Mixtures of polyoxyalkylene polymers and curable compositions

Abstract

Provided is a mixture of polyoxyalkylene-based polymers (A) and (B), both of which have a hydrolyzable silyl group. The polymer (A) has, per molecule, two or more molecular chain terminals containing a hydrolyzable silyl group or a reactive group able to introduce said silyl group. The average ratio of the number of silyl groups positioned at a molecular chain terminal relative to the number of molecular chain terminals in the polymer (A) is 0.85-1.00. The number average molecular weight of the polymer (A) is 25,000 or less. The silyl group in the polymer (A) is represented by the formula SiR1X1 2. R1 is a hydrocarbon group. X1 is a hydroxyl group or a hydrolyzable group. The polymer (B) has one molecular chain terminal containing a hydrolyzable silyl group or a reactive group able to introduce said silyl group per molecule. The number average molecular weight of the polymer (B) is less than that of the polymer (A).

Description

Technical Field

[0001] The present invention relates to a mixture of polyoxyalkylene polymers having a hydrolyzable silyl group, and a curable composition containing the mixture.

Background Art

[0002] Polymers having a hydrolyzable silyl group are known as moisture-reactive polymers and are included in many industrial products such as adhesives, sealants, coating agents, paints, adhesives, etc., and are used in a wide range of fields.

[0003] As the main chain skeleton of such polymers, polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth)acrylate ester polymers, etc. are known. In particular, polyoxyalkylene polymers having a hydrolyzable silyl group (for example, see Patent Document 1) are relatively low-viscosity at room temperature and easy to handle, and the cured product obtained after the reaction also exhibits good elasticity. Therefore, its scope of application is wide.

[0004] On the other hand, in the recent construction market, there is a demand for a sealing material that is less likely to cause bleed-out. For this reason, in a curable composition for a sealing material containing a polyoxyalkylene polymer having a hydrolyzable silyl group, instead of using a conventional phthalate plasticizer or PPG plasticizer, a method of blending a reactive diluent having a hydrolyzable silyl group introduced therein has been studied (for example, see Patent Documents 2 and 3).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

[0006] When a reactive diluent containing the aforementioned hydrolyzable silyl group is incorporated 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 (e.g., tear strength and elongation) tended to decrease along with the decrease in viscosity.

[0007] In view of the above situation, the present invention aims to provide a mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers that have low viscosity and 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 it is possible to provide a mixture of polyoxyalkylene polymers containing hydrolyzable silyl groups that exhibits low viscosity before curing but good mechanical properties after curing, by using a specific ratio of polymer (A) which may have hydrolyzable silyl groups at both ends and polymer (B) which may have hydrolyzable silyl groups at only one end, controlling the rate of introduction of hydrolyzable silyl groups to the molecular chain ends of polymer (A) within a specific range, using hydrolyzable silyl groups with a specific structure for polymer (A), and further controlling the number-average molecular weight of polymers (A) and (B), thereby providing a mixture of polyoxyalkylene polymers containing hydrolyzable silyl groups that exhibits low viscosity before curing but good mechanical properties after curing, leading to the present invention.

[0009] That is, the present invention is a mixture of polyoxyalkylene polymers (A) and (B) each having a hydrolyzable silyl group, wherein the polyoxyalkylene polymer (A) has two or more molecular chain ends containing a hydrolyzable silyl group or a reactive group into which a hydrolyzable silyl group can be introduced in one molecule, and the average ratio of the number of the hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer (A) to the number of the molecular chain ends of the polyoxyalkylene polymer (A) is 0.85 or more and 1.00 or less, the number average molecular weight of the polyoxyalkylene polymer (A) is 25,000 or less, and the hydrolyzable silyl group of the polyoxyalkylene polymer (A) is represented by the general formula (1): -SiR X 1 2(1) (In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X 1 represents, the same or different, a hydroxyl group or a hydrolyzable group.) The polyoxyalkylene polymer (B) has one molecular chain end containing a hydrolyzable silyl group or a reactive group into which a hydrolyzable silyl group can be introduced in one molecule, the number average molecular weight of the polyoxyalkylene polymer (B) is smaller than the number average molecular weight of the polyoxyalkylene polymer (A), and the hydrolyzable silyl group of the polyoxyalkylene polymer (B) is represented by the general formula (1'): -SiR 2 a X 2 3-a (1') (In the formula, R 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X 2 represents, the same or different, a hydroxyl group or a hydrolyzable group. a represents 0, 1 or 2. However, the hydrolyzable silyl group of the polyoxyalkylene polymer (B) may be the same as or different from the hydrolyzable silyl group of the polyoxyalkylene polymer (A).) The present invention relates to a mixture in which the mixing ratio of the polyoxyalkylene polymer (A):(B) is 95:5 to 30:70 by weight. Preferably, the polyoxyalkylene polymer (A) has a linear polymer backbone. Preferably, the viscosity of the mixture at 23°C is less than 15 Pa.s. Preferably, a in the general formula (1') represents 1. Preferably, the number-average molecular weight of the polyoxyalkylene polymer (B) is 10,000 or less. Preferably, the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer (B) to the number of molecular chain ends of the polyoxyalkylene polymer (B) is 0.50 or more and 1.00 or less. The present invention also relates to a curable composition containing the above mixture, or a cured product of the curable composition. Furthermore, the present invention relates to a method for producing the aforementioned mixture, comprising the steps of: polymerizing an epoxy compound in the presence of a mixture of an initiator having two or more hydroxyl groups in one molecule and an initiator having one hydroxyl group in one molecule to form a mixture of polyoxyalkylene polymers having hydroxyl groups at the molecular chain ends; and introducing hydrolyzable silyl groups at the molecular chain ends of the polyoxyalkylene polymer. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a mixture of hydrolyzable silyl group-containing polyoxyalkylene polymers that have low viscosity and 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 will be described in detail below. (A mixture of polyoxyalkylene polymers (A) and (B)) 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.

[0012] Polyoxyalkylene polymers (A) and (B) each have a polyoxyalkylene polymer backbone and molecular chain ends bonded to the polymer backbone. The polymer backbone and the molecular chain ends may be directly bonded or indirectly bonded via an intermediate structure. Examples of the intermediate structure include structures derived from the epoxy compound (G3) described later (i.e., the n structures in parentheses in formula (4) described later).

