Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• the present invention relates to a mixture of polyoxyalkylene polymers having hydrolyzable silyl groups, and a curable composition containing the mixture.
• Polymers with hydrolyzable silyl groups are known as moisture-reactive polymers, and are included in many industrial products such as adhesives, sealants, coating agents, paints, and pressure-sensitive adhesives, and are used in a wide range of fields. It's being used.
• Polyoxyalkylene-based polymers saturated hydrocarbon-based polymers, (meth)acrylic acid ester-based polymers and the like are known as the main chain skeleton of such polymers.
• a polyoxyalkylene polymer having a (for example, see Patent Document 1) has a relatively low viscosity at room temperature and is easy to handle, and the cured product obtained after the reaction exhibits good elasticity. Wide range.
• curable composition having a low viscosity and being easy to handle by blending a polyoxyalkylene polymer having a hydrolyzable silyl group with the above-mentioned reactive diluent into which the hydrolyzable silyl group is introduced. can be done.
• the mechanical properties after curing eg, tear strength, elongation, etc.
• the present invention provides a mixture of a hydrolyzable silyl group-containing polyoxyalkylene polymer that has a low viscosity and can exhibit good mechanical properties after curing, and a curable composition containing the same.
• the purpose is to provide goods.
• a polymer (A ) and a polymer (B) that can have a hydrolyzable silyl group only at one end are used in combination at a specific ratio, and the introduction rate of the hydrolyzable silyl group to the molecular chain end of the polymer (A) is set to a specific range.
• the present invention provides a mixture of polyoxyalkylene polymers (A) and (B), both of which have hydrolyzable silyl groups, wherein the polyoxyalkylene polymer (A) contains hydrolyzable silyl groups Or having two or more molecular chain ends in one molecule containing a reactive group capable of introducing a hydrolyzable silyl group, the polyoxyalkylene relative to the number of molecular chain ends of the polyoxyalkylene polymer (A)
• the average ratio of the number of the hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer (A) is 0.85 or more and 1.00 or less, and the number average of the polyoxyalkylene polymer (A) It has a molecular weight of 25,000 or less, and the hydrolyzable silyl group of the polyoxyalkylene polymer (A) has the general formula (1): —SiR 1 X 1 2 (1) (Wherein, R 1 represents a substituted or unsubstit
• X 1 are the same or different and represent a hydroxyl group or a hydrolyzable group.
• the polyoxyalkylene-based polymer (B) has one molecular chain end containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule, and the polyoxyalkylene-based The number average molecular weight of the polymer (B) is smaller than the number average molecular weight of the polyoxyalkylene polymer (A), and the hydrolyzable silyl group of the polyoxyalkylene polymer (B) has the general formula (1′): —SiR 2 a X 2 3-a (1′) (wherein R 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms; X 2 is the same or different and represents a hydroxyl group or a hydrolyzable group; a is 0; , 1 or 2.
• the hydrolyzable silyl group of the polyoxyalkylene polymer (B) is the same as the hydrolyzable silyl group of the polyoxyalkylene polymer (A). may be different), and the mixture ratio of the polyoxyalkylene polymer (A):(B) is 95:5 to 30:70 by weight.
• the polyoxyalkylene polymer (A) has a linear polymer backbone.
• said mixture has a viscosity of 15 Pa.s at 23°C. less than s.
• a in the general formula (1') represents 1.
• the polyoxyalkylene polymer (B) has a number average molecular weight of 10,000 or less.
• the average ratio of the number of the hydrolyzable silyl groups located at the molecular chain terminals of the polyoxyalkylene polymer (B) to the number of the molecular chain terminals of the polyoxyalkylene polymer (B) is 0.50 or more and 1.00 or less.
• the present invention also relates to a curable composition containing the mixture or a cured product of the curable composition. Further, the present invention is a method for producing the above mixture, wherein an epoxy compound is produced in the presence of a mixture of an initiator having two or more hydroxyl groups in one molecule and an initiator having one hydroxyl group in one molecule.
• a step of polymerizing to form a mixture of polyoxyalkylene polymers having hydroxyl groups at the molecular chain ends; and a step of introducing a hydrolyzable silyl group to the molecular chain ends of the polyoxyalkylene polymer. also relates to a manufacturing method.
• a mixture of a hydrolyzable silyl group-containing polyoxyalkylene polymer, which has a low viscosity and can exhibit good mechanical properties after curing, and a curable composition containing the same are provided. can do.
• the mixture according to this embodiment contains a polyoxyalkylene polymer (A) having a hydrolyzable silyl group and a polyoxyalkylene polymer (B) having a hydrolyzable silyl group.
• the mixture according to this embodiment refers to a mixture substantially containing only the polyoxyalkylene polymers (A) and (B). Since the polyoxyalkylene polymers (A) and (B) each have a hydrolyzable silyl group, the mixture exhibits curability based on hydrolysis and dehydration condensation reaction of the hydrolyzable silyl group.
• Each of the polyoxyalkylene-based polymers (A) and (B) has a polyoxyalkylene polymer backbone and a molecular chain end bonded to the polymer backbone.
• the polymer skeleton and the molecular chain end may be directly bonded or indirectly bonded via an intermediate structure.
• the intermediate structure include a structure derived from an epoxy compound (G3) described later (that is, a structure in parentheses having n structures in formula (4) described later).
• the polymer backbone refers to a polymer main chain composed of oxyalkylene repeating units.
• the polymer backbones of the polyoxyalkylene-based polymers (A) and (B) may each be linear or branched.
• a linear polymer skeleton is preferable because the cured product of the curable composition has high elongation, and a branched polymer skeleton is preferable because the cured product of the curable composition has high strength.
• a linear polymer backbone can be formed by using an initiator having one or two hydroxyl groups per molecule in the polymerization process to form the polymer backbone, and a branched polymer The backbone can be formed by using initiators with 3 or more hydroxyl groups in one molecule.
• the polymer skeleton is a polymer skeleton composed only of a plurality of oxyalkylene repeating units linked to each other, or is derived from the initiator used during polymerization in addition to the plurality of oxyalkylene repeating units. It preferably contains a structure and is a polymer skeleton composed only of these.
• the oxyalkylene repeating unit refers to a repeating unit constituting a polyether, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
• the polymer skeleton of polyoxyalkylene is not particularly limited, but examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxy A butylene copolymer etc. are mentioned. Polyoxypropylene is preferred. As the polymer skeleton, only one type may be used, or two or more types may be used in combination.
• molecular chain end refers to a site located at the end of a polyoxyalkylene polymer.
• the molecular chain end does not include a molecular chain end containing a hydrolyzable silyl group, a molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group, or a hydrolyzable silyl group and the reactive group. It is classified as a molecular chain end.
