Polyoxyalkylene polymer and curable composition

Abstract

To provide a hydrolyzable silyl group-containing polyoxyalkylene-based polymer capable of forming a cured product having enhanced restorative properties while exhibiting low modulus.SOLUTION: There is provided a polyoxyalkylene-based polymer having a polyoxyalkylene main chain structure and a terminal structure bonded to the end of the main chain structure, wherein the terminal structure has a hydrolyzable silyl group, a terminal olefin group and / or an internal olefin group, the total number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups is 1.0 or more per terminal structure on average and the molar number of hydrolyzable silyl groups in the polyoxyalkylene-based polymer / (the total molar number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups) is 0.3 to 0.7.SELECTED DRAWING: None

Description

[Technical field]

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

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

[0003] Known examples of the main chain skeleton of such polymers include polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers. In particular, polyoxyalkylene polymers having hydrolyzable silyl groups have a wide range of applications due to their relatively low viscosity at room temperature and ease of handling, and the cured products obtained after the reaction also exhibit good elasticity.

[0004] Patent Document 1 discloses a room-temperature curable composition containing a polyoxyalkylene polymer having a hydrolyzable silyl group at at least one end, and describes a method for producing the polymer in which a terminal hydroxyl group of the polyoxyalkylene polymer is converted to an alkoxide group, and then an organic halide such as allyl chloride is reacted therewith to introduce a carbon-carbon double bond at the end, and further, hydrosilanes are added to convert the terminal hydroxyl group into a hydrolyzable silyl group.

[0005] Furthermore, Patent Document 2 discloses a polyoxyalkylene polymer having two or more hydrolyzable silyl groups at one terminal site, and describes a method for producing the polymer in which a terminal hydroxyl group of the polymer is first converted to an alkoxide group, followed by reaction with an epoxy compound having a carbon-carbon double bond, and further reaction with an organic halide having a carbon-carbon double bond, such as allyl chloride, thereby introducing two or more carbon-carbon double bonds into one terminal site, and then subjecting hydrosilanes to an addition reaction.

[0006] On the other hand, in recent years, the construction market has been demanding sealants that are less susceptible to bleeding out. For this reason, in curable compositions for sealants, instead of using conventional phthalate ester plasticizers or PPG plasticizers, a method of blending reactive diluents with hydrolyzable silyl groups introduced only at one end of the polymer molecular chain has been studied. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 52-73998 [Patent Document 2] International Publication No. 2013 / 180203 Summary of the Invention [Problem to be solved by the invention]

[0008] When such a reactive diluent is blended into a curable composition containing a hydrolyzable silyl group-containing polyoxyalkylene polymer, bleeding out can be suppressed, but the restoring ability of the cured product (the ability to return to the original shape after a predetermined deformation) tends to decrease. To address this, a method of improving the restoring ability by increasing the modulus (the stress required to give a predetermined deformation, in this case, particularly the stress during elongation of a dumbbell-shaped test specimen) of the cured product of the hydrolyzable silyl group-containing polyoxyalkylene polymer, which is the base polymer, is considered. However, since an increase in modulus can lead to a decrease in flexibility, it is preferable to keep the modulus low.

[0009] In view of the above-mentioned current situation, an object of the present invention is to provide a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product having a low modulus and improved recovery, and a curable composition containing the same. [Means for solving the problem]

[0010] As a result of intensive research by the present inventors to solve the above problems, it has been found that a polyoxyalkylene polymer having a hydrolyzable silyl group, and a terminal olefin group and / or an internal olefin group in a terminal structure, in which the total number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups is on average more than 1.0 per terminal structure, and the number of moles of hydrolyzable silyl groups / (total number of moles of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups) is set to a relatively low value of 0.3 to 0.7, can be provided, which has led to the present invention.

[0011] That is, the present invention relates to a polyoxyalkylene polymer (A) having a polyoxyalkylene main chain structure and a terminal structure bonded to an end of the main chain structure, the terminal structure having a hydrolyzable silyl group, and a terminal olefin group and / or an internal olefin group, the total number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups being on average more than 1.0 per terminal structure, and the molar number of hydrolyzable silyl groups in the polyoxyalkylene polymer / (the total molar number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups) being 0.3 to 0.7.

[0012] Preferably, the terminal structure includes a moiety derived from an epoxy compound having a terminal olefin group, and more preferably, the number of moieties derived from the epoxy compound having a terminal olefin group is greater than 1.0 on average per terminal structure.

[0013] Preferably, the hydrolyzable silyl group is represented by the general formula (1): -(Si(R 1 2-b )(Y′ b )O) m SiR 2 3-a Y a (1) (In the formula, R 1 and R 2are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R')3SiO-. R' are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Y and Y' are the same or different and represent a hydroxyl group or a hydrolyzable group. a represents 0, 1, 2 or 3. b represents 0, 1 or 2, but when m is 2 or more, different numbers may coexist as b. m represents an integer of 0 to 19. However, a+m×b represents an integer of 1 or more. ) is preferably represented by R 1 , R 2 Or R' represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 3 carbon atoms.

[0014] More preferably, the hydrolyzable silyl group is represented by the general formula (2): -SiR 2 3-a Y a (2) (In the formula, R 2 are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R')3SiO-. R' are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Y are the same or different and represent a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3.

[0015] More preferably, the hydrolyzable silyl group is a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, or a (N,N-diethylaminomethyl)diethoxysilyl group.

[0016] Even more preferably, the hydrolyzable silyl group is represented by the general formula (3): -SiR2 Y2(3) (In the formula, R 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R')3SiO-. R' may be the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Y may be the same or different and represent a hydroxyl group or a hydrolyzable group.

[0017] Preferably, the number of hydrolyzable silyl groups per terminal structure is 0.85 or more on average.

[0018] Preferably, the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups per terminal structure is 1.1 or more on average, more preferably 1.3 or more on average, and preferably 10 or less on average, per terminal structure.

[0019] Preferably, the terminal olefin group has the following general formula (4): H2C=C(R 3 )-CH2- (4) The internal olefin group is represented by the following general formula (5): H3C-C(R 3 )=CH- (5) In the formulas (4) and (5), R 3 represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms. 3 represents hydrogen or a methyl group.

[0020] Preferably, the molar number of the hydrolyzable silyl groups / (the total molar number of the hydrolyzable silyl groups, the terminal olefin groups, and the internal olefin groups) is 0.65 or less, more preferably 0.6 or less, even more preferably 0.55 or less, and particularly preferably 0.5 or less. The ratio is preferably 0.35 or more, more preferably 0.4 or more.

[0021] Preferably, the cured product of the polyoxyalkylene polymer (A) has a recovery rate of 90% or more. Preferably, the cured product of the polyoxyalkylene polymer (A) has a stress at 100% elongation of 0.40 MPa or less.

[0022] The present invention also relates to a curable composition containing the polyoxyalkylene polymer (A). The curable composition may further contain a reactive diluent (D) which is a polymer having an average of 0.5 to less than 1.2 hydrolyzable silyl groups per molecule and has a lower viscosity at 23°C than the polyoxyalkylene polymer (A). The curable composition may further contain a (meth)acrylic acid ester polymer (B) having a hydrolyzable silyl group.

[0023] The present invention further relates to a cured product of the curable composition. Furthermore, the present invention also relates to uses of the polyoxyalkylene polymer (A) in sealing materials, adhesives, pressure sensitive adhesives, insulating materials, paints, sealants, or waterproofing materials. Effect of the Invention

[0024] According to the present invention, it is possible to provide a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product having a low modulus and improved recovery, and a curable composition containing the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Hereinafter, an embodiment of the present invention will be described in detail.

[0026] <Polyoxyalkylene polymer (A)> The polyoxyalkylene polymer (A) of the present invention has a polyoxyalkylene main chain structure and a terminal structure bonded to the end of the main chain structure.

[0027] The main chain structure refers to a polymer main chain composed of oxyalkylene repeating units. The main chain structure may be linear or branched. The main chain structure is preferably a polymer main chain composed only of oxyalkylene repeating units, or a polymer main chain composed only of oxyalkylene repeating units and including a structure derived from an initiator used during polymerization in addition to the oxyalkylene repeating units. Here, the oxyalkylene repeating units refer to repeating units constituting polyether, and are, for example, oxyalkylene units having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0028] The main chain structure of the polyoxyalkylene is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Polyoxypropylene is preferred. As the main chain structure, only one type may be used, or two or more types may be used in combination.

[0029] The terminal structure refers to a portion that does not contain an oxyalkylene repeating unit constituting the main chain structure and is bonded to the end of the main chain structure. When the main chain structure is linear, two terminal structures are present per polymer molecule, and when the main chain structure is branched, three or more terminal structures are present per polymer molecule. When the main chain structure is a mixture of linear and branched structures, the number of terminal structures per polymer molecule can be between 2 and 3 on average. It is preferable that the terminal structure is bonded to the oxyalkylene unit located at the end of the main chain structure via an oxygen atom.

[0030] The terminal structure in the polyoxyalkylene polymer (A) of the present invention has a hydrolyzable silyl group and either or both of a terminal olefin group and an internal olefin group. This does not refer to the terminal structure in a specific molecule of the polymer, but means that the terminal structure in the entire polymer containing a large number of polymer molecules may have a hydrolyzable silyl group and a terminal olefin group and / or an internal olefin group. In other words, the terminal structure in a specific molecule of the polymer may have only a hydrolyzable silyl group and no terminal olefin group or no internal olefin group, or may have either or both of a terminal olefin group and an internal olefin group but no hydrolyzable silyl group.

