Polyoxyalkylene polymers

Abstract

To provide a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product exhibiting good mechanical properties. [Solution] The hydrolyzable silyl group is -SiR a X 3-a (R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 0, 1, or 2.) The polyoxyalkylene polymer has one or more hydrolyzable silyl groups or reactive groups capable of introducing hydrolyzable silyl groups in a single molecule. The average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends to the total number of molecular chain ends is 0.85 or more and 1.00 or less. The average ratio of the total number of hydrolyzable silyl groups to the total number of molecular chain ends is 1.01 or more.

Description

[Technical Field]

[0001] The present invention relates to polyoxyalkylene polymers having hydrolyzable silyl groups, mixtures thereof, and curable compositions containing the polymers or mixtures thereof. [Background technology]

[0002] Polymers containing hydrolyzable silyl groups are known as moisture-reactive polymers and are included in many industrial products such as adhesives, sealants, coatings, paints, and sealants, and are used in a wide range of fields.

[0003] Known main chain skeletons for such polymers include polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers. In particular, polyoxyalkylene polymers having hydrolyzable silyl groups (see, for example, Patent Document 1) have relatively low viscosity at room temperature, making them easy to handle, and the cured product obtained after the reaction exhibits good elasticity, thus giving them a wide range of applications.

[0004] On the other hand, in recent years, the construction market has been seeking sealants that are less prone to bleed-out. For this reason, in curable compositions for sealants that contain polyoxyalkylene polymers having hydrolyzable silyl groups, methods are being investigated that do not use conventional phthalate ester plasticizers or PPG plasticizers, but instead incorporate reactive diluents with introduced hydrolyzable silyl groups (see, for example, Patent Documents 2 and 3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 52-73998 [Patent Document 2] Japanese Patent Publication No. 2018-104670 [Patent Document 3] International Publication No. 2020 / 066551 [Overview of the project] [Problems that the invention aims to solve]

[0006] Polyoxyalkylene polymers containing hydrolyzable silyl groups are required to exhibit good mechanical properties (e.g., tensile stress, fracture stress, and resilience) after curing. Furthermore, by incorporating the aforementioned hydrolyzable silyl group into a polyoxyalkylene polymer having a hydrolyzable silyl group, a curable composition with low viscosity and easy handling can be provided. However, in conventionally reported curable compositions, the mechanical properties after curing tended to decrease as the viscosity decreased.

[0007] In view of the above situation, the first aspect of the present invention aims to provide a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product exhibiting good mechanical properties, and a curable composition containing the same. A second aspect of the present invention aims to provide a mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers that have low viscosity but exhibit good mechanical properties after curing, and a curable composition containing the same. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by a novel polyoxyalkylene polymer having hydrolyzable silyl groups in a specific ratio, and a mixture containing said polymer, leading to the present invention.

[0009] In other words, the first aspect of the present invention is a polyoxyalkylene polymer having a hydrolyzable silyl group, wherein the hydrolyzable silyl group is of general formula (1): -SiR a X 3-a (1) (wherein R, which are identical or different, each represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X, which are identical or different, each represent a hydroxyl group or a hydrolyzable group. a represents 0, 1 or 2), wherein the polyoxyalkylene-based polymer has, per molecule, one or two or more molecular chain terminals containing a hydrolyzable silyl group or a reactive group into which a hydrolyzable silyl group can be introduced; the average ratio of the number of the hydrolyzable silyl groups located at the molecular chain terminals to the number of the molecular chain terminals is 0.85 or more and 1.00 or less; and the average ratio of the total number of the hydrolyzable silyl groups to the number of the molecular chain terminals is 1.01 or more. The present invention relates to said polyoxyalkylene-based polymer. Preferably, the polyoxyalkylene-based polymer has a linear polymer skeleton. Preferably, the number average molecular weight of the polyoxyalkylene-based polymer is 9,000 or more. Preferably, the polyoxyalkylene-based polymer has a structure represented by general formula (2) described later. Preferably, the polyoxyalkylene-based polymer has two or more molecular chain terminals per molecule. A second aspect of the present invention is a mixture of polyoxyalkylene-based polymers (A) and (B) both having hydrolyzable silyl groups, wherein the polyoxyalkylene-based polymer (A) is a polyoxyalkylene-based polymer according to the first aspect that has two or more molecular chain terminals per molecule, the polyoxyalkylene-based polymer (B) has, per molecule, one molecular chain terminal containing a hydrolyzable silyl group or a reactive group into which a hydrolyzable silyl group can be introduced, the hydrolyzable silyl group of the polyoxyalkylene-based polymer (B) is represented by general formula (1), the number average molecular weight of the polyoxyalkylene-based polymer (B) is smaller than the number average molecular weight of the polyoxyalkylene-based polymer (A), and the mixing ratio by weight of the polyoxyalkylene-based polymer (A) to (B) is 95:5 to 30:70. The present invention relates to said mixture. Preferably, a in the general formula (1) represents 1. Preferably, the number average molecular weight of the polyoxyalkylene-based polymer (B) is 10,000 or less. Preferably, the polyoxyalkylene polymer (B) is the polyoxyalkylene polymer according to the first aspect. A second aspect of the present invention relates to a curable composition containing the polyoxyalkylene polymer according to the first aspect or the mixture, and also relates to a cured product of the curable composition. Effects of the Invention

[0010] According to the first aspect of the present invention, there can be provided a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product exhibiting good mechanical properties, and a curable composition containing the same. According to the second aspect of the present invention, there can be provided a mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers which has a low viscosity and can exhibit good mechanical properties after curing, and a curable composition containing the same. Modes for Carrying Out the Invention

[0011] Embodiments of the present invention are described in detail below. <Polyoxyalkylene Polymer According to the First Aspect> First, an embodiment of the hydrolyzable silyl group-containing polyoxyalkylene polymer according to the first aspect is described. The polyoxyalkylene polymer according to the present embodiment has a polyoxyalkylene polymer backbone and a molecular chain terminal bound to the polymer backbone. The polymer backbone and the molecular chain terminal may be directly bonded, but are preferably bonded indirectly via an intermediate structure. Examples of the intermediate structure include a structure derived from the epoxy compound (G1) described below (that is, the structure in parentheses that exists n times in formula (2) described later).

[0012] The polymer skeleton refers to the polymer main chain composed of oxyalkylene repeating units. The polymer skeleton may be linear or branched. A linear polymer skeleton is preferred in that the cured product of the curable composition has high elongation, and a branched polymer skeleton is preferred in that the cured product of the curable composition has high strength. A linear polymer skeleton can be formed by using an initiator having one or two hydroxyl groups per molecule in a polymerization method for forming the polymer skeleton, and a branched polymer skeleton can be formed by using an initiator having three or more hydroxyl groups per molecule.

[0013] The polymer skeleton is preferably composed solely of a plurality of interconnected oxyalkylene repeating units, or, in addition to the plurality of oxyalkylene repeating units, a structure derived from an initiator used during polymerization is included, and the polymer skeleton is composed solely of these. Here, the oxyalkylene repeating unit refers to a repeating unit that constitutes a polyether, and for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0014] The polymer skeleton of the polyoxyalkylene is not particularly limited, but examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Polyoxypropylene is preferred. Only one polymer skeleton may be used, or two or more may be used in combination.

[0015] The aforementioned molecular chain end refers to the region located at the end of a polyoxyalkylene polymer. The molecular chain end can be classified into one containing a hydrolyzable silyl group, one containing a reactive group to which a hydrolyzable silyl group can be introduced, or one containing neither a hydrolyzable silyl group nor the aforementioned reactive group. The aforementioned reactive group to which a hydrolyzable silyl group can be introduced refers to a reactive group that can be converted to a hydrolyzable silyl group through one or more reaction steps. Specific examples of such reactive groups are not particularly limited, but include, for example, hydroxyl groups and carbon-carbon unsaturated bonds (carbon-carbon double bonds or carbon-carbon triple bonds).

[0016] The polyoxyalkylene polymer according to this embodiment has one or more molecular chain ends containing a hydrolyzable silyl group or a reactive group to which a hydrolyzable silyl group can be introduced. Hereinafter, a polyoxyalkylene polymer having two or more such molecular chain ends will be referred to as a multiple reactive end polymer (a), and a polyoxyalkylene polymer having one such molecular chain end will be referred to as a single reactive end polymer (b).

[0017] When a multiple reactive-terminated polymer (a) has a linear polymer backbone, there are two molecular chain ends, and both of these molecular chain ends contain a hydrolyzable silyl group or a reactive group to which a hydrolyzable silyl group can be introduced. Specifically, (i) a polymer molecule in which both molecular chain ends contain a hydrolyzable silyl group, (ii) a polymer molecule having one molecular chain end containing a hydrolyzable silyl group and one molecular chain end containing a reactive group to which a hydrolyzable silyl group can be introduced, and (iii) a polymer molecule in which both molecular chain ends contain a reactive group to which a hydrolyzable silyl group can be introduced are all considered multiple reactive-terminated polymers (a).

[0018] Such multiple reactive-terminated polymers (a) can be produced, for example, by polymerizing an epoxy compound in the presence of an initiator having two hydroxyl groups in one molecule, followed by a one-step or two-step reaction to introduce hydrolyzable silyl groups. If the introduction rate of hydrolyzable silyl groups in the introduction reaction is 100%, all molecular chain ends in polymer (a) will contain hydrolyzable silyl groups. On the other hand, if the introduction rate is less than 100%, polymer (a) will contain both molecular chain ends containing hydrolyzable silyl groups and molecular chain ends containing reactive groups to which hydrolyzable silyl groups can be introduced.

[0019] Furthermore, if the multiple reactive-terminated polymer (a) has a branched polymer backbone, there are three or more molecular chain ends, and at least two of these molecular chain ends (preferably all molecular chain ends) contain a hydrolyzable silyl group, or a reactive group into which a hydrolyzable silyl group can be introduced. Such a multiple reactive-terminated polymer (a) can be produced, for example, by polymerizing an epoxy compound in the presence of an initiator having three or more hydroxyl groups in one molecule, followed by a one-step or two-step reaction to introduce a hydrolyzable silyl group.

[0020] The multiple reactive-end polymer (a) is preferably a polymer having a linear polymer backbone. However, a polymer having a branched polymer backbone may be used as the multiple reactive-end polymer (a), or a polymer having a linear polymer backbone and a polymer having a branched polymer backbone may be used in combination.

[0021] On the other hand, a single reactive-terminated polymer (b) refers to a polymer that has only one molecular chain end containing a hydrolyzable silyl group or a reactive group to which a hydrolyzable silyl group can be introduced in a single molecule. That is, when a single reactive-terminated polymer (b) has a linear polymer backbone, (iv) a polymer molecule containing one molecular chain end containing a hydrolyzable silyl group and one molecular chain end that does not contain either a hydrolyzable silyl group or the aforementioned reactive group (hereinafter also referred to as a "non-reactive molecular chain end"), and (v) a polymer molecule containing one molecular chain end containing a reactive group to which a hydrolyzable silyl group can be introduced and one non-reactive molecular chain end are considered single reactive-terminated polymers (b).

[0022] Such a single reactive-terminated polymer (b) can be produced, for example, by polymerizing an epoxy compound in the presence of an initiator having only one hydroxyl group per molecule, followed by a one-step or two-step reaction to introduce a hydrolyzable silyl group. The resulting polyoxyalkylene polymer contains a structure derived from the initiator at one of its molecular chain ends. For example, when butanol is used as the initiator, the resulting polyoxyalkylene polymer contains a butyl group at one of its molecular chain ends. Such an initiator-derived structure results in a non-reactive molecular chain end that does not contain either a hydrolyzable silyl group or the reactive group.