• the reactive group into which a hydrolyzable silyl group can be introduced refers to a reactive group that can be converted into a hydrolyzable silyl group through one-step or two-step or more reactions. Specific examples of the reactive group include, but are not limited to, hydroxyl groups and carbon-carbon unsaturated bonds (carbon-carbon double bonds or carbon-carbon triple bonds).
• the polyoxyalkylene-based polymer (A) refers to one having two or more molecular chain ends containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule.
• the polyoxyalkylene polymer (A) has a linear polymer skeleton, there are two molecular chain ends, and both of the two molecular chain ends are hydrolyzable silyl groups, or It contains a reactive group capable of introducing a hydrolyzable silyl group.
• a polymer molecule having two molecular chain ends each containing a hydrolyzable silyl group (ii) one molecular chain end containing a hydrolyzable silyl group and a hydrolyzable silyl
• a polymer molecule having one molecular chain end containing a reactive group capable of introducing a group and (iii) a polymer molecule having two molecular chain ends each containing a reactive group capable of introducing a hydrolyzable silyl group. corresponds to the polyoxyalkylene polymer (A).
• Such a polyoxyalkylene polymer (A) can be prepared, for example, by one-step or two-step polymerization of introducing a hydrolyzable silyl group after polymerizing an epoxy compound in the presence of an initiator having two hydroxyl groups in one molecule. It can be produced by performing reactions in stages or more. If the introduction rate of the hydrolyzable silyl groups in the introduction reaction is 100%, then all of the molecular chain terminals in the polymer (A) will contain hydrolyzable silyl groups.
• the polymer (A) when the introduction rate is less than 100%, the polymer (A) has a molecular chain end containing a hydrolyzable silyl group and a molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group. will coexist.
• polyoxyalkylene-based polymer (A) when the polyoxyalkylene-based polymer (A) has a branched polymer skeleton, there are three or more molecular chain ends, and at least two of them (preferably, all end of the molecular chain) contains a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group.
• a polyoxyalkylene-based polymer (A) can be prepared, for example, by one step of introducing a hydrolyzable silyl group after polymerizing an epoxy compound in the presence of an initiator having three or more hydroxyl groups in one molecule, or It can be produced by performing reactions in two or more stages.
• the polyoxyalkylene polymer (A) is preferably a polymer having a linear polymer skeleton.
• a polymer having a branched polymer skeleton may be used, or a polymer having a linear polymer skeleton and a branched polymer A polymer having a combined skeleton may be used in combination.
• the polyoxyalkylene-based polymer (B) refers to a polymer having only one molecular chain end containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule.
• polyoxyalkylene polymer (B) has a linear polymer skeleton, (iv) one molecular chain end containing a hydrolyzable silyl group, a hydrolyzable silyl group and the reactive group (v) a molecular chain containing a reactive group capable of introducing a hydrolyzable silyl group
• a polymer molecule containing one terminal and one non-reactive molecular chain terminal corresponds to the polyoxyalkylene polymer (B).
• Such a polyoxyalkylene-based polymer (B) can be obtained, for example, by one step of introducing a hydrolyzable silyl group after polymerizing an epoxy compound in the presence of an initiator having only one hydroxyl group in one molecule, or It can be produced by performing reactions in two or more stages.
• the resulting polyoxyalkylene polymer contains a structure derived from the initiator at one molecular chain end.
• the resulting polyoxyalkylene polymer contains a butyl group at one molecular chain end. Structures derived from such initiators result in non-reactive chain ends that contain neither hydrolyzable silyl groups nor the aforementioned reactive groups.
• the polyoxyalkylene polymer (A) is a polymer with a high introduction rate of hydrolyzable silyl groups to the ends of its molecular chains.
• the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer (A) to the number of molecular chain ends of the polyoxyalkylene polymer (A) (hereinafter , also referred to as “the number of hydrolyzable silyl groups introduced to the molecular chain end”) is preferably 0.85 or more and 1.00 or less.
• a polyoxyalkylene polymer (A) having a large number of hydrolyzable silyl groups introduced at the molecular chain end is treated with a molecular chain containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group.
• the mixture according to the present embodiment has a low viscosity and exhibits good mechanical properties after curing. can.
• the number of hydrolyzable silyl groups introduced to the molecular chain end is calculated by NMR measurement of the polyoxyalkylene polymer (A), the molecular chain end containing the hydrolyzable silyl group, and the hydrolyzable It can be calculated from the ratio of the molecular chain ends containing the hydrolyzable silyl group to the total molecular chain ends containing a reactive group capable of introducing a silyl group.
• the number of hydrolyzable silyl groups introduced to the molecular chain end is [number of hydrolyzable silyl groups located at the molecular chain end of the polyoxyalkylene polymer (A)/polyoxyalkylene polymer (A) number of molecular chain ends], and the total number of molecular chain ends of the polyoxyalkylene polymer (A), including hydrolyzable silyl groups of the polyoxyalkylene polymer (A) It can also be rephrased as the average ratio of the number of molecular chain ends. "The number of molecular chain ends of the polyoxyalkylene polymer (A)" is 2 when the polymer skeleton is all linear, and is 3 or more when the polymer skeleton is all branched. .
• hydrolyzable silyl group located at the molecular chain end of the polyoxyalkylene polymer (A) is a concept excluding the hydrolyzable silyl group contained in the aforementioned intermediate structure.
• the number of hydrolyzable silyl groups introduced to the molecular chain end in the polyoxyalkylene polymer (A) is 0.85 or more, the mixture according to the present embodiment can exhibit better mechanical properties after curing. Therefore, it is preferably 0.88 or more, more preferably 0.90 or more, still more preferably 0.93 or more, and particularly preferably 0.95 or more. In addition, although the number of introduction is 1.00 or less, it is preferably 0.99 or less, more preferably 0.98 or less, because production is easy.
• the number of hydrolyzable silyl groups introduced to the molecular chain end in the polyoxyalkylene polymer (B) is not particularly limited, but from the viewpoint of the mechanical properties exhibited by the mixture according to the present embodiment, the polyoxyalkylene polymer Position at the molecular chain end of the polyoxyalkylene polymer (B) relative to the number of molecular chain ends containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group, which the polymer (B) has It is preferable that the average ratio of the number of hydrolyzable silyl groups to be 0.30 or more and 1.00 or less.
• the lower limit is more preferably 0.50 or more, more preferably 0.60 or more, and particularly preferably 0.70 or more.
• the upper limit is preferably 0.99 or less, more preferably 0.98 or less.
• the number of hydrolyzable silyl groups introduced to the molecular chain ends in the polyoxyalkylene polymer (B) is the number of hydrolyzable silyl groups or hydrolyzed silyl groups without considering the number of non-reactive molecular chain ends. It is the average ratio of the number of hydrolyzable silyl groups located at the molecular chain terminals to the number of molecular chain terminals containing reactive groups capable of introducing a silyl group.