[0013] The polymer skeleton refers to the polymer main chain composed of oxyalkylene repeating units. The polymer skeletons of polyoxyalkylene polymers (A) and (B) may be linear or branched. A linear polymer skeleton is preferred in that the cured product of the curable composition has high elongation, while 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 the 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.

[0014] 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.

[0015] 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.

[0016] 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).

[0017] Polyoxyalkylene polymers (A) refer to polymers that have two or more hydrolyzable silyl groups or reactive groups capable of introducing hydrolyzable silyl groups at the end of their molecular chains in a single molecule. When a polyoxyalkylene polymer (A) has a linear polymer backbone, there are two molecular chain ends, and both of these molecular chain ends contain either 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 hydrolyzable silyl groups, (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 reactive groups to which a hydrolyzable silyl group can be introduced are all considered polyoxyalkylene polymers (A).

[0018] Such polyoxyalkylene polymers (A) can be produced, for example, by polymerizing an epoxy compound in the presence of an initiator having two hydroxyl groups per 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 polyoxyalkylene 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 polyoxyalkylene 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 polyoxyalkylene polymer (A) is preferably a polymer having a linear polymer skeleton. However, a polymer having a branched polymer skeleton may be used as the polyoxyalkylene polymer (A), or a polymer having a linear polymer skeleton and a polymer having a branched polymer skeleton may be used in combination.

[0021] On the other hand, polyoxyalkylene polymers (B) refer to those that have 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 polyoxyalkylene polymers (B) have a linear polymer skeleton, (iv) polymer molecules 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) polymer molecules 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 polyoxyalkylene polymers (B).

[0022] Such polyoxyalkylene polymers (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 initiator-derived structures result in unreactive molecular chain ends that do not contain either a hydrolyzable silyl group or the aforementioned reactive group.

[0023] The polyoxyalkylene polymer (A) 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 (A) to the total number of molecular chain ends of the polyoxyalkylene polymer (A) (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. By using a polyoxyalkylene polymer (A) with a high number of hydrolyzable silyl groups introduced to the molecular chain ends in this way in combination with a polyoxyalkylene polymer (B) that has one hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group at the molecular chain end per molecule, the mixture according to this embodiment can exhibit good mechanical properties after curing, while having low viscosity.

[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 (A).

[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 polyoxyalkylene polymer (A) / number of molecular chain ends of polyoxyalkylene polymer (A)], which can also be rephrased as the average ratio of the number of molecular chain ends of polyoxyalkylene polymer (A) containing hydrolyzable silyl groups to the total number of molecular chain ends of polyoxyalkylene polymer (A). The "number of molecular chain ends of polyoxyalkylene polymer (A)" 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 can be between 2 and 3. In addition, "hydrolyzable silyl groups located at the molecular chain ends of polyoxyalkylene polymer (A)" is a concept that excludes the hydrolyzable silyl groups contained in the intermediate structure mentioned above.

[0026] In the polyoxyalkylene polymer (A), 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, since it is easier to manufacture.

[0027] On the other hand, 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 of the polyoxyalkylene polymer (B) to the number of molecular chain ends of the polyoxyalkylene polymer (B) that contain hydrolyzable silyl groups or reactive groups to which hydrolyzable silyl groups can be introduced 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 preferably 0.99 or less, and 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.

[0028] The hydrolyzable silyl group of the polyoxyalkylene polymer (A) is represented by the following general formula (1). The presence of such a specific hydrolyzable silyl group in component (A) allows for improved mechanical properties of the resulting cured product. -SiR 1 X 1 2(1)

[0029] Furthermore, the hydrolyzable silyl group of the polyoxyalkylene polymer (B) is represented by the following general formula (1'). -SiR2 a X 2 3-a (1')

[0030] R 1 and R 2 Each of these represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 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.

[0031] R 1 and R 2 Examples 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, it 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. 1 For this purpose, only one type of group may be used, or two or more types of groups may be used in combination. 2 However, only one type of group may be used, or two or more types of groups may be used in combination. 1 and R 2 They may be the same or they may be different.

[0032] X 1 and X 2 Each of these represents either a hydroxyl group or a hydrolyzable group. 1 and X2 Examples of such groups include hydroxyl groups, hydrogen, halogens, alkoxy groups, acyloxy groups, ketoximate 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. 1 For this purpose, only one type of group may be used, or two or more types of groups may be used in combination. 2 However, only one type of group may be used, or two or more types of groups may be used in combination. 1 and X 2 They may be the same or they may be different.

[0033] 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. Furthermore, the hydrolyzable silyl group represented by general formula (1') may be the same as or different from the hydrolyzable silyl group represented by general formula (1).

[0034] Examples of hydrolyzable silyl groups represented by general formula (1) include 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, (chloromethyl)dimethoxysilyl group and (methoxymethyl)dimethoxysilyl group are more preferred. From the viewpoint of stability, methyldimethoxysilyl group and methyldiethoxysilyl group are more preferred. Furthermore, methyldimethoxysilyl group is more preferred because it is easy to manufacture.

[0035] 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.

[0036] The molecular chain ends of polyoxyalkylene polymer (A) that contain hydrolyzable silyl groups are not particularly limited, but a typical example is the molecular chain end represented by the following general formula (3). Furthermore, a typical example of a molecular chain end of polyoxyalkylene polymer (B) that contains hydrolyzable silyl groups is the -SiR in the following general formula (3). 1 X 1 2 is the general formula (1'):-SiR 2 a X 2 3-a Examples of replacements include:

[0037] -OR 3 -CH(R 4 )-CH2-SiR 1 X 1 2(3) In the formula, R 3 R represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. 4 R represents hydrogen or an alkyl group having 1 to 6 carbon atoms. The oxygen at the far left indicates the oxygen in the oxyalkylene unit located at the end of the polymer backbone. 1 , and X 1 This is the same as what was described above for the general formula (1).

[0038] R 3 Preferably, the hydrocarbon group has 1 to 3 carbon atoms, and more preferably, a hydrocarbon group has 1 to 2 carbon atoms. The hydrocarbon group is preferably an alkylene group, and methylene, ethylene, propylene, or butylene groups can be used. Methylene is particularly preferred.

[0039] R 4 Preferably, the alkyl group is hydrogen or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include hydrogen, methyl group, ethyl group, propyl group, and butyl group. 4As 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 4 For example, hydrogen and an alkyl group having 1 to 4 carbon atoms may coexist.