[0023] The polyoxyalkylene polymer according to this embodiment is a polymer with a high rate of hydrolyzable silyl groups introduced to the molecular chain ends. Specifically, it is preferable that the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer to the number of molecular chain ends of the polyoxyalkylene polymer (hereinafter also referred to as "number of hydrolyzable silyl groups introduced to the molecular chain ends") is 0.85 or more and 1.00 or less. A polyoxyalkylene polymer with a high number of hydrolyzable silyl groups introduced to the molecular chain ends, combined with the characteristics related to the total number of hydrolyzable silyl groups introduced, as described later, can exhibit good mechanical properties after curing.

[0024] The number of hydrolyzable silyl groups introduced to the molecular chain ends can be calculated from the ratio of molecular chain ends containing hydrolyzable silyl groups to the total number of molecular chain ends containing hydrolyzable silyl groups and molecular chain ends containing reactive groups to which hydrolyzable silyl groups can be introduced, which can be calculated by NMR measurement of the polyoxyalkylene polymer.

[0025] The number of hydrolyzable silyl groups introduced to the molecular chain ends is an average value expressed as [number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer / number of molecular chain ends of the polyoxyalkylene polymer (excluding the number of non-reactive molecular chain ends)], and can also be rephrased as the average ratio of the number of molecular chain ends containing hydrolyzable silyl groups of the polyoxyalkylene polymer to the total number of molecular chain ends of the polyoxyalkylene polymer (excluding the number of non-reactive molecular chain ends). The "number of molecular chain ends of the polyoxyalkylene polymer" is 2 if the polymer skeleton is entirely linear, and 3 or more if the polymer skeleton is entirely branched. Furthermore, if the polymer skeleton is a mixture of linear and branched structures, the average value may be between 2 and 3. In addition, "hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer" is a concept that excludes the hydrolyzable silyl groups contained in the intermediate structure mentioned above.

[0026] In polyoxyalkylene polymers, the number of hydrolyzable silyl groups introduced to the molecular chain ends is 0.85 or more, but since the mixture according to this embodiment exhibits better mechanical properties after curing, it is preferably 0.88 or more, more preferably 0.90 or more, even more preferably 0.93 or more, and particularly preferably 0.95 or more. Furthermore, although the number of introduced groups is 1.00 or less, it is preferably 0.99 or less, and more preferably 0.98 or less, because it facilitates manufacturing.

[0027] Furthermore, the number of hydrolyzable silyl groups introduced to the molecular chain ends in the single reactive-terminated polymer (b) is the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends to the number of molecular chain ends containing hydrolyzable silyl groups or reactive groups capable of introducing hydrolyzable silyl groups, without considering the number of non-reactive molecular chain ends.

[0028] Furthermore, the polyoxyalkylene polymer according to this embodiment also has hydrolyzable silyl groups in parts other than the molecular chain ends (specifically, in the intermediate structure), and is a polymer with a high total number of hydrolyzable silyl groups. Specifically, the average ratio of the total number of hydrolyzable silyl groups in the polyoxyalkylene polymer to the number of molecular chain ends (hereinafter also referred to as the "total number of hydrolyzable silyl groups introduced") is 1.01 or higher. A polyoxyalkylene polymer with such a high total number of hydrolyzable silyl groups introduced, combined with the aforementioned characteristics regarding the number of hydrolyzable silyl groups introduced to the molecular chain ends, can exhibit good mechanical properties after curing.

[0029] The total number of hydrolyzable silyl groups introduced can be calculated from the ratio of the total number of hydrolyzable silyl groups to the total number of molecular chain ends containing the hydrolyzable silyl groups and molecular chain ends containing reactive groups to which the hydrolyzable silyl groups can be introduced, which can be calculated by NMR measurement of the polyoxyalkylene polymer.

[0030] The total number of hydrolyzable silyl groups introduced is an average value expressed as [total number of hydrolyzable silyl groups in the polyoxyalkylene polymer / number of molecular chain ends of the polyoxyalkylene polymer (excluding the number of non-reactive molecular chain ends)], which can also be rephrased as the average ratio of the total number of hydrolyzable silyl groups in the polyoxyalkylene polymer to the total number of molecular chain ends of the polyoxyalkylene polymer (excluding the number of non-reactive molecular chain ends).

[0031] In this embodiment, the total number of hydrolyzable silyl groups introduced into the polyoxyalkylene polymer is 1.01 or more. However, since the polyoxyalkylene polymer exhibits better mechanical properties after curing, a total of 1.20 or more is preferred, 1.30 or more is more preferred, 1.50 or more is even more preferred, and 1.60 or more is particularly preferred. Furthermore, there is no particular upper limit to the total number of introduced groups, but a total of 5.00 or less is preferred, 4.00 or less is more preferred, 3.00 or less is even more preferred, and 2.00 or less is particularly preferred.

[0032] Furthermore, the total number of hydrolyzable silyl groups introduced in the single reactive-terminated polymer (b) is the average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain ends containing hydrolyzable silyl groups or reactive groups capable of introducing hydrolyzable silyl groups, without considering the number of non-reactive molecular chain ends.

[0033] The hydrolyzable silyl group of the polyoxyalkylene polymer according to this embodiment is represented by the following general formula (1). -SiR a X 3-a (1)

[0034] R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, either identical or different. Here, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. If the hydrocarbon group has substituents, the substituents are not particularly limited, but examples include halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups.

[0035] Examples of R include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl groups; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl groups; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, toluyl, and 1-naphthyl groups; and aralkyl groups such as benzyl groups. Preferably, R is a substituted or unsubstituted alkyl group, more preferably a methyl, ethyl, chloromethyl, or methoxymethyl group, even more preferably a methyl or methoxymethyl group, and particularly preferably a methyl group. Only one type of group may be used as R, or two or more types of groups may be used in combination.

[0036] X represents a hydroxyl group or a hydrolyzable group, either identical or different. Examples of X include hydroxyl groups, hydrogen, halogens, alkoxy groups, acyloxy groups, ketoxymate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. The aforementioned alkoxy groups may have substituents. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle, methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups are more preferred, methoxy groups and ethoxy groups are even more preferred, and methoxy groups are particularly preferred. Only one type of group may be used as X, or two or more types of groups may be used in combination.

[0037] In general formula (1), a is 0, 1, or 2. Since the mechanical properties of the resulting cured product are improved, a in general formula (1) is preferably 1.

[0038] Examples of hydrolyzable silyl groups represented by general formula (1) include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group. Among these, methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred. From the viewpoint of reactivity, trimethoxysilyl groups, (chloromethyl)dimethoxysilyl groups, and (methoxymethyl)dimethoxysilyl groups are more preferred. From the viewpoint of stability, methyldimethoxysilyl groups and methyldiethoxysilyl groups are more preferred. Furthermore, methyldimethoxysilyl groups are more preferred because they are easy to manufacture.

[0039] In the polyoxyalkylene polymer according to this embodiment, it is preferable that the molecular chain ends containing hydrolyzable silyl groups are indirectly bonded to the polymer backbone via an intermediate structure containing hydrolyzable silyl groups, as described above. In this case, the molecular chain ends containing hydrolyzable silyl groups and the intermediate structure containing hydrolyzable silyl groups of the polyoxyalkylene polymer can be represented, for example, by the following general formula (2).

[0040] [ka]

[0041] In general formula (2), -R 1 -CH(R 2 )-CH2-SiR a X 3-aThe moiety represented by corresponds to a molecular chain terminal containing a hydrolyzable silyl group, and the structure in the parentheses that exists n times corresponds to an intermediate structure. In addition, the "hydrolyzable silyl group located at the molecular chain terminal" refers to -R 1 -CH(R 2 )-CH2-SiR a X 3-a refers only to the hydrolyzable silyl group contained in the moiety represented by. The hydrolyzable silyl group contained in the intermediate structure is not located at a molecular chain terminal, and does not fall under the category of a hydrolyzable silyl group located at a molecular chain terminal. The hydrolyzable silyl group located at a molecular chain terminal and the hydrolyzable silyl group contained in the intermediate structure may be the same or different.

[0042] In general formula (2), R 1 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. R 2 represents hydrogen or an alkyl group having 1 to 6 carbon atoms. R 3 represents a direct bond or a divalent linking group having 1 to 6 carbon atoms. R 4 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. The oxygen at the left end represents oxygen in an oxyalkylene unit located at a terminal of a polymer skeleton formed by linking a plurality of oxyalkylene units. R, X, and a are the same as those described above for the above general formula (1).

[0043] R 1 is preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrocarbon group having 1 to 2 carbon atoms. As the hydrocarbon group, an alkylene group is preferred, and a methylene group, an ethylene group, a propylene group, and a butylene group can be used. A methylene group is particularly preferred.

[0044] R 2 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include hydrogen, a methyl group, an ethyl group, a propyl group, and a butyl group. R 2As such, the number of hydrolyzable silyl groups introduced to the molecular chain terminus is improved, making it easier to achieve 0.85 or more, therefore alkyl groups having 1 to 4 carbon atoms are preferred, alkyl groups having 1 to 3 carbon atoms are more preferred, methyl groups and ethyl groups are even more preferred, and methyl groups are particularly preferred. Also, R 2 For example, hydrogen and an alkyl group having 1 to 4 carbon atoms may coexist.

[0045] R 3 This may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. Preferably, it is -CH2OCH2-, -CH2O-, -CH2-, and more preferably -CH2OCH2-.

[0046] R 4 The hydrocarbon group is preferably hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. Particularly preferred are hydrogen and a methyl group, and most preferably hydrogen.

[0047] The number-average molecular weight of the polyoxyalkylene polymer according to this embodiment is not particularly limited, but the number-average molecular weight of the multiple reactive-terminated polymer (a) is preferably 9,000 or more in terms of polystyrene-based molecular weight in GPC. This allows for better mechanical properties of the resulting cured product. More preferably it is 10,000 or more, even more preferably 20,000 or more, and particularly preferably 25,000 or more. The upper limit of the number-average molecular weight of the multiple reactive-terminated polymer (a) is not particularly limited, but for example it is preferably 40,000 or less, more preferably 35,000 or less, and even more preferably 30,000 or less. The number-average molecular weight can be determined in terms of polystyrene-based molecular weight by GPC measurement. The number-average molecular weight of the single reactive-terminated polymer (b) is the same as described later regarding the number-average molecular weight of the polyoxyalkylene polymer (B).

[0048] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer according to this embodiment is not particularly limited, but a narrow range is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving various mechanical properties such as the durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and weight average molecular weight obtained in polystyrene equivalent by GPC measurement.

[0049] <Method for producing a polyoxyalkylene polymer according to the first embodiment> Next, a method for producing a polyoxyalkylene polymer according to the first embodiment will be described. In producing the polyoxyalkylene polymer, a multiple reactive-end polymer (a) or a single reactive-end polymer (b) can be synthesized individually, and a multiple reactive-end polymer (a) and a single reactive-end polymer (b) can also be synthesized simultaneously in a single system.

[0050] The polyoxyalkylene polymer according to the first embodiment can be produced by introducing a carbon-carbon unsaturated bond to a hydroxyl-terminated polyoxyalkylene polymer (E) by utilizing the reactivity of the hydroxyl group, and then reacting it with a hydrolyzable silyl group-containing compound that is reactive with the carbon-carbon unsaturated bond to introduce a hydrolyzable silyl group. Embodiments of the method for producing the polyoxyalkylene polymer will be described in detail below, but the method for producing the polyoxyalkylene polymer is not limited to the following description.

[0051] (polymerization) The polymer skeleton of polyoxyalkylene polymers can be formed by polymerizing an epoxy compound onto a hydroxyl group-containing initiator using conventionally known methods, thereby obtaining a hydroxyl-terminated polyoxyalkylene polymer (E). While there are no particular limitations on the specific polymerization method, a polymerization method using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferred because it yields a hydroxyl-terminated polymer with a small molecular weight distribution (Mw / Mn).

[0052] While there are no particular limitations on initiators having hydroxyl groups, examples of initiators having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, low molecular weight polyoxypropylenediol, low molecular weight polyoxypropylenetriol, glycerin, trimethylolpropane, triethylolethane, sorbitol, pentaerythritol, and the like.