• the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (A) is represented by the following general formula (1).
• the resulting cured product can have good mechanical properties. —SiR 1 X 1 2 (1)
• hydrolyzable silyl group possessed by the polyoxyalkylene polymer (B) is represented by the following general formula (1'). —SiR 2 a X 2 3-a (1′)
• R 1 and R 2 each represent 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 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
• the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. .
• R 1 and R 2 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group and n-dodecyl group.
• unsubstituted alkyl group such as chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group; unsaturated hydrocarbon group such as vinyl group, isopropenyl group and allyl group; cycloalkyl group such as cyclohexyl group groups; aryl groups such as phenyl group, toluyl group and 1-naphthyl group; and aralkyl groups such as benzyl group.
• substituted or unsubstituted alkyl groups more preferred are methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups, still more preferred are methyl groups and methoxymethyl groups, and particularly preferred are methyl groups.
• R 1 only one type of group may be used, or two or more types of groups may be used in combination.
• R 2 only one type of group may be used, or two or more types of groups may be used in combination.
• R 1 and R 2 may be the same or different.
• X 1 and X 2 each represent a hydroxyl group or a hydrolyzable group.
• X 1 and X 2 include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group.
• the above alkoxy group and the like may have a substituent.
• An alkoxy group is preferred because it is moderately hydrolyzable and easy to handle, methoxy, ethoxy, n-propoxy and isopropoxy are more preferred, methoxy and ethoxy are still more preferred, and methoxy is particularly preferred.
• X1 and X 2 may be the same or different.
• a in the general formula (1′) is 0, 1 or 2;
• the value of a in formula (1′) is preferably 1 because the mechanical properties of the resulting cured product are improved.
• the hydrolyzable silyl group represented by general formula (1') may be the same as or different from the hydrolyzable silyl group represented by general formula (1).
• hydrolyzable silyl groups represented by general formula (1) include methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, and (chloromethyl)diethoxysilyl group. group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group and the like.
• a methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred.
• a (chloromethyl)dimethoxysilyl group and a (methoxymethyl)dimethoxysilyl group are more preferable.
• a methyldimethoxysilyl group and a methyldiethoxysilyl group are more preferable.
• a methyldimethoxysilyl group is more preferable because it is easy to produce.
• hydrolyzable silyl groups represented by general formula (1′) include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N- diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group and the like.
• a methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred.
• trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferable.
• a methyldimethoxysilyl group and a methyldiethoxysilyl group are more preferable.
• a methyldimethoxysilyl group is more preferable because it is easy to produce.
• the molecular chain end containing a hydrolyzable silyl group possessed by the polyoxyalkylene polymer (A) is not particularly limited, but a typical example is a molecular chain end represented by the following general formula (3). be done.
• Representative examples of the molecular chain end containing a hydrolyzable silyl group possessed by the polyoxyalkylene polymer (B) include -SiR 1 X 1 2 in the following general formula (3), 1′): —SiR 2 a X 2 3-a .
• R 3 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms
• R 4 represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
• the leftmost oxygen indicates the oxygen in the oxyalkylene unit located at the end of the polymer backbone.
• R 1 and X 1 are the same as described above for general formula (1).
• R 3 is preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrocarbon group having 1 to 2 carbon atoms.
• the hydrocarbon group is preferably an alkylene group, and a methylene group, ethylene group, propylene group, or butylene group can be used. Methylene groups are particularly preferred.
• R 4 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
• the alkyl group include hydrogen, methyl group, ethyl group, propyl group, butyl group and the like.
• R 4 is preferably an alkyl group having 1 to 4 carbon atoms, such as 1 to 3 carbon atoms, because it improves the number of hydrolyzable silyl groups introduced to the ends of the molecular chain and easily achieves 0.85 or more. is more preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.
• hydrogen and an alkyl group having 1 to 4 carbon atoms may coexist.
• the molecular chain end represented by the general formula (3) is preferably directly bonded to the polymer skeleton of the polyoxyalkylene polymer (A), but as described above, it is indirectly bonded via an intermediate structure. may be connected to The intermediate structure may contain hydrolyzable silyl groups.
• the intermediate structure containing a molecular chain end containing a hydrolyzable silyl group and a hydrolyzable silyl group is represented by, for example, the following general formula (4).
• the intermediate structure containing a hydrolyzable silyl group-containing molecular chain end and a hydrolyzable silyl group, which the polyoxyalkylene polymer (B) has, is, for example, -SiR 1 X in the following general formula (4) 1 2 can be represented by the general formula (1′): —SiR 2 a X 2 3-a .
• the sites represented by —R 3 —CH(R 4 )—CH 2 —SiR 1 X 1 2 correspond to the ends of the molecular chains containing hydrolyzable silyl groups, and there are n of them. Structures in parentheses correspond to intermediate structures. Further, the “hydrolyzable silyl group located at the end of the molecular chain” means only the hydrolyzable silyl group contained in the site represented by —R 3 —CH(R 4 )—CH 2 —SiR 1 X 1 2 , and the hydrolyzable silyl group contained in the intermediate structure is not located at the molecular chain terminal and does not correspond to the hydrolyzable silyl group located at the molecular chain terminal.
• the hydrolyzable silyl group located at the molecular chain terminal and the hydrolyzable silyl group contained in the intermediate structure may be the same or different.
• R 5 is a direct bond or a divalent linking group having 1 to 6 carbon atoms.
• R 6 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
• n is an integer from 1 to 10;
• the oxygen at the left end represents the oxygen in the oxyalkylene unit located at the end of the polymer backbone composed of a plurality of oxyalkylene units linked together.
• R 1 , R 3 , R 4 and X 1 are the same as described above for general formulas (1) and (3).
• R 5 may be a divalent organic group having 1 to 6 carbon atoms.
• the organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom.
• the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2.
• -CH 2 OCH 2 -, -CH 2 O- and -CH 2 - are preferred, and -CH 2 OCH 2 - is more preferred.
• R 6 is preferably hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. . Hydrogen and methyl groups are particularly preferred, and hydrogen is most preferred.
• the number average molecular weight of the polyoxyalkylene polymer (A) is 25,000 or less in terms of polystyrene equivalent molecular weight in GPC.
• the number average molecular weight of component (A) is 25,000 or less, the resulting cured product can have good mechanical properties. It is preferably 22,000 or less, more preferably 16,000 or less.
• the lower limit of the number average molecular weight of component (A) is not particularly limited, it may be, for example, 3,000 or more, preferably 5,000 or more, and more preferably 7,000 or more.