[0040] The molecular chain ends represented by the general formula (3) are preferably directly bonded to the polymer backbone of the polyoxyalkylene polymer (A), but as mentioned above, they may be indirectly bonded via an intermediate structure. The intermediate structure may contain hydrolyzable silyl groups. When the polyoxyalkylene polymer (A) contains an intermediate structure containing hydrolyzable silyl groups, the molecular chain ends containing hydrolyzable silyl groups and the intermediate structure containing hydrolyzable silyl groups can be represented, for example, by the following general formula (4). Furthermore, the molecular chain ends containing hydrolyzable silyl groups and the intermediate structure containing hydrolyzable silyl groups of the polyoxyalkylene polymer (B) can be represented, for example, by the -SiR in the following general formula (4). 1 X 1 2 is the general formula (1'):-SiR 2 a X 2 3-a It can be represented by replacing it with...

[0041] [ka]

[0042] In general formula (4), -R 3 -CH(R 4 )-CH2-SiR 1 X 1 The part represented by 2 corresponds to the molecular chain end containing a hydrolyzable silyl group, and the n structures in parentheses correspond to intermediate structures. Furthermore, the "hydrolyzable silyl group located at the molecular chain end" is -R 3 -CH(R 4 )-CH2-SiR 1 X 1This refers only to the hydrolyzable silyl groups contained in the region represented by 2. Hydrolyzable silyl groups contained in the intermediate structure are not located at the end of the molecular chain and are not considered hydrolyzable silyl groups located at the end of the molecular chain. Furthermore, the hydrolyzable silyl groups located at the end of the molecular chain and the hydrolyzable silyl groups contained in the intermediate structure may be the same or different.

[0043] R 5 R is a direct bond or a divalent bond group having 1 to 6 carbon atoms. 6 R is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. The oxygen at the far left indicates oxygen in an oxyalkylene unit located at the end of a polymer backbone composed of multiple linked oxyalkylene units. 1 , R 3 , R 4 , and X 1 The same applies to the general formulas (1) and (3) described above.

[0044] R 5 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-.

[0045] R 6 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.

[0046] The number-average molecular weight of the polyoxyalkylene polymer (A) is 25,000 or less in terms of polystyrene-based molecular weight as measured by GPC. Having a number-average molecular weight of 25,000 or less for component (A) allows for good mechanical properties of the resulting cured product. Preferably, it is 22,000 or less, and more preferably 16,000 or less. The lower limit of the number-average molecular weight of component (A) is not particularly limited, but may be, for example, 3,000 or more, preferably 5,000 or more, and more preferably 7,000 or more. This number-average molecular weight can be determined in terms of polystyrene-based molecular weight by GPC measurement.

[0047] 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 this 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.

[0048] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymers (A) and (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, 1.2 or less is preferred. 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] The ratio of polyoxyalkylene polymers (A):(B) in the mixture according to this embodiment is 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 preferably 90:10 to 40:60, and more preferably 80:20 to 50:50.

[0050] The mixture according to this embodiment is low viscosity, and specifically, it is preferable that the viscosity measured at 23°C is less than 15 Pa.s. More preferably, it is 10 Pa.s or less, and even more preferably, 5 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).

[0051] <Method for producing polyoxyalkylene polymer (A) or (B), or a mixture of polymers (A) and (B)> Next, a method for producing polyoxyalkylene polymers (A) or (B), or a method for producing a mixture of polymers (A) and (B), will be described. To produce the mixture, polyoxyalkylene polymers (A) and (B) may be synthesized individually and then mixed, or polyoxyalkylene polymers (A) and (B) may be synthesized simultaneously in a single system.

[0052] Polyoxyalkylene polymers (A) or (B), or a mixture of polymers (A) and (B) when polyoxyalkylene polymers (A) and (B) are synthesized simultaneously in a single system, can all be produced by introducing a carbon-carbon unsaturated bond to a hydroxyl-terminated polyoxyalkylene polymer (E) using the reactivity of hydroxyl groups, and then introducing a hydrolyzable silyl group-containing compound that is reactive with the carbon-carbon unsaturated bond by reacting it with the polymer.

[0053] The following describes in detail one embodiment of a method for producing a polyoxyalkylene polymer (A) or (B), or a mixture of polymers (A) and (B). However, the method for producing a polyoxyalkylene polymer (A) or (B), or a mixture of polymers (A) and (B), is not limited to the description below.

[0054] (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).

[0055] 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.

[0056] 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.

[0057] Furthermore, examples of initiators having one hydroxyl group and one carbon-carbon unsaturated bond include allyl alcohol and low molecular weight polyoxypropylene monoallyl ether. These initiators can enable the synthesis of component (A). For example, when introducing a hydrolyzable silyl group by a hydrosilylation reaction between the hydrosilane compound (I), described later, and the carbon-carbon unsaturated bond, the aforementioned initiator can be used to synthesize component (A).

[0058] 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. After this, 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 polymers (A) and (B) in a single system.

[0059] Furthermore, if only initiators having two or more hydroxyl groups are used as initiators containing hydroxyl groups, polymer (A) can be synthesized, and if only initiators having one hydroxyl group are used, polymer (B) can be synthesized.

[0060] The epoxy compound is not particularly limited, but examples include alkylene oxides such as ethylene oxide and propylene oxide. Propylene oxide is preferred.

[0061] (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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] (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.

[0067] 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) and introduce a carbon-carbon unsaturated bond into the polyoxyalkylene polymer. Examples include organic halides having a carbon-carbon double bond (G1), organic halides having a carbon-carbon triple bond (G2), and epoxy compounds having a carbon-carbon double bond (G3).

[0068] An organic halide (G1) having a carbon-carbon double bond, which is one embodiment of the electrophile (E), can react with the metaloxy group by 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 (G1) having a carbon-carbon double bond is not limited to the following general formula (5): ZR 3 -C(R 4 )=CH2(5) It can be expressed as follows: In the formula, R 3 and R 4 These are the R values ​​mentioned above for general formula (3), respectively. 3 and R 4It is the same group as above. Z represents a halogen atom. When a polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the molecular chain end is obtained by reacting the organic halide (G1), a hydrolyzable silyl group, which will be explained later, can be introduced to it, the molecular chain end represented by the general formula (3) can be formed.

