Polyoxyalkylene-based 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 Art

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

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

[0004] Patent Document 1 discloses a room-temperature curable composition containing a polyoxyalkylene polymer having at least one hydrolyzable silyl group at one end. As a method for producing the polymer, after converting the terminal hydroxyl group of the polyoxyalkylene polymer into an alkoxide group, an organic halide such as allyl chloride is reacted to introduce a carbon-carbon double bond at the end, and further, a method of converting it into a hydrolyzable silyl group by an addition reaction with hydrosilanes is described.

[0005] Further, Patent Document 2 discloses a polyoxyalkylene polymer having two or more hydrolyzable silyl groups at one terminal site. As a method for producing the polymer, first, after converting the terminal hydroxyl group of the polymer into an alkoxide group, an epoxy compound having a carbon-carbon double bond is reacted, and further, an organic halide having a carbon-carbon double bond such as allyl chloride is reacted to introduce two or more carbon-carbon double bonds at one terminal site, and then a method of performing an addition reaction with hydrosilanes is described.

[0006] On the other hand, in recent years' construction markets, there has been a demand for sealing materials that are less likely to experience bleed-out. For this reason, in curable compositions for sealing materials, instead of using conventional phthalate plasticizers or PPG plasticizers, a method of blending a reactive diluent in which a hydrolyzable silyl group is introduced only at one end of the polymer molecular chain has been studied as a substitute for these plasticizers.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems 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, although bleed-out can be suppressed, the restorability of the cured product (the ability to return to its original shape after applying a predetermined deformation) tends to decrease. To address this, a method of improving restorability by increasing the modulus (the stress required to apply a predetermined deformation, in this case, particularly the elongation stress of a dumbbell-shaped specimen) of the cured product of the hydrolyzable silyl group-containing polyoxyalkylene-based polymer, which is the base polymer, can be considered. However, since an increase in modulus can lead to a decrease in flexibility, it is desirable to keep the modulus low.

[0009] In view of the above situation, an object of the present invention is to provide a hydrolyzable silyl group-containing polyoxyalkylene-based polymer that can form a cured product with high restorability while showing a low modulus, and a curable composition containing the same.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that a polyoxyalkylene polymer having a hydrolyzable silyl group, a terminal olefin group and / or an internal olefin group in its terminal structure, wherein the total number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups is more than 1.0 on average per terminal structure, and by setting the molar number of hydrolyzable silyl groups / (total molar number of hydrolyzable silyl groups, terminal olefin groups and internal olefin groups) to a relatively low value of 0.3 to 0.7, it is possible to provide a hydrolyzable silyl group-containing polyoxyalkylene polymer that forms a cured product having high resilience while showing a low modulus (i.e., high flexibility), and thus the present invention has been achieved.

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

[0012] Preferably, the terminal structure contains a site derived from an epoxy compound having a terminal olefin group. More preferably, the number of sites derived from the epoxy compound having a terminal olefin group is more than 1.0 on average per terminal structure.

[0013] Preferably, the hydrolyzable silyl group has 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 R2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R′)3SiO-. R′ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Y and Y′ each independently represent a hydroxyl group or a hydrolyzable group. a represents 0, 1, 2, or 3. b represents 0, 1, or 2, provided that when m is 2 or more, different numbers may coexist as b. m represents an integer from 0 to 19. However, a + m×b represents an integer of 1 or more.) 1 R 2 or R′ preferably 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 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R′)3SiO-. R′ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, which may be the same or different. a represents 1, 2, or 3.)

[0015] Even 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] ​More preferably, the hydrolyzable silyl group is represented by the general formula (3): -SiR 2 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′ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, which may be the same or different.)

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

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

[0019] Preferably, the terminal olefin group is represented by the following general formula (4): H2C=C(R 3 )-CH2- (4) and 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, or 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. Preferably, R 3 represents hydrogen or a methyl group.

[0020] Preferably, the number of moles of the hydrolyzable silyl group / (total number of moles of the hydrolyzable silyl group, terminal olefin group and internal olefin group) is 0.65 or less, more preferably 0.6 or less, still 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 recovery rate of the cured product of the polyoxyalkylene polymer (A) is 90% or more. Preferably, the stress at 100% elongation of the cured product of the polyoxyalkylene polymer (A) is 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) having an average of 0.5 or more and less than 1.2 hydrolyzable silyl groups per molecule and having a lower viscosity at 23 ° C than the polyoxyalkylene polymer (A). The curable composition may further contain a (meth) acrylate polymer (B) having a hydrolyzable silyl group.

[0023] Furthermore, the present invention also relates to a cured product of the curable composition. Furthermore, the present invention also relates to the use of the polyoxyalkylene polymer (A) in a sealing material, an adhesive, a pressure-sensitive adhesive, an insulating material, a paint, a sealing material, or a waterproof material.

Effects 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 high resilience while showing a low modulus, and a curable composition containing the same.

Modes for Carrying Out the Invention

[0025] Hereinafter, embodiments 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 terminal of the main chain structure.

[0027] The main chain structure refers to the 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 containing a structure derived from an initiator used during polymerization in addition to the oxyalkylene repeating units and composed only of these. Here, the oxyalkylene repeating unit refers to the repeating unit constituting the polyether, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

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

[0029] The terminal structure refers to a site that does not contain the oxyalkylene repeating unit constituting the main chain structure and is bonded to the terminal of the main chain structure. When the main chain structure is linear, two terminal structures exist per molecule of the polymer. When the main chain structure is branched, three or more terminal structures exist per molecule of the polymer. Also, when the main chain structure is a mixture of linear and branched structures, the number of terminal structures per molecule of the polymer can be an average value between 2 and 3. The terminal structure is preferably bonded to the oxyalkylene unit located at the terminal 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 have 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 and Y' may be 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 R2 In the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro group, alkoxy groups such as methoxy group, and amino groups such as 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, still more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2 carbon atoms. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro group, alkoxy groups such as methoxy group, and amino groups such as N,N-diethylamino group. The three R′s may be the same as each other or different from each other.

[0034] R 1 and R 2 Examples of R 1 and R 2 include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-dodecyl group; substituted alkyl groups such as chloromethyl group, methoxymethyl group, N,N-diethylaminomethyl group; unsaturated hydrocarbon groups such as vinyl group, isopropenyl group, allyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, toluyl group, 1-naphthyl group; aralkyl groups such as benzyl group; triorganosiloxy groups represented by (R′)3SiO- where R′ is a methyl group, phenyl group, etc. Preferably it is a substituted or unsubstituted alkyl group, more preferably methyl group, ethyl group, chloromethyl group, methoxymethyl group, still more preferably methyl group, ethyl group, and particularly preferably methyl group. R 1 and R 2 may be used alone or in combination of two or more kinds of groups.

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

[0036] m represents an integer from 0 to 19 as described above, but preferably represents 0. When m is 0, the general formula (1) becomes the following general formula (2): -SiR 2 3-a Y a (2) It is represented by. 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, (N, (N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group and the like can be mentioned. Among them, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group show high reactivity and are preferable because a cured product having good mechanical properties can be obtained. From the viewpoint of reactivity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group are more preferable. From the viewpoint of stability, methyldimethoxysilyl group, methyldiethoxysilyl group, triethoxysilyl group are more preferable, and methyldiethoxysilyl group, triethoxysilyl group are even more preferable. In addition, trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group are more preferable because they are easy to manufacture. Among them, methyldimethoxysilyl group is most preferable.