[0053] As initiators having one hydroxyl group, monohydric alcohols can be used, such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. Furthermore, low molecular weight polyoxypropylene monoalkyl ethers can also be used.

[0054] Here, as an initiator having hydroxyl groups, a mixture of an initiator having two or more hydroxyl groups per molecule and an initiator having one hydroxyl group per molecule is used, and by polymerizing an epoxy compound in the presence of this mixture to form a main chain skeleton, a hydroxyl-terminated polyoxyalkylene polymer (E) can be obtained as a mixture of two types of polymers. For example, when a mixture of an initiator having two hydroxyl groups and an initiator having one hydroxyl group, such as butanol, is used, the resulting hydroxyl-terminated polyoxyalkylene polymer (E) will be a mixture of a polyoxyalkylene polymer having hydroxyl groups at both ends and a polyoxyalkylene polymer having a hydroxyl group at one end. Subsequently, by carrying out the carbon-carbon unsaturated bond introduction step and the hydrolyzable silyl group introduction step described later, it becomes possible to synthesize a mixture of a multiple-reactive-terminated polymer (a) and a single-reactive-terminated polymer (b) in a single system.

[0055] Furthermore, by using only initiators having two or more hydroxyl groups, a multiple reactive-terminated polymer (a) can be synthesized, and by using only initiators having one hydroxyl group, a single reactive-terminated polymer (b) can be synthesized.

[0056] The epoxy compound is not particularly limited, but examples include alkylene oxides such as ethylene oxide and propylene oxide. Propylene oxide is preferred.

[0057] (Reaction with alkali metal salts) In introducing carbon-carbon unsaturated bonds to a hydroxyl-terminated polyoxyalkylene polymer (E), it is preferable to first react the hydroxyl-terminated polyoxyalkylene polymer (E) with an alkali metal salt to convert the terminal hydroxyl groups into metal-oxy groups. Alternatively, a complex metal cyanide catalyst can be used instead of an alkali metal salt. Through these steps, a metal-oxy group-terminated polyoxyalkylene polymer (F) is formed.

[0058] The alkali metal salt is not particularly limited, but examples include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide, and the like. Due to their ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and sodium tert-butoxide being more preferred. Sodium methoxide is particularly preferred in terms of availability, and sodium tert-butoxide is particularly preferred in terms of reactivity. The alkali metal salt may be used in the reaction in a dissolved state in the solvent.

[0059] The amount of alkali metal salt used is not particularly limited, but the molar ratio to the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and even more preferably 0.8 or more. The molar ratio is preferably 1.2 or less, and more preferably 1.1 or less.

[0060] The alkali metal salt is used to convert the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) into metal-oxy groups. To ensure this conversion reaction proceeds efficiently, it is preferable to remove water and any other substances containing hydroxyl groups from the reaction system beforehand. Known methods can be used for this removal, such as heating evaporation, vacuum defloration, spray vaporization, thin-film evaporation, and azeotropic defloration.

[0061] The temperature for reacting with the alkali metal salt can be set appropriately by those skilled in the art, but is preferably 50°C to 150°C, and more preferably 110°C to 145°C. The reaction time for the alkali metal salt is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0062] (Reaction with electrophile (G)) The metaloxy group-terminated polyoxyalkylene polymer (F) obtained as described above can be converted into a structure containing a carbon-carbon unsaturated bond by reacting it with an electrophile (G) having a carbon-carbon unsaturated bond. Preferably, as the electrophile (G), an epoxy compound (G1) having a carbon-carbon double bond is reacted first, followed by an organic halide (G2) having a carbon-carbon double bond. This can form a polyoxyalkylene polymer (H) having carbon-carbon unsaturated bonds at both the molecular chain ends and the intermediate structure.

[0063] An epoxy compound (G1) having a carbon-carbon double bond can react with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing a carbon-carbon double bond and a hydroxyl group into a polyoxyalkylene polymer. In the ring-opening addition reaction, one or more epoxy compounds (G1) can be added to a single metaloxy group by adjusting the amount of epoxy compound (G1) used and the reaction conditions. After the addition of the epoxy compound (G1), if a hydrolyzable silyl group is introduced, the structure derived from the epoxy compound (G1) becomes an intermediate structure containing the aforementioned hydrolyzable silyl group.

[0064] Epoxy compounds having a carbon-carbon double bond (G1) are not limited to the following, but include those with the general formula (3):

[0065] [ka]

[0066] It can be expressed as follows: In the formula, R 3 and R 4 These are the R values ​​mentioned above for general formula (2), respectively. 3 and R 4 It is the same base as [the other].

[0067] Specific examples of epoxy compounds (G1) having a carbon-carbon double bond are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide are preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.

[0068] The amount of epoxy compound (G1) having a carbon-carbon double bond added can be any amount, taking into consideration the amount of carbon-carbon double bond introduced into the polymer and its reactivity. In particular, the molar ratio of epoxy compound (G1) to hydroxyl groups of the polyoxyalkylene polymer (E) is preferably 0.2 or higher, more preferably 0.5 or higher. Furthermore, this molar ratio is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0069] The reaction temperature when a ring-opening addition reaction is carried out with a metaloxy-terminated polyoxyalkylene polymer (F) and an epoxy compound (G1) having a carbon-carbon double bond is preferably 60°C to 150°C, and more preferably 110°C to 140°C.

[0070] As described above, when a metal-oxy group-terminated polyoxyalkylene polymer (F) is reacted with an epoxy compound (G1) having a carbon-carbon double bond, a new metal-oxy group is generated by ring-opening of the epoxy group. Therefore, after reacting with the epoxy compound (G1), an organic halide (G2) having a carbon-carbon double bond can be reacted consecutively.

[0071] An organic halide (G2) having a carbon-carbon double bond can react with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby introducing a carbon-carbon double bond to the molecular chain end of a polyoxyalkylene polymer. The organic halide (G2) having a carbon-carbon double bond is not limited to the following general formula (4): ZR 1 -C(R 2 )=CH2(4) It can be expressed as follows: In the formula, R 1 and R 2 These are the R values ​​mentioned above for general formula (2), respectively. 1 and R 2 It is the same group. Z represents a halogen atom.

[0072] Specific examples of organic halides (G2) having a carbon-carbon double bond include, but are not limited to, 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 due to their ease of handling. Furthermore, methallyl chloride, methallyl bromide, and methallyl iodide are preferred because they increase the number of hydrolyzable silyl groups introduced to the molecular chain ends as described above.

[0073] There are no particular restrictions on the amount of organic halide (G2) having a carbon-carbon double bond added, but the molar ratio of organic halide (G2) to hydroxyl groups of the polyoxyalkylene polymer (E) is preferably 0.7 or higher, and more preferably 1.0 or higher. Furthermore, this molar ratio is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0074] The reaction temperature for reacting a metaloxy-terminated polyoxyalkylene polymer (F) with an organic halide (G2) having a carbon-carbon double bond is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0075] As described above, by reacting a metaloxy group-terminated polyoxyalkylene polymer (F) with an epoxy compound (G1) having a carbon-carbon double bond, and then reacting it with an organic halide (G2) having a carbon-carbon double bond, a polyoxyalkylene polymer (H) having carbon-carbon unsaturated bonds at both the molecular chain ends and the intermediate structure can be formed. When a hydrolyzable silyl group, as described below, is introduced into the polyoxyalkylene polymer (H), the structure represented by the general formula (2) above can be formed. In this case, the structure into which the hydrolyzable silyl group originates from the epoxy compound (G1) corresponds to the intermediate structure, and the structure into which the hydrolyzable silyl group originates from the organic halide (G2) corresponds to the molecular chain end. The hydrolyzable silyl group contained in the structure derived from the epoxy compound (G1), i.e., the intermediate structure, does not correspond to the hydrolyzable silyl group located at the dispersed chain end, as described above. The hydrolyzable silyl group contained in the structure derived from the organic halide (G2) corresponds to the hydrolyzable silyl group located at the dispersed chain end.

[0076] The reactions with alkali metal salts and electrophiles (G) described above may be repeated multiple times to increase the rate of introduction of carbon-carbon unsaturated bonds into the polymer (H). When these reactions are repeated multiple times, the reactants used in each step (alkali metal salts or electrophiles (G) having carbon-carbon unsaturated bonds) may be the same or different.

[0077] (Introduction of hydrolyzable silyl groups) By subjecting the polyoxyalkylene polymer (H), which has carbon-carbon unsaturated bonds at both the molecular chain ends and the intermediate structure obtained as described above, to a hydrosilylation reaction with a hydrosilane compound (I) having hydrolyzable silyl groups, hydrolyzable silyl groups can be introduced into the polymer. This forms the structure represented by the general formula (2), and a polyoxyalkylene polymer having hydrolyzable silyl groups at both the molecular chain ends and the intermediate structure can be produced. In addition to being easy to carry out, the hydrosilylation reaction has the advantages of being easy to adjust the amount of hydrolyzable silyl groups introduced, and the resulting polymer has stable physical properties.

[0078] Specific examples of the hydrosilane compound (I) having the hydrolyzable silyl group include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethyl Chilsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-triph (Diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-tri Examples include alkoxysilanes such as [fluoropropyl]dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; isopropenyloxysilanes (deacetone-free type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0079] The amount of hydrosilane compound (I) having hydrolyzable silyl groups used should be appropriately determined considering the amount of carbon-carbon unsaturated bonds in the polyoxyalkylene polymer (H) and the desired number of hydrolyzable silyl groups to be introduced at the end of the molecular chain.

[0080] Hydrosilylation reactions are preferably carried out in the presence of a hydrosilylation catalyst to accelerate the reaction. Known hydrosilylation catalysts include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as complexes thereof, and these can be used. Specifically, examples include platinum supported on a carrier such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid with alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [e.g., Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphine complexes [e.g., Pt{P(OPh)3}4]. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

[0081] The hydrosilylation reaction is preferably carried out in the presence of a quinone compound in addition to the hydrosilylation catalyst. The quinone compound can further enhance the acceleration of the hydrosilylation reaction by the hydrosilylation catalyst. Specific examples of quinone compounds include 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 9,10-anthraquinone, 1-ethylanthraquinone, and 2-(1,2-dimethylpropyl)-9,10-anthraquinone. From the viewpoint of reaction efficiency, 2,5-di-tert-butyl-1,4-benzoquinone and 2,6-di-tert-butyl-1,4-benzoquinone are preferred. Further details regarding the use of the quinone compound can be found in Japanese Patent Application Publication No. 2000-94105.

[0082] Although the hydrosilylation reaction can be carried out without a solvent, an organic solvent may be added to ensure uniform dissolution of the polyoxyalkylene polymer (H), the hydrosilane compound (I), and the hydrosilylation catalyst, and to facilitate temperature control of the reaction system and the addition of the hydrosilylation catalyst.

[0083] The temperature conditions for the hydrosilylation reaction are not particularly limited and can be set appropriately by those skilled in the art. However, to lower the viscosity of the reaction system and improve reactivity, the reaction is preferably carried out under heating conditions. Specifically, a reaction at 50°C to 150°C is more preferable, and a reaction at 70°C to 120°C is even more preferable. The reaction time can also be set appropriately, but it is preferable to adjust the reaction time along with the temperature conditions to prevent unintended condensation reactions between polymers. Specifically, the reaction time is preferably 30 minutes to 5 hours, and more preferably 3 hours or less.

[0084] Furthermore, the hydrosilylation reaction may be carried out in the presence of an orthocarboxylic acid trialkyl ester. This suppresses the thickening during the hydrosilylation reaction and improves the storage stability of the resulting polymer.

[0085] Examples of orthocarboxylic acid trialkyl esters include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Trimethyl orthoformate and trimethyl orthoacetate are preferred.

[0086] When using orthocarboxylic acid trialkyl esters, the amount used is not particularly limited, but it is preferably about 0.1 to 10 parts by weight, and more preferably about 0.1 to 3 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer.