• the number average molecular weight can be determined in terms of polystyrene by GPC measurement.
• the number average molecular weight of the polyoxyalkylene polymer (B) is smaller than the number average molecular weight of the polyoxyalkylene polymer (A) in order to reduce the viscosity of the mixture according to the present embodiment.
• the polystyrene equivalent molecular weight in GPC is preferably 10,000 or less, more preferably 8,500 or less. In order to further reduce the viscosity of the mixture, the number average molecular weight is preferably 7,000 or less.
• the lower limit of the number average molecular weight of component (B) is not particularly limited, it may be, for example, 1,000 or more, preferably 1,200 or more, and more preferably 1,500 or more.
• the number average molecular weight can be determined in terms of polystyrene by GPC measurement.
• the molecular weight distribution (Mw/Mn) of each of the polyoxyalkylene-based polymers (A) and (B) is not particularly limited, it is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4 or less. Moreover, from the viewpoint of improving various mechanical properties such as improving the durability and elongation of the cured product, it is preferably 1.2 or less.
• the molecular weight distribution (Mw/Mn) can be calculated from the number-average molecular weight and the weight-average molecular weight obtained in terms of polystyrene by GPC measurement.
• the weight ratio of the polyoxyalkylene polymer (A):(B) in the mixture according to the present embodiment is 95:5 to 30:70.
• the ratio is preferably 90:10 to 40:60, more preferably 80:20 to 50:50.
• the mixture according to the present embodiment has a low viscosity, specifically, a viscosity of 15 Pa.s measured at 23°C. It is preferred to indicate less than s. More preferably, 10 Pa.s. s or less, more preferably 5 Pa.s or less. s or less.
• the viscosity is measured at 23° C. with an E-type viscometer (RE-85U manufactured by Tokyo Keiki, measurement cone: 3° ⁇ R14).
• a hydroxyl group-terminated polyoxyalkylene polymer (E) is introduced with a carbon-carbon unsaturated bond using the reactivity of the hydroxyl group, and then the reactivity with the carbon-carbon unsaturated bond is reduced. It can be produced by reacting a hydrolyzable silyl group-containing compound having a hydrolyzable silyl group to introduce a hydrolyzable silyl group.
• the polymer backbone of the polyoxyalkylene-based 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-based polymer (E) can be obtained. is obtained.
• a hydroxyl-terminated polyoxyalkylene-based polymer (E) can be obtained.
• Mw/Mn small molecular weight distribution
• a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is used. is preferred.
• the initiator having a hydroxyl group is not particularly limited, examples of the initiator having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1 ,4-butanediol, 1,6-hexanediol, low molecular weight polyoxypropylene diol, low molecular weight polyoxypropylene triol, glycerin, trimethylolpropane, triethylolethane, sorbitol, pentaerythritol and the like.
• monohydric alcohols can be used, for example, methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethyl hexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.
• low-molecular-weight polyoxypropylene monoalkyl ethers and the like are also included.
• examples of initiators having one hydroxyl group and one carbon-carbon unsaturated bond include allyl alcohol and low-molecular-weight polyoxypropylene monoallyl ether.
• the initiator can realize the synthesis of component (A). For example, in the case of introducing a hydrolyzable silyl group by a hydrosilylation reaction between a hydrosilane compound (I) and a carbon-carbon unsaturated bond, which will be described later, the above initiator can be used to synthesize component (A).
• the initiator having a hydroxyl group a mixture of an initiator having two or more hydroxyl groups in one molecule and an initiator having one hydroxyl group in one molecule is used, and an epoxy compound is produced in the presence of the mixture.
• a hydroxyl group-terminated polyoxyalkylene polymer (E) can be obtained as a mixture of two types of polymers.
• the resulting hydroxyl-terminated polyoxyalkylene polymer (E) is a polyoxyalkylene polymer having hydroxyl groups at both ends.
• a mixture of an alkylene polymer and a polyoxyalkylene polymer having a hydroxyl group at one end is obtained. Thereafter, a step of introducing a carbon-carbon unsaturated bond and a step of introducing a hydrolyzable silyl group, which will be described later, are performed to synthesize a mixture of the polymers (A) and (B) in one system. becomes possible.
• the polymer (A) can be synthesized, and if only an initiator having one hydroxyl group is used, the polymer (B) can be synthesized.
• epoxy compound is not particularly limited, examples thereof include alkylene oxides such as ethylene oxide and propylene oxide. Propylene oxide is preferred.
• reaction with alkali metal salt In introducing a carbon-carbon unsaturated bond to the hydroxyl group-terminated polyoxyalkylene polymer (E), first, an alkali metal salt is allowed to act on the hydroxyl group-terminated polyoxyalkylene polymer (E) to obtain a terminal hydroxyl group. is preferably converted to a metaloxy group.
• a double metal cyanide complex catalyst can also be used instead of the alkali metal salt.
• the metaloxy group-terminated polyoxyalkylene-based polymer (F) is thus formed.
• the alkali metal salt is not particularly limited, examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide and the like.
• Sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoint of ease of handling and solubility, and sodium methoxide and sodium tert. -butoxide is more preferred. From the standpoint of availability, sodium methoxide is particularly preferred, and from the standpoint of reactivity, sodium tert-butoxide is particularly preferred.
• the alkali metal salt may be dissolved in a solvent before being subjected to the reaction.
• the amount of the alkali metal salt to be used is not particularly limited. 7 or more is more preferable, and 0.8 or more is even more preferable.
• the molar ratio is preferably 1.2 or less, more preferably 1.1 or less.
• the alkali metal salt is used to convert the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) into metaloxy groups. It is preferable to previously remove substances having hydroxyl groups other than the alkylene polymer from the reaction system. For removal, known methods may be used, such as heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, and the like.
• the temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 145°C or lower.
• the time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.
• reaction with electrophile (G) The metaloxy group-terminated polyoxyalkylene polymer (F) obtained as described above is reacted with an electrophilic agent (G) having a carbon-carbon unsaturated bond to convert the metaloxy group to a carbon - can be converted into structures containing carbon unsaturation. As a result, a polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the molecular chain end can be formed.
• the electrophilic agent (G) having a carbon-carbon unsaturated bond reacts with the metaloxy group possessed by the polyoxyalkylene polymer (F) to add a carbon-carbon unsaturated bond to the polyoxyalkylene polymer.
• a compound that can be introduced for example, an organic halide (G1) having a carbon-carbon double bond, an organic halide (G2) having a carbon-carbon triple bond, and a carbon-carbon double bond Epoxy compounds (G3) and the like can be mentioned.
• An organic halide (G1) having a carbon-carbon double bond which is one embodiment of the electrophile (E), reacts with the metaloxy group through a halogen substitution reaction to form an ether bond to form a polyoxy
• a carbon-carbon double bond can be introduced at the molecular chain end of the alkylene polymer.
