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

Abstract

A curable composition that yields a cured product with excellent weather resistance, 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 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 alkyl (meth)acrylate polymer having a reactive silicon 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 comprising an oxyalkylene polymer having two or more reactive silicon groups per molecule and a (meth)acrylic acid ester polymer having an average of 0.5 or more reactive silicon groups per molecule. It is stated that the cured product of the above curable composition has excellent weather resistance and elongation properties. For example, Example 2 of the examples in Patent Document 1 describes a curable composition comprising a (meth)acrylic acid ester polymer with a number average molecular weight of 15,500 having an average of 1.4 reactive silicon groups per molecule and an oxyalkylene polymer with a silylation rate of 60% and a number average molecular weight of 23,000 having an average of 2.4 reactive silicon groups per molecule. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2024-2114

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] When the inventors of the present application produced a cured product using the curable composition described in Patent Document 1, it was found that there was a problem of insufficient weather resistance.

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition capable of obtaining a cured product having excellent weather resistance, a cured product of the curable composition, and a method for producing the curable composition.

MEANS FOR SOLVING THE PROBLEMS

[0008] The present invention is as follows [1] to [9]. [1] A curable composition comprising a polymer A and a polymer B, The polymer A has two or more terminal groups in one molecule, the terminal groups do not have a divalent organic group represented by -C(=O)NH-, and the terminal groups are a reactive silicon group represented by the following formula 1, an unsaturated group, and a hydroxyl group. It is an oxyalkylene polymer having at least one selected from the group consisting of groups and having a silylation rate calculated by the following formula f1 of 85 to 100 mol%, The polymer B is a (meth)acrylic acid alkyl ester polymer having a reactive silicon group represented by the following formula 1, a curable composition. -SiR a X 3-a Formula 1 [In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms, which represents an organic group other than a hydrolyzable group, and X represents a hydroxyl group or a hydrolyzable group. a is an integer of 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 group of the polymer A and the reactive silicon group of the polymer B may be the same or different from each other.]

Number

[0009] According to the present invention, it is possible to provide a curable composition that yields a cured product with excellent weather resistance, 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 "~". (Meth)acrylate alkyl ester polymer refers to a polymer containing repeating units based on (meth)acrylate alkyl ester monomers. (Meth)acrylate alkyl ester monomer refers to either or both of alkyl acrylate and alkyl methacrylate. 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 that has a functional group that reacts with an unsaturated 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 alkyl (meth)acrylate polymer having a reactive silicon group represented by formula 1 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 polymer A. 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 groups may be the same or different. If polymer B has multiple reactive silicon groups, these 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. 11The 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 polymer A 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 terminal groups of polymer A have 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 as or different from the others.

[0031] 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. In addition, the weather resistance of the cured product obtained from the curable composition containing polymer A tends to be improved.

[0032] 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.

[0033] 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.

[0034] [ka]

[0035] In equation 2 above, R 2 , R 3Each 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.

[0036] R 2 , R 3 Examples include -CH2-, -C2H4-, -C3H6-, -C4H8-, and -C5H 10 -, -C6H 12 Examples 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.

[0037] 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.

[0038] 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.

[0039] R 1 , X 1 a1 is the same as R, X, and a in Equation 1 above.

[0040] 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, a cured product with good tensile strength can be obtained. In addition, the weather resistance of the cured product obtained from the curable composition containing polymer A tends to be improved.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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 0.6 or less, more preferably 0.3 or less, and even more preferably 0.1 or less.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] <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.

[0049] (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.

[0050] The initiator has active hydrogen atoms. Preferably, the initiator has two or more active hydrogen atoms, more preferably two to eight, and even more preferably two to six. The number of active hydrogen atoms in the initiator is equal to the number of terminal groups in polymer A. Therefore, the initiator should be selected to match the number of terminal groups in polymer A. Initiating agents may be used individually or in combination of two or more.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] The Mw / Mn of an oxyalkylene polymer whose terminal group is a hydroxyl group is preferably set such that the Mw / Mn of polymer A is less than or equal to the upper limit mentioned above. For example, the Mw / Mn 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.

[0058] 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.

[0059] 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.

[0060] (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).

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] As epoxy compounds having a carbon-carbon double bond, compounds represented by the following formula 4 are preferred.

[0068] [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.

[0069] (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.

[0070] (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-aExamples 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.

[0071] 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.

[0072] (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.