[0038] In the general formula (2), in order to balance the storage stability and reactivity of the polymer and the flexibility of the cured product, a preferably represents 2. When a is 2, the general formula (2) is the following general formula (3): -SiR 2 Y2(3) represented by. In the formula, R 2 and Y are as described above. However, in the general formula (1) or (2), two or more hydrolyzable silyl groups having different a may be used in combination.

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

[0040] R 3 Examples of R 3 include hydrogen, alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. In particular, R 3 is preferably hydrogen or an alkyl group, more preferably hydrogen, methyl group, or ethyl group, and still more preferably hydrogen or methyl group. Further, a plurality of R

[0041] The internal olefin group refers to a carbon-carbon double bond that does not have a methylidene group (H2C=). Specifically, it is represented by the following general formula (5): H3C-C(R 3 )=CH- (5) In the formula (5), R 3 usually represents the same group as R 3 in the formula (4), but within the definition range of R 3 it may represent a group different from R 3 in the formula (4). Further, a plurality of R 3 in the polymer may be the same as or different from each other.

[0042] As will be described later, the internal olefin group is a group that can be generated by the internal transfer reaction of the terminal olefin group. When the terminal olefin group is an allyl group (R 3In the case of =H), the internal olefin group generated by the internal transfer reaction thereof is a 1-propenyl group.

[0043] The polyoxyalkylene polymer (A) of the present invention has a hydrolyzable silyl group, 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. Thus, when the introduction amount of the hydrolyzable silyl group is the same, the cured product of the polyoxyalkylene polymer (A) of the present invention can exhibit a lower modulus than the cured product of the polyoxyalkylene polymer having an average of 1.0 or less of the total number per terminal structure. The total number is preferably 1.1 or more, more preferably 1.3 or more, and further preferably 1.5 or more. Furthermore, it is preferably larger than 1.5, particularly preferably 2.0 or more, and most preferably 2.5 or more. The upper limit value of the total number is not limited, but from the viewpoints of economy and the introduction efficiency of the relevant structure, it is preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less.

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

[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 those skilled in the art. As an example, as described later, when producing the polyoxyalkylene polymer (A) of the present invention through a method of 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, the equivalent number of the epoxy compound with respect to the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) (the number of olefin groups introduced by the epoxy compound) is added to 1 (the number of olefin groups introduced by the organic halide) to calculate the total number. In addition, the total number can also be calculated by analysis such as 1 1H NMR and iodine value / hydroxyl value by titration of the polyoxyalkylene polymer (A) of the present invention and its precursor intermediate.

[0046] Furthermore, by relatively lowering the proportion of the hydrolyzable silyl group in the polyoxyalkylene polymer (A) of the present invention with respect to the total of the hydrolyzable silyl group, the terminal olefin group, and the internal olefin group, it is possible to form a cured product having high resilience while maintaining a low modulus. That is, in the polyoxyalkylene polymer (A) of the present invention, the number of moles of the hydrolyzable silyl group / (the total number of moles of the hydrolyzable silyl group, the terminal olefin group, and the internal olefin group) is on average 0.3 or more and 0.7 or less. By setting the ratio to 0.3 or more and 0.7 or less, a cured product containing the polyoxyalkylene polymer (A) of the present invention can achieve both a low modulus and good resilience. In order to further lower the modulus of the cured product containing the polyoxyalkylene polymer (A) of the present invention, the ratio is preferably 0.65 or less, more preferably 0.6 or less, still more preferably 0.55 or less, and even more preferably 0.5 or less. In order to further improve the resilience of the cured product containing the polyoxyalkylene polymer (A) of the present invention, the ratio is preferably 0.35 or more, and more preferably 0.4 or more. Note that "the number of moles of the hydrolyzable silyl group / (the total number of moles of the hydrolyzable silyl group, the terminal olefin group, and the internal olefin group)" can also be expressed as the "hydrolyzable silyl group introduction rate". Further, the ratio can also be expressed as a percentage. For example, the ratio being 0.3 and 30% have the same meaning.

[0047] In the present invention, the ratio 1 can be determined by 1H NMR. For example, when the terminal olefin group is an allyl group and a hydrosilane compound having a hydrolyzable silyl group is subjected to a hydrosilylation reaction as described later to introduce a hydrolyzable silyl group into the terminal structure in this case, it may be calculated using the integral values of the following respective signals. · Hydrolyzable silyl group: CH2 bonded to the silyl group (around 0.6 ppm, 2H) · Terminal olefin group: CH2 of the methylidene group (around 5.2 ppm, 2H) · Internal olefin group: CH bonded to the terminal CH3 group (total of around 4.3 ppm and around 4.8 ppm, 1H) In addition, when other signals overlap, the integrated value of the signal is excluded from the calculation.

[0048] The polyoxyalkylene polymer (A) of the present invention has a hydrolyzable silyl group within a range that satisfies both the total number of the above-described hydrolyzable silyl group, terminal olefin group, and internal olefin group, and the molar number of the hydrolyzable silyl group / (total molar number of the hydrolyzable silyl group, terminal olefin group, and internal olefin group). The number of hydrolyzable silyl groups is preferably 0.7 or more, more preferably 0.85 or more, still more preferably 1.0 or more, and particularly preferably 1.2 or more, on average per one terminal structure. Thereby, the polyoxyalkylene polymer (A) of the present invention can exhibit good curability. The number of hydrolyzable silyl groups per one terminal structure can be calculated by multiplying the above-described "total number of hydrolyzable silyl group, terminal olefin group, and internal olefin group per one terminal structure" by the above-described "ratio occupied by the hydrolyzable silyl group with respect to the total of the hydrolyzable silyl group, terminal olefin group, and internal olefin group".

[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. As an example of a terminal structure having a hydrolyzable silyl group and a terminal olefin group, the following general formula (6):

[0050]

Chemical formula

[0051] can be shown. Further, as another example, the following general formula (7):

[0052]

Chemical formula

[0053] can be shown. The oxygen atoms at the left ends in General Formulas (6) and (7) represent the oxygen in the oxyalkylene unit located at the terminal of the main chain structure of polyoxyalkylene. In said General Formulas (6) and (7), the group represented by General Formula (2) described above is shown as the hydrolyzable silyl group, but the present invention is not limited thereto.

[0054] In General Formulas (6) and (7), d and e each represent an integer of 0 or more, but the total of d and e is greater than 0 on average per one terminal structure. The total of said d and e is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more. Further, it is preferably greater than 0.5, particularly preferably 1.0 or more, and most preferably 1.5 or more. Also, the total of said d and e is preferably 9 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 4 or less.

[0055] R 2 and R 3 are as described above. Multiple Rs existing in each formula 2 or R 3 may be the same as or different from each other.

