / Mn were determined by analyzing the peaks appearing between 6 and 11 minutes of collection. A calibration curve was created using polystyrene as the standard substance.

[0148] [Silylation rate] The silylation rate is 1 Analysis was performed using 1H-NMR.

[0149] [Curing speed test] Measurements were performed according to the "5.19 Touch-dry time test" of JIS A 1439:2016. During the finger touch evaluation after drying at 23°C for 12 hours, products that were not sufficiently cured and had a large amount of curable composition adhering to the finger were marked with ×, products that were cured but not sufficiently and had some curable composition visible on the finger were marked with ○, and products that were sufficiently cured and had no curable composition adhering to the finger were marked with ◎.

[0150] [Tensile properties test] The curable composition to be measured was filled into a 2 mm thick mold, cured at 23°C and 50% humidity for 3 days, and then cured again at 50°C and 65% humidity for 4 days. The hardened material was punched out using a dumbbell mold to obtain test specimens. These specimens were subjected to tensile testing at a tensile speed of 500 mm / min using a Tensilon testing machine, and the modulus (M50, unit: N / mm²) of the stress at 50% elongation was measured. 2 ), tensile strength (Tmax, unit: N / mm²), which is the maximum point cohesive force. 2 ) and maximum point elongation (E, unit: %) were measured.

[0151] [Manufacturing Example 1] Using propylene glycol as an initiator and a zinc hexacyanocobaltate complex with t-butyl alcohol as a ligand (hereinafter referred to as "TBA-DMC catalyst") as a catalyst, propylene oxide was polymerized to obtain oxypropylene polymer A1, an oxyalkylene polymer with hydroxyl groups as terminal groups. The number-average molecular weight of oxypropylene polymer A1 was 25,000.

[0152] 1.05 molar equivalents of sodium methoxide were added to the hydroxyl groups of oxypropylene polymer A1, and methanol was removed by distillation under reduced pressure. Subsequently, an excess amount of allyl chloride was added to the hydroxyl groups of oxypropylene polymer A1 and the reaction was carried out, and unreacted allyl chloride was removed under reduced pressure. The mixture was purified to remove the metal salts, and the hydroxyl groups of oxypropylene polymer A1 were converted to allyloxy groups to obtain unsaturated group-containing oxyalkylene polymer A1.

[0153] Crotonic acid was added to the unsaturated group-containing oxyalkylene polymer A1 in a ratio of 1 mole per mole of unsaturated groups. Then, a solution (premix) of platinum catalysts, hexachloroplatin(IV) acid hexahydrate, phenylpropiolic acid, and triethylsilane, dissolved in acetonitrile was added. The amount of hexachloroplatin(IV) acid hexahydrate added was 6.5 mg per 1000 g of unsaturated group-containing oxyalkylene polymer A1, the amount of phenylpropiolic acid added was 9.2 mg per 1000 g of unsaturated group-containing oxyalkylene polymer A1, and the amount of triethylsilane added was 7.3 mg per 1000 g of unsaturated group-containing oxyalkylene polymer A1. For every mole of unsaturated groups in the unsaturated group-containing oxyalkylene polymer A1, 0.9 moles of dimethoxymethylsilane were added as a silylation agent, and the silylation reaction was carried out at 70°C for 3 hours. After that, the unreacted silylation agent was removed under reduced pressure to obtain polymer A-1, which is a reactive silicon group-containing oxyalkylene polymer. The number of terminal groups in polymer A-1, and R in formula 3 above. 11 The number of reactive silicon groups in one molecule, the silylation rate, Mn, and Mw / Mn are shown in Table 1 (the same applies to polymers A-2 to A-6 below).

[0154] [Manufacturing Example 2] Polymer A-2, a reactive silicon group-containing oxyalkylene polymer, was obtained in the same manner as in Production Example 1, except that the amount of dimethoxymethylsilane added was changed to 1.0 mole per mole of unsaturated groups in unsaturated group-containing oxyalkylene polymer A1.

[0155] [Manufacturing Example 3] Polymer A-3, a reactive silicon group-containing oxyalkylene polymer, was obtained in the same manner as in Production Example 1, except that glycerin was used as an initiator instead of propylene glycol, and the amount of alkylene oxide and reaction conditions (reaction temperature, time) were changed so that the Mn was as shown in Table 1.