[0087] <Mixture relating to the second aspect> Next, an embodiment of a mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers according to a second embodiment will be described. The mixture according to this embodiment comprises a polyoxyalkylene polymer (A) having hydrolyzable silyl groups and a polyoxyalkylene polymer (B) having hydrolyzable silyl groups. The mixture according to this embodiment refers to a mixture that substantially contains only polyoxyalkylene polymers (A) and (B). The mixture exhibits curability based on hydrolysis and dehydration condensation reactions of hydrolyzable silyl groups, as polyoxyalkylene polymers (A) and (B) each have hydrolyzable silyl groups.

[0088] <Polyoxyalkylene polymer (A)> As the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) included in the mixture according to this embodiment, a polyoxyalkylene polymer with multiple reactive terminals (a) according to the first embodiment (i.e., a polyoxyalkylene polymer according to the first embodiment having two or more hydrolyzable silyl groups or reactive groups that can be introduced into a single molecular chain terminal) can be used.

[0089] <Polyoxyalkylene polymer (B)> The hydrolyzable silyl group-containing polyoxyalkylene polymer (B) contained in the mixture according to this embodiment is a polymer having one hydrolyzable silyl group or a molecular chain end containing a reactive group to which a hydrolyzable silyl group can be introduced in one molecule. The polyoxyalkylene polymer (B) is a polymer generally known as a reactive diluent and may be a conventionally known polymer, or it may be a polyoxyalkylene polymer corresponding to the single reactive-end polymer (b) according to the first embodiment.

[0090] The polymer skeleton of the polyoxyalkylene polymer (B) may be linear or branched, but a linear polymer skeleton is preferred because it is easier to manufacture. The linear polymer skeleton in the polyoxyalkylene polymer (B) can be formed by using an initiator having only one hydroxyl group per molecule in the polymerization method for forming the polymer skeleton. The details of the polymer skeleton and initiator of the polyoxyalkylene polymer (B) are the same as those of the polymer skeleton of the polyoxyalkylene polymer according to the first embodiment and the details of the initiator used in the manufacture of the single reactive terminal polymer (b).

[0091] A polyoxyalkylene polymer (B) refers to a polymer that has only one molecular chain end containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group per molecule. That is, when a polyoxyalkylene polymer (B) has a linear polymer backbone, (iv) a polymer molecule containing one molecular chain end containing a hydrolyzable silyl group and one non-reactive molecular chain end, and (v) a polymer molecule containing one molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group and one non-reactive molecular chain end are considered polyoxyalkylene polymers (B).

[0092] The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxyalkylene polymer (B) is not particularly limited, but from the viewpoint of the mechanical properties exhibited by the mixture according to this embodiment, it is preferable that the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends to the number of molecular chain ends containing hydrolyzable silyl groups or reactive groups capable of introducing hydrolyzable silyl groups in the polyoxyalkylene polymer (B) is 0.30 or more and 1.00 or less. The lower limit is more preferably 0.50 or more, even more preferably 0.60 or more, and particularly preferably 0.70 or more. The upper limit is more preferably 0.99 or less, and even more preferably 0.98 or less. Furthermore, the number of hydrolyzable silyl groups introduced to the molecular chain ends in polyoxyalkylene polymer (B) is the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends to the number of molecular chain ends containing hydrolyzable silyl groups or reactive groups capable of introducing hydrolyzable silyl groups, without considering the number of non-reactive molecular chain ends.

[0093] The hydrolyzable silyl group of polyoxyalkylene polymer (B) can be represented by the general formula (1) above. However, the hydrolyzable silyl group of polyoxyalkylene polymer (A) and the hydrolyzable silyl group of polyoxyalkylene polymer (B) may be the same or different. In the hydrolyzable silyl group of polyoxyalkylene polymer (B), 1 is preferred for a in the general formula (1) above, as this improves the mechanical properties of the resulting cured product.

[0094] Examples of hydrolyzable silyl groups in polyoxyalkylene polymer (B) include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group. Among these, methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred. From the viewpoint of reactivity, trimethoxysilyl groups, (chloromethyl)dimethoxysilyl groups, and (methoxymethyl)dimethoxysilyl groups are more preferred. From the viewpoint of stability, methyldimethoxysilyl groups and methyldiethoxysilyl groups are more preferred. Furthermore, methyldimethoxysilyl groups are more preferred because they are easy to manufacture.

[0095] The number-average molecular weight of the polyoxyalkylene polymer (B) is smaller than that of the polyoxyalkylene polymer (A) in order to reduce the viscosity of the mixture according to the second embodiment. While there are no particular limitations on the specific numerical value, a polystyrene-equivalent molecular weight of 10,000 or less, and more preferably 8,500 or less, is preferred in terms of GPC. To further reduce the viscosity of the mixture, a number-average molecular weight of 7,000 or less is preferred. The lower limit of the number-average molecular weight of component (B) is not particularly limited, but may be, for example, 1,000 or more, preferably 1,200 or more, and more preferably 1,500 or more. This number-average molecular weight can be determined in terms of polystyrene equivalent by GPC measurement.

[0096] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (B) is not particularly limited, but a narrow range is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving various mechanical properties such as the durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and weight average molecular weight obtained in polystyrene equivalent by GPC measurement.

[0097] The ratio of polyoxyalkylene polymers (A) to (B) in the mixture according to this embodiment is preferably 95:5 to 30:70 by weight. By including components (A) and (B) in a ratio within this range, it is possible to have low viscosity before curing while exhibiting good mechanical properties after curing. The ratio is more preferably 90:10 to 40:60, and even more preferably 80:20 to 50:50.

[0098] The mixture according to this embodiment is low viscosity, and specifically, it is preferable that the viscosity measured at 23°C is less than 30 Pa.s. More preferably, it is 25 Pa.s or less, and even more preferably, 20 Pa.s or less. The viscosity is measured at 23°C using an E-type viscometer (RE-85U, manufactured by Tokyo Keiki, measuring cone: 3° × R14).

[0099] <Method for producing polyoxyalkylene polymer (B)> Next, a method for producing polyoxyalkylene polymer (B) will be described. Polyoxyalkylene polymer (B) can be synthesized on its own, or, as previously described, it can be synthesized simultaneously with polyoxyalkylene polymer (A) in a single system. When polyoxyalkylene polymer (A) and polyoxyalkylene polymer (B) are synthesized simultaneously, polyoxyalkylene polymer (B) corresponds to the single reactive terminal polymer (b) among the polyoxyalkylene polymers according to the first embodiment. The following describes the case in which only polyoxyalkylene polymer (B) is synthesized.

[0100] Polyoxyalkylene polymer (B) can be produced by introducing a carbon-carbon unsaturated bond to a hydroxyl-terminated polyoxyalkylene polymer (E) by utilizing the reactivity of the hydroxyl group, and then reacting it with a hydrolyzable silyl group-containing compound that is reactive with the carbon-carbon unsaturated bond to introduce the hydrolyzable silyl group. The following describes in detail an embodiment of a method for producing polyoxyalkylene polymer (B), but the method for producing polyoxyalkylene polymer (B) is not limited to the description below.

[0101] First, the polymer skeleton of the polyoxyalkylene polymer (B) can be formed by polymerizing an epoxy compound onto an initiator having a hydroxyl group using a conventionally known method, thereby obtaining a hydroxyl-terminated polyoxyalkylene polymer (E). Details are as described in the description of the polyoxyalkylene polymer according to the first embodiment, but as the initiator, an initiator having one hydroxyl group may be used.

[0102] Next, it is preferable to react the hydroxyl-terminated polyoxyalkylene polymer (E) with an alkali metal salt to convert the terminal hydroxyl groups into metal-oxy groups. Alternatively, a complex metal cyanide catalyst can be used instead of the alkali metal salt. Through the above steps, a metal-oxy group-terminated polyoxyalkylene polymer (F) is formed. The details of this reaction are as described in detail for the polyoxyalkylene polymer according to the first embodiment.

[0103] (Reaction with electrophile (G)) By reacting the metal-oxy group-terminated polyoxyalkylene polymer (F) obtained as described above with an electrophile (G) having a carbon-carbon unsaturated bond, the metal-oxy group can be converted into a structure containing a carbon-carbon unsaturated bond. This can lead to the formation of a polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the end of the molecular chain.

[0104] The electrophile (G) having a carbon-carbon unsaturated bond is not particularly limited as long as it is a compound that can react with the metaloxy group of the polyoxyalkylene polymer (F) to introduce a carbon-carbon unsaturated bond into the polyoxyalkylene polymer. Examples include epoxy compounds having a carbon-carbon double bond (G1), organic halides having a carbon-carbon double bond (G2), and organic halides having a carbon-carbon triple bond (G3). These may be used individually or in combination of two or more. Details of (G1) and (G2) are described in detail with respect to the polyoxyalkylene polymer according to the first embodiment.

[0105] Organic halides (G3) having a carbon-carbon triple bond can react with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby introducing a carbon-carbon triple bond to the molecular chain end of a polyoxyalkylene polymer. Organic halides (G3) having a carbon-carbon triple bond are not limited to those specified in the following general formula (5): ZR 5 -C≡CR 6 (5) It can be expressed as follows: In the formula, R 5 R represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. 5 As a concrete example, consider the R mentioned above for general formula (2). 1 The same group can be cited. R 6 R represents hydrogen or an alkyl group having 1 to 10 carbon atoms, with hydrogen or an alkyl group having 1 to 8 carbon atoms being preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. 6 Hydrogen is particularly preferred as the halogen atom. Z represents a halogen atom.

[0106] Specific examples of organic halides (G3) having a carbon-carbon triple bond include, but are not limited to, 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 Examples include bromo-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. Among these, propargyl chloride, propargyl bromide, or propargyl iodide are preferred.

[0107] There are no particular restrictions on the amount of organic halide (G3) having a carbon-carbon triple bond added, but the molar ratio of organic halide (G3) to hydroxyl groups of the polyoxyalkylene polymer (E) is preferably 0.7 or higher, and more preferably 1.0 or higher. Furthermore, this molar ratio is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0108] The reaction temperature for reacting a metaloxy-terminated polyoxyalkylene polymer (F) with an organic halide (G3) having a carbon-carbon triple bond is preferably 50°C to 150°C, and more preferably 50°C to 80°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0109] Furthermore, a metaloxy group-terminated polyoxyalkylene polymer (F) may be reacted with both an organic halide having a carbon-carbon double bond (G2) and an organic halide having a carbon-carbon triple bond (G3). In this case, the organic halide having a carbon-carbon double bond (G2) or the organic halide having a carbon-carbon triple bond (G3) may be reacted simultaneously or sequentially. When reacting sequentially, the order does not matter, and either can be reacted first. This makes it possible to synthesize a polyoxyalkylene polymer (H) having both carbon-carbon double bonds and carbon-carbon triple bonds at the ends of the molecular chain.

[0110] (Introduction of hydrolyzable silyl groups) By subjecting the polyoxyalkylene polymer (H) having carbon-carbon unsaturated bonds at the molecular chain ends obtained above to a hydrosilylation reaction with a hydrosilane compound (I) having hydrolyzable silyl groups, hydrolyzable silyl groups can be introduced into the polymer. This makes it possible to produce a polyoxyalkylene polymer (B) having hydrolyzable silyl groups. Details of this reaction are as described in detail with respect to the polyoxyalkylene polymer according to the first embodiment.

[0111] Another method for producing polyoxyalkylene polymer (B) involves reacting a hydroxyl-terminated polyoxyalkylene polymer (E) with a compound (J) having a hydrolyzable silyl group and an isocyanate group in one molecule to form a urethane bond and introduce a hydrolyzable silyl group. This method also allows for the production of polyoxyalkylene polymer (B) having a hydrolyzable silyl group.