[0031] The hydrolyzable silyl group refers to a silyl group that can form a siloxane bond by hydrolysis and dehydration condensation and bond to each other. The polyoxyalkylene polymer (A) of the present invention exhibits curability based on a dehydration condensation reaction by having the hydrolyzable silyl group. Specifically, the hydrolyzable silyl group is represented by the following general formula (1): -(Si(R 1 2-b )(Y′ b )O) m SiR 2 3-a Y a (1) In formula (1), R 1 and R 2 are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R')3SiO-. R' are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Y and Y' are the same or different and represent a hydroxyl group or a hydrolyzable group. a represents 0, 1, 2 or 3. b represents 0, 1 or 2, but when m is 2 or more, different numbers may coexist as b. m represents an integer of 0 to 19. However, a+m×b represents an integer of 1 or more.

[0032] R 1 or R 2In the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I), the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as a chloro group, alkoxy groups such as a methoxy group, and amino groups such as an N,N-diethylamino group.

[0033] R' in the triorganosiloxy group represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as a chloro group, alkoxy groups such as a methoxy group, and amino groups such as an N,N-diethylamino group. The three R's may be the same or different from each other.

[0034] R 1 and R 2 Examples of the alkyl group 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; aralkyl groups such as benzyl; and triorganosiloxy groups represented by (R')3SiO-, where R' is a methyl group, a phenyl group, or the like. Preferably, it is a substituted or unsubstituted alkyl group, more preferably a methyl group, an ethyl group, a chloromethyl group, or a methoxymethyl group, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. R 1 and R 2 As the alkyl group, only one type of group may be used, or two or more types of groups may be used in combination.

[0035] Examples of Y and Y' include hydroxyl, hydrogen, halogen, alkoxy, acyloxy, ketoximate, amino, amide, acid amide, aminooxy, mercapto, and alkenyloxy. The alkoxy may have a substituent. Since it is mildly hydrolyzable and easy to handle, an alkoxy is preferred, a methoxy, ethoxy, n-propoxy, and isopropoxy are more preferred, a methoxy and ethoxy are even more preferred, and a methoxy is particularly preferred. As Y and Y', only one type of group may be used, or two or more types of groups may be used in combination.

[0036] As described above, m represents an integer of 0 to 19, and preferably represents 0. When m is 0, the general formula (1) can be changed to the following general formula (2): -SiR 2 3-a Y a (2) In this general formula (2), a represents 1, 2 or 3.

[0037] Examples of the hydrolyzable silyl group represented by the general formula (2) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, and a (N,N-diethylaminomethyl)diethoxysilyl group. Among them, the methyldimethoxysilyl group, the trimethoxysilyl group, the triethoxysilyl group, the (chloromethyl)dimethoxysilyl group, the (methoxymethyl)dimethoxysilyl group, the (methoxymethyl)diethoxysilyl group, and the (N,N-diethylaminomethyl)dimethoxysilyl group are preferred because they show high reactivity and can give a cured product having good mechanical properties. From the viewpoint of reactivity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferred. From the viewpoint of stability, methyldimethoxysilyl group, methyldiethoxysilyl group, and triethoxysilyl group are more preferred, and methyldiethoxysilyl group and triethoxysilyl group are even more preferred. In addition, trimethoxysilyl group, triethoxysilyl group, and methyldimethoxysilyl group are more preferred because they are easy to produce. Among them, methyldimethoxysilyl group is the most preferred.

[0038] In the general formula (2), in order to achieve both the storage stability and reactivity of the polymer and the flexibility of the cured product, it is preferable that a represents 2. When a is 2, the general formula (2) is represented by the following general formula (3): -SiR 2 Y2(3) In the formula, R 2 and Y are as defined above, provided that in the general formula (1) or (2), two or more types of hydrolyzable silyl groups having different a's may be used in combination.

[0039] The terminal olefin group refers to a carbon-carbon double bond having a methylidene group (H2C=), and specifically, is represented by the following general formula (4): H2C=C(R 3 )-CH2- (4) In formula (4), R 3 represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The aryl group preferably has 6 to 8 carbon atoms, more preferably 6 to 7 carbon atoms. The aralkyl group more preferably has 7 to 8 carbon atoms. When the alkyl group, aryl group, or aralkyl group has a substituent, the substituent is not particularly limited, and examples thereof include a halogen group such as a chloro group, an alkoxy group such as a methoxy group, and an amino group such as an N,N-diethylamino group.

[0040] R 3 Examples of the alkyl group include hydrogen, alkyl groups such as methyl, ethyl, propyl, and butyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 3 is preferably hydrogen or an alkyl group, more preferably hydrogen, a methyl group or an ethyl group, and further preferably hydrogen or a methyl group. 3 may be the same or different from each other.

[0041] The internal olefin group refers to a carbon-carbon double bond that does not have a methylidene group (H2C=), and specifically, is represented by the following general formula (5): H3C-C(R 3 )=CH- (5) It can be expressed as follows. R in Equation (5) 3 is usually R in the formula (4). 3 represents the same group as R 3 Within the scope of the definition of R in formula (4), 3 In addition, R may represent a group different from that of the polymer. 3may be the same or different from each other.

[0042] The internal olefin group is a group that can be generated by an internal rearrangement reaction of the terminal olefin group, as described below. 3 =H), the internal olefin group produced by its internal rearrangement is a 1-propenyl group.

[0043] The polyoxyalkylene polymer (A) of the present invention has a hydrolyzable silyl group and a terminal olefin group and / or an internal olefin group in its terminal structure, and the total number of the hydrolyzable silyl group, the terminal olefin group, and the internal olefin group is more than 1.0 on average per terminal structure. As a result, the cured product of the polyoxyalkylene polymer (A) of the present invention can exhibit a lower modulus when the amount of hydrolyzable silyl groups introduced is the same, compared with a cured product of a polyoxyalkylene polymer in which the total number is 1.0 or less on average per terminal structure. The total number is preferably 1.1 or more, more preferably 1.3 or more, and even more preferably 1.5 or more. Furthermore, it is preferably more than 1.5, particularly preferably 2.0 or more, and most preferably 2.5 or more. The upper limit of the total number is not limited, but from the viewpoint of economic efficiency and introduction efficiency of the corresponding structure, it is preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, and especially preferably 5 or less.

[0044] The total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups per terminal structure can be expressed as the average ratio of the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups to the number of ends of the main chain structure, and can also be expressed as the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups per polymer molecule / the number of ends of the main chain structure in one polymer molecule.

[0045] In the present invention, the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups per terminal structure can be appropriately determined by a person skilled in the art. As an example, when the polyoxyalkylene polymer (A) of the present invention is produced by reacting a hydroxyl-terminated polyoxyalkylene polymer (E) with an epoxy compound having a terminal olefin group, and then reacting with an organic halide having a terminal olefin group, as described below, the total number can be calculated by adding the number of equivalents of the epoxy compound relative to the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) (the number of olefin groups introduced by the epoxy compound) and 1 (the number of olefin groups introduced by the organic halide). In addition, the total number can be calculated by the following method: 1 It can also be calculated by analysis of iodine value / hydroxyl value, etc., by H NMR or titration.

[0046] Furthermore, the polyoxyalkylene polymer (A) of the present invention can form a cured product with improved restorability while maintaining a low modulus by relatively lowering the ratio of hydrolyzable silyl groups to the total of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups. That is, in the polyoxyalkylene polymer (A) of the present invention, the molar number of hydrolyzable silyl groups / (the total molar number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups) is 0.3 to 0.7 on average. By setting the ratio to 0.3 to 0.7, the cured product containing the polyoxyalkylene polymer (A) of the present invention can achieve both low modulus and good restorability. The ratio is preferably 0.65 or less, more preferably 0.6 or less, even more preferably 0.55 or less, and even more preferably 0.5 or less, in order to further reduce the modulus of the cured product containing the polyoxyalkylene polymer (A) of the present invention. The ratio is preferably 0.35 or more, more preferably 0.4 or more, in order to further improve the restorability of the cured product containing the polyoxyalkylene polymer (A) of the present invention. The "molar number of hydrolyzable silyl groups / (total mole number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups)" can also be expressed as the "hydrolyzable silyl group introduction rate." The ratio can also be expressed as a percentage, and for example, a ratio of 0.3 and a ratio of 30% have the same meaning.

[0047] In the present invention, the ratio is: 1 For example, when the terminal olefin group is an allyl group and a hydrolyzable silyl group is introduced into the terminal structure by a hydrosilylation reaction of a hydrosilane compound having a hydrolyzable silyl group as described below, the integral value of each of the following signals may be used for calculation. Hydrolyzable silyl group: CH2 bonded to silyl group (around 0.6 ppm, 2H) Terminal olefin group: Methylidene group CH2 (around 5.2 ppm, 2H) Internal olefin group: CH bonded to terminal CH3 group (total of around 4.3 ppm and around 4.8 ppm, 1H) When other signals overlap, the integral values ​​of those signals are excluded from the calculation.

[0048] The polyoxyalkylene polymer (A) of the present invention has hydrolyzable silyl groups in a range that satisfies both the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups, and the molar number of hydrolyzable silyl groups / (total molar number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups). The number of hydrolyzable silyl groups is preferably 0.7 or more on average per terminal structure, more preferably 0.85 or more, even more preferably 1.0 or more, and particularly preferably 1.2 or more. This allows the polyoxyalkylene polymer (A) of the present invention to exhibit good curability. The number of hydrolyzable silyl groups per terminal structure can be calculated by multiplying the above-mentioned "total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups per terminal structure" by the above-mentioned "proportion of hydrolyzable silyl groups to the total of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups".

[0049] The terminal structure of the polyoxyalkylene polymer (A) of the present invention is not particularly limited as long as it has a hydrolyzable silyl group and a terminal olefin group and / or an internal olefin group. An example of the terminal structure having a hydrolyzable silyl group and a terminal olefin group is represented by the following general formula (6):

[0050] [ka]

[0051] Another example is the following general formula (7):

[0052] [ka]

[0053] The oxygen atom at the left end in the general formulae (6) and (7) represents the oxygen atom in the oxyalkylene unit located at the end of the main chain structure of the polyoxyalkylene. In the general formulae (6) and (7), the hydrolyzable silyl group is represented by the above-mentioned general formula (2), but the present invention is not limited thereto.