• organic halide (G1) represented by the general formula (5) are not particularly limited, but vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, iodide vinyl, allyl iodide, methallyl iodide, and the like. Allyl chloride and methallyl chloride are preferred for ease of handling. Moreover, methallyl chloride, methallyl bromide, and methallyl iodide are preferable because the number of hydrolyzable silyl groups introduced to the ends of the molecular chains described above is improved.
• An organic halide (G2) having a carbon-carbon triple bond which is another embodiment of the electrophile (E), reacts with the metaloxy group through a halogen substitution reaction to form an ether bond to form a polyoxy
• a carbon-carbon triple bond can be introduced at the molecular chain end of the alkylene polymer.
• Organic halides (G2) having a carbon-carbon triple bond include, but are not limited to, the following general formula (6): ZR 7 —C ⁇ C—R 8 (6) can be expressed as In the formula, R 7 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples of R 7 include the same groups as R 3 described above for general formula (3).
• R 8 represents hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen or an alkyl group having 1 to 8 carbon atoms.
• alkyl group include methyl group, ethyl group, propyl group, butyl group and the like. Hydrogen is particularly preferred as R8 .
• Z represents a halogen atom.
• organic halide (G2) represented by the general formula (6) are not particularly limited, but propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro- 2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, Propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octy
• the amount of the organic halide having a carbon-carbon double bond (G1) or the organic halide having a carbon-carbon triple bond (G2) is not particularly limited, but the polyoxyalkylene polymer (E) has
• the molar ratio of the organic halide (G1) or (G2) to the hydroxyl group is preferably 0.7 or more, more preferably 1.0 or more. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
• the temperature at which the organic halide having a carbon-carbon double bond (G1) or the organic halide having a carbon-carbon triple bond (G2) is reacted with the metaloxy group-terminated polyoxyalkylene polymer (F) is preferably 50° C. or higher and 150° C. or lower.
• the temperature is more preferably 110 ° C. or higher and 140 ° C. or lower, while the organic halide (G2) having a carbon-carbon triple bond is reacted. , 50° C. or higher and 80° C. or lower.
• the reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.
• both the organic halide having a carbon-carbon double bond (G1) and the organic halide having a carbon-carbon triple bond (G2) are reacted with the metaloxy group-terminated polyoxyalkylene polymer (F).
• the organic halide (G1) having a carbon-carbon double bond and the organic halide (G2) having a carbon-carbon triple bond may be reacted simultaneously or sequentially. In the case of sequential reaction, the order may be irrelevant, and any one may be reacted first.
• a polyoxyalkylene polymer (H) having both carbon-carbon double bonds and carbon-carbon triple bonds at the molecular chain ends can be synthesized.
• An epoxy compound (G3) having a carbon-carbon double bond which is still another embodiment of the electrophilic agent (G), reacts with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond.
• a structure containing a carbon-carbon double bond and a hydroxyl group can be introduced into the polyoxyalkylene polymer.
• one or more epoxy compounds (G3) are added to one metaloxy group by adjusting the amount of the epoxy compound (G3) used for the metaloxy group and the reaction conditions. can be made
• the hydrolyzable silyl group is introduced after adding the epoxy compound (G3), the structure derived from the epoxy compound (G3) becomes the above-described intermediate structure containing the hydrolyzable silyl group.
• the epoxy compound (G3) having a carbon-carbon double bond is, but not limited to, the following general formula (6):
• R 5 and R 6 are the same groups as R 5 and R 6 described above for general formula (4), respectively.
• epoxy compound (G3) having a carbon-carbon double bond examples include, but are not limited to, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, 1,4-cyclopentadiene mono Epoxide is preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.
• the amount of the epoxy compound (G3) having a carbon-carbon double bond to be added can be any amount in consideration of the introduction amount and reactivity of the carbon-carbon double bond to the polymer.
• the molar ratio of the epoxy compound (G3) to the hydroxyl groups of the polyoxyalkylene polymer (E) is preferably 0.2 or more, more preferably 0.5 or more.
• the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
• the reaction temperature for the ring-opening addition reaction of the epoxy compound (G3) having a carbon-carbon double bond to the metaloxy group-terminated polyoxyalkylene polymer (F) is 60° C. or higher and 150° C. or lower. is preferred, and 110° C. or higher and 140° C. or lower is more preferred.
• the epoxy compound (G3) having a carbon-carbon double bond is allowed to act on the metaloxy group-terminated polyoxyalkylene polymer (F), a new metaloxy group is generated due to the ring opening of the epoxy group. do. Therefore, after reacting the epoxy compound (G3), the organic halide (G1) having a carbon-carbon double bond can be reacted continuously. Thereby, a carbon-carbon double bond can be introduced at the molecular chain end of the polyoxyalkylene polymer.
• the organic halide (G1) having a carbon-carbon double bond used in this embodiment the same compound as described above can be used, and the amount and reaction temperature thereof are also the same as described above. .
• This method is preferable because the amount of carbon-carbon double bonds introduced into the polymer and the amount of hydrolyzable silyl groups introduced can be increased.
• the polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the end of the molecular chain, obtained by the method of using the epoxy compound (G3) and the organic halide (G1) in combination, is described below.
• Introduction of a hydrolyzable silyl group can form the structure represented by the general formula (4).
• the structure in which the hydrolyzable silyl group is introduced from the epoxy compound (G3) corresponds to the intermediate structure described above, and the structure in which the hydrolyzable silyl group is introduced from the organic halide (G1) is the molecular chain. at the end.
• the structure derived from the epoxy compound (G3), that is, the hydrolyzable silyl group contained in the intermediate structure does not correspond to the hydrolyzable silyl group located at the end of the dispersed chain, as described above.
• the hydrolyzable silyl group contained in the structure derived from the organic halide (G1) corresponds to the hydrolyzable silyl group located at the end of the dispersed chain.
• reaction with the alkali metal salt and the reaction with the electrophilic agent (G) described above are repeated multiple times in order to increase the introduction rate of the carbon-carbon unsaturated bond to the polymer (H).
• the reactants (alkali metal salt or electrophile having a carbon-carbon unsaturated bond (G)) used in each step may be the same. , can be different.
• the obtained polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the molecular chain end is subjected to a hydrosilylation reaction with a hydrosilane compound (I) having a hydrolyzable silyl group to obtain a polymer.
• a hydrolyzable silyl group can be introduced into the coalescence.
• a polyoxyalkylene polymer (A) or (B) having a hydrolyzable silyl group, or a mixture of polymers (A) and (B) can be produced.
• the hydrosilylation reaction has the advantage that it can be easily carried out, the amount of hydrolyzable silyl groups to be introduced can be easily adjusted, and the physical properties of the obtained polymer are stable.