[0112] The compound (J) having a hydrolyzable silyl group and an isocyanate group in one molecule is not particularly limited as long as it has both an isocyanate group capable of urethane reaction with the hydroxyl group of the polyoxyalkylene polymer (E) and a hydrolyzable silyl group in one molecule. Specific examples include (3-isocyanate propyl)trimethoxysilane, (3-isocyanate propyl)dimethoxymethylsilane, (3-isocyanate propyl)triethoxysilane, (3-isocyanate propyl)diethoxymethylsilane, (isocyanate methyl)trimethoxysilane, (isocyanate methyl)triethoxysilane, (isocyanate methyl)dimethoxymethylsilane, and (isocyanate methyl)diethoxymethylsilane.

[0113] As yet another method for producing polyoxyalkylene polymer (B), a polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the end of its molecular chain, can be treated with a compound (K) having a hydrolyzable silyl group and a mercaptan group in one molecule. This method involves introducing a hydrolyzable silyl group by forming a sulfide bond through the addition of the mercaptan group to the carbon-carbon double bond. This method also allows for the production of polyoxyalkylene polymer (B) having a hydrolyzable silyl group.

[0114] The compound (K) having a hydrolyzable silyl group and a mercaptan group in one molecule is not particularly limited as long as it has both a mercaptan group capable of addition to the carbon-carbon double bond of the polyoxyalkylene polymer (H) and a hydrolyzable silyl group in one molecule. Specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, and (mercaptomethyl)triethoxysilane.

[0115] <Curable composition> According to this embodiment, a curable composition comprising a polyoxyalkylene polymer according to the first embodiment or a mixture according to the second embodiment can be provided.

[0116] (Silanol condensation catalyst) In this embodiment, the curable composition preferably contains a silanol condensation catalyst for the purpose of promoting the hydrolysis and condensation reaction of the hydrolyzable silyl groups of the polyoxyalkylene polymer, i.e., the curing reaction.

[0117] Conventional silanol condensation catalysts can be used, specifically organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc.

[0118] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), reaction products of dibutyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalate esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethylmaleate), dioctyltin bis(octylmaleate), dioctyltin bis(acetylacetonate), and reaction products of dioctyltin oxide and silicate compounds. Due to the growing environmental concerns in recent years, dioctyltin compounds are preferred.

[0119] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and cesium carboxylate. Various metals can be combined with the following carboxylic acids as carboxylate groups.

[0120] Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butyl biguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0121] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0122] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxy titanium bis (ethylacetoacetate), aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0123] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0124] The silanol condensation catalyst may be used in combination with two or more different catalysts. For example, combining the amine compound with a carboxylic acid or an amine compound with an alkoxy metal may improve reactivity.

[0125] Regarding the amount of silanol condensation catalyst to be blended, from the viewpoint of achieving both improved condensation reaction rate and workability during curing, it is preferable to blend it in an amount of 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment. Furthermore, some silanol condensation catalysts may seep out onto the surface of the cured product or contaminate the surface of the cured product after the curable composition has cured. In such cases, by using an amount of silanol condensation catalyst of 0.01 to 3.0 parts by weight, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0126] ((meth)acrylic acid ester polymer (D)) The curable composition according to this embodiment preferably further contains a (meth)acrylic acid ester polymer (D) having a hydrolyzable silyl group. Further inclusion of the (meth)acrylic acid ester polymer (D) tends to improve the weather resistance of the cured product. The hydrolyzable silyl group in the (meth)acrylic acid ester polymer (D) may be located at the end of the polymer main chain or in the middle of the main chain.

[0127] The (meth)acrylic acid ester monomers constituting the main chain of the (meth)acrylic acid ester polymer (D) are not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylic acid esters are not particularly limited. Nyl, Decyl (meth)acrylate, Dodecyl (meth)acrylate, Phenyl (meth)acrylate, Toluyl (meth)acrylate, Benzyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 3-Methoxybutyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, Stearyl (meth)acrylate, Glycidyl (meth)acrylate, (3-Trimethoxysilyl)propyl (meth)acrylate, (3-Dimethyl Examples of (meth)acrylic acid monomers include toxymethylsilyl)propyl, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

[0128] Other monomer units include, for example, acrylic acids such as acrylic acid and methacrylic acid; monomers containing amide groups such as N-methylolacrylamide and N-methylolmethacrylamide; epoxy groups such as glycidyl acrylate and glycidyl methacrylate; and nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

[0129] As the (meth)acrylic acid ester polymer (D), a polymer obtained by copolymerizing a (meth)acrylic acid ester monomer with a vinyl monomer copolymerizable thereto may also be used. The vinyl monomer is not particularly limited and includes, for example, styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and cyclohexyl maleimide. Examples include maleimide monomers such as: nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. Multiple of these can also be used as copolymerization components.

[0130] The number of hydrolyzable silyl groups in the (meth)acrylic acid ester polymer (D) is preferably 0.3 to 5.0 per molecule on average, more preferably 0.5 or more from the viewpoint of the mechanical properties of the curable composition after curing, and more preferably 3.0 or less from the viewpoint of the stability of the (meth)acrylic acid ester polymer (D).

[0131] The method for introducing hydrolyzable silyl groups into (meth)acrylic acid ester polymers is not particularly limited, and for example, the following methods can be used: (vi) A method of copolymerizing a compound having a polymerizable unsaturated group and a hydrolyzable silyl group together with the above-mentioned monomer. When this method is used, the hydrolyzable silyl group tends to be introduced randomly into the main chain of the polymer. (vii) A method of polymerizing (meth)acrylic acid ester polymers using a mercaptosilane compound having a hydrolyzable silyl group as a chain transfer agent. When this method is used, the hydrolyzable silyl group can be introduced to the ends of the polymer. (viii) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (V group), and then reacting the hydrolyzable silyl group with a compound having a functional group that reacts with the V group. Specifically, examples include a method of copolymerizing 2-hydroxyethyl acrylate and then reacting the hydroxyl group with an isocyanate silane having a hydrolyzable silyl group, or a method of copolymerizing glycidyl acrylate and then reacting the epoxy group with an aminosilane compound having a hydrolyzable silyl group. (ix) A method for introducing hydrolyzable silyl groups by modifying the terminal functional groups of (meth)acrylic acid ester polymers synthesized by living radical polymerization. (meth)acrylic acid ester polymers obtained by living radical polymerization readily accept the introduction of functional groups at the polymer ends, and by modifying these polymer ends, hydrolyzable silyl groups can be introduced.

[0132] Examples of silicon compounds that can be used to introduce a hydrolyzable silyl group into a (meth)acrylic acid ester polymer using the above method include the following: Compounds having a polymerizable unsaturated group and a hydrolyzable silyl group used in method (vi) include (meth)acrylic acid 3-(trimethoxysilyl)propyl, (meth)acrylic acid 3-(dimethoxymethylsilyl)propyl, (meth)acrylic acid 3-(triethoxysilyl)propyl, (meth)acrylic acid (trimethoxysilyl)methyl, (meth)acrylic acid (dimethoxymethylsilyl)methyl, (meth)acrylic acid (triethoxysilyl)methyl, (meth)acrylic acid (diethoxymethylsilyl)methyl, and (meth)acrylic acid 3-((methoxymethyl)dimethoxysilyl)propyl. From the viewpoint of availability, (meth)acrylic acid 3-trimethoxysilylpropyl and (meth)acrylic acid 3-(dimethoxymethylsilyl)propyl are particularly preferred.

[0133] Examples of mercaptosilane compounds having a hydrolyzable silyl group used in method (vii) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, and mercaptomethyltriethoxysilane.

[0134] Compounds having a functional group that reacts with the hydrolyzable silyl group and V group used in method (viii) include isocyanate silane compounds such as 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyl dimethoxymethylsilane, 3-isocyanate propyltriethoxysilane, isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, isocyanate methyldimethoxymethylsilane, and isocyanate methyldiethoxymethylsilane; and 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane, and glycidoxymethyltriethoxysilane. Examples include epoxysilane compounds such as glycidoxymethyldimethoxymethylsilane and glycidoxymethyldiethoxymethylsilane; and aminosilane compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-(2-aminoethyl)aminomethyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0135] In the method described in (ix) above, any modification reaction can be used. For example, a method can be used in which a compound having a functional group that can react with terminal reactive groups obtained by polymerization and a hydrolyzable silyl group is used, or a method can be used in which a compound having a functional group that can react with terminal reactive groups and a double bond is used to introduce a double bond to the polymer terminal, and then a hydrolyzable silyl group is introduced to it by hydrosilylation or the like.

[0136] These methods may be used in any combination. For example, combining method (viii) and method (vii) can yield a (meth)acrylic acid ester polymer having hydrolyzable silyl groups at both the molecular chain terminals and / or side chains.

[0137] Examples of hydrolyzable silyl groups in (meth)acrylic acid ester polymer (D) include those similar to those in polyoxyalkylene polymers (A) and / or (B). Among these, methyldimethoxysilyl, methyldiethoxysilyl, trimethoxysilyl, and triethoxysilyl groups are preferred. Furthermore, from the viewpoint of achieving both storage stability and curability of the curable composition containing (meth)acrylic acid ester polymer (D), the methyldimethoxysilyl group is more preferred, and the trimethoxysilyl group is even more preferred in that it can enhance the curability of the composition and the restorability of its cured product.

[0138] The monomer composition of the (meth)acrylic acid ester polymer (D) is generally selected according to the application and purpose, as is common practice among those skilled in the art. However, for applications requiring flexibility, such as sealing materials, a relatively low glass transition temperature (Tg) is preferred, preferably -100°C to 100°C, and more preferably -60°C to 0°C. The Tg can be determined using Fox's formula below. Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi represents the weight fraction of monomer i that constitutes the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of monomer i.)

[0139] The number-average molecular weight of the (meth)acrylic acid ester polymer (D) is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 2,000 to 30,000, based on polystyrene-equivalent molecular weight measured by GPC.

[0140] Methods for blending polyoxyalkylene polymers and (meth)acrylic acid ester polymers are proposed in Japanese Patent Publication Nos. 59-122541, 63-112642, 6-172631, and 11-116763. Alternatively, a method of polymerizing (meth)acrylic acid ester monomers in the presence of a polyoxypropylene polymer having hydrolyzable silyl groups can be used. This production method is specifically disclosed in Japanese Patent Publication Nos. 59-78223, 60-228516, and 60-228517. A polyoxyalkylene polymer according to the first embodiment or a mixture according to the second embodiment can be blended with a (meth)acrylic acid ester polymer (D) by a similar method, but is not limited to these.

[0141] The ratio of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment to the (meth)acrylic acid ester polymer (D) is not particularly limited, but a weight ratio of 95:5 to 10:90 is preferred, 90:10 to 20:80 is more preferred, and 80:20 to 40:60 is particularly preferred. Note that only one type of polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment and the (meth)acrylic acid ester polymer (D) may be used, or two or more types may be used in combination.

[0142] (Other additives) The curable composition according to this embodiment may also contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents. Furthermore, the curable composition according to this embodiment may contain various additives as needed to adjust the properties of the curable composition or cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0143] <Filler> Various fillers can be incorporated into the curable composition according to this embodiment. Examples of fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, settling silica, crystalline silica, fused silica, anhydrous silicic acid, hydrated silicic acid, carbon black, ferric oxide, aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fibers, and filaments. One type of filler may be used, or two or more types may be mixed and used.

[0144] The amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0145] Organic balloons and inorganic balloons may be added to reduce the weight (lower specific gravity) of the composition. The balloons are spherical fillers with a hollow interior. Examples of materials for these balloons include inorganic materials such as glass, shirasu (volcanic ash), and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. One type of balloon may be used, or two or more types may be mixed and used.

[0146] The amount of balloon used is preferably 0.1 to 100 parts by weight, and more preferably 1 to 20 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0147] <Adhesion-enhancing agent> The curable composition according to this embodiment may contain an adhesion promoter. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent may be added.

[0148] Specific examples of silane coupling agents include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; as well as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-iso Examples include isocyanate group-containing silanes such as cyanate-propylmethyldimethoxysilane, α-isocyanate-methyltrimethoxysilane, and α-isocyanate-methyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Reaction products of various silane coupling agents can also be used. The above adhesion-imparting agents may be used individually or in combination of two or more types.