[0156] [Manufacturing Examples 4, 5] Polymers A-4 and A-5, which are reactive silicon-containing oxyalkylene polymers, were obtained in the same manner as in Production Example 3, except that the amount of alkylene oxide and the reaction conditions (reaction temperature, time) were changed so that the Mn values ​​were as shown in Table 1.

[0157] [Manufacturing Example 6] 1.05 molar equivalents of sodium methoxide were added to the hydroxyl groups of oxypropylene polymer A1 from Production Example 1, and methanol was removed by distillation under reduced pressure. Subsequently, an excess amount of methallyl chloride (3-chloro-2-methyl-1-propene) was added to the hydroxyl groups of oxypropylene polymer A1, and the mixture was reacted at 130°C for 2 hours, after which unreacted methallyl chloride was removed under reduced pressure. The mixture was purified to remove the metal salts, and the hydroxyl groups of oxypropylene polymer A1 were converted to methallyloxy groups to obtain unsaturated group-containing oxyalkylene polymer a6. Except for using unsaturated group-containing oxyalkylene polymer a6 instead of unsaturated group-containing oxyalkylene polymer A1, the silylation reaction was carried out in the same manner as in Production Example 1 to obtain polymer A-6, which is a reactive silicon group-containing oxyalkylene polymer.

[0158] [Manufacturing Example 7] 0.97 molar equivalents of 3-isocyanate-propyltrimethoxysilane were added to the hydroxyl groups of oxypropylene polymer A1, and dioctyltin bisisooctylthioglycol (Neostan U-860: Nitto Chemical Co., Ltd. product name) was added as a catalyst. The mixture was heated to 80°C and stirred while maintaining the temperature at 80°C. Analysis using a Fourier transform infrared spectrophotometer confirmed the completion of the reaction between the hydroxyl group and the isocyanate group, yielding polymer B-1, a reactive silicon group-containing oxyalkylene polymer with a trimethoxysilyl group introduced as a terminal group. The number of terminal groups, reactive silicon group structure, number of reactive silicon groups in one molecule, silylation rate, Mn, and Mw / Mn of polymer B-1 are shown in Table 2.

[0159] [Manufacturing Example 8] In the unsaturated group-containing oxyalkylene polymer A1 of Production Example 1, hexachloroplatin(IV) acid hexahydrate, a platinum catalyst, was added. The amount of hexachloroplatin(IV) acid hexahydrate added was 6.5 mg per 1000 g of unsaturated group-containing oxyalkylene polymer A1. 0.75 moles of dimethoxymethylsilane were added as a silylation agent to 1 mole of unsaturated groups in the unsaturated groups of the unsaturated group-containing oxyalkylene polymer A1. The mixture was reacted at 70°C for 3 hours, and the unreacted silylation agent was removed under reduced pressure to obtain polymer C-1, an oxyalkylene polymer containing reactive silicon groups. The number of terminal groups, reactive silicon group structure, number of reactive silicon groups in one molecule, silylation rate, Mn, and Mw / Mn of polymer C-1 are shown in Table 3.

[0160] [Table 1]

[0161] [Table 2]

[0162] [Table 3]

[0163] [Other ingredients] The other components listed in Tables 4 and 5 are as follows: Shiratsuka CCR: Collagenous calcium carbonate with a fatty acid-treated surface; product name of Shiraishi Calcium Co., Ltd. Whiten SB: Untreated heavy calcium carbonate, product name of Shiraishi Calcium Co., Ltd. Irganox 1010: A hindered phenol antioxidant, a product name of BASF. KBM-1003: Vinyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-403: Glycidoxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. DBTDL: Dibutyltin dilaurate. DBU: 1,8-diazabicyclo[5,4,0]undecene-7. U-860: Dioctyl tin bisisooctyl thioglycolate, tin catalyst, Nitto Chemical Co., Ltd. product name. GF94: GENIOSIL (registered trademark) GF94 (3-(2-aminomethylamino)propyltriethoxysilane, product name of Asahi Kasei Wacker Silicone Co., Ltd.). N-GCF: Tetramethylguanidinepropyltrimethoxysilane. Versatic 10: Neodecanoic acid, manufactured by Japan Epoxy Resin Co., Ltd. DEAPA: 3-Diethylaminopropylamine, manufactured by Wako Pure Chemical Industries, Ltd. Typeque R-820: Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd. Orgatics ZC-570: Zirconium n-butoxide (acetylacetonate) bis(ethylacetoacetate) [containing 36 wt% 1-butanol], manufactured by Matsumoto Trading Co., Ltd. ALCH-50F: Aluminum diisopropoxide (ethyl acetoacetate) [containing 50 wt% No. 7 solvent (petroleum-based solvent)], manufactured by Kawaken Fine Chemicals Co., Ltd.