• hydrosilane compound (I) having a hydrolyzable silyl group examples include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloro halosilanes such as methyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, Ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysi
• alkoxysilanes alkoxysilanes; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; isopropenyloxysilanes (deacetone type) such as silane, (chloromethyl)diisopropenyloxysilane, (methoxymethyl)diisopropenyloxysilane, and the like;
• the amount of the hydrosilane compound (I) having a hydrolyzable silyl group used depends on the amount of carbon-carbon unsaturated bonds possessed by the polyoxyalkylene polymer (H) and the desired hydrolyzability to the end of the molecular chain. It may be appropriately set in consideration of the number of silyl groups to be introduced.
• the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction.
• a hydrosilylation catalyst metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, and complexes thereof are known, and these can be used.
• platinum-phosphine complexes [eg Ph(PPh 3 ) 4 , Pt(PBu 3 ) 4 ]; platinum-phosphite complexes [eg Pt ⁇ P(OPh) 3 ⁇ 4 ]; be done.
• platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.
• the hydrosilylation reaction is preferably carried out in the presence of a quinone compound in addition to the hydrosilylation catalyst.
• the quinone compound can further improve promotion of the hydrosilylation reaction by the hydrosilylation catalyst.
• Specific examples of quinone compounds include 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6- di-tert-butyl-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 9,10-anthraquinone, 1-ethylanthraquinone, and 2-(1,2-dimethylpropyl)-9,10-anthraquinone and the like.
• the hydrosilylation reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the polyoxyalkylene polymer (H), hydrosilane compound (I), and hydrosilylation catalyst, In order to easily control the temperature of the system and add the hydrosilylation catalyst, an organic solvent may be added.
• the temperature conditions for the hydrosilylation reaction are not particularly limited and can be appropriately set by those skilled in the art. However, in order to reduce the viscosity of the reaction system and improve the reactivity, the reaction is preferably performed under heating conditions. , 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 may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, more preferably 3 hours or less.
• the hydrosilylation reaction may be carried out in the presence of an orthocarboxylic acid trialkyl ester. This can suppress thickening during the hydrosilylation reaction and improve the storage stability of the resulting polymer.
• orthocarboxylic acid trialkyl esters examples include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Preferred are trimethyl orthoformate and trimethyl orthoacetate.
• the amount used is not particularly limited, but the polyoxyalkylene polymer (A) or (B), or the total of 100 parts by weight of the polymers (A) and (B) About 0.1 to 10 parts by weight is preferable, and about 0.1 to 3 parts by weight is more preferable.
• a compound having a hydrolyzable silyl group and an isocyanate group in one molecule (J ) to form a urethane bond and introduce a hydrolyzable silyl group.
• a polyoxyalkylene polymer (A) or (B) having a hydrolyzable silyl group, or a mixture of polymers (A) and (B) can be produced.
• an isocyanate group capable of a urethanization reaction with the hydroxyl group of the polyoxyalkylene polymer (E) and a hydrolyzable silyl group in one molecule examples include (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxymethylsilane, and (3-isocyanatopropyl)triethoxysilane.
• the amount of the compound (J) having a hydrolyzable silyl group and an isocyanate group in one molecule is determined by the amount of hydroxyl groups possessed by the polyoxyalkylene polymer (E) and the desired hydrolyzability to the end of the molecular chain. It may be appropriately determined in consideration of the number of silyl groups to be introduced.
• excess compound (J) may be removed by treatment such as devolatilization under reduced pressure after the urethanization reaction, or may be reacted with an active hydrogen group-containing compound or the like. It may be converted to another compound by using it, or it may remain in the polyoxyalkylene polymer to be produced.
• the compound (J) remaining in the produced polyoxyalkylene polymer or a derivative thereof can act as a silane coupling agent.
• the urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst for the purpose of improving the reaction rate or improving the reaction rate.
• a urethanization catalyst include, for example, conventionally known urethanization catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963.
• a catalyst can be used. Specific examples thereof include base catalysts such as organic tin compounds, bismuth compounds, and organic amines, but are not limited to these.
• highly active catalysts include tin octylate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutyl maleate, dibutyltin dilaurate, and 1,1,3,3-tetrabutyl.
• the amount of the urethanization catalyst added can be appropriately set by those skilled in the art, but from the viewpoint of reaction activity, it is preferably 1 to 1000 ppm, more preferably 10 to 100 ppm, relative to 100 parts by weight of the polyoxyalkylene polymer (E). Within this range, sufficient reaction activity can be obtained, and physical properties such as heat resistance, weather resistance, hydrolysis resistance, and storage stability of the polyoxyalkylene polymer to be produced can be maintained satisfactorily.
• the urethanization reaction can be performed without using a solvent, but for the purpose of uniformly dissolving the polyoxyalkylene polymer (E), the compound (J), and the urethanization catalyst, the In order to easily realize the temperature control of and the addition of the urethanization catalyst, an organic solvent may be added.
• the temperature of the urethanization reaction can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 120°C or lower, more preferably 70°C or higher and 100°C or lower.
• the reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed.
• the reaction time is preferably 15 minutes to 5 hours, more preferably 30 minutes to 3 hours.
• the compound (K) having a hydrolyzable silyl group and a mercaptan group in one molecule includes a mercaptan group capable of addition reaction to the carbon-carbon double bond of the polyoxyalkylene polymer (H), It is not particularly limited as long as it is a compound having both a decomposable silyl group in one molecule, but specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl ) methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, (mercaptomethyl)triethoxysilane, etc. mentioned.
• the amount of the compound (K) having a hydrolyzable silyl group and a mercaptan group in one molecule to be used depends on the amount of carbon-carbon double bonds possessed by the polyoxyalkylene polymer (H) and the desired molecular chain end. may be appropriately determined in consideration of the number of hydrolyzable silyl groups to be introduced into.
• excess compound (K) may be removed by treatment such as devolatilization under reduced pressure after the addition reaction, or may be reacted with an unsaturated group-containing compound or the like. It may be converted into another compound, or it may remain in the polyoxyalkylene polymer produced.
• the compound (K) remaining in the produced polyoxyalkylene polymer or a derivative thereof can act as a silane coupling agent.
• the addition reaction of the mercaptan group to the carbon-carbon double bond may be carried out without using a radical initiator.
• a radical initiator conventionally known ones can be used. Specific examples include azo initiators and peroxide initiators, but are not limited to these.
• radical initiators catalysts having low activity toward hydrolyzable silyl groups are preferred.