[0069] Specific examples of the organic halide (G1) represented by the general formula (5) above are not particularly limited, but include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred 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.

[0070] Another embodiment of the electrophile (E), an organic halide (G2) having a carbon-carbon triple bond, can react with the metaloxy group by 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. The organic halide (G2) having a carbon-carbon triple bond is not limited to the following general formula (6): ZR 7 -C≡CR 8 (6) It can be expressed as follows: In the formula, R 7 R represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. 7 As a concrete example, consider the R mentioned above for general formula (3). 3 The same group can be cited. R 8 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. 8 Hydrogen is particularly preferred as the halogen atom. Z represents a halogen atom.

[0071] Specific examples of the organic halogen (G2) represented by the general formula (6) are not particularly limited, but include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentine, 1,4-dichloro-2-butyne, 5-chloro-1-pentine, 6-chloro-1-hexine, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1 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.

[0072] There are no particular restrictions on the amount of organic halide (G1) having a carbon-carbon double bond or organic halide (G2) having a carbon-carbon triple bond added. However, the molar ratio of organic halide (G1) or (G2) to the 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.

[0073] The temperature at which a metaloxy-terminated polyoxyalkylene polymer (F) is reacted with an organic halide having a carbon-carbon double bond (G1) or an organic halide having a carbon-carbon triple bond (G2) is preferably 50°C to 150°C. When reacting with an organic halide having a carbon-carbon double bond (G1), a temperature of 110°C to 140°C is more preferable, while when reacting with an organic halide having a carbon-carbon triple bond (G2), a temperature of 50°C to 80°C is more preferable. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0074] Furthermore, both an organic halide having a carbon-carbon double bond (G1) and an organic halide having a carbon-carbon triple bond (G2) may be reacted with a metaloxy group-terminated polyoxyalkylene polymer (F). In this case, the organic halide having a carbon-carbon double bond (G1) and the organic halide having a carbon-carbon triple bond (G2) 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.

[0075] An epoxy compound (G3) having a carbon-carbon double bond, which is yet another embodiment of the electrophile (G), can react with the metaloxy group by 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 the polyoxyalkylene polymer. In the ring-opening addition reaction, by adjusting the amount of epoxy compound (G3) used relative to the metaloxy group and the reaction conditions, one or more epoxy compounds (G3) can be added to a single metaloxy group. After the addition of the epoxy compound (G3), if a hydrolyzable silyl group is introduced, the structure derived from the epoxy compound (G3) becomes an intermediate structure containing the aforementioned hydrolyzable silyl group.

[0076] Epoxy compounds (G3) having a carbon-carbon double bond are not limited to the following, but include those with the general formula (6):

[0077] [ka]

[0078] It can be expressed as follows: In the formula, R 5 and R 6 These are the R values ​​mentioned above for general formula (4), respectively. 5 and R 6 It is the same base as [the other].

[0079] Specific examples of epoxy compounds having a carbon-carbon double bond (G3) 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.

[0080] The amount of epoxy compound (G3) 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 (G3) 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.

[0081] The reaction temperature when a ring-opening addition reaction is carried out with a metaloxy-terminated polyoxyalkylene polymer (F) and an epoxy compound (G3) having a carbon-carbon double bond is preferably 60°C to 150°C, and more preferably 110°C to 140°C.

[0082] As described above, when an epoxy compound (G3) having a carbon-carbon double bond is reacted with a metal-oxy group-terminated polyoxyalkylene polymer (F), a new metal-oxy group is generated by ring-opening of the epoxy group. Therefore, after reacting with the epoxy compound (G3), the aforementioned organic halide (G1) having a carbon-carbon double bond can be reacted consecutively. This allows for the introduction of a carbon-carbon double bond to the molecular chain ends of the polyoxyalkylene polymer.

[0083] The same compound as described above can be used as the organic halide (G1) having a carbon-carbon double bond in this embodiment, and the amount used and the reaction temperature are also the same as described above. This method is preferable because it can increase the amount of carbon-carbon double bond and hydrolyzable silyl group introduced into the polymer. When a polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the molecular chain terminus is obtained by a method using an epoxy compound (G3) and an organic halide (G1), the structure represented by the general formula (4) can be formed by introducing a hydrolyzable silyl group, as described below. In this case, the structure in which the hydrolyzable silyl group is introduced from the epoxy compound (G3) corresponds to the intermediate structure described above, and the structure in which the hydrolyzable silyl group is introduced from the organic halide (G1) corresponds to the molecular chain terminus. The hydrolyzable silyl group contained in the structure derived from the epoxy compound (G3), i.e., the intermediate structure, does not correspond to the hydrolyzable silyl group located at the dispersed chain terminus, as described above. The hydrolyzable silyl group contained in the structure derived from the organic halide (G1) corresponds to the hydrolyzable silyl group located at the dispersed chain terminus.

[0084] 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.

[0085] (Introduction of hydrolyzable silyl groups) By subjecting the polyoxyalkylene polymer (H) having carbon-carbon unsaturated bonds at the molecular chain ends 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 makes it possible to produce polyoxyalkylene polymers (A) or (B) having hydrolyzable silyl groups, or a mixture of polymers (A) and (B). The hydrosilylation reaction has the advantages of being easy to carry out, allowing for easy adjustment of the amount of hydrolyzable silyl groups introduced, and resulting in polymers with stable physical properties.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] Examples of orthocarboxylic acid trialkyl esters include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Trimethyl orthoformate and trimethyl orthoacetate are preferred.

[0094] 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 polyoxyalkylene polymer (A) or (B), or the total of polymers (A) and (B).

[0095] Another method for producing polyoxyalkylene polymer (A) 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 produces polyoxyalkylene polymer (A) or (B) having a hydrolyzable silyl group, or a mixture of polymers (A) and (B).

[0096] 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.

[0097] The amount of compound (J) having hydrolyzable silyl groups and isocyanate groups in one molecule can be appropriately determined considering the amount of hydroxyl groups in the polyoxyalkylene polymer (E) and the desired number of hydrolyzable silyl groups to be introduced to the molecular chain ends. If unreacted compound (J) remains after the reaction, the excess compound (J) may be removed after the urethane reaction by treatment such as vacuum defloration, converted into other compounds by reacting with active hydrogen group-containing compounds, or left in the produced polyoxyalkylene polymer. Compound (J) or its derivatives remaining in the produced polyoxyalkylene polymer can act as silane coupling agents.