[0056] In General Formulas (6) and (7), R 4 represents a direct bond or a divalent organic group having 1 to 6 carbon atoms which may have an oxygen atom. The carbon number of said organic group is preferably 1 to 4, more preferably 1 to 2, and still more preferably 2. As R 4 , a divalent organic group having 1 to 6 carbon atoms which may have an oxygen atom is preferable, -CH2-, -CH2O-, -CH2OCH2-, -C(=O)-O-CH2- are more preferable, and -CH2OCH2- is still more preferable. Multiple Rs existing 4 may be the same as or different from each other.

[0057] In General Formulas (6) and (7), R 5 represents a direct bond or a divalent organic group having 1 to 6 carbon atoms which may have an oxygen atom. The carbon number of said organic group is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1. As R 5As for this, a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms is preferable, a direct bond, -CH2-, -CH2CH2- is more preferable, a direct bond, -CH2- is still more preferable, and -CH2- is particularly preferable.

[0058] The terminal structure represented by the general formula (6) has (e + 1) hydrolyzable silyl groups and d terminal olefin groups. The terminal structure represented by the 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 the general formula (6) or (7) respectively correspond to the sites derived from the epoxy compound having a terminal olefin group described later.

[0059] The terminal structure represented by the general formula (6) or (7) represents one terminal structure bonded to one terminal of the polymer main chain. Although a plurality of hydrolyzable silyl groups and / or terminal olefin groups are shown in the formula (6) or (7), each of the formula (6) or (7) does not represent two or more terminal structures, but represents one terminal structure, indicating that a plurality of hydrolyzable silyl groups and / or terminal olefin groups are present in one terminal structure. Further, the oxyalkylene repeating unit constituting the polymer main chain is not shown in the formula (6) or (7). That is, the structure within the parentheses in which d or e are present in the formula (6) or (7) does not correspond to the oxyalkylene repeating unit constituting the polymer main chain.

[0060] These general formulas are merely examples for explanation purposes, and the terminal structures in the present invention are not limited to these chemical structures. The terminal olefin groups contained in general formulas (6) and (7) may be internal olefin groups. In particular, some of the plurality of terminal olefin groups may be internal olefin groups. Also, the bonding order of the d terminal olefin group-containing units and the e hydrolyzable silyl group-containing units is not limited to the order shown in general formulas (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 can coexist. The terminal structure represented by general formula (6) and the terminal structure represented by 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 in terms of the polystyrene-equivalent molecular weight in GPC, it is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 3,000 to 30,000. When the number average molecular weight is less than 3,000, the relative amount of the hydrolyzable silyl group with respect to the whole polymer increases, which may be disadvantageous in terms of production cost. Also, when the number average molecular weight exceeds 100,000, the polymer may have a high viscosity and the workability may decrease.

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

[0063] The polyoxyalkylene polymer (A) of the present invention preferably has a stress at 100% elongation (100% modulus) of the cured product of the polymer of 0.40 MPa or less, more preferably 0.35 MPa or less, in terms of maintaining 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 the value measured under the following conditions.

[0064] <Method for measuring stress at 100% elongation of cured product of polymer> A mixture of polyoxyalkylene polymer / stannous octylate / laurylamine / distilled water = 40 / 1.2 / 0.2 / 0.24 (weight ratio) is filled into a 3 mm thick sheet-shaped mold. After storing at 23 °C and 50% relative humidity for 1 hour or more, it is cured in a dryer at 70 °C for 20 hours to obtain a sheet-shaped cured product. The obtained cured product is punched into No. 3 dumbbell-shaped test pieces according to JIS K 6251. Using the obtained test pieces, a tensile test (tensile speed: 200 mm / min) is performed at 23 °C and 50% relative humidity using an autograph, and the stress at 100% elongation is measured.

[0065] The polyoxyalkylene polymer (A) of the present invention preferably has a recovery rate of the cured product of the polymer of 90% or more in terms of enhancing the resilience of the cured product of the curable composition containing the polyoxyalkylene polymer (A) of the present invention. Here, the recovery rate of the cured product of the polymer is defined as the value measured under the following conditions and is defined as the value measured under the following conditions.

[0066] <Method for measuring recovery rate of cured product of polymer> A mixture of polyoxyalkylene polymer / 3-(N-2-aminoethylamino)propyltrimethoxysilane / stannous octylate / laurylamine / distilled water = 40 / 1.2 / 1.2 / 0.2 / 0.32 (by weight) is filled into a sheet-shaped mold with a thickness of 3 mm. After curing at 23°C and 50% relative humidity for 3 days, it is cured in a dryer at 50°C for 4 days to obtain a sheet-shaped cured product. The above sheet-shaped cured product is punched into a No. 7 dumbbell shape to obtain a dumbbell-shaped test piece. Two marking lines are drawn at intervals of 10 mm on the constricted part of the dumbbell-shaped test piece. The dumbbell-shaped test piece is fixed in an extended state so that the interval between the marking lines becomes 15 mm, and it is left standing in a dryer at 50°C. After 5 hours, the fixation is released, and the recovery rate is determined by measuring the interval between the marking lines after 1 hour at 23°C and 50% relative humidity.

[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 is obtained by introducing an average of more than 1.0 number of terminal olefin groups per terminal structure into a hydroxyl group-terminated polyoxyalkylene polymer (E) by utilizing the reactivity of the hydroxyl group, and then reacting with a hydrolyzable silyl group-containing compound having reactivity with the terminal olefin group to introduce a hydrolyzable silyl group.

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

[0069] [Chemical formula]

[0070] In the present invention, when introducing a hydrolyzable silyl group, instead of reacting all the terminal olefin groups capable of reacting with the hydrosilane compound, the reaction rate is suppressed and some of the terminal olefin groups are left unreacted, so that the molar number of the hydrolyzable silyl group / (the total molar number of the hydrolyzable silyl group, terminal olefin group and internal olefin group) satisfies the range of 0.3 to 0.7, and the polyoxyalkylene polymer (A) of the present invention can be obtained.

[0071] The internal olefin group can be generated by an internal transfer reaction (isomerization) of the terminal olefin group as a side reaction during the hydrosilylation reaction. Since the generated internal olefin group has low hydrosilylation activity, it remains in the polyoxyalkylene polymer (A) of the present invention without reacting with the hydrosilane compound in the hydrosilylation reaction.

[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, whereby a hydroxyl-terminated polyoxyalkylene polymer (E) is obtained. The specific polymerization method is not particularly limited, but since a hydroxyl-terminated polymer with a small molecular weight distribution (Mw / Mn) can be obtained, a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferred.

[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, and examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

[0076] (Introduction of terminal olefin group) As a method for introducing an average of more than 1.0 number of terminal olefin groups per one terminal structure of the polymer, after converting the terminal hydroxyl group to an alkoxide group by reacting an alkali metal salt with a hydroxyl group-terminated polyoxyalkylene polymer (E), first, reacting with an epoxy compound (8) having a terminal olefin group, and then reacting with an organic halide (10) having a terminal olefin group is preferred. Further, instead of the alkali metal salt, a double metal cyanide complex catalyst can also be used.

[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, cesium alkoxide, etc. 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 used in the reaction in a state dissolved in a solvent.