[0054] In the general formulas (6) and (7), d and e each represent an integer of 0 or more, and the sum of d and e is greater than 0 on average per terminal structure. The sum of d and e is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. Furthermore, it is preferably greater than 0.5, particularly preferably 1.0 or more, and most preferably 1.5 or more. The sum of d and e is preferably 9 or less, more preferably 7 or less, even more preferably 5 or less, and especially preferably 4 or less.

[0055] R 2 and R 3 Each of the R's is as described above. 2 or R 3 may be the same or different from each other.

[0056] In the general formulas (6) and (7), R 4 R represents a direct bond or a divalent organic group having 1 to 6 carbon atoms which may have an oxygen atom. The number of carbon atoms in the organic group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 2. 4 is preferably a divalent organic group having 1 to 6 carbon atoms which may have an oxygen atom, more preferably -CH2-, -CH2O-, -CH2OCH2-, -C(=O)-O-CH2-, and further preferably -CH2OCH2-. 4 may be the same or different from each other.

[0057] In the general formulas (6) and (7), R 5 R represents a direct bond or a divalent organic group having 1 to 6 carbon atoms which may have an oxygen atom. The number of carbon atoms in the organic group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. 5is preferably a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a direct bond, -CH2- or -CH2CH2-, further preferably a direct bond or -CH2-, and particularly preferably -CH2-.

[0058] The terminal structure represented by general formula (6) has (e+1) hydrolyzable silyl groups and d terminal olefin groups. The terminal structure represented by general formula (7) has e hydrolyzable silyl groups and (d+1) terminal olefin groups. The d terminal olefin group-containing units and the e hydrolyzable silyl group-containing units shown in general formula (6) or (7) each correspond to a moiety derived from an epoxy compound having a terminal olefin group described below.

[0059] The terminal structure represented by general formula (6) or (7) represents one terminal structure bonded to one end of the polymer main chain. Although multiple hydrolyzable silyl groups and / or terminal olefin groups are shown in formula (6) or (7), formula (6) or (7) does not represent two or more terminal structures, but represents one terminal structure, and indicates that multiple hydrolyzable silyl groups and / or terminal olefin groups exist in one terminal structure. In addition, formula (6) or (7) does not represent an oxyalkylene repeat unit constituting the polymer main chain. In other words, the structures in parentheses present in the number of d or e in formula (6) or (7) do not correspond to the oxyalkylene repeat unit constituting the polymer main chain.

[0060] These general formulae are merely illustrative examples, and the terminal structure in the present invention is not limited to these chemical structures. The terminal olefin groups contained in the general formulae (6) and (7) may be internal olefin groups. In particular, some of the multiple terminal olefin groups may be internal olefin groups. The bonding order of d terminal olefin group-containing units and e hydrolyzable silyl group-containing units is not limited to the order shown in the general formulae (6) and (7). The specific structural formula of the terminal structure of the polyoxyalkylene polymer (A) of the present invention is not limited to a single one, and usually various structural formulas may coexist. The terminal structure represented by the general formula (6) and the terminal structure represented by the general formula (7) may also coexist.

[0061] The number average molecular weight of the polyoxyalkylene polymer (A) of the present invention is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 3,000 to 30,000 in terms of polystyrene equivalent molecular weight by GPC. If the number average molecular weight is less than 3,000, the relative amount of hydrolyzable silyl groups to the entire polymer increases, which may be disadvantageous in terms of production costs. If the number average molecular weight exceeds 100,000, the polymer may become highly viscous and workability may decrease.

[0062] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) of the present invention is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. The molecular weight distribution (Mw / Mn) can be calculated from the number average molecular weight and weight average molecular weight determined by GPC measurement.

[0063] The polyoxyalkylene polymer (A) of the present invention has a stress at 100% elongation (100% modulus) of 0.40 MPa or less, more preferably 0.35 MPa or less, in order to maintain the flexibility of the cured product of the curable composition containing the polyoxyalkylene polymer (A) of the present invention. On the other hand, in order to maintain the mechanical properties of the cured product, the stress at 100% elongation of the cured product of the polymer is preferably 0.10 MPa or more, more preferably 0.15 MPa or more. Here, the stress at 100% elongation of the cured product of the polymer is defined as a value measured under the following conditions.

[0064] <Method for measuring stress at 100% elongation of cured polymer> A mixture of polyoxyalkylene polymer / tin(II) octylate / laurylamine / distilled water = 40 / 1.2 / 0.2 / 0.24 (weight ratio) is filled into a 3 mm thick sheet form. It is stored at 23°C and 50% relative humidity for at least 1 hour, and then cured in a 70°C dryer for 20 hours to obtain a sheet-like cured product. The resulting cured product is punched out into a No. 3 dumbbell-shaped test piece in accordance with JIS K 6251. Using the resulting test piece, a tensile test (tensile speed 200 mm / min) is carried out using an autograph at 23°C and a relative humidity of 50%, and the stress at 100% elongation is measured.

[0065] The polyoxyalkylene polymer (A) of the present invention preferably has a restoration rate of 90% or more for the cured product of the polymer, since the curable composition containing the polyoxyalkylene polymer (A) of the present invention has high restoration rate for the cured product. Here, the restoration rate of the cured product of the polymer is defined as a value measured under the following conditions.

[0066] <Method for measuring the recovery rate of a cured polymer> A mixture of polyoxyalkylene polymer / 3-(N-2-aminoethylamino)propyltrimethoxysilane / tin(II) octylate / laurylamine / distilled water = 40 / 1.2 / 1.2 / 0.2 / 0.32 (weight ratio) is filled into a 3 mm thick sheet form. It is cured for 3 days at 23°C and 50% relative humidity, and then aged in a 50°C dryer for 4 days to obtain a sheet-like cured product. The above sheet-like cured product is punched into a No. 7 dumbbell-shaped test piece. Two benchmark lines are drawn at the neck of the dumbbell-shaped test piece, spaced 10 mm apart. The dumbbell-shaped test piece is stretched and fixed so that the gap between the benchmark lines is 15 mm, and left to stand in a dryer at 50°C. After 5 hours, the test piece is released from the fixing position, and the gap between the benchmark lines is measured after 1 hour at 23°C and 50% relative humidity to determine the recovery rate.

[0067] <Method for producing polyoxyalkylene polymer (A)> Next, a method for producing the polyoxyalkylene polymer (A) of the present invention will be described. The polyoxyalkylene polymer (A) of the present invention can be produced by introducing more than 1.0 terminal olefin groups per terminal structure on average into the hydroxyl-terminated polyoxyalkylene polymer (E) by utilizing the reactivity of the hydroxyl groups, and then reacting the polymer with a hydrolyzable silyl-group-containing compound reactive with the terminal olefin groups to introduce the hydrolyzable silyl groups.

[0068] The method for producing the polyoxyalkylene polymer (A) of the present invention will be specifically described below, but is not limited thereto. First, a hydroxyl-terminated polyoxyalkylene polymer (E) is reacted with an epoxy compound (8) having a terminal olefin group, and further with an organic halide (10) having a terminal olefin group, to introduce an average of more than 1.0 terminal olefin groups per terminal structure of the polymer. Next, the terminal olefin groups are subjected to a hydrosilylation reaction with a hydrosilane compound (12) having a hydrolyzable silyl group, thereby introducing a hydrolyzable silyl group into the terminal structure, thereby obtaining the polyoxyalkylene polymer (A) of the present invention. In the above production method, the reaction of the terminal structure of the polymer can be represented, for example, by the following reaction formula. In the formula, X represents a halogen, and M represents an alkali metal.

[0069] [ka]

[0070] In the present invention, when introducing hydrolyzable silyl groups, all of the reactive terminal olefin groups are not reacted with the hydrosilane compound, but the reaction rate is suppressed to leave some of the terminal olefin groups unreacted, thereby making it possible to obtain the polyoxyalkylene polymer (A) of the present invention in which the ratio of the number of moles of hydrolyzable silyl groups / (the total number of moles of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups) satisfies the range of 0.3 to 0.7.

[0071] The internal olefin group can be generated as a side reaction during the hydrosilylation reaction by an internal rearrangement reaction (isomerization) of a terminal olefin group. Since the generated internal olefin group has low hydrosilylation activity, it does not react with a hydrosilane compound in the hydrosilylation reaction and remains in the polyoxyalkylene polymer (A) of the present invention.

[0072] Hereinafter, one embodiment of the method for producing the polyoxyalkylene polymer (A) of the present invention will be described in detail, but the method for producing the polyoxyalkylene polymer (A) of the present invention is not limited thereto.

[0073] (polymerization) The main chain structure of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a hydroxyl-terminated polyoxyalkylene polymer (E). Although the specific polymerization method is not particularly limited, a polymerization method using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it can obtain a hydroxyl-terminated polymer with a small molecular weight distribution (Mw / Mn).

[0074] The initiator having a hydroxyl group is not particularly limited, and examples thereof include organic compounds having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight polyoxypropylene monoalkyl ether.

[0075] The epoxy compound is not particularly limited, but examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether, etc. Propylene oxide is preferred.

[0076] (Introduction of terminal olefin groups) A preferred method for introducing an average of more than 1.0 terminal olefin groups per terminal structure of a polymer is to react an alkali metal salt with a hydroxyl-terminated polyoxyalkylene polymer (E) to convert the terminal hydroxyl groups to alkoxide groups, then react the polymer with an epoxy compound (8) having a terminal olefin group, and then react the polymer with an organic halide (10) having a terminal olefin group. A composite metal cyanide complex catalyst can also be used in place of the alkali metal salt.

[0077] The alkali metal salt is not particularly limited, and examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium methoxide are more preferred. From the viewpoint of availability, sodium methoxide is particularly preferred. The alkali metal salt may be dissolved in a solvent and then subjected to the reaction.

