Polymer mixtures, curable compositions, and cured products thereof

Abstract

To provide a mixture containing a hydrolyzable silyl group-containing polyoxyalkylene polymer that achieves low viscosity while maintaining good mechanical properties after curing. [Solution] A polymer mixture comprising polyoxyalkylene polymers (A0), (A1), and (A2). Polymer (A0) does not have hydrolyzable silyl groups and has a number average molecular weight of 500 to 100,000; Polymer (A1) has a hydrolyzable silyl group at only one of the ends of the polymer skeleton and has a number average molecular weight of 3,000 to 25,000; Polymer (A2) has -OCH2CH2CH2SiR at least two ends of the polymer skeleton 1 3-a X a It has a hydrolyzable silyl group-containing structure represented by , with an average number of hydrolyzable silyl groups per terminal cell of 0.90 or more, and a number-average molecular weight of 3,000 to 100,000.

Description

[Technical Field]

[0001] The present invention relates to a polymer mixture containing a polyoxyalkylene polymer having a hydrolyzable silyl group, a curable composition, and a cured product thereof. [Background technology]

[0002] Organic polymers having silicon groups (hereinafter also referred to as "hydrolyzable silyl groups") on which a hydroxyl group or hydrolyzable group is located on a silicon atom and which can form siloxane bonds through hydrolysis and condensation reactions are known to yield a rubbery cured product when cured in the presence of water.

[0003] Among these organic polymers, polyoxyalkylene polymers having hydrolyzable silyl groups are widely used in applications such as sealants and adhesives because they offer a good balance of performance characteristics in terms of mechanical properties, weather resistance, and dynamic durability of the cured product (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 52-73998 [Overview of the project] [Problems that the invention aims to solve]

[0005] Hydrolyzable silyl group-containing polyoxyalkylene polymers are required to have low viscosity before curing in order to facilitate handling, such as application to the target object. To date, known methods for reducing the viscosity of hydrolyzable silyl group-containing polyoxyalkylene polymers include adding plasticizers and reducing the molecular weight of the polymer. However, generally speaking, reducing the viscosity of hydrolyzable silyl group-containing polyoxyalkylene polymers tended to result in a corresponding decrease in their mechanical properties after curing.

[0006] In view of the above situation, the present invention aims to provide a mixture containing a hydrolyzable silyl group-containing polyoxyalkylene polymer that can achieve low viscosity while maintaining good mechanical properties after curing. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that by mixing a polyoxyalkylene polymer having a hydrolyzable silyl group at two or more terminals of its polymer backbone and a large number of hydrolyzable silyl groups per terminal with a polyoxyalkylene polymer having a hydrolyzable silyl group at one terminal and a predetermined number-average molecular weight, it is possible to achieve both low viscosity before curing and good mechanical properties after curing, and thus completed the present invention.

[0008] In other words, the present invention relates to a polymer mixture comprising polyoxyalkylene polymers (A0), (A1), and (A2), Polyoxyalkylene polymers (A0) do not have hydrolyzable silyl groups and have a number-average molecular weight of 500 to 100,000. Polyoxyalkylene polymer (A1) has a hydrolyzable silyl group at only one terminal of the polymer backbone, and its number average molecular weight is between 3,000 and 25,000. The polyoxyalkylene polymer (A2) has at least two terminals of the polymer backbone that are part of the following general formula (2): -OCH2CH2CH2SiR 1 3-a X a (2) (In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1Alternatively, when there are a plurality of Xs, they may be the same or different. It relates to a polymer mixture having a hydrolyzable silyl group-containing structure represented by (), wherein the average number of the hydrolyzable silyl groups per terminal is 0.90 or more, and the number average molecular weight is 3,000 or more and 100,000 or less. The present invention also relates to the polymer mixture, a curable composition containing a silanol condensation catalyst, and a cured product obtained by curing the curable composition.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a mixture containing a hydrolyzable silyl group-containing polyoxyalkylene polymer, which can achieve a low viscosity while having good mechanical properties after curing. Further, according to the present invention, by changing the blending ratio of the three types of polymers, it is possible to adjust the mechanical properties after curing. Conventionally, in a hydrolyzable silyl group-containing polyoxyalkylene polymer, it has been necessary to synthesize a large number of varieties according to the desired mechanical properties. However, according to the present invention, by synthesizing three types of polymers in advance and blending them by changing their blending ratios, various mechanical properties can be realized. Therefore, it is possible to reduce the labor of synthesizing a large number of varieties.

Modes for Carrying Out the Invention

[0010] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below, and various modifications are possible within the scope defined by the claims. Also, each configuration described below can be arbitrarily combined, and such a combination can also be an aspect of the present invention. The polymer mixture according to this embodiment contains three types of polyoxyalkylene polymers (A0), (A1), and (A2). The polymer mixture according to this embodiment substantially refers to those containing only polyoxyalkylene polymers (A0), (A1), and (A2). Since the polyoxyalkylene polymers (A1) and (A2) each have a hydrolyzable silyl group, the polymer mixture exhibits curability based on the hydrolysis and dehydration condensation reactions of the hydrolyzable silyl group. Hereinafter, each polymer will be described in order.

[0011] [Polymer (A2)] Polymer (A2) is a polyoxyalkylene polymer having a hydrolyzable silyl group. The hydrolyzable silyl group can be represented by the following general formula (1). -SiR 1 3-a X a (1) In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. When there are a plurality of R 1 or X, they may be the same or different from each other.

[0012] R in the general formula (1) 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. When the general formula (1) contains a plurality of R 1 , they may be the same as or different from each other. The hydrocarbon group may be either saturated or unsaturated, and may be any of aliphatic, alicyclic, or aromatic. The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogeno groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups.

[0013] R 1Examples of substituted alkyl groups include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, toluyl, and 1-naphthyl; and aralkyl groups such as benzyl. Preferably, the alkyl group is substituted or unsubstituted, more preferably methyl, ethyl, chloromethyl, or methoxymethyl, even more preferably methyl or methoxymethyl, and particularly preferably methyl.

[0014] In general formula (1), X represents a hydroxyl group or a hydrolyzable group. If general formula (1) contains multiple Xs, they may be the same or different from each other. The hydrolyzable group is not particularly limited and may be any known hydrolyzable group, such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, or an alkenyloxy group. Among these, alkoxy groups, acyloxy groups, ketoximate groups, and alkenyloxy groups are preferred. Because they are mildly hydrolyzable and easy to handle, alkoxy groups are more preferred, methoxy groups and ethoxy groups are even more preferred, and methoxy groups are particularly preferred.

[0015] In general formula (1), a represents one of 1, 2, or 3. From the viewpoint of curability, 2 or 3 is preferred.

[0016] Specific examples of hydrolyzable silyl groups represented by general formula (1) include, but are not limited to, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl 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, dimethoxymethylsilyl group, trimethoxysilyl group, triethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are preferred because they yield cured products with good mechanical properties. From the viewpoint of activity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferred, and trimethoxysilyl group and (methoxymethyl)dimethoxysilyl group are particularly preferred. From the viewpoint of stability, dimethoxymethylsilyl group and triethoxysilyl group are more preferred, and dimethoxymethylsilyl group is particularly preferred.

[0017] Polymer (A2) has hydrolyzable silyl groups as a hydrolyzable silyl group-containing structure represented by the following general formula (2). This hydrolyzable silyl group-containing structure contains a hydrolyzable silyl group represented by the general formula (1). -OCH2CH2CH2SiR 1 3-a X a (2) In the formula, R 1 X and a are the same as those described above for general formula (1).

[0018] In general formula (2), the divalent group sandwiched between the oxygen atom and the silicon atom represents a C3 trimethylene group. Because the silicon atom is bonded to an unsubstituted trimethylene group, there is little steric hindrance that would hinder the condensation reaction, and the polymer (A2) can exhibit good curability. Furthermore, since the trimethylene group does not have an unsaturated bond, it has good stability. This trimethylene group can be formed by a hydrosilylation reaction with an allyl group, as will be described later.

[0019] In general formula (2), the leftmost oxygen atom is bonded to the polymer backbone of the polyoxyalkylene polymer.

[0020] Polymer (A2) has the hydrolyzable silyl group-containing structure at at least two ends of the polymer backbone. The average number of hydrolyzable silyl groups per end is 0.90 or more. The high average number of hydrolyzable silyl groups introduced per end in polymer (A2), which is 0.90 or more, improves the crosslinking density when the polymer mixture according to this embodiment is cured, resulting in high strength after curing. The average number is preferably 0.93 or more, more preferably 0.95 or more, and even more preferably 0.97 or more. There is no particular upper limit, and it may be 1.0 or less.