[0149] The amount of adhesion-imparting agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0150] <Plasticizer> A plasticizer may be incorporated into the curable composition according to this embodiment. Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkyl sulfonate phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

[0151] Furthermore, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like.

[0152] The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment. The plasticizer may be used alone or in combination of two or more types.

[0153] <Solvents, Diluents> The curable composition according to this embodiment may contain a solvent or diluent. While not particularly limited, the solvent and diluent can include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like. When using a solvent or diluent, to address the issue of air pollution when the composition is used indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher. The solvent or diluent may be used alone or in combination of two or more.

[0154] <Drip-preventing agent> The curable composition according to this embodiment may contain a drip inhibitor as needed to prevent dripping and improve workability. The drip inhibitor is not particularly limited, but examples include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These drip inhibitors may be used individually or in combination of two or more.

[0155] The amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0156] <Antioxidant> The curable composition according to this embodiment may contain an antioxidant (anti-aging agent). Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731.

[0157] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0158] <Light stabilizer> The curable composition according to this embodiment may contain a light stabilizer. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, but hindered amine-based compounds are particularly preferred.

[0159] The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0160] <UV absorber> The curable composition according to this embodiment may contain an ultraviolet absorber. Using an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate compounds, but benzotriazole-based compounds are particularly preferred, and examples include commercially available products such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all manufactured by BASF).

[0161] The amount of ultraviolet absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0162] <Property modifier> The curable composition according to this embodiment may contain a property modifier to adjust the tensile properties of the resulting cured product as needed. The property modifier is not particularly limited, but examples include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using the property modifier, the hardness of the composition after curing can be increased, or conversely, the hardness can be decreased to increase the elongation at break. For example, the addition of diphenyldimethoxysilane can lower the hardness of the composition after curing while maintaining resilience. The above-mentioned property modifiers may be used alone or in combination of two or more.

[0163] In particular, compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis have the effect of reducing the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are especially preferred. Examples of compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and produce silane monool upon hydrolysis.

[0164] The amount of the property modifier used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0165] <Adhesive-granting resin> The curable composition according to this embodiment may contain a tackifying resin to enhance adhesion to the substrate or as needed. There are no particular restrictions on the tackifying resin; commonly used resins can be used.

[0166] Specific examples include terpene resins, aromatically modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used individually or in combination of two or more types.

[0167] The amount of tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0168] <Compounds containing epoxy groups> The curable composition according to this embodiment may contain a compound containing an epoxy group. Using a compound with an epoxy group can improve the resilience of the cured product. Examples of compounds with an epoxy group include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, epoxybutyl stearate, and the like. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0169] <Photocurable substance> The curable composition according to this embodiment may contain a photocurable substance. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many types of compounds of this kind are known, including organic monomers, oligomers, resins, or compositions containing them. Typical examples include unsaturated acrylic compounds, vinyl polycinnamates, or azidized resins, which are monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups.

[0170] The photocurable substance is preferably used in an amount of 0.1 to 20 parts by weight, and more preferably in an amount of 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0171] <Oxygen curing substance> The curable composition according to this embodiment may contain an oxygen-curable substance. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. These react with oxygen in the air to form a cured film near the surface of the cured product, preventing stickiness and the adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used individually or in combination of two or more.

[0172] The amount of oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment. As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0173] <Epoxy resin> The curable composition according to this embodiment may contain an epoxy resin. Compositions containing epoxy resins are particularly preferred as adhesives, especially as adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins or novolac type epoxy resins.

[0174] The ratio of these epoxy resins to the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment is preferably in the range of polyoxyalkylene polymer according to the first embodiment or mixture according to the second embodiment / epoxy resin = 100 / 1 to 1 / 100 by weight.

[0175] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to this embodiment. There are no particular restrictions on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be used.

[0176] When using a curing agent for epoxy resin, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

[0177] <<Preparation of Curable Composition>> The curable composition according to this embodiment can be prepared as a one-component type in which all components are pre-mixed and sealed for storage, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which components such as a silanol condensation catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and these components are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

[0178] When the curable composition is a one-component type, all components are pre-mixed. Therefore, it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them during mixing by reducing pressure. Furthermore, storage stability can be further improved by adding alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane in addition to the dehydration and drying method.

[0179] The amount of dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, is preferably in the range of 0.1 to 20 parts by weight, and more preferably in the range of 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer according to the first embodiment or the mixture according to the second embodiment.

[0180] <Application> The curable composition according to this embodiment can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., a waterproofing material, a waterproof coating material, a molding material, a vibration damping material, a soundproofing material, a foaming material, a paint, or a spray material. The cured product obtained by curing the curable composition according to this embodiment has excellent flexibility and adhesion, and can therefore be suitably used as a sealing material or an adhesive.

[0181] Furthermore, the curable composition according to this embodiment is used for electrical and electronic component materials such as back-surface sealing materials for solar cells, electrical and electronic component and device insulating coatings such as wire and cable insulating coatings, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray sealants, crack repair materials, tile adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealing materials, dental impression materials, food packaging materials, and sealants for joints of exterior materials such as sizing boards. It can be used in a wide variety of applications, including adhesives, coatings, anti-slip coatings, cushioning materials, primers, conductive materials for electromagnetic shielding, thermally conductive materials, hot-melt materials, potting agents for electrical and electronic applications, films, gaskets, concrete reinforcement materials, temporary adhesives, various molding materials, and liquid sealants used in rust prevention and waterproofing of wired glass and laminated glass edges (cut sections), as well as in automotive parts, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical components, and various machine parts. Taking automobiles as an example, it can be used in a wide variety of applications, such as adhesive attachment of plastic covers, trims, flanges, bumpers, window mounting, interior components, and exterior components. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin molded products, either alone or with the help of a primer, it can also be used as various types of sealing and adhesive compositions. Furthermore, the curable composition according to this embodiment can be used as an adhesive for interior panels, exterior panels, tile, stone, ceiling finishes, floor finishes, wall finishes, vehicle panels, electrical / electronic / precision equipment assembly, adhesives for bonding leather, textiles, fabrics, paper, boards, and rubber, post-reactive crosslinking pressure-sensitive adhesives, direct glazing sealants, double-glazed glass sealants, SSG method sealants, working joint sealants for buildings, and materials for civil engineering and bridges. In addition, it can be used as an adhesive material such as adhesive tape or adhesive sheet. [Examples]

[0182] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "both-ended components" refers to polyoxypropylene having a hydrolyzable silyl group and / or a reactive group capable of introducing a hydrolyzable silyl group (e.g., a hydroxyl group, an allyl group, or a methallyl group) at each end of a linear polyoxypropylene chain. "One-ended component" refers to polyoxypropylene having a hydrolyzable silyl group and / or a reactive group capable of introducing a hydrolyzable silyl group at only one of the ends of a linear polyoxypropylene chain, while the other end does not have either a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group. "Both-ended components" may qualify as a multiple reactive-ended polymer (a) or polymer (A) if they satisfy the specified requirements. "One-ended components" may qualify as a single reactive-ended polymer (b) or polymer (B) if they satisfy the specified requirements.

[0183] The number-average molecular weight is the GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0184] Viscosity is measured at 23°C using an E-type viscometer (Tokyo Keiki RE-85U, measuring cone: 3° × R14).

[0185] (Synthesis Example 1-1) Using a commercially available polyoxypropylenediol with a number-average molecular weight of approximately 4,500 and hydroxyl groups at both ends as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate grime complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-1) containing only the terminal components and having a number-average molecular weight of approximately 28,000.

[0186] (Synthesis Example 1-2) Using a commercially available polyoxypropylenediol with a number-average molecular weight of approximately 4,500 and hydroxyl groups at both ends as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate grime complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-2) containing only the terminal components and having a number-average molecular weight of approximately 15,000.

[0187] (Synthesis Examples 1-3) Using n-butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-glim complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-3) containing only one terminal component and having a number-average molecular weight of approximately 8,000.

[0188] (Synthesis Examples 1-4) Using n-butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-glim complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-4) containing only one terminal component and having a number-average molecular weight of approximately 2,000.

[0189] (Synthesis Examples 1-5) Using a commercially available polyoxypropylenediol with a number-average molecular weight of approximately 4,500 and hydroxyl groups at both ends as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate grime complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-5) containing only the terminal components and having a number-average molecular weight of approximately 10,000.

[0190] (Synthesis Example 2-1) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-1), 1.0 equivalent of a methanol solution of sodium methoxide was added, and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an allyl group. Then, 1.5 equivalents of 3-chloro-2-methyl-1-propene (metharyl chloride) was added at 130°C to convert the terminal hydroxyl group to a metharyl group. After that, 0.4 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of (E-1), and the methanol was removed by distillation at 130°C. Subsequently, 0.8 equivalents of 3-chloro-1-propene (allyl chloride) was added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual metal salts and other impurities, 100 parts by weight of the resulting metharyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of metharyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defloration was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer (A-1) containing only the terminal components and having methyldimethoxysilyl groups at the end of the molecular chain, with a number-average molecular weight of 28,000. In polyoxypropylene polymer (A-1), the number of hydrolyzable silyl groups introduced to the molecular chain ends (average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends to the total number of molecular chain ends) was 0.95. In addition, polyoxypropylene polymer (A-1) also has methyldimethoxysilyl groups in locations other than the molecular chain ends (intermediate structure), and the number of these groups per molecular chain end was 0.80. When these are added together, the total number of hydrolyzable silyl groups introduced (average ratio of the total number of hydrolyzable silyl groups to the total number of molecular chain ends) was 1.75.

[0191] (Synthesis Example 2-2) 1.1 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-1), and the methanol was removed by distillation at 130°C. Subsequently, 1.3 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl group to a metharyl group. Furthermore, 0.4 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of (E-1), and the methanol was removed by distillation at 130°C. Subsequently, 0.8 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual impurities such as metal salts, 100 parts by weight of the resulting metharyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of metharyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defloration was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer (C-1) containing only the terminal components and having methyldimethoxysilyl groups at the end of the molecular chain, with a number-average molecular weight of 28,000. The polyoxypropylene polymer (C-1) did not have hydrolyzable silyl groups at any site other than the molecular chain ends, and the "number of hydrolyzable silyl groups introduced to the molecular chain ends" and the "total number of hydrolyzable silyl groups introduced" were both 0.95.

[0192] (Synthesis Example 2-3) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-1), 1.0 equivalent of a methanol solution of sodium methoxide was added and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an allyl group, and then 1.5 equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl group to an allyl group. After that, 0.4 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of (E-1) and the methanol was removed by distillation at 130°C, and then 0.8 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual impurities such as metal salts, 100 parts by weight of the obtained allyl-terminated polyoxypropylene mixture was mixed with 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol at 3% by mass in terms of platinum) and 1.7 parts by weight of methyldimethoxysilane. The mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (C-2) containing only the terminal components, having methyldimethoxysilyl groups at the end of the molecular chain, and having a number-average molecular weight of 28,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer (C-2) was 0.75. In addition, the polyoxypropylene polymer (C-2) also had methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.75. When these are added together, the total number of hydrolyzable silyl groups introduced was 1.50.

[0193] (Synthesis Example 2-4) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-2), 1.0 equivalent of a methanol solution of sodium methoxide was added, and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an allyl group, and then 1.5 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl group to a metharyl group. Furthermore, 0.4 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of (E-2), and the methanol was removed by distillation at 130°C, and then 0.8 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual impurities such as metal salts, 100 parts by weight of the resulting metharyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of metharyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defoliation was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer (A-2) containing only the terminal components and having methyldimethoxysilyl groups at the end of the molecular chain, with a number-average molecular weight of 15,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of polyoxypropylene polymer (A-2) was 0.95. In addition, polyoxypropylene polymer (A-2) also has methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.80. When added together with the number of hydrolyzable silyl groups introduced to the molecular chain ends, the total number of hydrolyzable silyl groups introduced was 1.75.