[0078] The amount of the alkali metal salt used is not particularly limited, but the molar ratio to the hydroxyl group of the hydroxyl group-terminated polyoxyalkylene polymer (E) is preferably 0.5 or more, more preferably 0.6 or more, still 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. On the contrary, if the amount used is too large, the alkali metal salt may remain as an impurity, and side reactions may proceed.

[0079] The alkali metal salt is used to convert the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer (E) into an alkoxide group. In order to efficiently proceed this conversion reaction, it is preferable to previously remove moisture and substances having a hydroxyl group other than the polyoxyalkylene polymer from the reaction system. For the removal, known methods can be used, for example, heating evaporation, devolatilization under reduced pressure, spray vaporization, thin film evaporation, azeotropic devolatilization, etc. can be utilized.

[0080] The temperature at the time of allowing the alkali metal salt to act can be appropriately set by those skilled in the art, but it is preferably 50°C or higher and 150°C or lower, and more preferably 110°C or higher and 145°C or lower. The time at the time of allowing the alkali metal salt to act is preferably 10 minutes or longer and 5 hours or shorter, and more preferably 30 minutes or longer and 3 hours or shorter.

[0081] Next, by subjecting the polyoxyalkylene polymer to a ring-opening addition reaction with an epoxy compound (8) having a terminal olefin group, a terminal structure (9) containing a site derived from the epoxy compound having a terminal olefin group is formed.

[0082] The epoxy compound having a terminal olefin group can be represented by the chemical formula (8) in the above 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 monooxide, 1,4-cyclopentadiene monoepoxide, etc., and allyl glycidyl ether is particularly preferable.

[0083] The amount of the epoxy compound (8) having the terminal olefin group 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 to be used. Specifically, the amount of the epoxy compound (8) used is preferably such that the molar ratio to the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer (E) is 0.1 or more, more preferably 0.3 or more, and still more preferably 0.5 or more. Further, it is preferably greater than 0.5, particularly preferably 1.0 or more, and most preferably 1.5 or more. Also, the molar ratio is preferably 9 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 4 or less.

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

[0085] Next, an organic halide (10) having a terminal olefin group is reacted with a polyoxyalkylene polymer having a terminal structure (9) containing a site derived from the epoxy compound having a terminal olefin group, so as to form an ether bond by a substitution reaction of a halogen and convert the alkoxide group at the polymer terminal to a terminal olefin group. Thereby, a terminal structure (11) having an average of more than 1.0 terminal olefin groups per terminal structure is formed.

[0086] The organic halide having a terminal olefin group can be represented by the chemical formula (10) in the above 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. Allyl chloride and methallyl chloride are preferred from the viewpoint of ease of handling.

[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 number of terminal olefins per terminal structure obtained by the above method is on average more than 1.0. A hydrosilane compound (12) having a hydrolyzable silyl group is hydrosilylated to a polyoxyalkylene polymer having a terminal structure (11) having an olefin group, to introduce a hydrolyzable silyl group into a part of the terminal olefin groups. In this case, the remaining part of the terminal olefin group is allowed to remain in the polymer without reacting with the hydrosilane compound (12). In addition, as described above, in the hydrosilylation reaction, a part of the terminal olefin group may be isomerized to an internal olefin group by 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, the amount of hydrolyzable silyl group introduced is easily adjusted, and the physical properties of the resulting polymer are stable.

[0090] The hydrosilane compound having a hydrolyzable silyl group can be represented by Chemical Formula (12) in the reaction formula, but is not limited thereto. Specific examples of the hydrosilane compound include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; alkoxysilanes such as 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, (3,3,3-trifluoropropyl)dimethoxysilane, (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-trifluoropropyl)dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane, diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate)methylsilane; isopropenoxy silanes (acetone-eliminated type) such as triisopropenoxysilane, (chloromethyl)diisopropenoxysilane, (methoxymethyl)diisopropenoxysilane, etc.

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

[0092] For the hydrosilylation reaction, it is preferably carried out in the presence of a hydrosilylation catalyst for promoting the reaction. As the hydrosilylation catalyst, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, and their complexes are known and can be used. Specifically, those obtained by supporting platinum on carriers such as alumina, silica, carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, ketones, etc.; platinum-olefin complexes [for example, Pt(CH2=CH2)2(PPh3) , Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [for example, Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [for example, Ph(PPh3)4, Pt(PBu3)4]; platinum-phosphite complexes [for example, Pt{P(OPh)3}4] and the like. 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. However, for the purpose of reducing the viscosity of the reaction system or improving the reactivity, the reaction under heating conditions is preferred. Specifically, the reaction at 50°C to 150°C is more preferred, and the reaction at 70°C to 120°C is even more preferred. The reaction time can also be appropriately set, but it is preferably adjusted 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, and more preferably 3 hours or less.

[0094] Further, the hydrosilylation reaction may be carried out in the presence of a trialkyl orthocarboxylate. By this, thickening during the hydrosilylation reaction can be suppressed, and the storage stability of the resulting polymer can be improved.

[0095] Examples of the trialkyl orthocarboxylate include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate and the like. Trimethyl orthoformate and trimethyl orthoacetate are preferable.

[0096] When using the trialkyl orthocarboxylate, its usage amount is not particularly limited, but it is preferably about 0.1 to 10 parts by weight, more preferably about 0.1 to 3 parts by weight, based on 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) For the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl group of the polyoxyalkylene polymer (A) of the present invention, that is, the curing reaction, it is preferable to blend a silanol condensation catalyst in the curable composition of the present invention.

[0099] As the silanol condensation catalyst, conventionally known ones can be used. Specifically, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids and the like can be used.

[0100] Specific examples of the organotin 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, and the like. Due to the recent increasing interest in the environment, dioctyltin compounds are preferred.

[0101] Specific examples of the metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, and the like. As the carboxyl group, various metals can be combined with the following carboxylic acids.

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

[0103] Specific examples of the carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, and the like.

[0104] Specific examples of the metal alkoxide include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0105] As other silanol condensation catalysts, fluoride anion-containing compounds, photoacid generators, and photobase generators can also be used.

[0106] Two or more different types of silanol condensation catalysts may be used in combination. For example, by using the above amine compound and carboxylic acid in combination, there may be an effect of improving the reactivity.

[0107] The blending 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, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If the blending amount of the silanol condensation catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, if the blending amount of the silanol condensation catalyst exceeds 20 parts by weight, the reaction rate is too fast, so the usable time of the composition is shortened, resulting in poor workability or poor storage stability. Furthermore, in some cases, after the curable composition is cured, it may ooze out onto the surface of the cured product or contaminate the surface of the cured product. In such a case, by setting the usage amount of the silanol condensation catalyst to 0.01 to 3.0 parts by weight, the surface state of the cured product can be kept good while ensuring curability.

[0108] The curable composition of the present invention preferably further contains a reactive diluent (D) which has an average of 0.5 or more and 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, it is possible to reduce the viscosity of the composition and suppress bleed-out while maintaining high resilience. Examples of the main chain skeleton of such a reactive diluent (D) include polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth)acrylate polymers, polyorganosiloxane polymers, and the like. Among these, from the viewpoint of compatibility with the polyoxyalkylene polymer (A) of the present invention, a polyoxyalkylene polymer is also preferable as the main chain skeleton of the reactive diluent (D).