[0021] The method for calculating the average number of hydrolyzable silyl groups per terminal of the polymer skeleton is not particularly limited and can rely on known methods. For example, the average number of hydrolyzable silyl groups per terminal can be calculated as the ratio of the number of hydrolyzable silyl groups to the total number of hydrolyzable silyl groups, 1-propenyl groups, propyl groups, and allyl groups.

[0022] Polymer (A2) can be produced by hydrosilylation of a polyoxyalkylene polymer having an allyl group at its terminus with a hydrosilane compound. In such a hydrosilylation reaction, a 1-propenyl group may be formed by isomerization of the allyl group, or a propyl group may be formed by hydrogenation of the allyl group. In some cases, the allyl group may remain unreacted. As a result, the resulting polymer may have at least one of the following groups in addition to hydrolyzable silyl groups: 1-propenyl groups, propyl groups, and allyl groups. In polymer (A2), the formation of these 1-propenyl groups, propyl groups, and allyl groups is suppressed, and the average number of hydrolyzable silyl groups per terminus is high.

[0023] The ratio of the number of hydrolyzable silyl groups to the total number of hydrolyzable silyl groups, 1-propenyl groups, propyl groups, and allyl groups is: 1 By 1H NMR, it can be determined based on the integrated signal value corresponding to each group. For example, a polyoxyalkylene polymer having a hydrolyzable silyl group is dissolved in deuterated chloroform, 1 When 1H NMR measurements are performed, the peaks of hydrolyzable silyl groups, 1-propenyl groups, propyl groups, and allyl groups can be clearly distinguished. For example, as an example of a hydrolyzable silyl group-containing structure represented by general formula (2), the 3-(dimethoxymethylsilyl)propyloxy group shows a peak originating from two protons around 0.6 ppm. The 1-propenyl group shows multiple peaks originating from one proton around 5.9-6.3 ppm. The propyl group shows a peak originating from three protons around 0.9 ppm. The allyl group shows two peaks originating from two protons around 5.1-5.3 ppm. The aforementioned proportions can be determined based on the integral values ​​of these peaks.

[0024] Since polymer (A2) has an average of 0.90 or more hydrolyzable silyl groups per terminal, it may include polymer molecules having hydrolyzable silyl groups at each terminal of the polymer skeleton, polymer molecules having a hydrolyzable silyl group at one terminal of the polymer skeleton and a 1-propenyl group, a propyl group, or an allyl group at the other terminal, and polymer molecules having a group selected from the group consisting of 1-propenyl groups, propyl groups, and allyl groups at each terminal of the polymer skeleton.

[0025] In polymer (A2), the average number of hydrolyzable silyl groups per polymer molecule is not particularly limited as long as it satisfies the average number of hydrolyzable silyl groups per terminal as described above. When polymer (A2) has a linear polymer skeleton, there are 2 terminals per polymer molecule, so the average number of hydrolyzable silyl groups per polymer molecule is 1.80 or more. The average number is preferably 1.86 or more, more preferably 1.90 or more, and even more preferably 1.94 or more.

[0026] In polymer (A2), there is no particular upper limit to the average number of hydrolyzable silyl groups per polymer molecule, however, if polymer (A2) has a linear polymer skeleton, it may be 2.0 or less.

[0027] Polymer (A2) has a polymer skeleton of polyoxyalkylene. Preferably, the polymer skeleton is composed only of a plurality of interconnected oxyalkylene repeating units, or is composed only of the plurality of oxyalkylene repeating units and a structure derived from the initiator used during polymerization. Here, the oxyalkylene repeating unit refers to a repeating unit that constitutes a polyether, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0028] The polymer skeleton of polymer (A2) may be linear or branched. From the viewpoint of improving the elongation of the cured product obtained by curing the polymer mixture, it is preferable that the polymer skeleton of polymer (A2) be linear. Furthermore, polymer (A2) may be a combination of a polymer having a linear polymer skeleton and a polymer having a branched polymer skeleton.

[0029] A linear polymer skeleton can be formed by using an initiator having two hydroxyl groups per molecule in a polymerization method for forming the polymer skeleton. A branched polymer skeleton can be formed by using an initiator having three or more hydroxyl groups per molecule.

[0030] There are no particular limitations on specific examples of polyoxyalkylene polymer skeletons, 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.

[0031] When the polymer mixture according to this embodiment is used as a curable resin such as a sealant or adhesive, a polyoxypropylene polymer having oxypropylene repeating units at a concentration of 50% by weight or more, more preferably 80% by weight or more, of the polymer backbone is preferred as polymer (A2) because it is amorphous and has relatively low viscosity.

[0032] The number-average molecular weight of polymer (A2) is in the range of 3,000 to 100,000 as polystyrene-equivalent molecular weight in GPC. Due to the high number-average molecular weight of polymer (A2) of 3,000 or more, the polymer mixture according to this embodiment can exhibit good mechanical properties such as higher modulus, tensile strength, and elongation after curing, and can be suitably used as a curable resin for adhesives, sealants, elastic coatings, and other adhesives.

[0033] From the above-mentioned viewpoint, the number-average molecular weight of polymer (A2) is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. On the other hand, there is no particular upper limit to the number-average molecular weight of polymer (A2), but from the viewpoint of making the polymer mixture low viscosity, it is preferably 100,000 or less, more preferably 60,000 or less, and even more preferably 40,000 or less.

[0034] The molecular weight distribution (Mw / Mn) of polymer (A2) is not particularly limited. A narrow molecular weight distribution is preferred, preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and most preferably 1.2 or less. The molecular weight distribution of polymer (A2) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0035] [Method for producing polymer (A2)] Next, specific examples of methods for producing polymer (A2) will be described in detail, but the methods for producing polymer (A2) are not limited to those described below.

[0036] (polymerization) The polymer skeleton of polyoxyalkylene polymers can be formed by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator, using conventionally known methods, thereby obtaining a hydroxyl-terminated polyoxyalkylene polymer (B). While there are no particular limitations on the specific polymerization method, a polymerization method using a complex metal cyanide 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).

[0037] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used individually or in combination of two or more. Among the cyclic ether compounds, propylene oxide is particularly preferred because it yields amorphous, relatively low-viscosity polyoxyalkylene polymers.

[0038] As initiators, initiators having two or more hydroxyl groups can be used. Specific examples include alcohols such as ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and hydroxyl-terminated polyoxyalkylene polymers with a number-average molecular weight of 300 to 4,000, such as polyoxypropylenediol, polyoxypropylenetriol, polyoxyethylenediol, and polyoxyethylenetriol.

[0039] Examples of synthesis methods for polyoxyalkylene polymers include, but are not limited to, polymerization methods using alkaline catalysts such as KOH, polymerization methods using transition metal compound-porphyrin complex catalysts such as the complex obtained by reacting an organoaluminum compound with porphyrin as shown in Japanese Patent Publication No. 61-215623, polymerization methods using complex metal cyanide complex catalysts as shown in Japanese Patent Publication Nos. 46-27250, 59-15336, U.S. Patent Nos. 3278457, 3278458, 3278459, 3427256, 3427334, and 3427335, polymerization methods using catalysts consisting of polyphosphazene salts as exemplified in Japanese Patent Publication No. 10-273512, and polymerization methods using catalysts consisting of phosphazene compounds as exemplified in Japanese Patent Publication No. 11-060722. Polymerization using complex metal cyanide catalysts is more preferable due to reasons such as lower manufacturing costs and the ability to obtain polymers with a narrow molecular weight distribution.

[0040] (Reaction with alkali metal salts) When introducing allyl groups to a hydroxyl-terminated polyoxyalkylene polymer (B), it is preferable to first react the hydroxyl-terminated polyoxyalkylene polymer (B) with an alkali metal salt to convert the terminal hydroxyl groups into alkoxytes. Alternatively, a complex metal cyanide catalyst can be used instead of an alkali metal salt.

[0041] 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.

[0042] The amount of alkali metal salt used is not particularly limited, but it is preferably 0.5 to 1.2 in molar ratio to the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (B).

[0043] 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 reacting with the alkali metal salt is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0044] (Reaction with organic halides (H) containing an allyl group) After reacting the hydroxyl-terminated polyoxyalkylene polymer (B) with an alkali metal salt as described above, an organic halide (H) containing an allyl group is reacted with it. The organic halide (H) containing an allyl group reacts with the alkoxyde through a halogen substitution reaction to form an ether bond, thus allowing an allyl group to be introduced to the molecular chain ends of the polyoxyalkylene polymer. This can result in the formation of a polyoxyalkylene polymer (C) containing an allyl group.