[0073] 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.

[0074] 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.

[0075] It is known that even when a silylation reaction is carried out using a Group 8 metal catalyst and 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. In other words, it is preferable to use a co-catalyst to produce polymer A.

[0076] <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.

[0077] (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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] (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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] (Silane compounds) It is preferable to further include a silane compound represented by the following formula 5 as a co-catalyst. Including a silane compound tends to improve the silylation rate. HSiR 6 3 formula 5

[0092] In the above formula 5, R 6 R is a monovalent organic group having 1 to 20 carbon atoms, and represents an organic group other than a hydrolyzable group. 6 They may be the same or different from each other.

[0093] R 6 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 6 It is preferable that they are the same.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] When a silane compound represented by formula 5 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 suppressed.

[0098] 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.

[0099] <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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] (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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] <Polymer B> The curable composition of this embodiment contains polymer B. Polymer B is an alkyl (meth)acrylate polymer having a reactive silicon group represented by the above formula 1. The curable composition of this embodiment may contain one type of polymer B or two or more types. In polymer B, the reactive silicon group may be introduced at the main chain terminal group, at the side chain, or at both the main chain terminal group and the side chain. The average number of reactive silicon groups per molecule of polymer B is preferably 1.0 or more. From the viewpoint of strength after curing, 1.2 or more is preferred, and 1.6 or more is more preferred. From the viewpoint of good elongation of the cured product, 4.0 or less is preferred, and 3.0 or less is more preferred. The average number of reactive silicon groups per molecule of polymer B is calculated as "concentration of reactive silicon groups in polymer B [mol / g] × Mn of polymer B". The concentration of reactive silicon groups in polymer B [mol / g] can be measured by NMR. Examples of monomers that constitute the main chain of polymer B include conventionally known monomers described in Japanese Patent Publication No. 3-14068, Japanese Patent Application Publication No. 6-211922, and Japanese Patent Application Publication No. 11-130931. Examples of monomers containing reactive silicon groups and unsaturated groups that can be copolymerized with the above monomers include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, tris(2-methoxyethoxy)vinylsilane, (meth)acrylate-3-(methyldimethoxylyl)propyl, (meth)acrylate-3-(trimethoxysilyl)propyl, and (meth)acrylate-3-(triethoxysilyl)propyl. These may be used individually or in combination of two or more. The alkyl (meth)acrylate monomer is preferably present in an amount of 50% by mass or more, more preferably 70% by mass or more, and may even be 100% by mass, relative to the total monomers constituting polymer B.

[0109] Polymer B can be polymerized using conventionally known polymerization methods described in Japanese Patent Publication No. 2006-257405, Japanese Patent Publication No. 2006-37076, Japanese Patent Publication No. 2008-45059, etc. Conventionally known auxiliary materials such as initiators necessary for polymerization can also be used, and reaction conditions such as reaction temperature and reaction pressure can be appropriately selected. Polymerization methods include solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization using radical polymerization initiators, as well as living radical polymerization. Examples of living radical polymerization methods include those using cobalt porphyrin complexes as shown in the Journal of American Chemical Society (J.Am.Chem.Soc.), 1994, Vol. 116, p. 7943; those using nitrooxide radicals as shown in Japanese Patent Publication No. 2003-500378; atom transfer radical polymerization (ATRP method) using organic halides or sulfonyl halogen compounds as initiators and transition metal complexes as catalysts as shown in Japanese Patent Publication No. 11-130931; and reversible complexation-mediated polymerization as shown in Japanese Patent Publication No. 2024-2114. Polymers obtained by living radical polymerization tend to have a narrow molecular weight distribution and low viscosity. Commercially available polymer B can also be used. Examples of commercially available products include the XMAP series (Kaneka Corporation product name), the ARUFON US-6000 series (e.g., US-6110, US-6120, etc., all Toagosei Co., Ltd. product names), and the Actflow NE series (e.g., NE-1000, NE-3000, both Soken Chemical Co., Ltd. product names).

[0110] The manganese content of polymer B is preferably 10,000 to 100,000, more preferably 12,000 to 80,000, and even more preferably 13,000 to 60,000. If the manganese content is above the lower limit of the above range, the cured product tends to have excellent elongation properties and weather resistance, while if it is below the upper limit, it tends to have excellent workability. The molecular weight distribution of polymer B is preferably 4.0 or less, and more preferably 3.0 or less. When it is below the above upper limit, it tends to have good workability.