[0098] The urethane reaction may be carried out without a urethane catalyst, but it may also be carried out in the presence of a urethane catalyst to improve the reaction rate or reaction efficiency. Such urethane catalysts include, for example, those listed in *Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963*, and other conventionally known urethane catalysts. Specifically, examples include, but are not limited to, organotin compounds, bismuth compounds, and base catalysts such as organic amines.

[0099] Among known urethane catalysts, those with high activity include tin octylate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl malate, dibutyltin dibutyl malate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyldistanoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis(o-phenylphenoxide), and dibutyltin. Organotin compounds such as tin oxide, dibutyltinbis(triethoxysilicate), dibutyltin distearate, dibutyltinbis(isononyl-3-mercaptopropionate), dibutyltinbis(isooctyl mercaptopropionate), dibutyltinbis(isooctyl thioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin diversate are preferred. Furthermore, catalysts with low activity towards hydrolyzable silyl groups are preferred, and from this viewpoint, tin catalysts containing sulfur atoms, such as dibutyltinbis(isononyl-3-mercaptopropionate), dibutyltinbis(isooctyl mercaptopropionate), and dibutyltinbis(isooctyl thioglycolate), are particularly preferred.

[0100] The amount of urethane catalyst added can be appropriately determined by those skilled in the art, but from the viewpoint of reaction activity, 1 to 1000 ppm and more preferably 10 to 100 ppm per 100 parts by weight of polyoxyalkylene polymer (E) is preferred. Within this range, in addition to obtaining sufficient reaction activity, the physical properties of the produced polyoxyalkylene polymer, such as heat resistance, weather resistance, hydrolysis resistance, and storage stability, can be well maintained.

[0101] The urethane reaction can be carried out without the use of a solvent, but an organic solvent may be added to ensure uniform dissolution of the polyoxyalkylene polymer (E), compound (J), and urethane catalyst, and to facilitate temperature control of the reaction system and addition of the urethane catalyst.

[0102] The temperature for the urethane formation reaction can be set appropriately by those skilled in the art, but it is preferably between 50°C and 120°C, and more preferably between 70°C and 100°C. 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 between 15 minutes and 5 hours, and more preferably between 30 minutes and 3 hours.

[0103] As yet another method for producing polyoxyalkylene polymers (A), 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 can also produce polyoxyalkylene polymers (A) or (B) having a hydrolyzable silyl group, or a mixture of polymers (A) and (B).

[0104] 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.

[0105] The amount of compound (K) having hydrolyzable silyl groups and mercaptan groups in one molecule should be appropriately determined considering the amount of carbon-carbon double bonds in the polyoxyalkylene polymer (H) and the desired number of hydrolyzable silyl groups to be introduced to the molecular chain ends. If unreacted compound (K) remains after the reaction, the excess compound (K) may be removed after the addition reaction by treatment such as vacuum defloration, converted into another compound by reacting with an unsaturated group-containing compound, or left in the produced polyoxyalkylene polymer. Compound (K), or its derivatives, remaining in the produced polyoxyalkylene polymer can act as a silane coupling agent.

[0106] The addition reaction of a mercaptan group to a carbon-carbon double bond may be carried out without the use of a radical initiator, but it may also be carried out in the presence of a radical initiator to improve the reaction rate or reaction rate. Conventional known radical initiators can be used. Specifically, azo initiators and peroxide initiators are examples, but are not limited to these.

[0107] Among known radical initiators, catalysts with low activity towards hydrolyzable silyl groups are preferred, and from this viewpoint, azo-based initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitride) (V-40) are particularly preferred.

[0108] The amount of radical initiator added can be appropriately determined by those skilled in the art, but from the viewpoint of reaction activity, 0.01 to 10 parts by weight, and more preferably 0.1 to 3 parts by weight, is preferred per 100 parts by weight of polyoxyalkylene polymer (H). The radical initiator may also be used in a state dissolved in an organic solvent.

[0109] The temperature of the addition reaction can be set appropriately by those skilled in the art, but it is preferably 50°C to 120°C, and more preferably 70°C to 100°C. 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 15 minutes to 10 hours, and more preferably 30 minutes to 6 hours.

[0110] <Curable composition> According to this embodiment, a curable composition comprising a mixture of the polyoxyalkylene polymers (A) and (B) can be provided.

[0111] (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 polymers (A) and (B), i.e., the curing reaction.

[0112] Conventional silanol condensation catalysts can be used, specifically organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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).

[0118] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0119] 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.

[0120] Regarding the amount of silanol condensation catalyst to be added, from the viewpoint of achieving both improved condensation reaction rate and workability during curing, it is preferable to add 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 mixture of polyoxyalkylene polymers (A) and (B) according to this 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 0.01 to 3.0 parts by weight of silanol condensation catalyst, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0121] ((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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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).

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.)

[0134] 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.

[0135] 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 mixture of polyoxyalkylene polymers (A) and (B) and (meth)acrylic acid ester polymer (D) according to this embodiment can also be blended by a similar method, but is not limited to these.

[0136] The ratio of the mixture of polyoxyalkylene polymers (A) and (B) to the (meth)acrylic acid ester polymer (D) according to this embodiment 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 the mixture of polyoxyalkylene polymers (A) and (B) and the (meth)acrylic acid ester polymer (D) may be used individually or in combination of two or more.

[0137] (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.

[0138] <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.

[0139] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0140] 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.

[0141] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0142] <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.

[0143] 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.

[0144] The amount of adhesion promoter 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 mixture of polyoxyalkylene polymers (A) and (B).

[0145] <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.

[0146] 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.

[0147] 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 mixture of polyoxyalkylene polymers (A) and (B). The plasticizer may be used alone or in combination of two or more types.

[0148] <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.

[0149] <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.

[0150] The amount of anti-slip agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the mixture of polyoxyalkylene polymers (A) and (B).

[0151] <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.

[0152] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0153] <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.

[0154] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0155] <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).

[0156] The amount of UV 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 mixture of polyoxyalkylene polymers (A) and (B).

[0157] <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.

[0158] 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.

[0159] The amount of 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 mixture of polyoxyalkylene polymers (A) and (B).

[0160] <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.

[0161] 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.