[0045] Specific examples of organic halides (H) having an allyl group include, but are not limited to, allyl chloride, allyl bromide, and allyl iodide. Allyl chloride is preferred due to its ease of handling.

[0046] The amount of organic halide (H) having an allyl group added is not particularly limited, but the molar ratio of organic halide (H) to hydroxyl groups of the polyoxyalkylene polymer (B) is preferably 0.7 to 2.0.

[0047] The reaction temperature for the organic halide (H) containing an allyl group is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0048] (Introduction of hydrolyzable silyl groups) By subjecting the polyoxyalkylene polymer (C) having an allyl group obtained as described above to a hydrosilylation reaction with a hydrosilane compound (J) having a hydrolyzable silyl group, a hydrolyzable silyl group can be introduced into the polymer.

[0049] <Hydrosilane compound (J)> The hydrosilane compound (J) is not particularly limited, but one represented by the following general formula (3) is preferred. HSiR 1 3-a X a (3) In the formula, R 1X and a are the same as those described above for general formula (1).

[0050] Specific examples of hydrosilane compounds (J) include, for example, trimethoxysilane, triethoxysilane, triphenoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethyl Examples include aminomethyl diethoxysilane, diphenoxymethylsilane, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, triethylsilane, methyldiethylsilane, dimethylethylsilane, chlorodimethylsilane, dichloromethylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenylmethylsilane, phenyldimethylsilane, diphenylmethylsilane, ethylphenylsilane, diethylphenylsilane, and ethyldiphenylsilane.

[0051] From the viewpoint of the curability and post-curing strength of the resulting polymer, the hydrosilane compound (J) is particularly preferably trimethoxysilane or dimethoxymethylsilane.

[0052] The amount of hydrosilane compound (J) used (charged) is preferably 1 molar equivalent or more and 20 molar equivalents or less in terms of the amount of substance relative to the allyl groups in the allyl group-containing polyoxyalkylene polymer (C).

[0053] Hydrosilylation reactions can be carried out in the presence of a hydrosilylation catalyst. The hydrosilylation catalyst is not particularly limited and can be a metal such as iron, cobalt, nickel, iridium, platinum, palladium, rhodium, or ruthenium, or a complex thereof. However, carrying out the hydrosilylation reaction in the presence of a ruthenium complex (D) in particular can produce polymers (A2) with a high average number of hydrolyzable silyl groups per terminal.

[0054] <Ruthenium complex (D)> Ruthenium complex (D) is a ruthenium complex having compound (E) as a ligand. Compared to hydrosilylation catalysts such as Karstedt catalysts (platinum divinyldisiloxane complex), ruthenium complex (D) exhibits high selectivity in hydrosilylation reactions, suppresses the by-production of 1-propenyl or propyl groups, and can efficiently produce polymer (A2) with a high average number of hydrolyzable silyl groups per terminal.

[0055] <Compound (E)> Compound (E) is a compound that can coordinate to a ruthenium complex. Compound (E) has at least one carbon-carbon double bond in one molecule, and at least one of the carbon atoms forming the carbon-carbon double bond has an electron-withdrawing group bonded to it.

[0056] Examples of basic skeletons containing the carbon-carbon double bond in compound (E) include norbornadiene skeleton, cyclooctadiene skeleton, benzene ring skeleton, and benzoquinone skeleton. More specifically, examples include 2,5-norbornadiene skeleton, 1,5-cyclooctadiene skeleton, p-cymene skeleton, mesitylene skeleton, benzene ring skeleton, and benzoquinone skeleton. Preferably, it is the norbornadiene skeleton or the benzene ring skeleton.

[0057] Examples of electron-withdrawing groups include halogen groups such as fluoro, chloro, bromo, and iodo groups, as well as cyano, aldehyde, and nitro groups. If a molecule contains multiple electron-withdrawing groups, they may be of different types. Compound (E) may have one or more electron-withdrawing groups in a single molecule, but it is preferable to have two or more, more preferably two to four, and particularly preferable to have two or three.

[0058] Furthermore, as for the type of electron-withdrawing group, a halogeno group is preferred, a fluoro group, a bromo group, or an iodine group is more preferred, a bromo group or an iodine group is even more preferred, and a bromo group is particularly preferred. Compound (E) preferably has one or more electron-withdrawing groups selected from a fluoro group, a bromo group, and an iodine group in one molecule, and more preferably two or more. These electron-withdrawing groups are preferably directly bonded to the carbon atoms forming the carbon-carbon double bond of compound (E). In particular, if compound (E) has a benzene ring skeleton, these electron-withdrawing groups are preferably directly bonded to the benzene ring.

[0059] The specific type of compound (E) is not particularly limited, and for example, 2-bromonolbornadiene, 2,3-dibromonolbornadiene, 1,4-dibromobenzene and its structural isomers, 1-bromo-4-iodobenzene and its structural isomers, 1,3,5-tribromobenzene and its structural isomers, 1,2,4,5-tetrabromobenzene and its structural isomers, hexabromobenzene, 1-bromo-3,5-difluorobenzene and its structural isomers, 1-bromo-3,5-dichlorobenzene and its structural isomers, 1-bromo-3,5-diiodobenzene and its structural isomers, 1-bromo-3-chloro-5-fluorobenzene and its structural isomers, 1,4-diiodobenzene and its structural isomers, 1,3,5-triiodobenzene and its structural isomers, 1,2 Examples include 4,5-tetraiodobenzene and its structural isomers, hexaiodobenzene, 1,3-difluoro-5-iodobenzene and its structural isomers, 1,3-dichloro-5-iodobenzene and its structural isomers, 1,3-dibromo-5-iodobenzene and its structural isomers, 1,3-dibromo-5-chlorobenzene and its structural isomers, 1-chloro-3,5-diiodobenzene and its structural isomers, 1-fluoro-3,5-dibromobenzene and its structural isomers, 1-fluoro-3,5-diiodobenzene and its structural isomers, 1-chloro-3-fluoro-5-iodobenzene and its structural isomers, 1-bromo-3-chloro-5-iodobenzene and its structural isomers, and 1-bromo-3-fluoro-5-iodobenzene and its structural isomers. In particular, from the viewpoint of suppressing by-products, compound (E) is preferably 2,3-dibromonolbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,3,5-tribromobenzene, 1,4-diiodobenzene, or hexabromobenzene, and is especially preferably 2,3-dibromonolbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, or 1,3,5-tribromobenzene. Only one type of compound (E) may be used, or two or more types may be used in combination.

[0060] The ruthenium complex (D) may have a ligand, compound (E) and a compound (E') that is not compound (E). Compound (E') can be any compound that can coordinate to the ruthenium complex (D), and specific examples include 2,5-norbornadiene ligand, 1,5-cyclooctadiene ligand, p-cymene ligand, mesitylene ligand, benzene ligand, carbonyl ligand, isocyanide ligand, and arene ligand.

[0061] When a ruthenium complex (D) has both compound (E) and compound (E') as ligands, it is preferable that compound (E) accounts for a higher proportion of the total ligands of the ruthenium complex (D), as this can provide higher selectivity. The proportion of compound (E) among the total ligands is preferably 50 to 100% moles, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%.

[0062] Ruthenium complex (D) can be produced by methods in accordance with known production methods. Examples of raw materials for ruthenium complex (D) include anhydrous or hydrated ruthenium compounds such as ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. A specific method for producing ruthenium complex (D) is to add compound (E) to an ethanol solution of ruthenium(III) chloride hydrate, heat under reflux, filter, and then dry. In this case, heating under reflux may be carried out in the presence of a basic compound such as sodium carbonate or sodium bicarbonate to neutralize the hydrogen chloride generated during heating under reflux. From the viewpoint of reaction rate, it is preferable to use compound (E) in an amount of 1 molar equivalent or more relative to the raw material ruthenium compound.

[0063] The ruthenium complex (D) can also be obtained by adding compound (E) to a system containing a ruthenium compound (D') that does not have compound (E) as a ligand, thereby converting the ruthenium compound (D') to the ruthenium complex (D), as described later.

[0064] The ruthenium complex (D) may be a nanoparticle catalyst. In this case, the particle size (cumulative median diameter) of the ruthenium complex (D) nanoparticles is preferably 0.3 nm to 200 nm. The cumulative median diameter can be measured by a transmission electron microscope (TEM).

[0065] In the hydrosilylation reaction, the amount of ruthenium complex (D) used (charge amount) is typically 0.01 ppm to 10% by weight relative to the allyl group-containing polyoxyalkylene polymer (C), preferably 1 ppm to 0.1%. Within this range, hydrolyzable silyl groups can be introduced with high efficiency.