[0109] The hydrolyzable silyl group in the reactive diluent (D) may be located at either the molecular chain end, the side chain, or both. In particular, when the hydrolyzable silyl group is at the molecular chain end, it is more preferable because the molecular weight between crosslinking points becomes longer and a rubbery cured product with good mechanical properties is easily obtained. The number of hydrolyzable silyl groups is 0.5 or more and less than 1.2 on average per molecule, but from the viewpoint of the mechanical properties during curing, the lower limit is preferably 0.6 or more, and preferably less than 1.0 in order to efficiently lower the modulus of the cured product. Further, 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 the hydrolyzable silyl group, the terminal olefin group, and the internal olefin group may be 1.0 or less on average per terminal structure.

[0110] The polymer which is the reactive diluent (D) preferably has a number average molecular weight in terms of 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 increase and a 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 only at one end is more preferable. Also, the main chain structure does not have to be a single one, and each polymer may be a mixture of separately produced ones, or may be produced simultaneously so as to obtain any polymer.

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

[0114] The blending 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, based on 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 deteriorate.

[0115] Further, the curable composition of the present invention preferably further contains a (meth)acrylate polymer (B) having a hydrolyzable silyl group. By further containing the (meth)acrylate polymer (B), the weather resistance of the cured product tends to be improved. The position of the hydrolyzable silyl group in the (meth)acrylate 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 ones 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, nonyl (meth)acrylate, 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-dimeth xmethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate and other (meth)acrylic acid monomers can be mentioned.

[0117] Examples of monomer units other than those described above include acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylolacrylamide and N-methylolmethacrylamide, an epoxy group such as glycidyl acrylate and glycidyl methacrylate, and a nitrogen-containing group 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 and 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 monomers such as 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. These can also be used as a plurality of copolymerization components.

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

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

[0121] Examples of the silicon compound that can be used for introducing a hydrolyzable silyl group into a (meth)acrylate polymer using the above method include the following compounds. Examples of the compound 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, 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate, and the like. 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 method (v) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, mercaptomethyltriethoxysilane, and the like.

[0123] Examples of the compound having a functional group reactive with the hydrolyzable silyl group and the V group used in method (vi) include isocyanate silane compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane; epoxy silane compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyldiethoxymethylsilane; amino silane compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-(2-aminoethyl)aminomethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and the like.

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

[0125] These methods may be used in any combination. For example, when method (vi) and method (v) are combined, a (meth)acrylic acid ester polymer having hydrolyzable silyl groups at both the molecular chain terminal and / or the side chain can be obtained.

[0126] (Meta)acrylic acid ester polymer (B) has a hydrolyzable silyl group, which is the same as the hydrolyzable silyl group of the polyoxyalkylene polymer (A) of the present invention, and 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 represented by. For R 1 , R 2 , Y, Y′, a, b, and m, they are the same as those in the general formula (1). Also, when m is 0, the general formula (8) becomes the following general formula (9): -SiR 2 3-a Y a (9) In this general formula (9), a represents 1, 2, or 3. As the hydrolyzable silyl group of the (meta)acrylic acid ester polymer (B), specifically, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group, and a triethoxysilyl group are preferable. Further, from the viewpoint of achieving both storage stability and curability of the curable composition containing the (meta)acrylic acid ester polymer (B), a methyldimethoxysilyl group is more preferable, and a trimethoxysilyl group is more preferable in terms of enhancing the restorability of the cured product of the composition.

[0127] The monomer composition of the (meta)acrylic acid ester polymer (B) is generally selected by those skilled in the art according to the use and purpose. However, for applications that require flexibility such as sealants, those having a relatively low glass transition temperature (Tg) are preferable, preferably having a Tg of -100°C or higher and 100°C or lower, more preferably -60°C or higher and 0°C or lower. Note that Tg is determined by the following Fox's equation. Fox's equation: 1 / (Tg(K)) = Σ(Mi / Tgi) (In the formula, Mi represents the weight fraction of the monomer i component constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of the monomer i.)

[0128] (Meta)acrylate polymer (B) has no particular limitation on its number average molecular weight, but in terms of the polystyrene-equivalent molecular weight measured by GPC, 500 to 100,000 is preferred, 1,500 to 50,000 is more preferred, and 5,000 to 30,000 is particularly preferred.

[0129] Methods for blending a polyoxyalkylene polymer and a (meta)acrylate polymer have been proposed in, for example, JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, JP-A-11-116763, etc. Additionally, a method of polymerizing a (meta)acrylate monomer in the presence of a polyoxypropylene polymer having a hydrolyzable silyl group can be used. This production method is specifically disclosed in each of the publications such as JP-A-59-78223, JP-A-60-228516, JP-A-60-228517, etc. The polyoxyalkylene polymer (A) and the (meta)acrylate polymer (B) of the present invention can be blended by the same method, but are not limited thereto.

[0130] The mixing ratio of the polyoxyalkylene polymer (A) and the (meta)acrylate polymer (B) of the present invention is not particularly limited, but in terms of weight ratio, 95:5 to 10:90 is preferred, 90:10 to 20:80 is more preferred, and 80:20 to 40:60 is particularly preferred. Note that the polyoxyalkylene polymer (A) and the (meta)acrylate polymer (B) of the present invention may each be used alone or in combination of two or more.

[0131] (Other additives) In the curable composition of the present invention, as other additives, a silicon compound, an adhesion promoter, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a physical property modifier, a tackifying resin, a compound containing an epoxy group, a photocurable substance, an oxygen-curable substance, a surface property improver, an epoxy resin, other resins, a flame retardant, and a foaming agent may be added. Further, in the curable composition of the present invention, various additives may be added as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, a curing modifier, a radical inhibitor, a metal deactivator, an ozone deterioration inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, a fungicide, and the like.

[0132] <Filler> Various fillers can be incorporated into the composition of the present invention. Examples of the filler include heavy 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, aluminum fine powder, zinc oxide, activated zinc white, 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] For the purpose of reducing the weight (lowering the specific gravity) of the composition, organic balloons and inorganic balloons may be added. A balloon is a spherical filler with a hollow interior. Examples of the material of this balloon include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. The above balloons may be used alone or in combination of two or more.

[0135] The amount of the balloon 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 can 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 can 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; isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, and α-isocyanatomethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Further, reaction products of various silane coupling agents can also be used. The above adhesion promoter 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. with respect to

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

[0140] In addition, a high molecular weight plasticizer can be used. Specific examples of the high molecular weight 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, and derivatives obtained by converting the hydroxy groups of these polyether polyols into ester groups, ether groups, etc., such as polyethers; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like.

[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 with respect to 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. The plasticizer may be used alone or in combination of two or more.

[0142] <Solvent, diluent> 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, due to the problem of air pollution when the composition is used indoors, the boiling point of the solvent is preferably 150 °C or higher, more preferably 200 °C or higher, and particularly preferably 250 °C or higher. The above solvent or diluent may be used alone or in combination of two or more.

[0143] <Anti-sagging agent> An anti-sagging agent may be added to the composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples include 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 anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0145] <Antioxidant> An antioxidant (anti-aging agent) can be used in the composition of the present invention. Using an antioxidant can improve the weather resistance of the cured product. Examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based. Specific examples of the antioxidant 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, with respect to 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.