[0078] The amount of the alkali metal salt used is not particularly limited, but the molar ratio to the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer (E) is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and even more preferably 0.8 or more. The molar ratio is preferably 1.2 or less, more preferably 1.1 or less. If the amount of the alkali metal salt used is too small, the reaction may not proceed sufficiently. Conversely, if the amount used is too large, the alkali metal salt may remain as an impurity, and a side reaction may proceed.

[0079] The alkali metal salt is used to convert the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer (E) to an alkoxide group, and in order to efficiently proceed with this conversion reaction, it is preferable to remove moisture and substances having hydroxyl groups other than the polyoxyalkylene polymer from the reaction system in advance.To remove them, a known method may be used, for example, heating evaporation, reduced pressure devolatilization, spray evaporation, thin film evaporation, azeotropic devolatilization, etc. may be used.

[0080] The temperature for reacting with the alkali metal salt can be appropriately set by those skilled in the art, but is preferably from 50° C. to 150° C., and more preferably from 110° C. to 145° C. The time for reacting with the alkali metal salt is preferably from 10 minutes to 5 hours, and more preferably from 30 minutes to 3 hours.

[0081] Next, an epoxy compound (8) having a terminal olefin group is subjected to a ring-opening addition reaction with the polyoxyalkylene polymer to form a terminal structure (9) including a moiety derived from the epoxy compound having a terminal olefin group.

[0082] The epoxy compound having a terminal olefin group can be represented by chemical formula (8) in the reaction formula, but is not limited thereto. Specific examples of the epoxy compound include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, 1,4-cyclopentadiene monoepoxide, etc., and allyl glycidyl ether is particularly preferred.

[0083] The amount of the epoxy compound (8) having a terminal olefin group used is not particularly limited, and may be appropriately set in consideration of the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups in the terminal structure of the target polymer, and the reactivity of the epoxy compound used. Specifically, the amount of the epoxy compound (8) used is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, in terms of the molar ratio to the hydroxyl groups in the hydroxyl-terminated polyoxyalkylene polymer (E). Furthermore, it is preferably more than 0.5, particularly preferably 1.0 or more, and most preferably 1.5 or more. Moreover, the molar ratio is preferably 9 or less, more preferably 7 or less, even more preferably 5 or less, and especially preferably 4 or less.

[0084] The reaction temperature when the epoxy compound (8) having a terminal olefin group is subjected to a ring-opening addition reaction can be appropriately set by those skilled in the art, but is preferably from 60° C. to 150° C., more preferably from 110° C. to 145° C. The reaction time is preferably from 10 minutes to 5 hours, more preferably from 1 hour to 4 hours.

[0085] Next, the polyoxyalkylene polymer having a terminal structure (9) including a moiety derived from an epoxy compound having a terminal olefin group is reacted with an organic halide (10) having a terminal olefin group to form an ether bond by a halogen substitution reaction, and the alkoxide group at the polymer end is converted to a terminal olefin group, thereby forming a terminal structure (11) having an average of more than 1.0 terminal olefin group per terminal structure.

[0086] The organic halide having a terminal olefin group can be represented by chemical formula (10) in the reaction formula, but is not limited thereto.Specific examples of the organic halide include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide, etc.In view of ease of handling, allyl chloride and methallyl chloride are preferred.

[0087] The amount of the organic halide (10) having a terminal olefin group to be used is not particularly limited, but the molar ratio to the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) is preferably 0.7 or more, more preferably 1.0 or more, and the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

[0088] The temperature for reacting the organic halide (10) having a terminal olefin group can be appropriately set by those skilled in the art, but is preferably from 50° C. to 150° C., more preferably from 110° C. to 140° C. The reaction time is preferably from 10 minutes to 5 hours, more preferably from 20 minutes to 2 hours.

[0089] (Introduction of hydrolyzable silyl groups) The polyoxyalkylene polymer having the terminal structure (11) having an average of more than 1.0 terminal olefin groups per terminal structure obtained as above is subjected to a hydrosilylation reaction with a hydrosilane compound (12) having a hydrolyzable silyl group to introduce hydrolyzable silyl groups into some of the terminal olefin groups. At this time, the remaining terminal olefin groups are allowed to remain in the polymer without reacting with the hydrosilane compound (12). In addition, as described above, in the hydrosilylation reaction, some of the terminal olefin groups may be isomerized to internal olefin groups due to a side reaction. In this manner, the polyoxyalkylene polymer (A) of the present invention having a hydrolyzable silyl group and terminal structures (6) and / or (7) having a terminal olefin group and / or an internal olefin group can be produced. The hydrosilylation reaction has the advantages of being easily carried out, easy adjustment of the amount of hydrolyzable silyl groups introduced, and stable physical properties of the resulting polymer.

[0090] The hydrosilane compound having a hydrolyzable silyl group can be represented by chemical formula (12) in the above reaction scheme, but is not limited thereto. Specific examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, and (3,3,3-trifluoropropylsilane. (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoro alkoxysilanes such as [3-(2-propyl)dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0091] The amount of the hydrolyzable silyl group-containing hydrosilane compound (12) used may be appropriately determined in consideration of the amount of terminal olefin groups in the polyoxyalkylene polymer before the hydrosilylation reaction so that the mole number of hydrolyzable silyl groups / (total mole number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups) falls within the range of 0.3 to 0.7. Specifically, the molar ratio of the hydrosilane compound to the terminal olefin groups in the polyoxyalkylene polymer before the hydrosilylation reaction is preferably 0.3 to 0.7.

[0092] The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction. Known examples of the hydrosilylation catalyst include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and complexes thereof. Specifically, platinum is supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid and 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-phosphite complexes [e.g., Pt{P(OPh)3}4], etc. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

[0093] The temperature conditions of the hydrosilylation reaction are not particularly limited and can be appropriately set by those skilled in the art, but for the purpose of reducing the viscosity of the reaction system and improving the reactivity, the reaction is preferably carried out under heating conditions, more preferably at 50°C to 150°C, and even more preferably at 70°C to 120°C. The reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction of the polymer does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, more preferably 3 hours or less.

[0094] The hydrosilylation reaction may be carried out in the presence of a trialkyl orthocarboxylate, which can suppress thickening during the hydrosilylation reaction and improve the storage stability of the resulting polymer.

[0095] Examples of the orthocarboxylate trialkyl ester include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, etc. Preferred are trimethyl orthoformate and trimethyl orthoacetate.

[0096] When a trialkyl orthocarboxylate is used, its amount is not particularly limited, but is preferably about 0.1 to 10 parts by weight, more preferably about 0.1 to 3 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0097] <Curable composition> The present invention can provide a curable composition containing the polyoxyalkylene polymer (A).

[0098] (Silanol condensation catalyst) The curable composition of the present invention preferably contains a silanol condensation catalyst for the purpose of promoting the hydrolysis and condensation reaction of the hydrolyzable silyl groups in the polyoxyalkylene polymer (A) of the present invention, that is, the curing reaction.

[0099] As the silanol condensation catalyst, any of the conventionally known catalysts can be used. Specifically, an organic tin compound, a metal carboxylate, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid, etc. can be used.

[0100] Specific examples of organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalic acid ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), a reaction product of dioctyltin oxide and a silicate compound, etc. Dioctyltin compounds are preferred due to the increasing interest in the environment in recent years.

[0101] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, etc. The carboxylate group can be a combination of the following carboxylic acid with various metals.

[0102] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0103] 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.

[0104] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxy titanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0105] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0106] The silanol condensation catalyst may be a combination of two or more different catalysts. For example, the combination of the above-mentioned amine compound and carboxylic acid may provide an effect of improving reactivity.

[0107] The amount of the silanol condensation catalyst 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, relative to 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If the amount of the silanol condensation catalyst is less than 0.001 parts by weight, the reaction rate may be insufficient. On the other hand, if the amount of the silanol condensation catalyst is more than 20 parts by weight, the reaction rate is too fast, so that the usable time of the composition is shortened, which tends to deteriorate the workability and storage stability. Furthermore, some silanol condensation catalysts may seep out onto the surface of the cured product after the curable composition is cured, or may contaminate the surface of the cured product. In such cases, the amount of the silanol condensation catalyst used is 0.01 to 3.0 parts by weight, so that the surface condition of the cured product can be maintained good while ensuring the curability.

[0108] The curable composition of the present invention preferably further contains a reactive diluent (D) which is a polymer having an average of 0.5 to less than 1.2 hydrolyzable silyl groups per molecule and has a lower viscosity measured at 23°C than the polyoxyalkylene polymer (A) of the present invention. In the present invention, when such a reactive diluent (D) is blended, the viscosity of the composition can be reduced and bleeding out can be suppressed while maintaining high recovery. Examples of the main chain skeleton of such a reactive diluent (D) include polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth)acrylic acid ester polymers, and polyorganosiloxane polymers. Among these, polyoxyalkylene polymers are preferred as the main chain skeleton of the reactive diluent (D) from the viewpoint of compatibility with the polyoxyalkylene polymer (A) of the present invention.

[0109] The hydrolyzable silyl group in the reactive diluent (D) may be at the molecular chain end, side chain, or both. In particular, when the hydrolyzable silyl group is at the molecular chain end, the molecular weight between crosslinking points becomes long, and it is more preferable to obtain a rubber-like cured product with good mechanical properties. The number of hydrolyzable silyl groups is 0.5 or more and less than 1.2 on average per molecule, but the lower limit is preferably 0.6 or more from the viewpoint of mechanical properties during curing, and is preferably less than 1.0 in order to efficiently lower the modulus of the cured product. In addition, the reactive diluent (D) may have a terminal olefin group and / or an internal olefin group in addition to the hydrolyzable silyl group, or may not have a terminal olefin group and / or an internal olefin group, but the total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups may be 1.0 or less on average per terminal structure.

[0110] The polymer that is the reactive diluent (D) preferably has a number average molecular weight, calculated as polystyrene by GPC, of ​​3,000 or more and less than 15,000. If the number average molecular weight is less than 3,000, sufficient mechanical properties may not be obtained, and if it is 15,000 or more, the viscosity may become high and sufficient dilution effect may not be obtained.