[0162] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0163] <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 mixture of polyoxyalkylene polymers (A) and (B).

[0164] <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.

[0165] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0166] <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.

[0167] 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 mixture of polyoxyalkylene polymers (A) and (B). As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0168] <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.

[0169] The ratio of these epoxy resins to the mixture of polyoxyalkylene polymers (A) and (B) is preferably in the range of polyoxyalkylene polymer mixture (A) and (B) / epoxy resin = 100 / 1 to 1 / 100 by weight.

[0170] 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.

[0171] 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.

[0172] <<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.

[0173] 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.

[0174] 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 mixture of polyoxyalkylene polymers (A) and (B).

[0175] <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.

[0176] 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]

[0177] 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. If both-ended components meet certain requirements, they may qualify as polyoxyalkylene polymers (A). If one-ended components meet certain requirements, they may qualify as polyoxyalkylene polymers (B).

[0178] 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℃

[0179] Viscosity is measured at 23°C using an E-type viscometer (Tokyo Keiki RE-85U, measuring cone: 3° × R14).

[0180] Furthermore, a linear polyoxypropylenediol (commercial product) with a number-average molecular weight of approximately 4,500 and hydroxyl groups at both ends is defined as "polymer (E-1)". Furthermore, a linear polyoxypropylenediol (commercial product) with a number-average molecular weight of approximately 3,000 and hydroxyl groups at both ends is defined as "polymer (E-2)".

[0181] (Synthesis Example 1-1) Polymer (E-1) was used as an initiator, and propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-3) containing only the terminal components and having a number average molecular weight of approximately 15,000.

[0182] (Synthesis Example 1-2) Polymerization of propylene oxide was carried out using polymer (E-1) and n-butanol as initiators, with a zinc hexacyanocobaltate grime complex catalyst, to obtain a hydroxyl-terminated polyoxypropylene mixture (E-4) containing both terminal components and one terminal component, with a number average molecular weight of approximately 11,000. The weight ratio of both terminal components to one terminal component in the polyoxypropylene mixture (E-4) was approximately 7 / 3. Furthermore, the number average molecular weights of the both terminal components and the one terminal component, respectively, estimated from the peak tops and chromatogram shapes in GPC were 15,000 and 8,000, respectively. The number average molecular weights of the both terminal components and the one terminal component in the polymer mixture described below were similarly estimated from the peak tops and chromatogram shapes in GPC.

[0183] (Synthesis Examples 1-3 to 1-9) According to the instructions in Table 1-1, polymer (E-1) and / or n-butanol were used as initiators, and the same procedure as in Synthesis Example 1-1 or Synthesis Example 1-2 was followed to obtain hydroxyl-terminated polyoxypropylene or hydroxyl-terminated polyoxypropylene mixtures (E-5) to (E-11). The initiators used and the properties of the obtained polymers (E) are shown in Table 1-1.

[0184] [Table 1-1]

[0185] (Synthesis Example 2-1) 1.1 equivalents of a methanol solution of sodium methoxide (SM) was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-3), and the methanol was removed by distillation at 130°C. Subsequently, 1.3 equivalents of 3-chloro-2-methyl-1-propene (metharyl chloride: MAC) 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 (SM) was added to the hydroxyl group of (E-3), and the methanol was removed by distillation at 130°C. Subsequently, 0.6 equivalents of 3-chloro-1-propene (allyl chloride: ACL) 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 (DMS) relative to the total of the metharyl and allyl groups. The mixture was reacted at 100°C for 5 hours. By removing the excess methyldimethoxysilane by vacuum defoliation, a polyoxypropylene polymer (A-1) with a number-average molecular weight of 15,000 was obtained, containing only the terminal components and having methyldimethoxysilyl groups at the ends. The number of hydrolyzable silyl groups introduced to the molecular chain ends in polyoxypropylene polymer (A-1) was 0.95.

[0186] (Synthesis Examples 2-2 to 2-8) Using each polymer (E) listed in Table 1-2, polyoxypropylene polymers (A-3), (A-4), (B-1), (B-5), (C-9), or polyoxypropylene polymer mixtures (AB-1), (AB-2) were obtained by following the same procedure as in Synthesis Example 2-1. The polymers (E) used and the properties of each polymer or polymer mixture obtained are shown in Table 1-2. In Synthesis Example 2-5, polymer (E) was a mixture of polymer (E-3) and polymer (E-7) in a weight ratio of 7:3. Polyoxypropylene polymer mixtures (AB-1) and (AB-2) each contain both polyoxyalkylene polymer (A) and polyoxyalkylene polymer (B). While each polymer in these mixtures could be referred to separately as polymer (A) and polymer (B), for convenience, the mixture of both polymers is referred to as (AB-1), etc., since they are manufactured simultaneously. Furthermore, since polyoxyalkylene polymers (A) and (B) in polyoxypropylene polymer mixture (AB-1) undergo simultaneous terminal modification, the number of hydrolyzable silyl groups introduced to the molecular chain ends of polymers (A) and (B) can be considered identical. The same applies to polymer mixture (AB-2) and the polymer mixtures (CB-1) and (CB-2) described later.

[0187] [Table 1-2]

[0188] (Synthesis Example 3-1) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-7), a methanol solution of 1.2 equivalents of sodium methoxide (SM) was added, and the methanol was removed by distillation at 130°C. Subsequently, 1.5 equivalents of 3-chloro-1-propene (allyl chloride: ACL) were added at 130°C to convert the terminal hydroxyl group to an allyl group. After removing any remaining 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 1.8 parts by weight of methyldimethoxysilane (DMS) were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (B-2) having a methyldimethoxysilyl group at the end and containing only one terminal component, with a number-average molecular weight of 8,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends in polyoxypropylene polymer (B-2) was 0.78.

[0189] (Synthesis Example 3-2) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-7), a methanol solution of sodium methoxide (SM) was added, and the methanol was removed by distillation at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether (AGE) was added at 140°C and reacted for 2 hours to introduce an unsaturated bond, and then 1.5 equivalents of 3-chloro-1-propene (allyl chloride: ACL) were added at 130°C to convert the terminal hydroxyl group to an allyl group. After removing any remaining 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 3.4 parts by weight of methyldimethoxysilane (DMS) were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (B-3) having a methyldimethoxysilyl group at the end and containing only one terminal component, with 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-3) was 0.75. Furthermore, polyoxypropylene polymer (B-3) also had methyldimethoxysilyl groups introduced at sites other than the molecular chain ends, with a total of 0.75 such groups per molecular chain end. When this is added to the number of hydrolyzable silyl groups introduced at the molecular chain ends, the average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain ends was 1.50.