[0111] <Other ingredients> The curable composition may contain other components besides polymers A and B described above. Examples of other components include curable compounds, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropic agents, stabilizers, adhesion modifiers, property modifiers, tackifying resins, reinforcing materials such as fillers, surface modifiers (surfactants), flame retardants, foaming agents, solvents, and silicates. Other components can be used in any combination without limitation of those that are conventionally known and 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.

[0112] <Curable composition> The content of polymer A 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 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 weather resistance of the curable composition will be better. If it is below the upper limit of the above range, the elongation of the cured product will be better.

[0113] 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. If the content is above the lower limit of the above range, the cured product will have excellent tensile strength and good weather resistance.

[0114] 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 and weather resistance of the cured product are improved. If the content is below the upper limit of the above range, the tensile strength and modulus are excellent.

[0115] 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.

[0116] The curable composition may be a one-component type in which all 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 reactive silicon group 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.

[0117] It is preferable that a 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 one-component curable composition or a two-component main component composition may be mixed with a lower alcohol such as methanol or ethanol, or a conventionally known dehydrating agent such as alkoxysilane.

[0118] As shown in the examples described below, the curable composition of the present invention, when used in combination with polymer A and polymer B, yields a cured product with excellent tensile strength and weather resistance.

[0119] ≪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.

[0120] ≪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.

[0121] <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]

[0122] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0123] [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.

[0124] [Silylation rate] The silylation rate is 1Analysis was performed using 1H-NMR.

[0125] [Average number of reactive silicon groups per molecule of polymer B] The average number of reactive silicon groups per molecule of polymer B was calculated using the formula: "Concentration of reactive silicon groups in polymer B [mol / g] × Mn of polymer B". The concentration of reactive silicon groups in polymer B [mol / g] is: 1 Analysis was performed using 1H-NMR.

[0126] [Curing speed evaluation] Measurements were performed according to the "5.19 Touch-dry time test" of JIS A 1439:2016. When evaluated by touch after drying at 23°C for 24 hours, products that were insufficiently cured and had the curable composition adhere to the finger were classified as "slow," and products that were sufficiently cured and did not have the curable composition adhere to the finger were classified as "fast."

[0127] [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.

[0128] [Weather resistance test] The curable composition was filled into a mold measuring 40 mm in length, 40 mm in width, and 5 mm in thickness, cured for 3 days in an atmosphere of 23°C and 50% humidity, and then cured for 4 days in an atmosphere of 50°C and 65% relative humidity to allow it to harden. The resulting cured material was used as a test specimen, and a static weathering test was performed using a metal halide lamp type accelerated weathering tester ("i Super UV Tester", manufactured by Iwasaki Electric Co., Ltd.; black panel temperature 63°C, relative humidity 50%, shower 120 seconds / 118 minutes) in accordance with the WX-A method of JIS A 1415:2013. 600 hours after the start of the test, the test specimens were visually inspected for cracks. A "○" indicated no cracks, a "△" indicated slight cracks, and a "×" indicated clear cracks. A "○" rating indicates high weather resistance.

[0129] [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.

[0130] 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.

[0131] 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. The silylation reaction was carried out at 70°C for 3 hours, and the unreacted silylation agent was removed under reduced pressure to obtain polymer A-1, a reactive silicon-containing oxyalkylene polymer. The number of terminal groups in polymer A-1, and R in formula 3 are... 11 Table 1 shows the structure, average number of reactive silicon groups per molecule, silylation rate, Mn, and Mw / Mn (the same applies to polymers A-2 to A-6 below).

[0132] [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.

[0133] [Manufacturing Example 3] Except for using glycerin as an initiator instead of propylene glycol and changing the amount of alkylene oxide and reaction conditions (reaction temperature, time) to achieve the Mn values ​​listed in Table 1, an unsaturated group-containing oxyalkylene polymer A3 was obtained in the same manner as in Production Example 1, and polymer A-3, a reactive silicon group-containing oxyalkylene polymer, was obtained from the obtained unsaturated group-containing oxyalkylene polymer A3.

[0134] [Manufacturing Examples 4, 5] Except for changing the amount of alkylene oxide and the reaction conditions (reaction temperature, time) to achieve the Mn values ​​shown in Table 1, unsaturated group-containing oxyalkylene polymers A4 and A5 were obtained in the same manner as in Production Example 3, and polymers A-4 and A-5, which are reactive silicon group-containing oxyalkylene polymers, were obtained from the obtained unsaturated group-containing oxyalkylene polymers A4 and A5.