[0066] The hydrosilylation reaction may be carried out in the presence of a solvent or without one. If a solvent is used, the type of solvent is not particularly limited, but it is preferable that the solvent is a compound that does not react with the starting materials or catalyst. Specific examples include hydrocarbon solvents such as hexane, and halogenated solvents such as dichloromethane. It is preferable to use a solvent that has been dehydrated and deoxygenated.

[0067] The reaction temperature for the hydrosilylation reaction can be appropriately determined considering the reactivity (reaction rate) and the heat resistance temperature of the reaction vessel. The lower limit is usually 0°C or higher, preferably 20°C or higher, and more preferably 40°C or higher. The upper limit is usually 200°C or lower, preferably 150°C or lower. A higher reaction temperature may allow the reaction to be completed in a shorter time and suppress side reactions. The reaction time is not particularly limited and may be around 5 minutes to 12 hours, or 10 minutes to 5 hours.

[0068] Hydrosilylation reactions are preferably carried out under an inert atmosphere such as nitrogen or argon.

[0069] In the hydrosilylation reaction, it is preferable to add compound (E) in addition to the ruthenium complex (D) to the reaction system, as this can increase the average number of hydrolyzable silyl groups per terminal. In this case, it is preferable that the ruthenium complex (D) and compound (E) come into contact before the start of the hydrosilylation reaction. For example, one example of a preferred embodiment is a method in which an allyl group-containing polyoxyalkylene polymer (C) is stirred at a predetermined temperature, and then the ruthenium complex (D) and compound (E) are added and mixed, followed by the addition of a hydrosilane compound (J).

[0070] In another embodiment, polymer (A2) can also be produced by mixing a polyoxyalkylene polymer (C) having an allyl group, a hydrosilane compound (J), a ruthenium compound (D') that does not have compound (E) as a ligand, and compound (E), and then carrying out a hydrosilylation reaction.

[0071] According to this embodiment, as in the manufacturing method described above, polymer (A2) can be efficiently produced by mixing ruthenium compound (D') and compound (E) to generate ruthenium complex (D) in situ, without using a pre-synthesized ruthenium complex (D), and then using it as a catalyst. The mixing order of the polyoxyalkylene polymer (C) having an allyl group, hydrosilane compound (J), ruthenium compound (D'), and compound (E) is not particularly specified and can be mixed in any order.

[0072] <Ruthenium compound (D')> Ruthenium compound (D') does not have compound (E) as a ligand. As ruthenium compound (D'), ruthenium(III) chloride hydrate or a ruthenium complex having compound (E') as a ligand that does not correspond to compound (E) can be used. Compound (E') is as described above.

[0073] From the viewpoint of suppressing by-products, the ruthenium compound (D') is preferably a ruthenium complex having a ligand selected from a 2,5-norbornadiene ligand, a benzene ligand, and a p-cymene ligand.

[0074] The amount of preferred ruthenium compound (D') used (charge amount) is the same as the amount of preferred ruthenium complex (D) used (charge amount) described above. Furthermore, the preferred conditions for the amount of preferred hydrosilane compound (J) used (charge amount) in the reaction step, the type of solvent used in the reaction step, and the reaction temperature are the same as those described above. This manufacturing method includes an operation to mix ruthenium compound (D') and compound (E) to produce ruthenium complex (D) in situ. For this reason, for example, it is preferable to add ruthenium compound (D') and compound (E) to the allyl group-containing polyoxyalkylene polymer (C) while stirring at a predetermined temperature, and then add the hydrosilane compound (J).

[0075] The amount of compound (E) added is not particularly limited, and is usually 0.01 ppm to 10% by weight relative to the allyl group-containing polyoxyalkylene polymer (C), preferably 1 ppm to 0.1%.

[0076] When polymer (A2) is produced by the manufacturing method described above, polymer (A2) may contain ruthenium complex (D). In this case, the content of ruthenium complex (D) is in accordance with the amount used (charged amount) of ruthenium complex (D) or ruthenium compound (D') described above, but specifically, it is usually 0.01 ppm or more, preferably 0.1 ppm or more, and more preferably 1 ppm or more, by weight relative to polymer (A2). The upper limit is usually 10% or less, preferably 1% or less, and more preferably 0.1% or less.

[0077] [Polishing ratio of polymer (A2)] In the polymer mixture according to this embodiment, the blending ratio of polymer (A2) is preferably 40 to 90% by weight of the total amount of polymers (A0), (A1), and (A2). Within this range, the desired values ​​for mechanical properties after curing can be achieved while reducing the viscosity of the entire polymer mixture. The lower limit is more preferably 50% by weight or more, and even more preferably 55% by weight or more, from the viewpoint of mechanical properties after curing. The upper limit is more preferably 80% by weight or less, and even more preferably 70% by weight or less, from the viewpoint of reducing viscosity.

[0078] [constitution(A1)] Polymer (A1) is a polyoxyalkylene polymer having hydrolyzable silyl groups, but only one of the ends of the polymer skeleton has a hydrolyzable silyl group. Polymer (A1) can also be described as a polymer having a hydrolyzable silyl group at only one end.

[0079] The hydrolyzable silyl group of polymer (A1) can be represented by the general formula (1) described above. However, the hydrolyzable silyl group of polymer (A1) and the hydrolyzable silyl group of polymer (A2) may be the same, or they may be different from each other within the range shown by general formula (1).

[0080] The polymer (A1) preferably has a hydrolyzable silyl group-containing structure represented by the general formula (2) described above. However, the hydrolyzable silyl group-containing structure of polymer (A1) and the hydrolyzable silyl group-containing structure of polymer (A2) may be the same, or they may be different from each other within the range shown by general formula (2).

[0081] Polymer (A1) has a hydrolyzable silyl group at only one terminal of the polymer backbone. The average number of hydrolyzable silyl groups per polymer molecule is not particularly limited, but is preferably 0.50 or more from the viewpoint of achieving good curability. A higher average number improves the crosslinking density in the cured product, resulting in high strength after curing. Therefore, it is more preferable to have 0.60 or more, 0.70 or more, and even more preferable to have 0.80 or more. In particular, 0.90 or more is preferred, 0.93 or more is more preferred, 0.95 or more is even more preferred, and 0.97 or more is even more preferred. There is no particular upper limit, and it may be 1.0 or less.

[0082] In polymer (A1), the method for calculating the average number of hydrolyzable silyl groups per polymer molecule is not particularly limited and can rely on known methods. When polymer (A1) has a hydrolyzable silyl group-containing structure represented by the general formula (2), the average number of hydrolyzable silyl groups per polymer molecule can be calculated as the ratio of the number of hydrolyzable silyl groups to the total number of hydrolyzable silyl groups, 1-propenyl groups, propyl groups, and allyl groups. This calculation method is described in detail for polymer (A2).

[0083] The polymer skeleton of polymer (A1), like that of polymer (A2), has a polyoxyalkylene polymer skeleton. Specific examples are the same as those described above for polymer (A2), but polyoxypropylene is preferred. However, the repeating units constituting the polymer skeletons of polymer (A1) and polymer (A2) may be the same or different. Furthermore, the polymer skeleton of polymer (A1) is not particularly limited, but it is preferably linear.

[0084] The number-average molecular weight of polymer (A1) is in the range of 3,000 to 25,000 as polystyrene-equivalent molecular weight in GPC. A number-average molecular weight of 3,000 or more for polymer (A1) improves the tensile strength and elongation at break of the cured product. Preferably, it is 4,000 or more, and more preferably 5,000 or more.

[0085] Furthermore, the viscosity of the polymer mixture can be reduced by having a number-average molecular weight of 25,000 or less of polymer (A1). Preferably, it is 15,000 or less, more preferably 10,000 or less, and even more preferably 6,000 or less.

[0086] Furthermore, it is preferable that the number-average molecular weight of polymer (A1) is 1,000 or more lower than the number-average molecular weight of polymer (A2). This reduces the viscosity of polymer (A2) by incorporating polymer (A1), making it possible to obtain a low-viscosity polymer mixture. More preferably, it is 5,000 or more lower than the number-average molecular weight of polymer (A2), even more preferably 10,000 or more lower, and particularly preferably 15,000 or more lower.

[0087] The method for producing polymer (A1) can be carried out in accordance with the method for producing polymer (A2), except that an initiator having one hydroxyl group is used as the initiator.

[0088] 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.

[0089] Furthermore, by using a combination of an initiator having two or more hydroxyl groups and an initiator having one hydroxyl group, polymers (A2) and (A1) can be synthesized in the same system.