[0111] The molecular weight distribution of the reactive diluent (D) is not particularly limited, but is preferably less than 2.0, more preferably 1.6 or less, and particularly preferably 1.4 or less.

[0112] The main chain structure of the reactive diluent (D) may be a linear or branched structure, or a structure having a plurality of hydrolyzable silyl groups at one end. Among them, a linear polymer having a hydrolyzable silyl group introduced at only one end is more preferable. In addition, the main chain structure does not have to be a single one, and each polymer may be mixed with one produced separately, or may be produced simultaneously to obtain any polymer.

[0113] The hydrolyzable silyl group of the reactive diluent (D) can be selected arbitrarily, but it is preferable that the reactive diluent (D) has the same hydrolyzable silyl group as the polyoxyalkylene polymer (A) of the present invention, since it is easy to adjust the physical properties of the cured product. In particular, it is preferable that the reactive diluent (D) has a methyldimethoxysilyl group.

[0114] The amount of the reactive diluent (D) is preferably 1 part by weight or more and 200 parts by weight or less, more preferably 10 parts by weight or more and 100 parts by weight or less, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If it is less than 1 part by weight, the effect of reducing the viscosity of the composition becomes small, and if it exceeds 200 parts by weight, the mechanical properties of the cured product tend to decrease.

[0115] In addition, the curable composition of the present invention preferably further contains a (meth)acrylic acid ester polymer (B) having a hydrolyzable silyl group. By further containing the (meth)acrylic acid ester polymer (B), the weather resistance of the cured product tends to be improved. The position of the hydrolyzable silyl group in the (meth)acrylic acid ester polymer (B) may be at the end of the polymer main chain or in the middle of the main chain.

[0116] The (meth)acrylic acid ester monomer constituting the main chain of the (meth)acrylic acid ester polymer (B) is not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonaphthalene (meth)acrylate, methyl methacrylate, ethyl meth ...butyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonaphthalene (meth)acrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate nyl, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, (3-trimethoxysilyl)propyl (meth)acrylate, (3-dimethyl)propyl (meth)acrylate Examples of (meth)acrylic acid monomers include (meth)acrylic acid (2-trimethoxysilyl)propyl, (meth)acrylic acid (2-trimethoxysilyl)ethyl, (meth)acrylic acid (2-dimethoxymethylsilyl)ethyl, (meth)acrylic acid trimethoxysilylmethyl, (meth)acrylic acid (dimethoxymethylsilyl)methyl, (meth)acrylic acid ethylene oxide adducts, (meth)acrylic acid trifluoromethylmethyl, (meth)acrylic acid 2-trifluoromethylethyl, (meth)acrylic acid 2-perfluoroethylethyl, (meth)acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth)acrylic acid perfluoroethyl, (meth)acrylic acid trifluoromethyl, (meth)acrylic acid bis(trifluoromethyl)methyl, (meth)acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth)acrylic acid 2-perfluorohexylethyl, (meth)acrylic acid 2-perfluorodecylethyl, and (meth)acrylic acid 2-perfluorohexadecylethyl.

[0117] Examples of monomer units other than those mentioned above include monomers containing acrylic acids such as acrylic acid and methacrylic acid; amide groups such as N-methylol acrylamide and N-methylol methacrylamide; epoxy groups such as glycidyl acrylate and glycidyl methacrylate; and nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

[0118] As the (meth)acrylic acid ester polymer (B), a polymer obtained by copolymerizing a (meth)acrylic acid ester monomer with a vinyl monomer copolymerizable therewith can also be used. The vinyl monomer is not particularly limited, and examples thereof include styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide. nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol, and it is also possible to use a plurality of these as copolymerization components.

[0119] The number of hydrolyzable silyl groups in the (meth)acrylic acid ester polymer (B) is preferably 0.5 to 5.0 on average per molecule, and from the viewpoint of the mechanical properties of the curable composition when cured, is more preferably 1.0 or more, and from the viewpoint of the stability of the (meth)acrylic acid ester polymer (B), is more preferably 3.0 or less.

[0120] The method of introducing a hydrolyzable silyl group into a (meth)acrylic acid ester polymer is not particularly limited, and the following methods can be used, for example. (iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a hydrolyzable silyl group with the above-mentioned monomer. When this method is used, the hydrolyzable silyl group tends to be randomly introduced into the main chain of the polymer. (v) A method of polymerizing a (meth)acrylic acid ester polymer using a mercaptosilane compound having a hydrolyzable silyl group as a chain transfer agent. When this method is used, the hydrolyzable silyl group can be introduced into the polymer end. (vi) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (V group), and then reacting the hydrolyzable silyl group with a compound having a functional group that reacts with the V group. Specifically, examples of the method include a method of copolymerizing 2-hydroxyethyl acrylate, and then reacting the hydroxyl group with an isocyanate silane having a hydrolyzable silyl group, and a method of copolymerizing glycidyl acrylate, and then reacting the epoxy group with an aminosilane compound having a hydrolyzable silyl group. (vii) A method of modifying a terminal functional group of a (meth)acrylic acid ester polymer synthesized by a living radical polymerization method to introduce a hydrolyzable silyl group. A (meth)acrylic acid ester polymer obtained by a living radical polymerization method has a terminal functional group that can be easily introduced, and by modifying the polymer, a hydrolyzable silyl group can be introduced at the terminal of the polymer.

[0121] Examples of silicon compounds that can be used to introduce hydrolyzable silyl groups into (meth)acrylic acid ester polymers using the above method include the following compounds. Compounds having a polymerizable unsaturated group and a hydrolyzable silyl group used in method (iv) include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(dimethoxymethylsilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, (trimethoxysilyl)methyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, (triethoxysilyl)methyl (meth)acrylate, (diethoxymethylsilyl)methyl (meth)acrylate, and 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate. From the viewpoint of availability, 3-trimethoxysilylpropyl (meth)acrylate and 3-(dimethoxymethylsilyl)propyl (meth)acrylate are particularly preferred.

[0122] Examples of the mercaptosilane compound having a hydrolyzable silyl group used in the method (v) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, and mercaptomethyltriethoxysilane.

[0123] Examples of the compound having a hydrolyzable silyl group and a functional group reactive with the V group used in the method (vi) include isocyanate silane compounds such as 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl dimethoxymethylsilane, 3-isocyanate propyl triethoxysilane, isocyanate methyl trimethoxysilane, isocyanate methyl triethoxysilane, isocyanate methyl dimethoxymethylsilane, and isocyanate methyl diethoxymethylsilane; 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethylsilane, glycidoxymethyl trimethoxysilane, and glycidoxymethyl triethoxysilane; Epoxy silane compounds such as glycidoxymethyldimethoxymethylsilane and glycidoxymethyldiethoxymethylsilane; and amino silane compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-(2-aminoethyl)aminomethyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0124] In the above method (vii), any modification reaction can be used. For example, a method using a compound having a hydrolyzable silyl group and a functional group capable of reacting with the terminal reactive group obtained by polymerization, or a method using a compound having a double bond and a functional group capable of reacting with the terminal reactive group to introduce a double bond into the polymer terminal, and then introducing a hydrolyzable silyl group therein by hydrosilylation or the like can be used.

[0125] These methods may be used in any combination. For example, by combining method (vi) and method (v), it is possible to obtain a (meth)acrylic acid ester polymer having hydrolyzable silyl groups at both the molecular chain terminals and / or side chains.

[0126] The hydrolyzable silyl group contained in the (meth)acrylic acid ester polymer (B) is represented by the following general formula (8): -(Si(R 1 2-b )(Y′ b )O) m SiR 2 3-a Y a (8) It can be expressed as R 1 , R 2 , Y, Y′, a, b, and m are the same as those in the general formula (1). When m is 0, the general formula (8) can be expressed by the following general formula (9): -SiR 2 3-a Y a (9) In this general formula (9), a represents 1, 2 or 3. Specifically, the hydrolyzable silyl group of the (meth)acrylic acid ester polymer (B) is preferably a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group or a triethoxysilyl group. From the viewpoint of achieving both storage stability and curability of the curable composition containing the (meth)acrylic acid ester polymer (B), a methyldimethoxysilyl group is more preferred, and a trimethoxysilyl group is more preferred from the viewpoint of enhancing the restorability of the cured product of the composition.

[0127] It is common knowledge among those skilled in the art that the monomer composition of the (meth)acrylic acid ester polymer (B) is selected depending on the application and purpose, but for applications requiring flexibility such as sealing materials, it is preferable to use one having a relatively low glass transition temperature (Tg), preferably a Tg of -100°C or higher and 100°C or lower, more preferably a Tg of -60°C or higher and 0°C or lower. Tg can be calculated by the following Fox formula. Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi represents the weight fraction of monomer i constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of monomer i.)

[0128] The number average molecular weight of the (meth)acrylic acid ester polymer (B) is not particularly limited, but is preferably from 500 to 100,000, more preferably from 1,500 to 50,000, and particularly preferably from 5,000 to 30,000, in terms of polystyrene equivalent molecular weight measured by GPC.

[0129] Methods of blending polyoxyalkylene polymers and (meth)acrylic acid ester polymers have been proposed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, JP-A-11-116763, etc. In addition, a method of polymerizing (meth)acrylic acid ester monomers in the presence of a polyoxypropylene polymer having a hydrolyzable silyl group can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-60-228516, JP-A-60-228517, etc. The polyoxyalkylene polymer (A) and (meth)acrylic acid ester polymer (B) of the present invention can also be blended by the same method, but are not limited thereto.

[0130] The mixing ratio of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) of the present invention is not particularly limited, but is preferably 95:5 to 10:90, more preferably 90:10 to 20:80, and particularly preferably 80:20 to 40:60, by weight ratio. The polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) of the present invention may each be used alone or in combination of two or more kinds.