[0135] [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.

[0136] [Manufacturing Example 7] Alkyl (meth)acrylate polymers were produced by ATRP-based living radical polymerization, and reactive silyl groups were introduced at the terminal ends of the main chain skeleton of the polymers. First, in a 1 L reactor equipped with a stirrer and thermometer, under a nitrogen gas atmosphere, butyl acrylate (hereinafter referred to as "BA"): 269.1 g (70.0 parts by mass), lauryl acrylate (hereinafter referred to as "LA"): 115.32 g (30.0 parts by mass), copper bromide (CuBr): 2.80 g (0.78 parts by mass), acetonitrile: 34.5 g, and diethyl 2,5-dibromoadipate: 18.01 g (1.5 parts by mass) were charged. The reactor was thoroughly degassed by bubbling with nitrogen gas, and the liquid temperature was maintained at 70-80°C while stirring for 30 minutes. Then, pentamethyldiethylenetriamine (hereinafter also referred to as "PMDT") was added as a ligand for CuBr, and the polymerization reaction was started. The liquid temperature was maintained at 70-90°C while stirring, and PMDT was added to a total of 0.564g during the reaction for approximately 3 hours. The reaction system was heated and stirred at 0.3kPa and 80°C to remove volatile components, then 139g of acrylonitrile, 35.8g of 1,7-octadiene, and 1.13g of PMDT were added, and the reaction was carried out for 8 hours while stirring. The reaction system was heated and stirred at 0.3kPa and 80°C to remove volatile components, then toluene was added to dissolve the polymer, diatomaceous earth was added as a filter aid, and aluminum silicate and hydrotalcite were added as adsorbents, and the mixture was heated and stirred at 100°C under an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6 vol%). The stirred liquid was filtered, and the filtrate was heated and stirred at 0.3 kPa and 100°C to remove volatile components. Then, aluminum silicate and hydrotalcite were added again as adsorbents, and a thermal degradation inhibitor ("SumiLizer® GS", manufactured by Sumitomo Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 175°C and below 1.3 kPa. Further addition of aluminum silicate and hydrotalcite was added, as well as an antioxidant ("Irganox® 245", manufactured by BASF Japan Ltd.), and the mixture was heated and stirred at 150°C under an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6 vol%). Toluene was added to the stirred liquid to dissolve the polymer, and the mixture was filtered. The filtrate was heated and stirred at 0.3 kPa and 100°C to remove volatile components, yielding a precursor polymer having an octenyl group.300 g of this precursor polymer was mixed with 2.0 molar equivalents of dimethoxymethylsilane relative to the octenyl group, 1.0 molar equivalent of methyl orthoformate relative to the octenyl group, and 0.028 g (3.34 mg as platinum) of a xylene solution (20% by mass) of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex as a catalyst. The mixture was heated and stirred at 100°C under a nitrogen gas atmosphere until the octenyl group disappeared. The reaction system was dried under reduced pressure at 0.3 kPa and 100°C to obtain polymer B-1. The average number of reactive silicon groups per molecule of polymer B-1, the reactive silicon group structure, Mn, and Mw / Mn are shown in Table 2 (the same applies to polymers B-2 to B-4 below).

[0137] [Manufacturing Example 8] A "monomer mixed solution" was prepared by mixing 800g of BA, 100g of LA, 100g of stearyl acrylate (hereinafter referred to as "StA") with 1000g of the monomers, 23.2g of 3-methacryloxypropylmethyldimethoxysilane (hereinafter referred to as "MPDMS"), and 20.0g of 2,2'-azobis-2-methylbutyronitrile (product name: "V-59", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The "monomer mixed solution" was added dropwise to 154g of toluene heated to 80°C under a nitrogen atmosphere while stirring for 2 hours, and the reaction was continued for another 2 hours while maintaining the temperature at 80°C. Next, the internal temperature was raised to 125°C while the pressure was reduced to 0.3kPa, and the mixture was degassed for 2 hours to remove unreacted monomers and solvent, obtaining polymer B-2.

[0138] [Manufacturing Example 9] Polymer B-3 was obtained by following the same procedure as in Production Example 8, except that the amount of MPDMS was changed from 23.2 g to 46.4 g.