[0090] When synthesizing polymer (A1) having an average of 0.90 or more hydrolyzable silyl groups per polymer molecule, it is preferable to use the aforementioned ruthenium complex (D) as the hydrosilylation reaction catalyst.

[0091] On the other hand, when synthesizing polymer (A1) in which the average number of hydrolyzable silyl groups per polymer molecule is less than 0.90, hydrosilylation catalysts other than ruthenium complex (D) can be used. Such hydrosilylation catalysts can be any known ones and are not particularly limited. Specific 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]; 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.

[0092] [Polishing ratio of polymer (A1)] In the polymer mixture according to this embodiment, the blending ratio of polymer (A1) is preferably 1 to 20% by weight of the total amount of polymers (A0), (A1), and (A2). Within this range, the viscosity of the entire polymer mixture can be reduced while achieving desired values ​​for mechanical properties after curing. From the viewpoint of reducing viscosity, the lower limit is more preferably 3% by weight or more, even more preferably 5% by weight or more, and particularly preferably 10% by weight or more. From the viewpoint of mechanical properties after curing, the upper limit is more preferably 15% by weight or less.

[0093] [conversion(A0)] Polymer (A0) is a polyoxyalkylene polymer that does not have hydrolyzable silyl groups. In other words, it is a polyoxyalkylene polymer in which hydrolyzable silyl groups have not been introduced, and its terminals usually contain hydroxyl groups or carbon-carbon double bond-containing groups such as allyl groups, but are not limited to these. The number of these hydroxyl groups and carbon-carbon double bond-containing groups is also not particularly limited.

[0094] The polymer skeleton of polymer (A0), like polymers (A2) and (A1), has a polyoxyalkylene polymer skeleton. Specific examples are the same as those described above for polymer (A2), but polyoxypropylene is preferred. However, the repeating units constituting the polymer skeleton of polymer (A0) and the polymer skeletons of polymers (A1) and (A2) may be the same or different. Furthermore, the polymer skeleton of polymer (A0) is not particularly limited, but it is preferably linear.

[0095] The number-average molecular weight of polymer (A0) is in the range of 500 to 100,000 as polystyrene-equivalent molecular weight in GPC. A number-average molecular weight of 500 or more for polymer (A0) suppresses the bleed-out of low molecular weight components from the cured product. Preferably, it is 1,000 or more, and more preferably 2,000 or more.

[0096] Furthermore, the viscosity of the polymer mixture can be reduced by having a number-average molecular weight of 100,000 or less for the polymer (A0). Preferably, it is 50,000 or less, more preferably 25,000 or less, even more preferably 10,000 or less, and particularly preferably 6,000 or less.

[0097] Furthermore, it is preferable that the number-average molecular weight of polymer (A0) is 1,000 or more lower than the number-average molecular weight of polymer (A2). This reduces the viscosity of polymer (A2) by incorporating polymer (A0), making it possible to obtain a low-viscosity polymer mixture. More preferably, it is 5,000 or more lower than the number-average molecular weight of polymer (A2), even more preferably 10,000 or more lower, even more preferably 15,000 or more lower, and particularly preferably 20,000 or more lower.

[0098] The method for producing polymer (A0) can be carried out in accordance with the method for producing polymer (A2), except that the hydrosilylation reaction is not performed.

[0099] [Polishing ratio of polymer (A0)] In the polymer mixture according to this embodiment, the blending ratio of polymer (A0) is preferably 1 to 40% by weight of the total amount of polymers (A0), (A1), and (A2). Within this range, the viscosity of the entire polymer mixture can be reduced while achieving the desired values ​​for mechanical properties after curing. From the viewpoint of reducing viscosity, the lower limit is more preferably 5% by weight or more, even more preferably 10% by weight or more, even more preferably 15% by weight or more, and particularly preferably 20% by weight or more. From the viewpoint of mechanical properties after curing, the upper limit is more preferably 35% by weight or less.

[0100] [Percentage of polymer in polymer mixture] The polymer mixture according to this embodiment consists substantially only of polyoxyalkylene polymers (A0), (A1), and (A2). The total proportion of polyoxyalkylene polymers (A0), (A1), and (A2) in the polymer mixture is preferably 90% by weight or more, more preferably 95% by weight or more, and even more preferably 99% by weight or more. There is no particular upper limit, and it may be 100% by weight.

[0101] [Viscosity of polymer mixtures] The polymer mixture according to this embodiment is low viscosity, and more preferably, the viscosity measured at 23°C is lower than that of the polyoxyalkylene polymer (A2). Specifically, it is preferably 40 Pa.s or less, more preferably 30 Pa.s or less, and even more preferably 20 Pa.s or less. This viscosity was measured at 23°C using an E-type viscometer (RE-85U, manufactured by Tokyo Keiki, measuring cone: 3° × R14).

[0102] [Method for producing polymer mixtures] The method for producing the polymer mixture according to this embodiment is not particularly limited. It can be produced by synthesizing or obtaining polymer (A0), polymer (A1), and polymer (A2) individually, and then mixing each polymer. Alternatively, polymer (A1) and polymer (A2) may be synthesized simultaneously in a single system, and polymer (A0) may be mixed into the resulting mixture of polymer (A1) and polymer (A2).

[0103] [Curable composition] A curable composition can be constructed by blending a curing catalyst, a filler, or other additives into the polymer mixture according to this embodiment. The curable composition hardens in the presence of moisture, yielding a cured product.

[0104] (curing catalyst) The curable composition according to this embodiment preferably contains a curing catalyst for the purpose of promoting the reaction of hydrolysis and condensation of hydrolyzable silyl groups, i.e., the curing reaction. This curing catalyst is also called a silanol condensation catalyst.

[0105] Conventional known curing catalysts can be used, specifically organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, and mixtures thereof.

[0106] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), 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(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, and reaction products of dioctyltin oxide and silicate compounds. Due to the growing environmental concerns in recent years, dioctyltin compounds are preferred.

[0107] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. Various metals can be combined with the following carboxylic acids as carboxylic acid groups.

[0108] Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine; 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; and ketimine compounds.

[0109] 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.

[0110] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), titanium ethyl acetoacetate, and diisopropoxytitanium bis (ethylacetoacetate), as well as aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethyl acetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0111] Other curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0112] The curing catalyst may be used in combination with two or more different catalysts. For example, using the aforementioned amine compound with a carboxylic acid, or with an amine compound with an alkoxy metal, may improve reactivity.

[0113] The amount of curing catalyst added according to this embodiment is preferably 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 polymer mixture. Furthermore, some curing 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 the curing catalyst, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0114] 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, epoxy compounds, photocurable substances, oxygen-curable substances, surface modifiers, 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 composition or the 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.

[0115] (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, anhydrous silicic acid, hydrated silicic acid, ferric oxide, aluminum fine powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber, filament, and reinforcing fillers.

[0116] Reinforcing fillers are generally known as rubber reinforcing fillers, and known ones can be used. Reinforcing fillers improve the mechanical properties of cured products, increasing their modulus and tensile strength, and are applied to automotive glass sealants and other applications where strength is required.

[0117] Specific examples of reinforcing fillers include carbon blacks such as channel black, furnace black, thermal black, lamp black, and acetylene black, as well as silicas such as fume silica, precipitated silica, crystalline silica, and fused silica. These may be used individually or in combination.

[0118] Examples of carbon black include Printex30, Printex25, HIBLACK30, HIBLACK10, HIBLACK5L, HIBLACK20L, HIBLACK30L (manufactured by Orion Engineered Carbons), Monarch M430, Monarch M570 (manufactured by Cabot), Show Black N-219, Show Black N-220 (manufactured by Showa Cabot), Nitelon #200, #300, HTC #SL (manufactured by Shin-Nippon Chemical Carbon), Asahi #120, Asahi #55, Asahi #60, Asahi #70, Asahi Thermal, Asahi #15 (manufactured by Asahi Carbon), Seast S (manufactured by Tokai Carbon), Dia Black SA, Dia Black N234 (manufactured by Mitsubishi Chemical), Statex N121 (Columbia Carbon Japan), HTC #20 (manufactured by Shin-Nippon Chemical Carbon), Huber N-907 (manufactured by Huber), and Denka Acetylene Black (manufactured by Denki Kagaku). Among carbon blacks, carbon black with a small primary particle size is preferred, and the primary particle size is preferably between 10 nm and 80 μm, and preferably between 15 nm and 50 μm. Reinforcing fillers may be used alone or in combination of multiple types.

[0119] 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 polymer mixture according to this embodiment.

[0120] 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, and 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.

[0121] 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 polymer mixture according to this embodiment.

[0122] (Adhesion-enhancing agent) Adhesion-imparting agents may be added to the curable composition according to this embodiment. As adhesion-imparting agents, silane coupling agents and reaction products of silane coupling agents may be added.