[0131] (Other additives) The curable composition of the present invention may contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, physical property regulators, tackifier resins, compounds containing epoxy groups, photocurable substances, oxygen curable substances, surface property improvers, epoxy resins, other resins, flame retardants, and foaming agents. In addition, the curable composition of the present invention may contain various additives as necessary for the purpose of adjusting the various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.

[0132] <Filling agent> Various fillers can be blended into the composition of the present invention. Examples of fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament. The above fillers may be used alone or in combination of two or more.

[0133] The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 250 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0134] Organic balloons or inorganic balloons may be added to reduce the weight (low specific gravity) of the composition. The balloons are spherical fillers that are hollow inside, and examples of the materials for the balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran. The above balloons may be used alone or in combination of two or more types.

[0135] The amount of the balloons used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0136] <Adhesion promoter> An adhesion promoter may be added to the composition of the present invention. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent may be added.

[0137] Specific examples of the silane coupling agent 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; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isopropyltrimethoxysilane; Examples of the silanes include isocyanate group-containing silanes such as cyanate propyl methyl dimethoxy silane, α-isocyanate methyl trimethoxy silane, and α-isocyanate methyl dimethoxy methyl silane; mercapto group-containing silanes such as γ-mercapto propyl trimethoxy silane, γ-mercapto propyl triethoxy silane, and γ-mercapto propyl methyl dimethoxy silane; and epoxy group-containing silanes such as γ-glycidoxy propyl trimethoxy silane and β-(3,4-epoxy cyclohexyl) ethyl trimethoxy silane. Also, reaction products of various silane coupling agents can be used. The above adhesion promoters may be used alone or in combination of two or more.

[0138] The amount of the adhesion promoter used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0139] <Plasticizer> A plasticizer may be added to the composition of the present invention. Specific examples of plasticizers include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylate diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil; and epoxy plasticizers such as epoxy benzyl stearate.

[0140] Also, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers, polyester plasticizers, polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, polyethers such as derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, etc., polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc.

[0141] The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If the amount is less than 5 parts by weight, the effect of the plasticizer is not exhibited, and if the amount exceeds 150 parts by weight, the mechanical strength of the cured product is insufficient. The plasticizer may be used alone or in combination of two or more kinds.

[0142] <Solvents, diluents> A solvent or diluent can be added to the composition of the present invention. 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 using a solvent or diluent, 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, in view of the problem of air pollution when the composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more kinds.

[0143] <Anti-sagging agent> The composition of the present invention may contain an anti-sagging agent as necessary to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but may be, for example, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

[0144] The amount of the sagging prevention agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0145] <Antioxidants> An antioxidant (antiaging agent) can be used in the composition of the present invention. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.

[0146] The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0147] <Light stabilizer> A light stabilizer can be used in the composition of the present invention. The use of a light stabilizer can prevent photooxidative deterioration of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.

[0148] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0149] <Ultraviolet absorbing agent> The composition of the present invention can use an ultraviolet absorber. The use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred, and examples of such compounds include those commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329 and Tinuvin 571 (all manufactured by BASF).

[0150] The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0151] <Physical property adjusters> The curable composition of the present invention may contain a physical property adjuster for adjusting the tensile properties of the resulting cured product, if necessary. The physical property adjuster is not particularly limited, but examples thereof 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; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using the physical property adjuster, the hardness of the composition of the present invention when cured can be increased, or conversely, the hardness can be decreased to provide a breaking elongation. The physical property adjuster may be used alone, or two or more types may be used in combination.

[0152] In particular, compounds that produce compounds having monovalent silanol groups in the molecule by hydrolysis have the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are particularly preferred. Examples of compounds that produce compounds having monovalent silanol groups in the molecule by hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and that produce silane monool by hydrolysis.

[0153] The amount of the physical property adjusting agent used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0154] <Tackifier resin> In the present invention, a tackifier resin can be added for the purpose of increasing the adhesiveness or adhesion to the substrate, or for other reasons as required. There are no particular limitations on the tackifier resin, and any commonly used resin can be used.

[0155] Specific examples include terpene resins, aromatic 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 alone or in combination of two or more.

[0156] The amount of the tackifier 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, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If it is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion to the substrate, and if it exceeds 100 parts by weight, the viscosity of the composition becomes too high, which may make it difficult to handle.

[0157] <Compounds containing epoxy groups> In the composition of the present invention, a compound containing an epoxy group can be used. The use of a compound having an epoxy group can improve the restorability of the cured product. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0158] <Photocurable substance> A photocurable substance can be used in the composition of the present invention. 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 compounds of this type are known, such as organic monomers, oligomers, resins, or compositions containing them. Representative compounds that can be used include unsaturated acrylic compounds, which are monomers, oligomers, or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, polyvinyl cinnamates, or azido resins.

[0159] The photocurable substance is preferably used in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If it is less than 0.1 part by weight, there is no effect of improving weather resistance, and if it is more than 20 parts by weight, the cured product becomes too hard and tends to crack.

[0160] <Oxygen curing substance> An oxygen curing substance can be used in the composition of the present invention. Examples of oxygen curing 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 the surface from becoming sticky and preventing dirt and dust from adhering to the surface of the cured product. Specific examples of oxygen curing 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 C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used alone or in combination of two or more types.

[0161] The amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If the amount used is less than 0.1 part by weight, the improvement in stain resistance is insufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0162] <Epoxy resin> The composition of the present invention can be used in combination with an epoxy resin. The composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.

[0163] The ratio by weight of these epoxy resins to the polyoxyalkylene polymer (A) of the present invention is preferably in the range of polyoxyalkylene polymer (A) / epoxy resin=100 / 1 to 1 / 100. If the ratio of polyoxyalkylene polymer (A) / epoxy resin is less than 1 / 100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the epoxy resin cured product, whereas if the ratio of polyoxyalkylene polymer (A) / epoxy resin exceeds 100 / 1, the strength of the polymer cured product becomes insufficient.

[0164] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the composition of the present invention. There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.

[0165] When a curing agent for an epoxy resin is used, the amount used is preferably in the range of 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy resin.

[0166] <<Preparation of Curable Composition>> The curable composition of the present invention can be prepared as a one-component type in which all ingredients are mixed in advance and stored in a sealed state, and then cured by moisture in the air after application, or as a two-component type in which ingredients such as a silanol condensation catalyst, a filler, a plasticizer, and water are mixed separately as a curing agent, and the ingredients are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

[0167] When the curable composition is of one-component type, all the components are mixed in advance, and therefore, it is preferable to use the components containing water after dehydration and drying in advance, or to dehydrate them by reducing pressure during mixing and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane.

[0168] The amount of the dehydrating agent, particularly the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0169] <Application> The curable composition of the present invention can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproofing material, a coating waterproofing material, a mold release agent, an anti-vibration material, a vibration-damping material, a sound-proofing material, a foaming material, a paint, a spraying material, etc. The cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, and therefore can be suitably used as a sealing material or adhesive.

[0170] The curable composition of the present invention can be used in a wide range of applications, including electrical and electronic component materials such as a sealing material for the back surface of a solar cell, electrical insulating materials for electrical and electronic components and devices such as insulating coating materials for electric wires and cables, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, and joint sealants for exterior materials such as sizing boards. It can be used for various applications such as coating materials, anti-slip coating materials, buffer materials, primers, conductive materials for electromagnetic wave shielding, thermally conductive materials, hot melt materials, potting agents for electrical and electronic devices, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and sealing materials for rust prevention and waterproofing of wired glass and laminated glass end faces (cut parts), liquid sealants used in automobile parts, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical parts, various machine parts, etc. For example, in automobiles, it can be used in a wide variety of applications such as adhesive installation of plastic covers, trims, flanges, bumpers, window mounting, interior parts, exterior parts, etc. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., either alone or with the help of a primer, it can also be used as various types of sealing compositions and adhesive compositions. The curable composition of the present invention can also be used as an adhesive for interior panels, exterior panels, tile adhesives, stone veneers, ceiling finish adhesives, floor finish adhesives, wall finish adhesives, vehicle panels, electrical / electronic / precision equipment assembly adhesives, adhesives for bonding leather, textile products, fabrics, paper, boards and rubber, reactive post-crosslinking pressure-sensitive adhesives, direct glazing sealants, double-glazing sealants, SSG construction sealants, or building working joint sealants, civil engineering and bridge materials. It can also be used as an adhesive material such as an adhesive tape or adhesive sheet. EXAMPLES

[0171] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0172] Example 1 Using polyoxypropylene diol with a number average molecular weight of about 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-1) with a number average molecular weight of 19,000. Next, 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140°C. 0.3 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an unsaturated bond, and 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of platinum divinyldisiloxane complex (a 3 mass% isopropyl alcohol solution calculated as platinum) and 1.47 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the mixture was allowed to react at 90°C for 2 hours to obtain a linear polyoxypropylene (A-1) having methyldimethoxysilyl groups at its terminals, with a total number of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups per terminal structure (hereinafter referred to as the total number of groups per terminal structure) of 1.3, a number of moles of hydrolyzable silyl groups / (total number of moles of hydrolyzable silyl groups, terminal olefin groups, and internal olefin groups) (hereinafter referred to as the hydrolyzable silyl group introduction rate) of 68%, a number of hydrolyzable silyl groups per terminal structure of 0.88, and a number average molecular weight of 19,000.

[0173] Example 2 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 1.89 parts by weight, thereby obtaining a linear polyoxypropylene (A-2) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 46%, the number of hydrolyzable silyl groups per terminal structure of 1.38, and a number average molecular weight of 19,000.

[0174] Example 3 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 3.0 equivalents and the amount of methyldimethoxysilane used was 2.23 parts by weight, thereby obtaining a linear polyoxypropylene (A-3) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 4.0, a hydrolyzable silyl group introduction rate of 42%, the number of hydrolyzable silyl groups per terminal structure of 1.68, and a number average molecular weight of 19,000.