[0139] [Manufacturing Example 10] 800g of BA, 100g of LA, and 100g of StA were placed in a 2L flask equipped with a reflux condenser, stirrer, and thermometer. Next, 17g of 1-iodononafluorobutane, 11.6g of MPDMS, and 10.5g of tetrabutylammonium iodide were added. Then, the flask was purged with nitrogen, and polymerization was carried out for 6 hours at an internal temperature of 130°C while stirring the reaction system. The reaction rate after 6 hours from the start of polymerization was 80 mol%. Next, 11.6g of MPDMS was added, and polymerization was carried out for a further 4 hours at 130°C. The reaction rate of the obtained polymer was 93 mol%. Next, a solution of 6.2g of V-59 dissolved in 12.5g of butyl acetate was added dropwise to the polymer solution over 2 hours. The reaction rate of the obtained polymer after dropwise addition was 99 mol%. Subsequently, polymer B-4 was obtained by vacuum drying at 0.3kPa and 95°C for 2 hours.

[0140] [Manufacturing Example 11] 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. 0.80 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, average number of reactive silicon groups per molecule, silylation rate, Mn, and Mw / Mn of polymer C-1 are shown in Table 3 (the same applies to polymers C-2 to C-3 below).

[0141] [Manufacturing Example 12] In the unsaturated group-containing oxyalkylene polymer A3 of Production Example 3, 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 A3. For every mole of unsaturated groups in the unsaturated group-containing oxyalkylene polymer A3, 0.80 moles of dimethoxymethylsilane were added as a silylation agent. The mixture was reacted at 70°C for 3 hours, and the unreacted silylation agent was removed under reduced pressure to obtain polymer C-2, a reactive silicon-containing oxyalkylene polymer.

[0142] [Manufacturing Example 13] In the unsaturated group-containing oxyalkylene polymer A4 of Production Example 4, 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 A4. For 1 mole of unsaturated groups in the unsaturated group-containing oxyalkylene polymer A4, 0.80 moles of dimethoxymethylsilane were added as a silylation agent, and the mixture was reacted at 70°C for 3 hours. After that, the unreacted silylation agent was removed under reduced pressure to obtain polymer C-3, which is a reactive silicon group-containing oxyalkylene polymer.

[0143] [Table 1]

[0144] [Table 2]

[0145] [Table 3]

[0146] [Other ingredients] The other components listed in Table 4 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.

[0147] [Preparation of curable compositions] (Examples 1-14) Curable compositions were prepared using polymers and additives in the proportions (parts by mass) shown in Table 4. The resulting curable compositions were then subjected to the curing rate evaluation, tensile properties test, and weathering resistance test described above. Examples 1-9 are examples, and Examples 10-14 are comparative examples. The results are shown in Table 4.

[0148] [Table 4]

[0149] As shown in Table 4, the cured products of the curable compositions of Examples 1 to 9, which contain polymers A and B of the present invention, had high Tmax, good tensile strength, and excellent weather resistance. The cured product of the curable composition of Example 10, which does not contain polymer B, an alkyl ester polymer (meth)acrylate polymer having a reactive silicon group, had poor weather resistance. The cured products of the curable compositions of Examples 11 to 14, which do not contain polymer A with a high silylation rate, but contain polymer C with a low silylation rate and polymer B, an alkyl ester polymer (meth)acrylate polymer, had poor weather resistance, low Tmax, and poor tensile strength. The reason why the cured products of the curable compositions of Examples 1 to 9 had better weather resistance than those of Examples 11 to 14 is thought to be that a higher silylation rate results in fewer crosslinking defects, thus leading to better weather resistance. It was also found that Example 9, which does not have a reactive silicon group represented by the above formula 3, had a slower curing rate compared to Examples 1 to 8.

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 in which the polymer has a reactive silicon group represented by formula 1 below (meth)acrylate alkyl ester polymer. -SiR ａ X ３－ａ Formula 1 [In Formula 1 above, R represents a monovalent organic group having 1 to 20 carbon atoms, other than a hydrolyzable group, and X represents a hydroxyl group or a hydrolyzable group. 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. [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 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, 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 10,000 to 100,000.

5. The curable composition according to claim 1, wherein the molecular weight distribution of polymer B is 4.0 or less.

6. The curable composition according to claim 1, wherein polymer B has an average of 1.0 to 4.0 reactive silicon groups per molecule.

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