[0190] (Synthesis examples 3-3 to 3-12) Using each polymer (E) and other raw materials as described in Table 1-3, polyoxypropylene polymers (B-6), (C-1) to (C-8), or polyoxypropylene polymer mixture (CB-1) were obtained by following the same procedure as in Synthesis Example 3-1 (without AGE) or Synthesis Example 3-2 (with AGE). The polymers (E) and other raw materials used, as well as the physical properties of each obtained polymer or polymer mixture, are shown in Table 1-3.

[0191] [Table 1-3]

[0192] (Synthesis Example 4-1) To the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-3), 1.2 equivalents of a methanol solution of sodium methoxide were added, and the methanol was removed by distillation at 130°C. Subsequently, 1.5 equivalents of 3-chloro-1-propene (allyl chloride) were added at 130°C to convert the terminal hydroxyl group to an allyl group. After removing any remaining impurities such as metal salts, 6.7 parts by weight of (3-mercaptopropyl)methyldimethoxysilane and 0.1 parts by weight of 2,2'-azobis(2-methylbutyronitrile) were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the temperature was raised to 90°C. After 1 hour, 2 hours, and 3 hours, 0.1 parts by weight of 2,2'-azobis(2-methylbutyronitrile) were added again, and the reaction was continued for 4 hours. By removing excess (3-mercaptopropyl)methyldimethoxysilane and other components through vacuum defoliation, a polyoxypropylene polymer (A-2) with a number-average molecular weight of 16,000, containing only the terminal components and having methyldimethoxysilyl groups at its termini, was obtained. The number of hydrolyzable silyl groups introduced to the molecular chain termini in polyoxypropylene polymer (A-2) was 0.98.

[0193] (Synthesis Example 5-1) To 100 parts by weight of the hydroxyl-terminated polyoxypropylene polymer (E-3), 50 ppm of a mercaptotin-based catalyst (U-360, manufactured by Nitto Chemical Co., Ltd.) and 4.0 parts by weight of 3-isocyanate-propyltrimethoxysilane (Silquest A-Link 35: IPTMS, manufactured by Momentive Co., Ltd.) were added and reacted at 90°C for 2 hours to obtain a polyoxypropylene polymer (C-10) having trimethoxysilyl groups at the ends and containing only the terminal components, with a number-average molecular weight of 17,000. The number of hydrolyzable silyl groups introduced to the molecular chain ends in the polyoxypropylene polymer (C-10) was 0.90.

[0194] (Synthesis examples 5-2 to 5-5) Using each polymer (E) and IPTMS as described in Table 1-4, and following the same procedure as in Synthesis Example 5-1, polyoxypropylene polymers (C-11), (B-4), (B-7), or polyoxypropylene polymer mixture (CB-2) were obtained. The polymers (E) and IPTMS used, as well as the properties of each obtained polymer or polymer mixture, are shown in Table 1-4.

[0195] [Table 1-4]

[0196] (Examples 1-16, Comparative Examples 1-19, and Reference Examples 1-6) The following evaluations were performed using each polymer or polymer mixture produced in each synthesis example.

[0197] <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.

[0198] 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.

[0199] (Various additives used in the evaluation of the composition's physical properties) In evaluating the properties of the compositions in all examples, comparative examples, and reference 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: Use only (ii) if it contains polymer C-10, C-11, or CB-2. Otherwise, use only (i). (i) Dibutyltin bis(acetate) (U-220H, manufactured by Nitto Kasei Co., Ltd.), 2 parts by weight (ii) Dioctyl tin dilaurate (U-810, manufactured by Nitto Chemical Co., Ltd.), 0.2 parts by weight

[0200] (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, stress at fracture, and elongation at fracture were measured.

[0201] (Tearing 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 dumbbell shape (JIS Type A) for tear testing to obtain test specimens. Using the obtained test specimens, a tear test (tensile speed 200 mm / min) was performed using an autograph at 23°C and 50% relative humidity, and the stress at fracture was measured.

[0202] [Table 2-1]

[0203] Table 2-1 shows the evaluation results for examples of cured compositions with similar tensile stress. First, Example 1, Comparative Example 1, and Reference Example 1 compare the results of systems exhibiting relatively high tensile stress. Compared to the cured composition of Reference Example 1, which contains only polyoxyalkylene polymers with a small number of hydrolyzable silyl groups at the molecular chain ends, the cured composition of Example 1, which contains a mixture of polyoxyalkylene polymers (A) and (B) that satisfy the specified requirements, shows higher tear strength and elongation despite the lower viscosity of the polymer mixture used. Furthermore, compared to the cured composition of Comparative Example 1, which uses a polymer prepared to exhibit a viscosity similar to the polymer mixture of Example 1 by using a low molecular weight polymer, the cured composition of Example 1 shows significantly higher tear strength and elongation despite having a similar viscosity.

[0204] Next, we compared the results of systems exhibiting relatively low tensile stress in Example 2, Comparative Example 2, and Reference Example 2. These also show results equivalent to those of the comparison between Example 1, Comparative Example 1, and Reference Example 1.

[0205] [Table 2-2]

[0206] Table 2-2 summarizes the results of examples in which the structure of polymer (B) was mainly altered. It can be seen that the cured products of compositions in Examples 1 and 3-8, which used polymer mixtures with lower viscosity than the polymer used in Reference Example 1, exhibited higher tear strength and elongation at a similar viscosity compared to the cured product of the composition in Comparative Example 1, which contained only polyoxyalkylene polymers with a small number of hydrolyzable silyl groups introduced to the molecular chain ends.

[0207] Furthermore, as shown in Examples 9 and 10, it can be seen that the same results as in Example 1 are obtained when using polymer (E) which is a mixture of "both-ended components" and "one-ended components" (when polymer (AB-1) is synthesized using polymer (E-4)) or when using a mixture of polymer (E) with "both-ended components" and polymer (E) with "one-ended components" (when polymer (AB-2) is synthesized using a mixture of polymer (E-3) and polymer (E-7)).