[0194] (Synthesis Example 2-5) 1.1 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-2), and the methanol was removed by distillation at 130°C. Subsequently, 1.3 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl group to a metharyl group. Furthermore, 0.4 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl group of (E-2), and the methanol was removed by distillation at 130°C. Subsequently, 0.8 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual impurities such as metal salts, 100 parts by weight of the resulting methallyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of methallyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defoliation was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer (C-3) containing only the terminal components and having methyldimethoxysilyl groups at the end of the molecular chain, with a number-average molecular weight of 15,000. The polyoxypropylene polymer (C-3) did not have hydrolyzable silyl groups at any site other than the molecular chain ends, and the "number of hydrolyzable silyl groups introduced to the molecular chain ends" and the "total number of hydrolyzable silyl groups introduced" were both 0.95.

[0195] (Synthesis Example 2-6) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-2), 1.0 equivalent of a methanol solution of sodium methoxide was added and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an allyl group, and then 1.5 equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl group to an allyl group. After that, 0.4 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of (E-2) and the methanol was removed by distillation at 130°C, and then 0.8 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual metal salts and other impurities, 100 parts by weight of the obtained allyl-terminated polyoxypropylene mixture was mixed with 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol at 3% by mass in terms of platinum) and 3.4 parts by weight of methyldimethoxysilane. The mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (C-4) containing only the terminal components, having methyldimethoxysilyl groups at the end of the molecular chain, and having a number-average molecular weight of 15,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer (C-4) was 0.75. In addition, the polyoxypropylene polymer (C-4) also had methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.75. When these are added together, the total number of hydrolyzable silyl groups introduced was 1.50.

[0196] (Synthesis Example 3-1) 1.1 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-3), and the methanol was removed by distillation at 130°C. Subsequently, 1.3 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl group to a metharyl group. Furthermore, 0.4 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl group of (E-3), and the methanol was removed by distillation at 130°C. Subsequently, 0.8 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual impurities such as metal salts, 100 parts by weight of the resulting methallyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total number of methallyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defloration was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer (B-1) with a number-average molecular weight of 8,000, having a methyldimethoxysilyl group at only one end of the molecular chain. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer (B-1) was 0.95.

[0197] (Synthesis Example 3-2) A methanol solution of sodium methoxide in 1.2 equivalents was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-3), and the methanol was removed by distillation at 130°C. Subsequently, 1.5 equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl group to an allyl group. After removing residual metal salts and other impurities, 100 parts by weight of the obtained allyl-terminated polyoxypropylene mixture was mixed with 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol at 3% by mass in terms of platinum) and 1.8 parts by weight of methyldimethoxysilane. The mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (B-2) having a methyldimethoxysilyl group at only one end of the molecular chain and a number-average molecular weight of 8,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer (B-2) was 0.78.

[0198] (Synthesis Example 3-3) To the hydroxyl group of the aforementioned hydroxyl-terminated polyoxypropylene (E-3), a methanol solution of sodium methoxide was added, and the methanol was removed by distillation at 140°C. Subsequently, 0.8 equivalents of allyl glycidyl ether were added at 140°C and reacted for 2 hours to introduce an allyl group, and then 1.5 equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl group to an allyl group. After removing residual metal salts and other impurities, 100 parts by weight of the obtained allyl-terminated polyoxypropylene mixture was mixed with 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol at 3% by mass in terms of platinum) and 2.8 parts by weight of methyldimethoxysilane. The mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (B-3) having a methyldimethoxysilyl group at only one end of the molecular chain and a number-average molecular weight of 8,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of polyoxypropylene polymer (B-3) was 0.70. In addition, polyoxypropylene polymer (B-3) also has methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.60. When added together with the number of hydrolyzable silyl groups introduced to the molecular chain ends, the total number of hydrolyzable silyl groups introduced was 1.30.

[0199] (Synthesis Example 3-4) A methanol solution of sodium methoxide in 1.2 equivalents was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-4), and the methanol was removed by distillation at 130°C. Subsequently, 1.5 equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl group to an allyl group. After removing residual metal salts and other impurities, 100 parts by weight of the obtained allyl-terminated polyoxypropylene mixture was mixed with 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol at 3% by mass in terms of platinum) and 5.8 parts by weight of methyldimethoxysilane. The mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (B-4) having a methyldimethoxysilyl group at only one end of the molecular chain and a number-average molecular weight of 2,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer (B-4) was 0.78.

[0200] (Synthesis Examples 3-5) 1.1 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-4), and the methanol was removed by distillation at 130°C. Subsequently, 1.3 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl group to a metharyl group. Furthermore, 0.3 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl group of (E-4), and the methanol was removed by distillation at 130°C. Subsequently, 0.6 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl group to an allyl group. After removing residual impurities such as metal salts, 100 parts by weight of the resulting methallyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total number of methallyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defoliation was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer (B-5) with a number-average molecular weight of 2,000, having a methyldimethoxysilyl group at only one end of the molecular chain. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer (B-5) was 0.95.

[0201] (Synthesis Example 4-1) The hydroxyl-terminated polyoxypropylenes (E-5) and (E-4) were mixed in a weight ratio of approximately 6 / 4. 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this (E-5) and (E-4) mixture, and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce allyl groups. Then, 1.2 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl groups to metharyl groups. Furthermore, 0.3 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl groups of the (E-5) and (E-4) mixture, and the methanol was removed by distillation at 130°C. Subsequently, 0.6 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl groups to allyl groups. After removing residual impurities such as metal salts, 100 parts by weight of the resulting metharyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of metharyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defloration was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer mixture (AB-1) containing both terminal components and one terminal component, with methyldimethoxysilyl groups at both or one of the molecular chain ends, and having a number-average molecular weight of 4,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer mixture (AB-1) was 0.95. Furthermore, the polyoxypropylene polymer mixture (AB-1) also possessed methyldimethoxysilyl groups at locations other than the molecular chain ends, with a total of 0.80 groups per molecular chain end. Adding these to the number of hydrolyzable silyl groups introduced to the molecular chain ends, the total number of hydrolyzable silyl groups introduced was 1.75. The weight ratio of both-end components to one-end component in the polyoxypropylene polymer mixture (AB-1) was approximately 6 / 4. The number-average molecular weights of the both-end components and one-end component, estimated from the peak tops and chromatogram shapes in GPC, were 10,000 and 2,000, respectively. The number-average molecular weights of the both-end components and one-end component in the polymer mixture described below were similarly estimated from the peak tops and chromatogram shapes in GPC.

[0202] The polyoxypropylene polymer mixture (AB-1) contains both polyoxyalkylene polymer (A) and polyoxyalkylene polymer (B). Although each polymer in this polymer mixture could be referred to as polymer (A) and polymer (B), for convenience, since they are manufactured simultaneously, the mixture of both polymers is referred to as (AB-1). Furthermore, since the polyoxyalkylene polymers (A) and (B) in the polyoxypropylene polymer mixture (AB-1) undergo terminal modification simultaneously, the number of hydrolyzable silyl groups introduced to the molecular chain ends of polymers (A) and (B) can be considered the same, and the total number of hydrolyzable silyl groups introduced to polymers (A) and (B) can also be considered the same. The same applies to the polymer mixtures (AB-2), (AB-3), (CB-1), and (CB-2) shown below.

[0203] (Synthesis Example 4-2) Except for using 0.5 equivalents of allyl glycidyl ether, the procedure was the same as in Synthesis Example 4-1 to obtain a polyoxypropylene polymer mixture (AB-2) having a number average molecular weight of 4,000, containing both terminal components and one terminal component, and having a methyldimethoxysilyl group at both or one of the molecular chain ends. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer mixture (AB-2) was 0.95. In addition, the polyoxypropylene polymer mixture (AB-2) also had methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.40. When added together with the number of hydrolyzable silyl groups introduced to the molecular chain ends, the total number of hydrolyzable silyl groups introduced was 1.35. Furthermore, the weight ratio of both-end components to one-end component in the polyoxypropylene polymer mixture (AB-2) was approximately 6 / 4, and the number-average molecular weights of both-end components and one-end component were 10,000 and 2,000, respectively.

[0204] (Synthesis Example 4-3) The hydroxyl-terminated polyoxypropylenes (E-5) and (E-4) were mixed in a weight ratio of approximately 6 / 4. 1.1 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl groups of this (E-5) and (E-4) mixture, and the methanol was removed by distillation at 130°C. Subsequently, 1.3 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl groups to metharyl groups. Furthermore, 0.3 equivalents of a methanol solution of sodium methoxide were added to the hydroxyl groups of the (E-5) and (E-4) mixture, and the methanol was removed by distillation at 130°C. Subsequently, 0.6 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl groups to allyl groups. After removing residual impurities such as metal salts, 100 parts by weight of the resulting metharyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of metharyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defloration was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer mixture (CB-1) containing both terminal components and one terminal component, with methyldimethoxysilyl groups at both or one of the molecular chain ends, and having a number-average molecular weight of 4,000. The polyoxypropylene polymer mixture (CB-1) did not have hydrolyzable silyl groups at any sites other than the molecular chain ends. The "number of hydrolyzable silyl groups introduced to the molecular chain ends" and the "total number of hydrolyzable silyl groups introduced" were both 0.95. Furthermore, the weight ratio of both-end components to one-end component in the polyoxypropylene polymer mixture (CB-1) was approximately 6 / 4, and the number-average molecular weights of the two-end components and one-end component were 10,000 and 2,000, respectively.

[0205] (Synthesis Example 4-4) The hydroxyl-terminated polyoxypropylenes (E-1) and (E-3) were mixed in a weight ratio of approximately 6 / 4. 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this (E-1) and (E-3) mixture, and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce allyl groups, and then 1.3 equivalents of metharyl chloride were added at 130°C to convert the terminal hydroxyl groups to metharyl groups. Furthermore, 0.3 equivalents of a methanol solution of sodium methoxide was added to the hydroxyl groups of the (E-1) and (E-3) mixture, and the methanol was removed by distillation at 130°C, and then 0.6 equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl groups to allyl groups. After removing residual impurities such as metal salts, 100 parts by weight of the resulting metharyl / allyl-terminated polyoxypropylene mixture was mixed with 100 ppm platinum divinyldisiloxane complex (3% by mass in isopropyl alcohol solution based on platinum), 1000 ppm 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane relative to the total amount of metharyl / allyl groups. The mixture was reacted at 100°C for 5 hours. Subsequently, defoliation was performed under reduced pressure to remove excess methyldimethoxysilane, yielding a polyoxypropylene polymer mixture (AB-3) containing both terminal components and one terminal component, with methyldimethoxysilyl groups at both or one of the molecular chain ends, and having a number-average molecular weight of 15,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer mixture (AB-3) was 0.95. In addition, the polyoxypropylene polymer mixture (AB-3) also had methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.80. When added together with the number of hydrolyzable silyl groups introduced to the molecular chain ends, the total number of hydrolyzable silyl groups introduced was 1.75. Furthermore, the weight ratio of both-end components to one-end component in the polyoxypropylene polymer mixture (AB-3) was approximately 6 / 4, and the number-average molecular weights of both-end components and one-end component were 28,000 and 8,500, respectively.

[0206] (Synthesis Examples 4-5) The hydroxyl-terminated polyoxypropylenes (E-1) and (E-3) were mixed in a weight ratio of approximately 6 / 4. 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this (E-1) and (E-3) mixture, and the methanol was removed by distillation at 140°C. Subsequently, 1.2 equivalents of allyl glycidyl ether were added at 140°C and reacted for 2 hours to introduce allyl groups, and then 1.5 equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl groups to allyl groups. After removing residual impurities such as metal salts, 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol at 3% by mass in terms of platinum) and 2.2 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene mixture, and the mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer mixture (CB-2) containing both terminal components and one terminal component, with a methyldimethoxysilyl group at both or one of the molecular chain ends, and having a number average molecular weight of 15,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends of the polyoxypropylene polymer mixture (CB-2) was 0.75. In addition, the polyoxypropylene polymer mixture (CB-2) also had methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number of these groups per molecular chain end was 0.90. When added together with the number of hydrolyzable silyl groups introduced to the molecular chain ends, the total number of hydrolyzable silyl groups introduced was 1.65. Furthermore, the weight ratio of both-end components to one-end component in the polyoxypropylene polymer mixture (CB-2) was approximately 6 / 4, and the number-average molecular weights of both-end components and one-end component were 28,000 and 8,500, respectively.