[0164] [Preparation of curable compositions] (Examples 1-22) Curable compositions were prepared using polymers and additives in the proportions (parts by mass) shown in Tables 4 and 5. The curing rate evaluation and tensile property tests described above were performed using the obtained curable compositions. Examples 1-7 and 15-22 are examples, and Examples 8-14 are comparative examples. The results are shown in Tables 4 and 5.

[0165] [Table 4]

[0166] [Table 5]

[0167] As shown in Tables 4 and 5, the cured products of the curable compositions of Examples 1 to 7, which contain polymers A and B of the present invention, had high Tmax and good tensile strength. The cured products of the curable compositions of Examples 9 and 10, which do not contain polymer A with a high silylation rate, had low Tmax and poor tensile strength. The cured products of the curable compositions of Examples 8 and 11 to 14, which do not contain oxyalkylene polymer B having an organic group represented by formula i and contain only polymer A with a high silylation rate, also had low Tmax. Furthermore, the cured products of the curable compositions of Examples 15 to 22, which contain polymers A and B of the present invention with a modified curing catalyst, had high Tmax and good tensile strength. It was found that in Example 7, which does not have a reactive silicon group represented by formula 3, the curing rate was slower compared to Examples 1 to 6.

Claims

1. A curable composition comprising polymer A and polymer B, The polymer A is an oxyalkylene polymer having two or more terminal groups in one molecule, the terminal groups not having a divalent organic group represented by -C(=O)NH-, and the terminal groups having at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group represented by the following formula 1, and having a silylation rate of 85 to 100 mol% calculated by the following formula f1. The polymer B is a curable composition having two or more terminal groups in one molecule, and each terminal group has at least one group selected from the group consisting of a reactive silicon group represented by the following formula 1, an isocyanate group, an amino group, and a hydroxyl group, and is an oxyalkylene polymer having an organic group represented by the following formula i. -SiR ａ X ３－ａ Formula 1 In Formula 1 above, R represents a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups; X represents a hydroxyl group or a hydrolyzable group; and a is an integer from 0 to 2. When a is 2, R may be the same or different from each other; and when a is 0 or 1, X may be the same or different from each other. The reactive silicon groups of polymer A and polymer B may be the same or different from each other. -C(=O)NH- Formula i [Math 1]

2. The curable composition according to claim 1, wherein the number average molecular weight of polymer A is 5,000 to 100,000.

3. The curable composition according to claim 1, wherein the reactive silicon group of polymer A is a reactive silicon group represented by the following formula 3. -OR １１ -SiR １２ ａ２ X ２ ３－ａ２ Formula 3 In the formula 3, R １１ is a linear alkylene group having 1 to 20 carbon atoms, and R １２ , X ２ , and a2 are the same as R, X, and a in the formula 1, respectively. When a2 is 2, R １２ may be the same as or different from each other, and when a2 is 0 or 1, X ２ may be the same as or different from each other.

4. The curable composition according to claim 1, wherein the number average molecular weight of polymer B is 3,000 to 50,000.

5. The curable composition according to claim 1, further comprising a curing catalyst, wherein the content of the curing catalyst is 0.01 to 20 parts by mass per 100 parts by mass of the total content of polymer A and polymer B.

6. The curable composition according to claim 5, wherein the curing catalyst is a non-tin catalyst.

7. A cured product of a curable composition according to any one of claims 1 to 6.

8. A method for producing a curable composition according to any one of claims 1 to 6, Polymer A is obtained by reacting an unsaturated group-containing oxyalkylene polymer with a silylating agent in the presence of a group 8 metal catalyst and a co-catalyst containing either or both of a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond at the α-carbon position. A method for producing a curable composition, comprising mixing polymer A and polymer B.

9. The method for producing a curable composition according to claim 8, wherein the amount of silylation agent added is 0.85 to 1.50 molar times the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer.

Images