[0147] <Light stabilizer> In the composition of the present invention, a light stabilizer can be used. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, benzoate-based compounds, etc., and particularly the hindered amine-based is 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 absorber> In the composition of the present invention, an ultraviolet absorber can be used. Using an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, etc., and particularly the benzotriazole-based is preferred, and commercially available names such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (manufactured by BASF) can be mentioned.

[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 modifier> To the curable composition of the present invention, a physical property modifier for adjusting the tensile properties of the cured product generated as needed may be added. The physical property modifier is not particularly limited. For example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane, phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates such as tris(trimethylsilyl) borate, tris(triethylsilyl) borate; silicone varnishes; polysiloxanes and the like can be mentioned. By using the physical property modifier, the hardness when the composition of the present invention is cured can be increased, or conversely, the hardness can be decreased and the elongation at break can be increased. The above physical property modifier may be used alone or in combination of two or more kinds.

[0152] In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an effect of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. A compound that generates trimethylsilanol is particularly preferable. Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, etc. and generate silane monoalcohol by hydrolysis.

[0153] The amount of the physical property modifier 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. For

[0154] <Adhesion-imparting resin> For the purpose of enhancing the adhesiveness and close adhesiveness to a substrate, or as needed otherwise, an adhesion - imparting resin can be added. There is no particular limitation on the adhesion - imparting resin, and those commonly used can be employed.

[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 - based resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low - molecular - weight polystyrene - based resins, styrene copolymer resins, styrene - based block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5 - C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These can be used alone or in combination of two or more.

[0156] The amount of the adhesion - imparting 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 with respect to 100 parts by weight of the polyoxyalkylene - based polymer (A) of the present invention. If it is less than 2 parts by weight, it is difficult to obtain the adhesion and close - adhesion effects to the substrate, and if it exceeds 100 parts by weight, the viscosity of the composition may become too high and handling may be difficult.

[0157] <Compound containing an epoxy group> In the composition of the present invention, a compound containing an epoxy group can be used. When a compound having an epoxy group is used, the restorability of the cured product can be enhanced. Examples of the compound having an epoxy group include epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, epoxy butyl stearate, etc. can be mentioned. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 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, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many such compounds are known, such as organic monomers, oligomers, resins, or compositions containing them. Representative examples include monomers having one to several acrylic or methacrylic unsaturated groups, oligomers, or unsaturated acrylic compounds which are mixtures thereof, vinyl polycinnamate, or azide resins.

[0159] The photocurable substance is preferably used in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.5 to 10 parts by weight, with respect to 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 enhancing the weather resistance, and if it is more than 20 parts by weight, the cured product becomes too hard and tends to crack.

[0160] <Oxygen-curable substance> An oxygen-curable substance can be used in the composition of the present invention. Examples of the oxygen-curable substance include unsaturated compounds that can react with oxygen in the air. By reacting with oxygen in the air, a cured film is formed near the surface of the cured product, preventing stickiness on the surface and the adhesion of dust and dirt to the surface of the cured product. What kind of action it has. Specific examples of the oxygen-curable substance include drying oils typified by tung oil and linseed oil, and various alkyd resins obtained by modifying the compound; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; butadiene, chloroprene, isoprene, Liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as 1,3-pentadiene. These may be used alone or in combination of two or more.

[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, based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. When the amount used is less than 0.1 part by weight, the improvement of the contaminating property is not sufficient, and when 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> An epoxy resin can be used in combination with the composition of the present invention. The composition added with an epoxy resin is particularly preferable as an adhesive, especially 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 use ratio of these epoxy resins and the polyoxyalkylene polymer (A) of the present invention is preferably in the range of polyoxyalkylene polymer (A) / epoxy resin = 100 / 1 to 1 / 100 by weight. When 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 cured epoxy resin, and when the ratio of polyoxyalkylene polymer (A) / epoxy resin exceeds 100 / 1, the strength of the cured polymer 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 a silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. It is preferable to use it in the range of 0.5 to 10 parts by weight.

[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 waterproof material, a waterproof coating material, a mold release agent, a vibration-proof material, a vibration damping material, a sound-proof material, a foaming material, a paint, and a spraying material. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, it can be suitably used as a sealing material or an adhesive.

[0170] In addition, the curable composition of the present invention can be used in various applications such as electrical and electronic component materials such as back surface encapsulants for solar cells, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulation materials for electrical appliances and devices, acoustic insulation materials, elastic adhesives, binders, contact adhesives, spray sealants, crack repair materials, adhesives for tiling, 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, sealing materials for joints of exterior materials such as sizing boards, coating materials, anti-slip coatings, cushioning materials, primers, conductive materials for electromagnetic wave shielding, heat conductive materials, hot melt materials, potting agents for electrical and electronics, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and sealing materials for rust prevention and waterproofing of wire mesh glass and the end faces (cut parts) of laminated glass, automotive parts, parts of large vehicles such as trucks and buses, parts for train vehicles, aircraft parts, ship parts, electrical machine parts, and various mechanical parts, etc. Taking automobiles as an example, it can be used in a wide variety of applications such as adhesive attachment of plastic covers, trims, flanges, bumpers, window attachments, interior members, and exterior parts. Furthermore, it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings, either alone or with the help of a primer, so it can also be used as various types of sealing compositions and adhesive compositions. In addition, the curable composition of the present invention can also be used as adhesives for interior panels, adhesives for exterior panels, adhesives for tiling, adhesives for stone cladding, adhesives for ceiling finishing, adhesives for floor finishing, adhesives for wall finishing, adhesives for vehicle panels, adhesives for assembly of electrical, electronic, and precision instruments, adhesives for bonding leather, fiber products, fabrics, paper, boards, and rubber, reactive post-crosslinked pressure-sensitive adhesives, sealing materials for direct glazing, sealing materials for laminated glass, sealing materials for SSG method, or sealing materials for working joints of buildings, civil engineering and bridge materials. Furthermore, it can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.

Examples

[0171] Examples are given below to explain the present invention in more detail, 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. Subsequently, a methanol solution of 1.0 equivalent of sodium methoxide was added to the hydroxyl group of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140 °C. Then, 0.3 equivalent of allyl glycidyl ether was added at 140 °C and reacted for 2 hours to introduce an unsaturated bond. Further, 1.5 equivalents of 3-chloro-1-propene were added to convert the terminal hydroxyl group into an allyl group. Next, 36 ppm of a platinum divinyldisiloxane complex (a 3% by mass isopropyl alcohol solution in terms of platinum) and 1.47 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the mixture was reacted at 90 °C for 2 hours. As a result, the 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) was 1.3, the molar ratio 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) was 68%, the number of hydrolyzable silyl groups per terminal structure was 0.88, and a linear polyoxypropylene (A-1) having a methyl dimethoxysilyl group at the terminal and a number average molecular weight of 19,000 was obtained. The total number of groups per terminal structure was 1.3, the hydrolyzable silyl group introduction rate was 68%, the number of hydrolyzable silyl groups per terminal structure was 0.88, and a linear polyoxypropylene (A-1) having a methyl dimethoxysilyl group at the terminal and a number average molecular weight of 19,000 was obtained.