• AIBN 2,2'-azobis(isobutyronitrile)
• Azo initiators such as 2-methylbutyronitrile) (V-59)
• V-40 2,2′-azobis(1-methylcyclohexanecarbonitrile)
• the amount of the radical initiator to be added can be appropriately set by those skilled in the art, but from the viewpoint of reaction activity, it is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (H), and 0.1 to 10 parts by weight. 3 parts by weight is more preferred.
• a radical initiator may be used in a state of being dissolved in an organic solvent.
• the temperature for the addition reaction can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 120°C or lower, more preferably 70°C or higher and 100°C or lower.
• the reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed.
• the reaction time is preferably 15 minutes to 10 hours, more preferably 30 minutes to 6 hours.
• ⁇ Curable composition> it is possible to provide a curable composition containing a mixture of the polyoxyalkylene polymers (A) and (B).
• the curable composition according to the present embodiment is a reaction of hydrolyzing and condensing the hydrolyzable silyl groups of the polyoxyalkylene polymers (A) and (B), that is, for the purpose of promoting the curing reaction, silanol condensation It is preferred to incorporate a catalyst.
• silanol condensation catalyst conventionally known ones can be used. Specifically, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. can be used.
• organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds.
• dioctyltin diacetate dioctyltin dilaurate
• dioctyltin bis(ethyl maleate) dioctyltin bis(octyl maleate)
• dioctyltin bis(acetylacetonate) phosphate dioctyltin oxide and a silicate compound, and the like.
• Dioctyltin compounds are preferred due to recent heightened environmental concerns.
• carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and cesium carboxylate.
• carboxylic acid group the following carboxylic acid and various metals can be combined.
• amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenyl biguanide; amino group-containing silane coupling agents; ketimine compounds;
• carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
• alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetoacetate. and zirconium compounds such as zirconium tetrakis (acetylacetonate).
• fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
• the silanol condensation catalyst may be used in combination of two or more different catalysts.
• the combination of the amine compound and carboxylic acid or the amine compound and alkoxy metal may improve reactivity. have a nature.
• the amount of the silanol condensation catalyst from the viewpoint of achieving both improvement in the condensation reaction rate and workability during curing, 100 parts by weight of the mixture of the polyoxyalkylene-based polymers (A) and (B) according to the present embodiment
• 0.001 to 20 parts by weight is preferable, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable.
• some silanol condensation catalysts may ooze out or contaminate the surface of the cured product after the curable composition is cured. In such a case, the amount of the silanol condensation catalyst used is 0.01 to 3.0 parts by weight, so that the surface condition of the cured product can be kept good while ensuring the curability.
• the curable composition according to the present embodiment preferably further contains a (meth)acrylate polymer (D) having a hydrolyzable silyl group. Further containing the (meth)acrylate polymer (D) tends to improve the weather resistance of the cured product.
• the position of the hydrolyzable silyl group in the (meth)acrylic acid ester polymer (D) may be at the end of the main chain of the polymer or in the middle of the main chain.
• the (meth)acrylic acid ester monomer constituting the main chain of the (meth)acrylic acid ester polymer (D) is not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
• tert-butyl (meth)acrylate n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-(meth)acrylate -octyl, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate , glycidyl (meth)acrylate, (3
• Examples of monomer units other than the above include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as N-methylol acrylamide and N-methylol methacrylamide; epoxy groups such as glycidyl acrylate and glycidyl methacrylate; , diethylaminoethyl methacrylate, and the like.
• the (meth)acrylate polymer (D) a polymer obtained by copolymerizing a (meth)acrylate monomer and a vinyl monomer copolymerizable therewith can also be used.
• the vinyl-based monomer is not particularly limited, and examples thereof include styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like.
• Fluorine-containing vinyl monomers Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, maleic acid monoalkyl esters and dialkyl esters; Fumaric acid, fumaric acid monoalkyl esters and dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Containing vinyl-based monomers; amide group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl
• the average number of hydrolyzable silyl groups in the (meth)acrylic acid ester polymer (D) is preferably 0.3 to 5.0 per molecule, and the mechanical properties of the curable composition during curing From the viewpoint of , it is more preferably 0.5 or more, and from the viewpoint of the stability of the (meth)acrylic acid ester polymer (D), it is more preferably 3.0 or less.
• the method for introducing a hydrolyzable silyl group into the (meth)acrylate polymer is not particularly limited, and for example, the following method can be used.
• (vi) A method of copolymerizing a compound having a polymerizable unsaturated group and a hydrolyzable silyl group together with the aforementioned monomers. Using this method, hydrolyzable silyl groups tend to be randomly introduced into the backbone of the polymer.
• (vii) A method of polymerizing a (meth)acrylate polymer using a mercaptosilane compound having a hydrolyzable silyl group as a chain transfer agent. Using this method, a hydrolyzable silyl group can be introduced at the polymer terminal.
• a method of reacting an aminosilane compound having a silyl group can be exemplified.
• a method of modifying a terminal functional group of a (meth)acrylic acid ester-based polymer synthesized by a living radical polymerization method to introduce a hydrolyzable silyl group A (meth)acrylic acid ester-based polymer obtained by a 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.
• Examples of silicon compounds that can be used to introduce hydrolyzable silyl groups into the (meth)acrylic acid ester polymer using the above method include the following compounds.
• Compounds having a polymerizable unsaturated group and a hydrolyzable silyl group used in method (vi) include 3-(trimethoxysilyl)propyl (meth)acrylate and 3-(dimethoxymethylsilyl)acrylate (meth)acrylate.
• Mercaptosilane compounds having a hydrolyzable silyl group used in method (vii) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, mercaptomethyltriethoxysilane and the like.
• Compounds having a functional group reactive with the hydrolyzable silyl group and the V group used in method (viii) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatosilane compounds such as isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Epoxysilane compounds such as 3-glycidoxypropyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane, gly
• any modification reaction can be used.
• a method of introducing a double bond to the end of a polymer using a compound having a functional group capable of reacting with a functional group and a double bond and then introducing a hydrolyzable silyl group thereon by hydrosilylation or the like can be used.
• hydrolyzable silyl group possessed by the (meth)acrylic acid ester polymer (D) examples include the same hydrolyzable silyl groups possessed by the polyoxyalkylene polymer (A) and/or (B). be done. Among them, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group and a triethoxysilyl group are preferable.
• a methyldimethoxysilyl group is more preferable, and the curability of the composition and its A trimethoxysilyl group is more preferable because it can improve the restorability of the cured product.
• the monomer composition of the (meth)acrylic acid ester polymer (D) is generally selected according to the application and purpose among those skilled in the art.
• the glass transition temperature (Tg) is relatively low, preferably -100°C or higher and 100°C or lower, more preferably -60°C or higher and 0°C or lower.
• the number average molecular weight of the (meth)acrylic acid ester polymer (D) is not particularly limited, but the polystyrene equivalent molecular weight by GPC measurement is preferably 500 to 100,000, more preferably 1,000 to 50,000, and 2 ,000 to 30,000 are particularly preferred.