[0175] Comparative Example 1 The same procedure as in Example 1 was followed except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 1.31 parts by weight, thereby obtaining a linear polyoxypropylene (C-1) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 74%, the number of hydrolyzable silyl groups per terminal structure of 0.74, and a number average molecular weight of 19,000.

[0176] Example 4 Using polyoxypropylene diol with a number average molecular weight of about 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-2) with a number average molecular weight of 16,000. Next, 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140°C. 2.0 equivalents of allyl glycidyl ether were added at 140°C and reacted for 2 hours to introduce unsaturated bonds, and 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of platinum divinyldisiloxane complex (a 3% by mass platinum solution in isopropyl alcohol) and 2.02 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours to obtain a linear polyoxypropylene (A-4) having methyldimethoxysilyl groups at its terminals, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 42%, the number of hydrolyzable silyl groups per terminal structure of 1.26, and a number average molecular weight of 16,000.

[0177] Example 5 The same procedure as in Example 4 was followed except that the amount of methyldimethoxysilane used was 2.29 parts by weight, thereby obtaining a linear polyoxypropylene (A-5) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 48%, a number of hydrolyzable silyl groups per terminal structure of 1.44, and a number average molecular weight of 16,000.

[0178] Comparative Example 2 The same procedure as in Example 4 was followed except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 1.45 parts by weight, thereby obtaining a linear polyoxypropylene (C-2) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 77%, the number of hydrolyzable silyl groups per terminal structure of 0.77, and a number average molecular weight of 16,000.

[0179] Example 6 Using polyoxypropylene diol with a number average molecular weight of about 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-3) with a number average molecular weight of 28,000. Next, 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140°C. 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an unsaturated bond, and 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of platinum divinyldisiloxane complex (a 3 mass% isopropyl alcohol solution calculated as platinum) and 1.26 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours to obtain a linear polyoxypropylene (A-6) having methyldimethoxysilyl groups at its terminals, with a total number of groups per terminal structure of 2.0, a hydrolyzable silyl group introduction rate of 58%, the number of hydrolyzable silyl groups per terminal structure of 1.16, and a number average molecular weight of 28,000.

[0180] Comparative Example 3 The same procedure as in Example 6 was followed except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 0.94 parts by weight, thereby obtaining a linear polyoxypropylene (C-3) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 78%, the number of hydrolyzable silyl groups per terminal structure of 0.78, and a number average molecular weight of 28,000.

[0181] Comparative Example 4 The same procedure as in Example 6 was followed except that the amount of methyldimethoxysilane used was 1.85 parts by weight, thereby obtaining a linear polyoxypropylene (C-4) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 2.0, a hydrolyzable silyl group introduction rate of 80%, a number of hydrolyzable silyl groups per terminal structure of 1.60, and a number average molecular weight of 28,000.

[0182] Example 7 Using polyoxypropylene triol with a number average molecular weight of about 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-4) with a number average molecular weight of 20,000. Next, 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140°C. 1.6 equivalents of allyl glycidyl ether were added at 140°C and reacted for 2 hours to introduce an unsaturated bond, and 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of platinum divinyldisiloxane complex (a 3 mass% isopropyl alcohol solution calculated as platinum) and 1.69 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours to obtain a branched polyoxypropylene (A-7) having methyldimethoxysilyl groups at its terminals, with a total number of groups per terminal structure of 2.6, a hydrolyzable silyl group introduction rate of 38%, the number of hydrolyzable silyl groups per terminal structure of 0.99, and a number average molecular weight of 20,000.

[0183] Comparative Example 5 The same procedure as in Example 7 was followed except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 1.22 parts by weight, thereby obtaining a branched polyoxypropylene (C-5) having a methyldimethoxysilyl group at the terminal, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 61%, the number of hydrolyzable silyl groups per terminal structure of 0.61, and a number average molecular weight of 20,000.

[0184] Example 8 Using polyoxypropylene diol with a number average molecular weight of about 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polyoxypropylene (E-5) with a number average molecular weight of 21,000. Next, 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140°C. 2.2 equivalents of allyl glycidyl ether were added at 140°C and reacted for 2 hours to introduce an unsaturated bond, and 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of platinum divinyldisiloxane complex (a 3 mass% isopropyl alcohol solution calculated as platinum) and 1.89 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours to obtain a linear polyoxypropylene (A-8) having methyldimethoxysilyl groups at the terminals, with a total number of groups per terminal structure of 3.2, a hydrolyzable silyl group introduction rate of 47%, the number of hydrolyzable silyl groups per terminal structure of 1.50, and a number average molecular weight of 21,000.

[0185] Comparative Example 6 The same procedure as in Example 8 was followed except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 1.17 parts by weight, thereby obtaining a linear polyoxypropylene (C-6) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 77%, the number of hydrolyzable silyl groups per terminal structure of 0.77, and a number average molecular weight of 21,000.

[0186] Example 9 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 1.69 parts by weight, thereby obtaining a linear polyoxypropylene (A-9) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 41%, the number of hydrolyzable silyl groups per terminal structure of 1.23, and a number average molecular weight of 19,000.

[0187] Example 10 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 1.73 parts by weight, thereby obtaining a linear polyoxypropylene (A-10) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 43%, the number of hydrolyzable silyl groups per terminal structure of 1.29, and a number average molecular weight of 19,000.

[0188] Example 11 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 2.00 parts by weight, thereby obtaining a linear polyoxypropylene (A-11) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 47%, the number of hydrolyzable silyl groups per terminal structure of 1.41, and a number average molecular weight of 19,000.

[0189] Example 12 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 2.10 parts by weight, thereby obtaining a linear polyoxypropylene (A-12) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 49%, the number of hydrolyzable silyl groups per terminal structure of 1.47, and a number average molecular weight of 19,000.

[0190] (Example 13) The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 2.56 parts by weight, thereby obtaining a linear polyoxypropylene (A-13) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 60%, the number of hydrolyzable silyl groups per terminal structure of 1.80, and a number average molecular weight of 19,000.

[0191] Comparative Example 7 The same procedure as in Example 1 was followed except that the amount of allyl glycidyl ether used was 2.0 equivalents and the amount of methyldimethoxysilane used was 3.15 parts by weight, thereby obtaining a linear polyoxypropylene (C-7) having a methyldimethoxysilyl group at the end, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 75%, the number of hydrolyzable silyl groups per terminal structure of 2.25, and a number average molecular weight of 19,000.

[0192] (Synthesis Example 1) 54.5 parts by weight of isobutyl alcohol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution of 10.0 parts by weight of methyl methacrylate, 71.5 parts by weight of butyl acrylate, 15.0 parts by weight of stearyl methacrylate, 3.5 parts by weight of 3-(dimethoxymethylsilyl)propyl methacrylate, and 0.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 10.0 parts by weight of isobutyl alcohol was dropped therein over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60% by weight) of poly(meth)acrylic acid ester (B-1) having an average of 1.6 methyldimethoxysilyl groups per molecule, a number average molecular weight of 10,500, and a weight average molecular weight of 25,000.

[0193] (Synthesis Example 2) 52.1 parts by weight of isobutyl alcohol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 90°C under a nitrogen atmosphere. A mixed solution of 14.5 parts by weight of methyl methacrylate, 68.2 parts by weight of butyl acrylate, 14.9 parts by weight of stearyl methacrylate, 2.4 parts by weight of 3-(dimethoxymethylsilyl)propyl methacrylate, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 12.4 parts by weight of isobutyl alcohol was dropped therein over 7 hours. Polymerization was further carried out at 90°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60% by weight) of poly(meth)acrylic acid ester (B-2) having an average of 1.8 methyldimethoxysilyl groups per molecule, a number average molecular weight of 17,000, and a weight average molecular weight of 48,000.

[0194] (Synthesis Example 3) 54.5 parts by weight of isobutyl alcohol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution of 10.0 parts by weight of methyl methacrylate, 71.2 parts by weight of butyl acrylate, 15.0 parts by weight of stearyl methacrylate, 3.8 parts by weight of 3-(trimethoxysilyl)propyl methacrylate, and 0.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 10.0 parts by weight of isobutyl alcohol was dropped therein over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60% by weight) of poly(meth)acrylic acid ester (B-3) having an average of 1.5 trimethoxysilyl groups per molecule, a number average molecular weight of 9,800, and a weight average molecular weight of 23,000.

[0195] (Synthesis Example 4) 54.5 parts by weight of isobutyl alcohol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution of 10.0 parts by weight of methyl methacrylate, 71.7 parts by weight of butyl acrylate, 15.0 parts by weight of stearyl methacrylate, 3.3 parts by weight of 3-(trimethoxysilyl)propyl methacrylate, and 0.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 10.0 parts by weight of isobutyl alcohol was dropped therein over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60% by weight) of poly(meth)acrylic acid ester (B-4) having an average of 1.3 trimethoxysilyl groups per molecule, a number average molecular weight of 9,800, and a weight average molecular weight of 23,000.

[0196] Example 14 70 parts by weight of the polymer (A-10) obtained in Example 10 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-1) obtained in Synthesis Example 1 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-10) / polymer (B-1) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 36.

[0197] Example 15 70 parts by weight of the polymer (A-2) obtained in Example 2 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-1) obtained in Synthesis Example 1 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-2) / polymer (B-1) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 37.

[0198] Example 16 70 parts by weight of the polymer (A-10) obtained in Example 10 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-3) obtained in Synthesis Example 3 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-10) / polymer (B-3) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 38.

[0199] (Example 17) 70 parts by weight of the polymer (A-2) obtained in Example 2 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-3) obtained in Synthesis Example 3 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-2) / polymer (B-3) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 39.

[0200] (Example 18) 70 parts by weight of the polymer (A-10) obtained in Example 10 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-4) obtained in Synthesis Example 4 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-10) / polymer (B-4) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 40.

[0201] (Example 19) 70 parts by weight of the polymer (A-2) obtained in Example 2 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-4) obtained in Synthesis Example 4 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-2) / polymer (B-4) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 41.