[0123] 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. In addition, condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes and other alkoxysilanes; and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes, can also be used. The above adhesion-imparting agents may be used individually or in combination of two or more types.

[0124] The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer mixture according to this embodiment.

[0125] (Plasticizer) The curable composition according to this embodiment may further contain a plasticizer. 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.

[0126] Furthermore, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include vinyl polymers, polyester plasticizers, polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Plasticizers may be used alone or in combination of two or more types.

[0127] 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 polymer mixture according to this embodiment.

[0128] (Solvents, diluents) A solvent or diluent may be added to the curable composition according to this embodiment. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc., can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher, due to concerns about air pollution when the composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more.

[0129] (Drip prevention agent) The curable composition according to this embodiment may contain, if necessary, an anti-sagging agent to prevent sagging and improve workability. The anti-sagging agent 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 anti-sagging agents may be used individually or in combination of two or more.

[0130] The amount of anti-slip agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the polymer mixture according to this embodiment.

[0131] (Antioxidant) An antioxidant (anti-aging agent) can be used in the curable composition according to this embodiment. Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. For example, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON); and BHT. Similarly, hindered amine-based light stabilizers such as Chinuvin 622LD, Chinuvin 144, Chinuvin 292, CHIMASSORB944LD, CHIMASSORB119FL (all manufactured by BASF); Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63, Adekastab LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all manufactured by Sankyo Life Tech Co., Ltd.); and Nocrack CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants such as SONGNOX4120, Nowguard 445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731.

[0132] 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 polymer mixture according to this embodiment.

[0133] (Light stabilizer) A light stabilizer can be used in the curable composition according to this embodiment. 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.

[0134] 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 polymer mixture according to this embodiment.

[0135] (UV absorber) A UV absorber can be used in the curable composition according to this embodiment. Using a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-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, Tinuvin 571, Tinuvin 1600, and Tinuvin B75 (all manufactured by BASF).

[0136] The amount of ultraviolet absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer mixture according to this embodiment.

[0137] (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 above property modifier, the hardness of the curable composition according to this embodiment can be increased or decreased, resulting in increased elongation at break. The above property modifiers may be used alone or in combination of two or more.

[0138] 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. Specifically, examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0139] 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 polymer mixture according to this embodiment.

[0140] (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.

[0141] 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.

[0142] 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 polymer mixture according to this embodiment.

[0143] (Epoxy compound) The curable composition according to this embodiment may further contain an epoxy compound. The inclusion of an epoxy compound provides a cured product with good curability and high tensile shear strength. Furthermore, it can enhance the resilience of the cured product. The epoxy compound has one or more epoxy groups, preferably two or more.

[0144] Suitable specific examples of epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, hydrogenated versions of these bisphenol type epoxy resins, glycidyl ester type epoxy compounds, glycidylamine type epoxy compounds, alicyclic epoxy compounds, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol novolac type epoxy resins, urethane-modified epoxy resins, fluorinated epoxy resins, epoxidized rubbers such as epoxidized polybutadiene, and brominated epoxy compounds such as tetrabromobisphenol A diglycidyl ether. Among these, bisphenol A type epoxy resin is preferred because it easily forms a cured product that is excellent in both strength and elongation.

[0145] The amount of epoxy compound incorporated is not particularly limited as long as the desired effect is not impaired. The amount of epoxy compound incorporated is preferably 0.1 parts by weight or more and 500 parts by weight or less, more preferably 10 parts by weight or more and 200 parts by weight or less, and even more preferably 20 parts by weight or more and 100 parts by weight or less, per 100 parts by weight of the polymer mixture according to this embodiment. When the amount of epoxy compound used is within the above range, it is easy to form a cured product with sufficiently high tensile shear strength, and the peel strength of the cured product does not decrease easily.

[0146] Furthermore, as epoxy compounds, epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof can also be used. Specifically, examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, epoxybutyl stearate, etc. These epoxy compounds are preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the polymer mixture according to this embodiment.

[0147] <Epoxy curing agent> If the curable composition according to this embodiment contains an epoxy compound, it is preferable to further contain an epoxy curing agent as a component for curing the epoxy compound.

[0148] As the epoxy curing agent, any compound that has been conventionally used as a curing agent for various epoxy compounds can be used, provided that the desired effect is not impaired. Specific examples of epoxy curing agents include chain-like aliphatic amine compounds, alicyclic amine compounds, aromatic amine compounds, polyaminoamides, imidazoles, dicyandiamides, epoxy-modified amines, Mannich-modified amines, Michael-added modified amines, ketimines, polycarboxylic acid anhydrides, alcohols, and phenols. These epoxy curing agents may be used individually or in combination of two or more.

[0149] The amount of epoxy curing agent is not particularly limited. In terms of rapidly curing the epoxy compound, the amount of epoxy curing agent is preferably 0.1 parts by weight or more and 300 parts by weight or less per 100 parts by weight of epoxy compound, more preferably 1 part by weight or more and 200 parts by weight or less, and even more preferably 5 parts by weight or more and 100 parts by weight or less.

[0150] (light curing substance) A photocurable substance can be used in the curable composition according to this embodiment. 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, polyvinyl polycinnamates, or azidized resins, which are monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups.

[0151] The amount of photocurable substance 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 polymer mixture according to this embodiment.

[0152] (oxygen curing substance) An oxygen-curable substance can be used in the curable composition according to this embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing stickiness on the surface 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.

[0153] 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 polymer mixture according to this embodiment. As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0154] <<Preparation of Curable Composition>> The curable composition according to this embodiment can be prepared as a one-component type, where 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, where components such as a curing catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and the curing agent and the main component containing the polymer mixture according to this embodiment are mixed before use. From the viewpoint of workability, the one-component type is preferred.

[0155] In embodiments in which the curable composition includes an epoxy compound, the curable composition hardens rapidly. Therefore, it is preferable that the one-component curable composition be prepared at the site where the curable composition is to be applied and used immediately after preparation.

[0156] If the curable composition containing the epoxy compound does not contain an epoxy curing agent, a two-component curable composition consisting of two liquids can be prepared such that the polymer mixture according to this embodiment and the curing catalyst are separated. In this case, examples of two-component curable compositions include a main component containing the polymer mixture according to this embodiment and the epoxy compound, and a curing agent containing the curing catalyst; and a second component containing the polymer mixture according to this embodiment and the epoxy compound and the curing catalyst.

[0157] Furthermore, when a curable composition containing an epoxy compound contains an epoxy curing agent, examples of two-component curable compositions include a main component comprising the polymer mixture and epoxy compound according to this embodiment, and a curing agent comprising a curing catalyst and the epoxy curing agent; and a second component comprising a first agent comprising the polymer mixture and epoxy curing agent according to this embodiment, and an epoxy compound and the curing catalyst. In the two-component curable composition, other components besides the polymer mixture, epoxy compound, curing catalyst, and epoxy curing agent according to this embodiment may be blended into either liquid.

[0158] In the case of a one-component curable composition according to this embodiment, 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, in addition to dehydration and drying, the storage stability can be further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0159] <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.

[0160] 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.

[0161] The following sections list preferred embodiments of this disclosure, but the present invention is not limited to these sections. [Item 1] A polymer mixture comprising polyoxyalkylene polymers (A0), (A1), and (A2), Polyoxyalkylene polymers (A0) do not have hydrolyzable silyl groups and have a number-average molecular weight of 500 to 100,000. Polyoxyalkylene polymer (A1) has a hydrolyzable silyl group at only one terminal of the polymer backbone, and its number average molecular weight is between 3,000 and 25,000. The polyoxyalkylene polymer (A2) has at least two terminals of the polymer backbone that are part of the following general formula (2): -OCH2CH2CH2SiR 1 3-a X a (2) (In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 A polymer mixture having a hydrolyzable silyl group-containing structure represented by (or if there are multiple X's, they may be the same or different), wherein the average number of hydrolyzable silyl groups per terminal is 0.90 or more, and the number average molecular weight is 3,000 or more and 100,000 or less. [Item 2] The polymer mixture according to item 1, wherein the number average molecular weight of at least one of the polyoxyalkylene polymers (A0) and (A1) is 1,000 or more less than the number average molecular weight of the polyoxyalkylene polymer (A2). [Item 3] A polymer mixture as described in item 2, wherein the number-average molecular weights of polyoxyalkylene polymers (A0) and (A1) are 1,000 or more less than the number-average molecular weight of polyoxyalkylene polymer (A2). [Item 4] A polymer mixture according to any of items 1 to 3, wherein the number average molecular weight of the polyoxyalkylene polymer (A2) is 10,000 or more. [Item 5] A polymer mixture according to any one of items 1 to 4, wherein the number average molecular weight of the polyoxyalkylene polymers (A0) and (A1) is 10,000 or less. [Item 6] A polymer mixture according to item 5, wherein the number average molecular weight of the polyoxyalkylene polymers (A0) and (A1) is 6,000 or less. [Item 7] A polymer mixture according to any of items 1 to 6, wherein the polymer backbone of the polyoxyalkylene polymer (A2) is linear. [Item 8] Polyoxyalkylene polymer (A1) is a polymer mixture according to any of items 1 to 7, wherein the average number of hydrolyzable silyl groups per polymer molecule is 0.90 or more. [Item 9] A polymer mixture according to any one of items 1 to 8, wherein, of the total amount of polyoxyalkylene polymers (A0), (A1), and (A2), the proportion of polyoxyalkylene polymer (A0) is 1 to 40% by weight, the proportion of polyoxyalkylene polymer (A1) is 1 to 20% by weight, and the proportion of polyoxyalkylene polymer (A2) is 40 to 90% by weight. [Item 10] A curable composition containing a polymer mixture described in any of items 1 to 9, and a silanol condensation catalyst. [Item 11] A cured product obtained by curing the curable composition described in item 10. [Examples]