[0173] (Example 2) By following the same procedure as in Example 1 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, a linear polyoxypropylene (A-2) having a methyl dimethoxysilyl group at the terminal, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 46%, a number of hydrolyzable silyl groups per terminal structure of 1.38, and a number average molecular weight of 19,000 was obtained.

[0174] (Example 3) A linear polyoxypropylene (A-3) having a methyldimethoxysilyl group at the terminal 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 was obtained by following the same procedure as in Example 1 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.

[0175] (Comparative Example 1) A linear polyoxypropylene (C-1) 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 74%, the number of hydrolyzable silyl groups per terminal structure of 0.74, and a number average molecular weight of 19,000 was obtained by following the same procedure as in Example 1 except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 1.31 parts by weight.

[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. Subsequently, a methanol solution of 1.0 equivalent of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140 °C. Then, 2.0 equivalents of allyl glycidyl ether was added at 140 °C and reacted for 2 hours to introduce an unsaturated bond. Further, 1.5 equivalents of 3-chloro-1-propene was added to convert the terminal hydroxyl groups into allyl groups. Next, 36 ppm of a platinum divinyldisiloxane complex (a 3% by mass isopropyl alcohol solution in terms of platinum) and 2.02 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the mixture was reacted at 90 °C for 2 hours, thereby obtaining linear polyoxypropylene (A-4) having a methyl dimethoxysilyl group at the terminal, with a total number of groups per terminal structure of 3.0, a hydrolyzable silyl group introduction rate of 42%, a number of hydrolyzable silyl groups per terminal structure of 1.26, and a number average molecular weight of 16,000.

[0177] (Example 5) By following the same procedure as in Example 4 except that the amount of methyldimethoxysilane used was 2.29 parts by weight, linear polyoxypropylene (A-5) having a methyl dimethoxysilyl group at the terminal, 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 was obtained.

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

[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. Subsequently, a methanol solution of 1.0 equivalent 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. Further, 1.5 equivalents of 3-chloro-1-propene was added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of a platinum divinyldisiloxane complex (a 3% by mass isopropyl alcohol solution in terms of platinum) and 1.26 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the mixture was reacted at 90 °C for 2 hours. As a result, a linear polyoxypropylene (A-6) having a methyl dimethoxysilyl group at the terminal, with a total number of groups per terminal structure of 2.0, a hydrolyzable silyl group introduction rate of 58%, a number of hydrolyzable silyl groups per terminal structure of 1.16, and a number average molecular weight of 28,000 was obtained.

[0180] (Comparative Example 3) Without using allyl glycidyl ether and following the same procedure as in Example 6 except that the amount of methyldimethoxysilane used was 0.94 parts by weight, a linear polyoxypropylene (C-3) having a methyl dimethoxysilyl group at the terminal, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 78%, a number of hydrolyzable silyl groups per terminal structure of 0.78, and a number average molecular weight of 28,000 was obtained.

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

[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 a hydroxyl-terminated polyoxypropylene (E-4) with a number average molecular weight of 20,000. Subsequently, a methanol solution of 1.0 equivalent of sodium methoxide was added to the hydroxyl group of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140 °C. Then, 1.6 equivalents of allyl glycidyl ether was added at 140 °C and reacted for 2 hours to introduce an unsaturated bond. Further, 1.5 equivalents of 3-chloro-1-propene was added to convert the terminal hydroxyl group to an allyl group. Next, 36 ppm of a platinum divinyldisiloxane complex (a 3 mass% isopropyl alcohol solution in terms of platinum) and 1.69 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, and the mixture was reacted at 90 °C for 2 hours to obtain a branched polyoxypropylene (A-7) having a methyl dimethoxysilyl group at the end 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) By following the same procedure as in Example 7 except that allyl glycidyl ether was not used and the amount of methyldimethoxysilane used was 1.22 parts by weight, a branched polyoxypropylene (C-5) having a methyl dimethoxysilyl group at the end 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 was obtained.

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

[0185] (Comparative Example 6) Without using allyl glycidyl ether, by following the same procedure as in Example 8 except that the amount of methyldimethoxysilane used was 1.17 parts by weight, a linear polyoxypropylene (C-6) having a methyl dimethoxysilyl group at the terminal, with a total number of groups per terminal structure of 1.0, a hydrolyzable silyl group introduction rate of 77%, a number of hydrolyzable silyl groups per terminal structure of 0.77, and a number average molecular weight of 21,000, was obtained.

[0186] (Example 9) By following the same procedure as in Example 1 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, a linear polyoxypropylene (A-9) having a methyl dimethoxysilyl 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, was obtained.

[0187] (Example 10) By following the same procedure as in Example 1 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, a linear polyoxypropylene (A-10) having a methyl dimethoxysilyl 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, was obtained.

[0188] (Example 11) By following the same procedure as in Example 1 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, a linear polyoxypropylene (A-11) having a methyl dimethoxysilyl 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, was obtained.

[0189] (Example 12) By following the same procedure as in Example 1 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, a linear polyoxypropylene (A-12) having a methyl dimethoxysilyl 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, was obtained.

[0190] (Example 13) By following the same procedure as in Example 1 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, a linear polyoxypropylene (A-13) having a methyl dimethoxysilyl group at the terminal was obtained, 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) By following the same procedure as in Example 1 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, a linear polyoxypropylene (C-7) having a methyl dimethoxysilyl group at the terminal was obtained, 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 prepared by dissolving 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 part by weight of 2,2'-azobis(2-methylbutyronitrile) in 10.0 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Polymerization was further carried out at 105 °C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of poly(meth)acrylate (B-1) having an average of 1.6 methyl dimethoxysilyl 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 prepared by dissolving 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) in 12.4 parts by weight of isobutyl alcohol was added dropwise 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)acrylate (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 prepared by dissolving 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) in 10.0 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Poly(meth)acrylate (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 was obtained as an isobutyl alcohol solution (solid content: 60% by weight).

[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 prepared by dissolving 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) in 10.0 parts by weight of isobutyl alcohol was added dropwise thereto 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)acrylate (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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-10) / polymer (B-1) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-2) / polymer (B-1) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-10) / polymer (B-3) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-2) / polymer (B-3) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-10) / polymer (B-4) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-2) / polymer (B-4) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (C-1) / polymer (B-1) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture having a weight ratio of polymer (A-8) / polymer (B-1) 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture in which the weight ratio of the polymer (A-7) / polymer (B-1) was 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture in which the weight ratio of the polymer (A-6) / polymer (B-2) was 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 isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture in which the weight ratio of the polymer (C-3) / polymer (B-2) was 70 / 30. The obtained polymer mixture was used in Comparative Example 18.