[0207] (Examples 1-13 and Comparative Examples 1-22) The following evaluations were performed using each polymer or polymer mixture produced in each synthesis example.

[0208] <Method for evaluating the physical properties of a composition> The following additives—plasticizer, filler, titanium dioxide, anti-sagging agent, light stabilizer, and UV absorber—were thoroughly mixed and kneaded, then dispersed by passing through three paint rolls. After this, dehydration was performed under reduced pressure at 120°C for 2 hours using a planetary mixer, and after cooling to below 50°C, a dehydrating agent was added and the mixture was kneaded in a state where virtually no moisture was present. After degassing under reduced pressure, the mixture was sealed in a moisture-proof container, a cartridge, to obtain the masterbatch composition. Subsequently, each polymer or polymer mixture, an adhesion promoter, and a silanol condensation catalyst were added to the masterbatch composition and thoroughly mixed. The mixture was then uniformly kneaded and defoamed using a rotary-orbit mixer to prepare each curable composition. Using each of the prepared curable compositions, various test specimens were prepared under a constant temperature and humidity atmosphere of 23°C and 50% relative humidity, and various evaluations were performed.

[0209] (Various additives used in the evaluation of the composition's physical properties) In evaluating the properties of the compositions in all examples and comparative examples, the following additives were used. The amounts are given in parts by weight relative to 100 parts by weight of each polymer or polymer mixture that is the base polymer. Plasticizer: Diisononyl phthalate (DINP, manufactured by J-Plus Co., Ltd.), 90 parts by weight Filler: (i) Fatty acid treated precipitated calcium carbonate (Hakutsuka CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 160 parts by weight (ii) Heavy calcium carbonate (Whiten SB Red, manufactured by Shiraishi Calcium Co., Ltd.), 54 parts by weight Titanium dioxide: Typeque R-820, manufactured by Ishihara Sangyo Co., Ltd., 5 parts by weight Drip prevention agent: Fatty acid amide wax (Disparon #6500, Kusumoto Kasei Co., Ltd.), 2 parts by weight Light stabilizer: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770, manufactured by BASF), 1 part by weight UV absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (Tinuvin 326, manufactured by BASF), 1 part by weight Dehydrating agent: Vinyltrimethoxysilane (A-171, manufactured by Momentive Co., Ltd.), 2 parts by weight Adhesion-enhancing agent: 3-(N-2-aminoethylamino)propyltrimethoxysilane (A-1120, manufactured by Momentive Co., Ltd.), 3 parts by weight Silanol condensation catalyst: Dibutyltin bis(acetacetate) (U-220H, manufactured by Nitto Kasei Co., Ltd.), 2 parts by weight

[0210] (Dumbbell properties) The curable composition was filled into a 3 mm thick sheet-like mold at 23°C and 50% relative humidity. After curing for 3 days at 23°C and 50% relative humidity, it was cured in a 50°C dryer for 4 days to obtain a sheet-like cured material. The obtained cured material was punched out into a No. 3 dumbbell shape to obtain test specimens according to JIS K 6251. Using the obtained test specimens, a tensile test (tensile speed 200 mm / min) was performed using an autograph at 23°C and 50% relative humidity, and the stress at 100% elongation and the stress at fracture were measured.

[0211] (Resilience) The aforementioned sheet-like cured material was punched out into a No. 7 dumbbell shape to obtain a dumbbell-shaped test specimen. Two gauge marks were drawn at 10 mm intervals around the constricted portion of the dumbbell-shaped test specimen. The dumbbell-shaped test specimen was stretched and fixed in place so that the distance between the gauge marks was 20 mm, and left to stand in a drying oven at 50°C. After 24 hours, the fixation was released, and the recovery rate was determined by measuring the distance between the gauge marks after 24 hours at 23°C and 50% relative humidity. The results obtained from the above are shown in Tables 1 to 4.

[0212] [Table 1]

[0213] Table 1 shows the evaluation results for polymers (A-1), (C-1), or (C-2) synthesized using polymer (E-1), and the evaluation results for polymers (A-2), (C-3), or (C-4) synthesized using polymer (E-2). Each polymer contains only the terminal components. Polymers (A-1) and (A-2) satisfy the requirements of "number of hydrolyzable silyl groups introduced to the molecular chain ends" and "total number of hydrolyzable silyl groups introduced." Polymers (C-1) and (C-3) do not satisfy the requirement of "total number of hydrolyzable silyl groups introduced," and polymers (C-2) and (C-4) do not satisfy the requirement of "number of hydrolyzable silyl groups introduced to the molecular chain ends." Example 1, using polymer (A-1), showed a similar fracture stress but a higher recovery rate compared to Comparative Examples 1 and 2, which used polymers (C-1) or (C-2). The same result was observed when comparing Example 2, using polymer (A-2), with Comparative Examples 3 and 4, which used polymers (C-1) and (C-2).

[0214] [Table 2-1]

[0215] [Table 2-2]

[0216] Tables 2-1 and 2-2 show the evaluation results when polymers (A-1), (C-1), or (C-2) of both terminal components synthesized using polymer (E-1) are mixed with any of the polymers (B-1) to (B-4) of one terminal component. Example 3, in which polymer (B-1) was mixed with polymer (A-1), which satisfies the requirements of "number of hydrolyzable silyl groups introduced to the molecular chain ends" and "total number of hydrolyzable silyl groups introduced," showed better results in both fracture stress and recovery rate compared to Comparative Examples 5 and 6, in which polymer (B-1) was mixed with polymer (C-1) or (C-2), which did not satisfy either requirement. Furthermore, focusing on the rate of decrease in each physical property due to the mixing of each polymer (B), it can be seen that Example 3, which uses a mixture of polymer (A-1) and polymer (B-1), shows a small decrease in fracture stress and resilience compared to Example 1, which uses polymer (A-1) alone. On the other hand, Comparative Examples 5 or 6, which use a mixture of polymer (C-1) or (C-2) and polymer (B-1), show a large decrease in fracture stress and resilience compared to Comparative Example 1 or Comparative Example 2, which uses polymer (C-1) or (C-2) alone. The same applies to the comparison between Example 4 and Comparative Examples 7 and 8, between Example 5 and Comparative Examples 9 and 10, between Example 6 and Comparative Examples 11 and 12, and between Example 7 and Comparative Examples 13 and 14. Similar results are obtained even when the mixing ratio of polymer (A) and polymer (B) is changed, but when comparing Example 5 and Example 6, Example 5, in which polymer (B) has a smaller mixing ratio, yields better results.

[0217] [Table 3] Table 3 shows the evaluation results when one of the polymers (B-1), (B-2), or (B-5) of the single-ended component is mixed with polymers (A-2), (C-3), or (C-4) of both terminal components synthesized using polymer (E-2). Similar to Tables 2-1 and 2-2, the example in which each polymer (B) was mixed with polyoxyalkylene polymer (A-2) that satisfies the requirements of "number of hydrolyzable silyl groups introduced to the molecular chain ends" and "total number of hydrolyzable silyl groups introduced" showed better results in terms of fracture stress and recovery rate compared to the comparative example in which each polymer (B) was mixed with polymers (C-3) or (C-4) that did not satisfy either requirement. Furthermore, focusing on the rate of decrease in each physical property, it can be seen that the examples using polymer (A-2) and mixtures of each polymer (B) show smaller rates of decrease in fracture stress and recovery rate compared to Example 2, which uses polymer (A-2) alone.

[0218] [Table 4]

[0219] Table 4 shows the evaluation results of polymer mixtures synthesized using polymer (E), which is a mixture of both terminal components and one terminal component. Examples 11 and 12, which used polymer mixtures (AB-1) and polymer (AB-2) containing both terminal components that satisfy the requirements of "number of hydrolyzable silyl groups introduced to the molecular chain ends" and "total number of hydrolyzable silyl groups introduced," showed better results in both fracture stress and recovery rate compared to Comparative Example 21, which used polymer mixture (CB-1) in which the included terminal components did not satisfy the requirement of "total number of hydrolyzable silyl groups introduced." Furthermore, Example 13, which used a polymer mixture (AB-3) containing terminal components that satisfy the requirements of "number of hydrolyzable silyl groups introduced to the molecular chain ends" and "total number of hydrolyzable silyl groups introduced," showed better results in both fracture stress and recovery rate compared to Comparative Example 22, which used a polymer mixture (CB-2) in which the contained terminal components did not satisfy the requirement of "number of hydrolyzable silyl groups introduced to the molecular chain ends."

[0220] From the above results, it can be seen that polyoxyalkylene polymers that satisfy the requirements of "number of hydrolyzable silyl groups introduced to the molecular chain ends" and "total number of hydrolyzable silyl groups introduced" can be suitably used as base polymers for various elastic materials that require good fracture stress and recovery rate after curing, despite having low viscosity.

Claims

1. A polyoxyalkylene polymer having a hydrolyzable silyl group, The hydrolyzable silyl group is defined by general formula (1): -SiR ａ X ３－ａ (1) (In the formula, R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group, either identical or different. a represents 0, 1, or 2.) The polyoxyalkylene polymer has one or more molecular chain ends containing a hydrolyzable silyl group or a reactive group into which a hydrolyzable silyl group can be introduced, The average ratio of the number of hydrolyzable silyl groups located at the ends of the molecular chain to the number of molecular chain ends is 0.85 or more and 1.00 or less. A polyoxyalkylene polymer in which the average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain ends is 1.01 or more.

2. The polyoxyalkylene polymer according to claim 1, wherein the polyoxyalkylene polymer has a linear polymer skeleton.

3. The polyoxyalkylene polymer according to claim 1 or 2, wherein the number average molecular weight of the polyoxyalkylene polymer is 9,000 or more.

4. The polyoxyalkylene polymer is the polyoxyalkylene polymer according to any one of claims 1 to 3, having a structure represented by the following general formula (2). 【Chemistry 1】 (In the formula, R １ R represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. ２ R represents hydrogen or an alkyl group having 1 to 6 carbon atoms. ３ R represents a direct bond or a divalent bonding group having 1 to 6 carbon atoms. ４ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. R, X, and a are the same as those described above for general formula (1).

5. The polyoxyalkylene polymer according to any one of claims 1 to 4, wherein the polyoxyalkylene polymer has two or more molecular chain ends in one molecule.

6. Both are mixtures of polyoxyalkylene polymers (A) and (B) having hydrolyzable silyl groups, The polyoxyalkylene polymer (A) is the polyoxyalkylene polymer described in claim 5, The polyoxyalkylene polymer (B) has one hydrolyzable silyl group or a molecular chain terminal containing a reactive group to which a hydrolyzable silyl group can be introduced in each molecule. The hydrolyzable silyl group in the polyoxyalkylene polymer (B) is represented by the general formula (1), The number-average molecular weight of the polyoxyalkylene polymer (B) is smaller than the number-average molecular weight of the polyoxyalkylene polymer (A), A mixture in which the mixing ratio of the polyoxyalkylene polymers (A) and (B) is 95:5 to 30:70 by weight.

7. The mixture according to claim 6, wherein a in the general formula (1) represents 1.

8. The mixture according to claim 6 or 7, wherein the number average molecular weight of the polyoxyalkylene polymer (B) is 10,000 or less.

9. The mixture according to any one of claims 6 to 8, wherein the polyoxyalkylene polymer (B) is the polyoxyalkylene polymer according to any one of claims 1 to 4.

10. A curable composition containing a polyoxyalkylene polymer according to any one of claims 1 to 5, or a mixture according to any one of claims 6 to 9.

11. A cured product of the curable composition according to claim 10.

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