[0162] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0163] The number-average molecular weight in the examples is the GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSKgel SuperH series Solvent: THF (tetrahydrofuran) Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0164] Viscosity is measured at 23°C using an E-type viscometer (Tokyo Keiki RE-85U, measuring cone: 3° × R14).

[0165] The average number of hydrolyzable silyl groups per terminal molecule was determined using the following nuclear magnetic resonance (NMR) spectrometer: 1 The proportion of hydrolyzable silyl groups, 1-propenyl groups, propyl groups, or allyl groups was determined by 1H NMR measurement. Equipment: AVANCE III HD500 digital amplifier (manufactured by BRUKER) Furthermore, for polyoxyalkylene polymers having hydrolyzable silyl groups at only one end, the average number of hydrolyzable silyl groups per end refers to the number of hydrolyzable silyl groups per polymer molecule.

[0166] (Synthesis Example 1-1) Using polyoxypropylene glycol (A0-3) with a number-average molecular weight of approximately 4,500 as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate grime complex catalyst to obtain hydroxyl group-containing polyoxypropylene (A0-2) with a number-average molecular weight of 28,000 and hydroxyl groups at both ends.

[0167] (Synthesis Examples 1-2 to 1-6) Except for changing the type of initiator used as described in Table 1-1, the same procedure as in Synthesis Example 1-1 was followed to obtain hydroxyl group-containing polyoxypropylene (B2-1) or (B1-1) to (B1-4). The initiators used and their number-average molecular weights, as well as the number-average molecular weights of the obtained polymers, are shown in Table 1-1.

[0168] [Table 1-1]

[0169] (Synthesis Example 2-1) To the hydroxyl group-containing polyoxypropylene (A0-2) obtained in Synthesis Example 1-1, 1.1 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl group-containing polyoxypropylene (A0-2) as a 28% methanol solution. After removing methanol by vacuum distillation, 1.3 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl group-containing polyoxypropylene (A0-2) and the reaction was carried out at 130°C for 1 hour to convert the terminal hydroxyl groups to allyl groups, after which the allyl chloride was removed by vacuum distillation. Subsequently, 0.3 molar equivalents of sodium methoxide were added to the hydroxyl groups of the polymer (A0-2) as a 28% methanol solution. After removing methanol by vacuum distillation, 0.8 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer (A0-2) and the reaction was carried out at 130°C for 1 hour to convert the remaining terminal hydroxyl groups to allyl groups, after which the allyl chloride was removed by vacuum distillation. The obtained unpurified allyl group-containing polyoxypropylene was mixed and stirred with n-hexane and water. Water was removed by centrifugation, and the hexane was removed from the resulting hexane solution under reduced pressure to remove the metal salts from the polymer. This yielded allyl group-containing polyoxypropylene (C2-1). The number-average molecular weight of the polymer was 28,000.

[0170] (Synthesis Examples 2-2 to 2-6) Except for changing the type of polymer used (hydroxyl group-containing polyoxypropylene) as described in Table 1-2, allyl group-containing polyoxypropylene (A0-1) or (C1-1) to (C1-4) were obtained by following the same procedure as in Synthesis Example 2-1. The polymers used and the number-average molecular weights of the obtained polymers are shown in Table 1-2.

[0171] [Table 1-2]

[0172] (Synthesis Example 3-1) [RuCl2(nbd)] is used for allyl group-containing polyoxypropylene (C2-1). n50 ppm and 120 ppm of 2,3-dibromonolbornadiene were added, and the mixture was stirred at 90°C for 10 minutes. Furthermore, dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in allyl group-containing polyoxypropylene (C2-1)) was added, and the hydrosilylation reaction was carried out at 90°C. Every hour from the start of the reaction... 1 ¹H NMR measurements were performed to confirm that the allyl groups in the allyl group-containing polyoxypropylene (C2-1) were completely consumed within 3 hours from the start of the reaction. The volatile components were then removed by vacuum distillation to obtain hydrolyzable silyl group-containing polyoxypropylene (A2-1). The polymer skeleton of (A2-1) is linear, and hydrolyzable silyl groups are present at both ends of the linear polymer skeleton. The average number of hydrolyzable silyl groups per terminal of the obtained polymer 1 Based on the 1H NMR measurement results, the number of molecules was calculated to be 0.97. The number-average molecular weight of the polymer was 28,000.

[0173] (Synthesis examples 3-2 to 3-5) Following the procedure in the same manner as in Synthesis Example 3-1, except for changes in the type of polymer used (allyl group-containing polyoxypropylene) and the amount of dimethoxymethylsilane used, hydrolyzable silyl group-containing polyoxypropylene (A1-1) to (A1-2) or (E1-1) to (E1-2) were obtained. The equivalent amounts of the polymers and dimethoxymethylsilane used, as well as the average number of hydrolyzable silyl groups per molecule of the obtained polymers and the number-average molecular weight are shown in Table 1-3. The polymer skeletons of the polymers obtained here are linear, and hydrolyzable silyl groups are present at only one end of the linear polymer skeleton.

[0174] [Table 1-3]

[0175] (Synthesis Example 4-1) To allyl group-containing polyoxypropylene (C2-1), 50 ppm of platinum divinyldisiloxane complex (a solution of isopropyl alcohol equivalent to 3% by mass of platinum) and dimethoxymethylsilane (0.85 molar equivalents relative to the allyl groups in allyl group-containing polyoxypropylene (C2-1)) were added, and a hydrosilylation reaction was carried out at 90°C. Every hour from the start of the reaction... 1 ¹H NMR measurements were performed to confirm that the allyl groups in the allyl group-containing polyoxypropylene (C2-1) were completely consumed within 3 hours from the start of the reaction. The volatile components were then removed by vacuum distillation to obtain hydrolyzable silyl group-containing polyoxypropylene (D2-1). The polymer skeleton of (D2-1) is linear, and hydrolyzable silyl groups are present at both ends of the linear polymer skeleton. The average number of hydrolyzable silyl groups per terminal of the obtained polymer 1 Based on the 1H NMR measurement results, the number of molecules was calculated to be 0.79. The number-average molecular weight of the polymer was 28,000.

[0176] (Synthesis examples 4-2 to 4-3) Hydrolyzable silyl group-containing polyoxypropylene (D2-2) to (D2-3) were obtained by following the same procedure as in Synthesis Example 4-1, except that the amount of dimethoxymethylsilane used was changed as described in Table 1-4. (D2-2) to (D2-3) also have hydrolyzable silyl groups at both ends of the linear polymer backbone. The equivalent amount of dimethoxymethylsilane, the average number of hydrolyzable silyl groups per terminal of the obtained polymer, and the number-average molecular weight are shown in Table 1-4.