[0207] (Synthesis Example 5) Using n-butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 8,000 and a hydroxyl group at one end. Subsequently, a methanol solution of 1.0 equivalent of sodium methoxide was added to the hydroxyl group of the polyoxypropylene having a hydroxyl group at one end, and methanol was distilled off at 140 °C. Then, 1.5 equivalents of 3-chloro-1-propene was added to convert the terminal hydroxyl group into an allyl group. Next, 36 ppm of a platinum divinyldisiloxane complex (3% by 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 obtained polyoxypropylene having an allyl group at one end, and the mixture was reacted at 90 °C for 2 hours to obtain a 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 methyl dimethoxysilyl groups, which are hydrolyzable silyl groups, per molecule at one end. (D-1) was a polymer showing a lower viscosity at 23 °C than each polymer or polymer mixture obtained in Examples 1 to 22 and Comparative Examples 1 to 9.

[0208] (Examples 23 to 44 and Comparative Examples 10 to 18) Using each polymer or polymer mixture produced in Examples 1 to 22 or Comparative Examples 1 to 9, the following evaluations were carried out.

[0209] <Method for Measuring 100% Elongation Stress or Recovery Rate of Cured Product of Polymer> The 100% elongation stress or recovery rate of the cured product of each polymer was measured by the measurement method described above. For the polymer mixtures obtained in Examples 14 to 22 and Comparative Examples 8 to 9, the 100% elongation stress was measured under the same conditions using the polymer mixture.

[0210] <Evaluation Method for Physical Properties of Composition> Each polymer or polymer mixture was mixed with a filler, titanium oxide, anti-sagging agent, light stabilizer, and ultraviolet absorber among the following various additives, and after thorough mixing, it was passed through three paint rollers three times for dispersion to prepare the main agent. Thereafter, a dehydrating agent, an adhesion-imparting agent, and a silanol condensation catalyst were added and thoroughly mixed, and the mixture was uniformly kneaded and defoamed using a planetary mixer to prepare each curable composition. Using each of the prepared curable compositions, various test specimens were prepared in a constant temperature and humidity atmosphere of 23°C and 50% relative humidity, and various evaluations were performed.

[0211] (Various additives used in each example and comparative example regarding the evaluation of the physical properties of the composition) In the evaluation of the physical properties of the compositions of Examples 23 to 44 and Comparative Examples 10 to 18, the following additives were used. The compounding amounts are parts by weight based on 100 parts by weight of each polymer or polymer mixture which is the base polymer. Reactive diluent (D): Reactive diluent (D-1), 76 parts by weight Filler: (i) Fatty acid-treated precipitated calcium carbonate (White Swan CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 120 parts by weight (ii) Heavy calcium carbonate (Whiteon SB Red, manufactured by Shiraishi Calcium Co., Ltd.), 40 parts by weight Titanium oxide: Ty-Peak R-820, manufactured by Ishihara Sangyo Co., Ltd., 10 parts by weight Anti-sagging agent: Fatty acid amide wax (Disparon #6500, manufactured by Kusumoto Chemicals, 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 Ultraviolet absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (Tinuvin 326, manufactured by BASF), 1 part by weight Dehydrating agent: Vinyltrimethoxysilane (A-171, manufactured by Momentive Co., Ltd.), 2 parts by weight Adhesion-imparting agent: 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 physical properties) At 23°C and 50% relative humidity, the curable composition was filled into a 3 mm thick sheet-shaped mold. After curing for 3 days at 23°C and 50% relative humidity, it was cured in a dryer at 50°C for 4 days to obtain a sheet-shaped cured product. The obtained cured product was punched into No. 3 dumbbell-shaped test pieces according to JIS K 6251. Using the obtained test pieces, a tensile test (tensile speed: 200 mm / min) was performed at 23°C and 50% relative humidity using an autograph, and the stress at 50% elongation, the stress at 100% elongation, the stress at break, and the elongation at break were measured.

[0213] (Recovery) The above sheet-shaped cured product was punched into No. 7 dumbbell-shaped test pieces to obtain dumbbell-shaped test pieces. Two marking lines were drawn at intervals of 20 mm centering on the constricted part of the dumbbell-shaped test piece. The dumbbell-shaped test piece was fixed in a stretched state so that the distance between the marking lines became 40 mm and left standing in a dryer at 50°C. After 24 hours, the fixation was released, and the recovery rate was determined by measuring the distance between the marking lines after 24 hours at 23°C and 50% relative humidity.

[0214] The results obtained above are shown in Tables 1 to 8. Table 1 shows the results for polymers (A-1), (A-2), (A-3), or (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. Further, 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 for the mode in which the polyoxyalkylene polymer (A) of the present invention or the polyoxyalkylene polymer (C) that does not satisfy the requirements of the present invention, which was synthesized using hydroxyl-terminated polyoxypropylene (E-1) as a raw material, was combined with the (meth)acrylate polymer (B). Further, Table 8 shows the results for the mode in which the polyoxyalkylene polymer (A) of the present invention or the polyoxyalkylene polymer (C) that does not satisfy the requirements of the present invention, which was synthesized using a raw material other than hydroxyl-terminated polyoxypropylene (E-1), was combined with the (meth)acrylate 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, the cured products of the compositions of each example containing the polyoxyalkylene polymer (A) of the present invention have an equivalent main chain skeleton, but since the total number of groups per terminal structure is 1.0, they do not satisfy the requirements of the present invention. Compared with the cured products of the compositions of Comparative Examples 10 to 12, 14, 15, 17, and 18 containing the polyoxyalkylene polymer (C), it can be seen that even with a similarly low modulus, they exhibit high resilience. Also, no significant difference was confirmed in the dumbbell physical properties.

[0225] On the other hand, although the total number of groups per terminal structure exceeds 1.0, since the hydrolyzable silyl group introduction rate exceeds 70% and does not satisfy the requirements of the present invention, the compositions of Comparative Examples 13 and 16 containing the polyoxyalkylene polymer (C) show that although the cured products exhibit high resilience, the modulus of the cured products becomes too high, and thus it can be seen that they are not suitable as a sealing material.

[0226] From the above results, since the polyoxyalkylene polymer (A) of the present invention shows that the cured product of the curable composition containing it exhibits high resilience while showing a low modulus, and other physical properties are equivalent to those of existing products, it can be seen that it can be suitably used as the base polymer of a high-resilience sealing material with low bleed-out.

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 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 polyoxyalkylene polymer (A) according to claim 2, wherein the number of moieties derived from the epoxy compound having a terminal olefin group is more than 1.0 on average per terminal structure.

4. 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 any one of claims 1 to 3, represented by:

5. The polyoxyalkylene polymer (A) according to any one of claims 1 to 4, wherein the number of the hydrolyzable silyl groups per terminal structure is 0.85 or more on average.

6. The polyoxyalkylene polymer (A) according to any one of claims 1 to 5, wherein the polyoxyalkylene polymer (A) has a recovery rate of 90% or more in a cured product.

7. The polyoxyalkylene polymer (A) according to any one of claims 1 to 6, wherein a stress at 100% elongation of a cured product of the polyoxyalkylene polymer (A) is 0.40 MPa or less.

8. A curable composition comprising the polyoxyalkylene polymer (A) according to any one of claims 1 to 7.

9. The curable composition according to claim 8, further comprising 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 viscosity at 23°C lower than that of the polyoxyalkylene polymer (A).

10. The curable composition according to claim 8 or 9, further comprising a (meth)acrylic acid ester-based polymer (B) having a hydrolyzable silyl group.

11. A cured product of the curable composition according to any one of claims 8 to 10.

Images