[0208] Furthermore, as shown in Example 11, it can be seen that even when a polymer (A-2) in which hydrolyzable silyl groups are introduced in a different way than polymer (A-1) is used, the results are equivalent to those of Example 1.

[0209] [Table 2-3]

[0210] Table 2-3 summarizes the results of comparative examples in which polyoxyalkylene polymers with fewer than 0.85 hydrolyzable silyl groups at the molecular chain ends were used instead of polymer (A). Comparative Examples 3-9 have similar viscosity to Example 1, but at least their tear strength is inferior, indicating that they do not achieve both tear strength and elongation.

[0211] [Table 2-4]

[0212] Table 2-4 summarizes the results of comparative examples using polyoxyalkylene polymers of both terminal components instead of polymer (B) while maintaining a similar viscosity range, and the results of the corresponding examples. Comparative Example 10 has a similar viscosity to Example 1, but its elongation is significantly inferior, indicating that it does not achieve both tear strength and elongation. The same is true for Comparative Example 11 and Example 12, and for Comparative Example 12 and Example 13.

[0213] [Table 2-5]

[0214] Table 2-5 summarizes the results of examples and comparative examples using polymers or polymer mixtures in the low viscosity range. As with previous results, Example 13 shows both high tear strength and elongation compared to Comparative Examples 13-14, which exhibit similar viscosity. The same is true for Example 14 and Comparative Example 15.

[0215] [Table 2-6]

[0216] Table 2-6 shows the upper limit of the number average molecular weight of polymer (A). As shown in Example 1 and Comparative Example 3, or Example 15 and Comparative Example 4, it can be seen that polymer (A-1) or polymer (A-4) with a number average molecular weight of 25,000 or less, when used in combination with polymer (B-1), greatly improves the elongation of the cured product of the composition, and the tear strength becomes equal to or higher than before. On the other hand, as shown in Comparative Example 16 and Comparative Example 5, it can be seen that polymer (C-9) with a number average molecular weight exceeding 25,000, when used in combination with polymer (B-1), slightly improves the elongation of the cured product of the composition, but the tear strength significantly decreases.

[0217]

Table 2-7

[0218] Table 2-7 shows the structure of the hydrolyzable silyl group possessed by polymer (A). In Comparative Example 17 where a polyoxyalkylene polymer having both-terminal components with a hydrolyzable silyl group having 3 hydroxyl groups or hydrolyzable groups on the silyl group was used instead of polymer (A), it can be seen that compared with Example 1, the elongation and tear strength of the cured product of the composition significantly decreased. The same is true for Comparative Example 18 and Example 6, and Comparative Example 19 and Example 13.

[0219]

Table 2-8

[0220] Table 2-8 shows that the number of hydrolyzable silyl groups introduced to the molecular chain ends of polymer (A) is 0.85 or more. Compared to Reference Example 3, which uses polymer (A-1) alone, or Reference Example 6, which uses polymer (A-2) alone, Examples 1 and 6, which use polymer (A-1) and polymer (B) in combination, or Example 16, which uses polymer (A-2) and polymer (B) in combination, show a significant improvement in the elongation of the cured composition and a certain degree of improvement in tear strength. On the other hand, as shown in Reference Example 1 and Comparative Examples 7 and 9, or Comparative Examples 1 and 13, when polymer (C-2) or polymer (C-1), which has fewer than 0.85 hydrolyzable silyl groups introduced to the molecular chain ends instead of polymer (A), is used in combination with polymer (B), the elongation of the cured composition improves slightly, but the tear strength decreases significantly.

[0221] From the above results, it can be seen that a mixture of polyoxyalkylene polymers (A) and (B) that satisfies the aforementioned requirements has low viscosity, yet the cured product of a curable composition containing it exhibits high elongation and tear strength. Therefore, it can be suitably used as a base polymer for sealants and adhesives that require low viscosity and good mechanical properties after curing.

Claims

1. Both are mixtures of polyoxyalkylene polymers (A) and (B) having hydrolyzable silyl groups, The polyoxyalkylene polymer (A) has two or more molecular chain ends containing a hydrolyzable silyl group or a reactive group to which a hydrolyzable silyl group can be introduced, The average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer (A) to the number of molecular chain ends of the polyoxyalkylene polymer (A) is 0.90 or more and 1.00 or less. The number average molecular weight of the polyoxyalkylene polymer (A) is 25,000 or less. The hydrolyzable silyl group in the polyoxyalkylene polymer (A) is of general formula (1): -SiR １ X １ ２ (1) (In the formula, R １ X represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. １ These represent a hydroxyl group or a hydrolyzable group, either identical or different. 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 number-average molecular weight of the polyoxyalkylene polymer (B) is smaller than the number-average molecular weight of the polyoxyalkylene polymer (A), The hydrolyzable silyl group in the polyoxyalkylene polymer (B) is of general formula (1'): -SiR ２ ａ X ２ ３－ａ (1’) (In the formula, R ２ X represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. ２ represents a hydroxyl group or a hydrolyzable group, which may be the same or different. a represents 0, 1, or 2. However, the hydrolyzable silyl group of the polyoxyalkylene polymer (B) may be the same or different from the hydrolyzable silyl group 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.

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

3. The mixture according to claim 1 or 2, wherein the viscosity of the mixture at 23°C is less than 15 Pa·s.

4. The mixture according to any one of claims 1 to 3, wherein a in the general formula (1') represents 1.

5. The mixture according to any one of claims 1 to 4, wherein the number average molecular weight of the polyoxyalkylene polymer (B) is 10,000 or less.

6. The mixture according to any one of claims 1 to 5, wherein the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer (B) to the number of molecular chain ends of the polyoxyalkylene polymer (B) is 0.50 or more and 1.00 or less.

7. A curable composition containing the mixture described in any one of claims 1 to 6.

8. A cured product of the curable composition according to claim 7.

9. A method for producing the mixture according to any one of claims 1 to 6, A step of polymerizing an epoxy compound in the presence of a mixture of an initiator having two or more hydroxyl groups in one molecule and an initiator having one hydroxyl group in one molecule, thereby forming a mixture of polyoxyalkylene polymers having hydroxyl groups at the ends of the molecular chains, A method for producing the aforementioned polyoxyalkylene polymer, comprising the step of introducing a hydrolyzable silyl group to the molecular chain terminus.

Images