[0202] Comparative Example 8 70 parts by weight of the polymer (C-1) obtained in Comparative Example 1 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-1) obtained in Synthesis Example 1 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (C-1) / polymer (B-1) weight ratio of 70 / 30. The obtained polymer mixture was used in Comparative Example 17.

[0203] (Example 20) 70 parts by weight of the polymer (A-8) obtained in Example 8 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-1) obtained in Synthesis Example 1 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-8) / polymer (B-1) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 42.

[0204] Example 21 70 parts by weight of the polymer (A-7) obtained in Example 7 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-1) obtained in Synthesis Example 1 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-7) / polymer (B-1) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 43.

[0205] Example 22 70 parts by weight of the polymer (A-6) obtained in Example 6 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-2) obtained in Synthesis Example 2 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (A-6) / polymer (B-2) weight ratio of 70 / 30. The obtained polymer mixture was used in Example 44.

[0206] Comparative Example 9 70 parts by weight of the polymer (C-3) obtained in Comparative Example 3 and 50 parts by weight of an isobutyl alcohol solution of the polymer (B-2) obtained in Synthesis Example 2 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a polymer (C-3) / polymer (B-2) weight ratio of 70 / 30. The obtained polymer mixture was used in Comparative Example 18.

[0207] (Synthesis Example 5) Propylene oxide was polymerized using n-butanol as an initiator and zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 8,000 and a hydroxyl group at one end. Next, 1.0 equivalent of a methanol solution of sodium methoxide was added to the hydroxyl group of this polyoxypropylene having a hydroxyl group at one end, and methanol was distilled off at 140°C. 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl group to an allyl group. Next, 36 ppm of platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and 1.80 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the polyoxypropylene having an allyl group at one end, and reacted at 90°C for 2 hours to obtain reactive diluent (D-1), which is a linear polyoxypropylene polymer having a number average molecular weight of 8,000 and an average of 0.8 methyldimethoxysilyl groups per molecule, which are hydrolyzable silyl groups, at one end. (D-1) was a polymer that showed a lower viscosity at 23°C than the polymers or polymer mixtures obtained in Examples 1 to 22 and Comparative Examples 1 to 9.

[0208] (Examples 23 to 44 and Comparative Examples 10 to 18) The polymers or polymer mixtures produced in Examples 1 to 22 or Comparative Examples 1 to 9 were used to carry out the following evaluations.

[0209] <Method of measuring stress or recovery rate at 100% elongation of cured polymer> The stress at 100% elongation or the recovery rate of the cured product of each polymer was measured by the above-mentioned measuring method. For the polymer mixtures obtained in Examples 14 to 22 and Comparative Examples 8 to 9, the stress at 100% elongation was measured under the same conditions using the polymer mixtures.

[0210] <Method of evaluating composition properties> Each polymer or polymer mixture was mixed with the following various additives, including filler, titanium oxide, anti-sagging agent, light stabilizer, and UV absorber, and then dispersed through a triple paint roll three times to prepare a base material. Then, a dehydrating agent, an adhesion imparting agent, and a silanol condensation catalyst were added and mixed thoroughly, and each curable composition was prepared by kneading and defoaming the mixture uniformly using a planetary mixer. Using each of the prepared curable compositions, various test specimens were prepared under a constant temperature and humidity atmosphere of 23°C and 50% relative humidity, and various evaluations were performed.

[0211] (Various additives used in the examples and comparative examples for evaluating the composition properties) The additives shown below were used in evaluating the physical properties of the compositions of Examples 23 to 44 and Comparative Examples 10 to 18. The blending amount is the number of parts by weight per 100 parts by weight of each polymer or polymer mixture that is the base polymer. Reactive diluent (D): Reactive diluent (D-1), 76 parts by weight Filler: (i) fatty acid-treated precipitated calcium carbonate (Hakuenka CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 120 parts by weight (ii) Heavy calcium carbonate (Whiten SB Red, manufactured by Shiraishi Calcium Co., Ltd.), 40 parts by weight Titanium oxide: Typak R-820, manufactured by Ishihara Sangyo Kaisha, Ltd., 10 parts by weight Anti-sagging agent: fatty acid amide wax (Disparlon #6500, Kusumoto Chemicals Co., Ltd.), 2 parts by weight Light stabilizer: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770, manufactured by BASF), 1 part by weight UV absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (Tinuvin 326, manufactured by BASF), 1 part by weight Dehydrating agent: vinyltrimethoxysilane (A-171, Momentive Co., Ltd.), 2 parts by weight Adhesion promoter: 3-(N-2-aminoethylamino)propyltrimethoxysilane (A-1120, manufactured by Momentive Co., Ltd.), 3 parts by weight Silanol condensation catalyst: dioctyltin dilaurate (U-810, manufactured by Nitto Kasei Co., Ltd.), 2 parts by weight

[0212] (Dumbbell properties) The curable composition was filled into a 3 mm thick sheet mold at 23°C and 50% relative humidity. After curing for 3 days at 23°C and 50% relative humidity, the composition was aged in a 50°C dryer for 4 days to obtain a sheet-like cured product. The resulting cured product was punched into a No. 3 dumbbell-shaped test piece according to JIS K 6251. Using the resulting test piece, a tensile test (tensile speed 200 mm / min) was performed using an autograph at 23°C and 50% relative humidity to measure the stress at 50% elongation, stress at 100% elongation, stress at break, and elongation at break.

[0213] (Resilience) The above sheet-like cured product was punched out into a No. 7 dumbbell-shaped test piece. Two benchmark lines were drawn 20 mm apart, centered on the neck of the dumbbell-shaped test piece. The dumbbell-shaped test piece was fixed in an elongated state so that the gap between the benchmark lines was 40 mm, and left to stand in a dryer at 50°C. After 24 hours, the test piece was released from the fixing position, and the gap between the benchmark lines was measured at 23°C and 50% relative humidity to determine the recovery rate.

[0214] The results obtained by the above are shown in Tables 1 to 8. Table 1 shows the results for the polymers (A-1), (A-2), (A-3) and (C-1) synthesized using hydroxyl-terminated polyoxypropylene (E-1) as a raw material. Similarly, Table 2 shows the results for each polymer synthesized using hydroxyl-terminated polyoxypropylene (E-2) as a raw material, Table 3 shows the results for each polymer synthesized using hydroxyl-terminated polyoxypropylene (E-3) as a raw material, Table 4 shows the results for each polymer synthesized using hydroxyl-terminated polyoxypropylene (E-4) as a raw material, and Table 5 shows the results for each polymer synthesized using hydroxyl-terminated polyoxypropylene (E-5) as a raw material. Furthermore, Table 6 shows the results for each polymer synthesized using hydroxyl-terminated polyoxypropylene (E-1) as a raw material and having a total number of groups per terminal structure of 3.0.

[0215] Table 7 shows the results of an embodiment in which the polyoxyalkylene polymer (A) of the present invention or the polyoxyalkylene polymer (C) not satisfying the requirements of the present invention, which are synthesized from hydroxyl-terminated polyoxypropylene (E-1) as a raw material, is used in combination with the (meth)acrylic acid ester polymer (B). Table 8 shows the results of an embodiment in which the polyoxyalkylene polymer (A) of the present invention or the polyoxyalkylene polymer (C) not satisfying the requirements of the present invention, which are synthesized from a raw material other than hydroxyl-terminated polyoxypropylene (E-1), is used in combination with the (meth)acrylic acid ester polymer (B).

[0216] [Table 1]

[0217] [Table 2]

[0218] [Table 3]

[0219] [Table 4]

[0220] [Table 5]

[0221] [Table 6]

[0222] [Table 7]

[0223] [Table 8]

[0224] From the results shown in each table, it can be seen that the cured products of the compositions of each Example containing the polyoxyalkylene polymer (A) of the present invention exhibit high recovery even though they have a similarly low modulus, compared to the cured products of the compositions of Comparative Examples 10 to 12, 14, 15, 17, and 18 containing the polyoxyalkylene polymer (C) which has an equivalent main chain structure but does not satisfy the requirements of the present invention because the total number of groups per terminal structure is 1.0. Furthermore, no significant difference was confirmed in the dumbbell properties.

[0225] On the other hand, the compositions of Comparative Examples 13 and 16, which contain polyoxyalkylene polymer (C) that does not satisfy the requirements of the present invention because the introduction rate of hydrolyzable silyl groups exceeds 70% although the total number of groups per terminal structure exceeds 1.0, show that the cured product exhibits high recovery, but the modulus of the cured product is too high, making them unsuitable as sealants.

[0226] From the above results, it is found that the polyoxyalkylene polymer (A) of the present invention can be suitably used as a base polymer for a highly resilient sealant that is less prone to bleed-out, since the cured product of the curable composition containing the polyoxyalkylene polymer (A) exhibits low modulus but high resilience and other physical properties are equivalent to those of existing products.

Claims

1. A polyoxyalkylene polymer having a polyoxyalkylene main chain structure and a terminal structure bonded to an end of the main chain structure, the number of said terminal structures is three or more per polymer molecule, the terminal structure has a hydrolyzable silyl group and a terminal olefin group and / or an internal olefin group, the total number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups is greater than 1.0 on average per terminal structure, The polyoxyalkylene polymer (A), wherein the ratio of the number of moles of hydrolyzable silyl groups in the polyoxyalkylene polymer to the total number of moles of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups is 0.3 to 0.

7.

2. The polyoxyalkylene polymer (A) according to claim 1 , wherein the terminal structure contains a moiety derived from an epoxy compound having a terminal olefin group.

3. The hydrolyzable silyl group is represented by the general formula (3): -SiR ２ Y ２ (3) (In the formula, R ２ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or (R') ３ R' may be the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Y may be the same or different and represent a hydroxyl group or a hydrolyzable group. The polyoxyalkylene polymer (A) according to claim 1 or 2, represented by the formula:

4. A curable composition comprising the polyoxyalkylene polymer (A) according to any one of claims 1 to 3.

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