[0177] [Table 1-4]

[0178] [Evaluation Method (Single-Component Formulation)] A one-component curable composition was prepared using a 5L planetary mixer (manufactured by Dalton Co., Ltd.). First, 160 parts by weight of Shiratsuka CCR (manufactured by Shiraishi Calcium Co., Ltd.: colloidal calcium carbonate), 54 parts by weight of Whiteon SB (manufactured by Shiraishi Calcium Co., Ltd.: surface-untreated heavy calcium carbonate), and 20 parts by weight of Typeque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium dioxide) were dried under reduced pressure at 120°C for 2 hours. Next, 100 parts by weight of the polymer or polymer mixture listed in Table 2, 90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate), 2 parts by weight of Disparon 6500 (manufactured by Kusumoto Kasei Co., Ltd.: fatty acid amide wax), 1 part by weight of Chinuvin 328 (manufactured by BASF: ultraviolet absorber), and 1 part by weight of Chinuvin 770 (manufactured by BASF: light stabilizer) were each added to the mixer and kneaded for 10 minutes. The obtained mixture was removed, passed through a three-roll mill once for uniform dispersion, and then put back into a mixer and dehydrated under reduced pressure for 2 hours. After dehydration under reduced pressure, the mixture was cooled to below 50°C, and then 3 parts by weight of A-171 (Momentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and 2 parts by weight of Neostan U-220H (Nitto Kasei Co., Ltd., dibutyltin bis(acetylacetonate)) were added and kneaded for 3 minutes. Subsequently, degassing under reduced pressure was performed for 2 minutes, and the resulting mixture was immediately filled into a moisture-proof aluminum cartridge and sealed to obtain a curable composition.

[0179] [Evaluation Method (Masterbatch Formulation)] A masterbatch composition was prepared using a 5L planetary mixer (manufactured by Dalton Co., Ltd.). First, 160 parts by weight of Shiratsuka CCR (manufactured by Shiraishi Calcium Co., Ltd.: colloidal calcium carbonate), 54 parts by weight of Whiteon SB (manufactured by Shiraishi Calcium Co., Ltd.: surface-untreated heavy calcium carbonate), and 20 parts by weight of Typeque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium dioxide) were dried under reduced pressure at 120°C for 2 hours. Next, 90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate), 2 parts by weight of Disparon 6500 (manufactured by Kusumoto Kasei Co., Ltd.: fatty acid amide wax), 1 part by weight of Chinuvin 328 (manufactured by BASF: ultraviolet absorber), and 1 part by weight of Chinuvin 770 (manufactured by BASF: light stabilizer) were each added to the mixer and kneaded for 10 minutes. The resulting mixture was removed, passed through a three-roll mill once for uniform dispersion, and then the mixture was added back to the mixer and dehydrated under reduced pressure at 120°C for 2 hours. After cooling to below 50°C, 2 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane) were added and kneaded in a substantially moisture-free state. After degassing under reduced pressure, the mixture was sealed in a moisture-proof container, a cartridge, to obtain the masterbatch composition.

[0180] Subsequently, 100 parts by weight of the polymer or polymer mixture described in Table 3-1 or Table 3-2, 3 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and 2 parts by weight of Neostan U-220H (manufactured by Nitto Chemical Co., Ltd.: dibutyltin bis(acetylacetonate)) were added to 315 parts by weight of the masterbatch composition and thoroughly mixed. The mixture was then uniformly kneaded and defoamed using a rotary-orbit mixer to prepare each curable composition.

[0181] Each of the prepared curable compositions was subjected to the following dumbbell tensile property measurements under a constant temperature and humidity atmosphere of 23°C and 50% relative humidity.

[0182] (Dumbbell properties) The obtained curable composition was filled into a mold and cured for 3 days at 23°C and 50% relative humidity, and then for 4 days at 50°C to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched out into a No. 3 dumbbell shape, and a tensile strength test was performed in an atmosphere of 23°C and 50% relative humidity to measure the stress at 50% elongation (modulus; M50). The stress at fracture (TB) and elongation at fracture (EB) were also measured. The measurements were performed using a Shimadzu Autograph (AGS-J) at a tensile speed of 200 mm / min.

[0183] [Table 2]

[0184] Table 2 shows the viscosity of polymer mixtures adjusted to exhibit a modulus (stress at 50% extension) equivalent to that of hydrolyzable silyl group-containing polyoxypropylene (D2-1), and the results of the dumbbell properties of their one-component curable compositions. In Examples 1-1 and 1-2, which included polymers (A2), (A1), and (A0), each dumbbell property showed values ​​equivalent to those of Reference Example 1, and the viscosity showed a lower value than that of Reference Example 1. In particular, Example 1-1 showed good dumbbell properties. On the other hand, in Comparative Example 1, instead of polymer (A1), a single-ended polymer E1-1 with a number-average molecular weight of less than 3,000 was used. As a result, although the modulus was similar, both the strength (stress at fracture) and elongation decreased, and the dumbbell properties deteriorated.

[0185] [Table 3-1]

[0186] Table 3-1 shows the viscosity of polymer mixtures adjusted to exhibit a modulus equivalent to that of hydrolyzable silyl group-containing polyoxypropylene (D2-2), and the results of the dumbbell properties of the masterbatch-formulated curable compositions. In Examples 2-1 and 2-2, which included polymers (A2), (A1), and (A0), each dumbbell property showed values ​​equal to or greater than those of Reference Example 2, while the viscosity showed a lower value than that of Reference Example 2. On the other hand, in Comparative Example 2-1, although the modulus was similar, the strength (stress at fracture) decreased and the dumbbell properties deteriorated because polymer (A1) was not used. Also, in Comparative Example 2-2, since one-ended polymer E1-2 with a number-average molecular weight exceeding 25,000 was used instead of polymer (A1), although the individual dumbbell properties were similar to those of Reference Example 2, the viscosity was higher.

[0187] [Table 3-2]

[0188] Table 3-2 shows the viscosity of polymer mixtures adjusted to exhibit a modulus equivalent to that of hydrolyzable silyl group-containing polyoxypropylene (D2-3), and the results of the dumbbell properties of the masterbatch-formulated curable compositions. In Examples 3-1 and 3-2, which included polymers (A2), (A1), and (A0), each dumbbell property showed values ​​equivalent to those of Reference Example 3, and the viscosity showed a lower value than that of Reference Example 3. On the other hand, in Comparative Examples 3-1 and 3-2, instead of polymer (A1), a single-ended polymer E1-2 with a number-average molecular weight exceeding 25,000 was used. As a result, although the physical properties of each dumbbell were similar to those of Reference Example 3, they showed higher viscosity values.

Claims

1. A polymer mixture comprising polyoxyalkylene polymers (A0), (A1), and (A2), The polyoxyalkylene polymer (A0) does not have hydrolyzable silyl groups and has a number-average molecular weight of 500 to 100,000. The polyoxyalkylene polymer (A1) has a hydrolyzable silyl group at only one terminal of the polymer skeleton, and its number average molecular weight is 3,000 or more and 25,000 or less. The polyoxyalkylene polymer (A2) has at least two terminals of the polymer backbone that are part of the following general formula (2): -OCH ２ CH ２ CH ２ SiR １ ３－ａ X ａ (2) (In the formula, R １ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R １ A polymer mixture having a hydrolyzable silyl group-containing structure represented by (or if there are multiple X's, they may be the same or different), wherein the average number of hydrolyzable silyl groups per terminal is 0.90 or more, and the number average molecular weight is 3,000 or more and 100,000 or less.

2. The polymer mixture according to claim 1, wherein the number average molecular weight of at least one of the polyoxyalkylene polymers (A0) and (A1) is 1,000 or more smaller than the number average molecular weight of the polyoxyalkylene polymer (A2).

3. The polymer mixture according to claim 2, wherein the number average molecular weights of polyoxyalkylene polymers (A0) and (A1) are 1,000 or more smaller than the number average molecular weight of polyoxyalkylene polymer (A2).

4. The polymer mixture according to claim 1, wherein the number average molecular weight of the polyoxyalkylene polymer (A2) is 10,000 or more.

5. The polymer mixture according to claim 1, wherein the number average molecular weight of the polyoxyalkylene polymers (A0) and (A1) is 10,000 or less.

6. The polymer mixture according to claim 5, wherein the number average molecular weight of the polyoxyalkylene polymers (A0) and (A1) is 6,000 or less.

7. The polymer mixture according to claim 1, wherein the polymer backbone of the polyoxyalkylene polymer (A2) is linear.

8. The polymer mixture according to claim 1, wherein the polyoxyalkylene polymer (A1) has an average number of hydrolyzable silyl groups per polymer molecule of 0.90 or more.

9. The polymer mixture according to claim 1, wherein, of the total amount of polyoxyalkylene polymers (A0), (A1), and (A2), the proportion of polyoxyalkylene polymer (A0) is 1 to 40% by weight, the proportion of polyoxyalkylene polymer (A1) is 1 to 20% by weight, and the proportion of polyoxyalkylene polymer (A2) is 40 to 90% by weight.

10. A curable composition containing a polymer mixture according to any one of claims 1 to 9, and a silanol condensation catalyst.

11. A cured product obtained by curing the curable composition described in claim 10.

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