• a method of blending a polyoxyalkylene polymer and a (meth)acrylic acid ester polymer is disclosed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-116763. No. 5, 2003, etc.
• a method of polymerizing a (meth)acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a hydrolyzable silyl group can be used.
• This manufacturing method is specifically disclosed in each publication such as JP-A-59-78223, JP-A-60-228516 and JP-A-60-228517.
• the mixture of the polyoxyalkylene-based polymers (A) and (B) and the (meth)acrylic acid ester-based polymer (D) according to the present embodiment can also be blended by a similar method, but are not limited to these. .
• the ratio of the mixture of the polyoxyalkylene polymer (A) and (B) according to the present embodiment to the (meth)acrylic acid ester polymer (D) is not particularly limited, but the weight ratio is 95: 5 to 10. :90 is preferred, 90:10 to 20:80 is more preferred, and 80:20 to 40:60 is particularly preferred.
• the mixture of the polyoxyalkylene polymer (A) and (B) and the (meth)acrylic acid ester polymer (D) may be used singly or in combination of two or more. good.
• the curable composition according to the present embodiment contains other additives such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, and a light stabilizer. , UV absorbers, physical property modifiers, tackifier resins, compounds containing epoxy groups, photo-curing substances, oxygen-curing substances, surface property modifiers, epoxy resins, other resins, flame retardants, foaming agents. can be In addition, various additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the curable composition or cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, and the like. be done.
• additives such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent
• Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.
• the above fillers may be used alone or in combination of two or more.
• the amount of the filler used is preferably 1-300 parts by weight, more preferably 10-250 parts by weight, per 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B).
• Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition.
• the balloon is hollow inside with a spherical filler, and is made of inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. materials. Only one kind of balloon may be used, or a mixture of two or more kinds may be used.
• the amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B).
• the curable composition according to the present embodiment may contain an adhesion imparting agent.
• a silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
• silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
• the amount of adhesion-imparting agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymer (A) and (B). preferable.
• plasticizer can be added to the curable composition according to the present embodiment.
• plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl ole
• polymer plasticizer can be used.
• polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
• the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and 20 to 100 parts by weight with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymer (A) and (B). Part is more preferred.
• a plasticizer may be used individually and may use 2 or more types together.
• Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
• the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher, because of the problem of air pollution when the composition is used indoors. .
• the above solvents or diluents may be used alone or in combination of two or more.
• the curable composition according to the present embodiment may optionally contain an anti-sagging agent to prevent sagging and improve workability.
• the anti-sagging agent is not particularly limited, but examples thereof 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.
• the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B).
• the curable composition according to the present embodiment may contain an antioxidant (antiaging agent).
• an antioxidant can enhance the weather resistance of the cured product.
• antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). .
• a light stabilizer can be added to the curable composition according to the present embodiment.
• the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.
• the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). .
• the curable composition according to this embodiment may contain an ultraviolet absorber.
• the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
• UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred.
• Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
• the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). .
• a physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition according to the present embodiment, if necessary.
• the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
• arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes;
• the physical property modifier By using the physical property modifier, the hardness of the cured composition can be increased, or conversely, the hardness can be decreased and elongation at break can be obtained. For example, by adding diphenyldimethoxysilane, it is possible to maintain the restorability while lowering the hardness when the composition is cured.
• the physical property modifiers may be used alone or in combination of two or more.
• a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the surface stickiness of the cured product.
• Compounds that generate trimethylsilanol are particularly preferred.
• Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups. Mention may be made of silicon compounds that produce ols.
• the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). .
• a tackifying resin can be added to the curable composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes.
• the tackifying resin there is no particular limitation, and those commonly used can be used.
• terpene-based resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.
• petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C
• the amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). More preferably ⁇ 30 parts by weight.
• a compound containing an epoxy group can be blended in the curable composition according to the present embodiment.
• the use of a compound having an epoxy group can enhance the restorability of the cured product.
• Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.
• epoxidized soybean oil epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate , epoxy butyl stearate and the like.
• the epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B).
• a photocurable substance can be blended in the curable composition according to the present embodiment.
• 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 compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.
• the photocurable substance is preferably used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the mixture of the polyoxyalkylene polymer (A) and (B), more preferably 0.5 to 20 parts by weight. It is in the range of 10 parts by weight.
• the curable composition according to this embodiment may contain an oxygen-curable substance.
• oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust.
• Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins.
• silicone resins 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
• diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
• liquid polymers These may be used alone or in combination of two or more.
• the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0 parts by weight, per 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). .5 to 10 parts by weight.
• the oxygen-curable substance is preferably used in combination with the photo-curable substance.
• Epoxy resin can be blended into the curable composition according to the present embodiment.
• a composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles.
• epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.
• a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present embodiment.
• the epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.
• the amount used is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the curable composition according to the present embodiment can also be prepared as a one-component type in which all the ingredients are previously mixed and sealed and cured by moisture in the air after application, and a silanol condensation It can also be prepared as a two-component type in which components such as a catalyst, a filler, a plasticizer, and water are blended and the blending materials and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferred.
• the ingredients containing water are preliminarily dehydrated and dried before use, or dehydrated by decompression or the like during blending and kneading. is preferred.
• Storage stability is further improved by adding an alkoxysilane compound such as silane.
• the amount of the dehydrating agent, especially the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight per 100 parts by weight of the mixture of the polyoxyalkylene polymers (A) and (B). parts by weight, more preferably 0.5 to 10 parts by weight.
• the curable composition according to the present embodiment includes adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proof materials, vibration-damping materials, Can be used as soundproofing material, foaming material, paint, spraying material.
• a cured product obtained by curing the curable composition according to the present embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealant or an adhesive.
• the curable composition according to the present embodiment can be used for electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, and acoustic insulation.
• electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, and acoustic insulation.
• the curable composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone, a ceiling finishing adhesive, a floor finishing adhesive, a wall Finishing adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure sensitive adhesives , a sealing material for direct glazing, a sealing material for double glazing, a sealing material for the SSG construction method, a sealing material for working joints of buildings, a material for civil engineering, and a bridge material. Furthermore, it can be used as an adhesive material such as an adhesive tape and an adhesive sheet.
• the present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
• the "components at both ends” referred to below are hydrolyzable silyl groups and/or reactive groups capable of introducing hydrolyzable silyl groups at both ends of linear polyoxypropylene (e.g., hydroxyl groups , allyl group, methallyl group).
• the term "single-end component" refers to a hydrolyzable silyl group and/or a reactive group capable of introducing a hydrolyzable silyl group at only one of both ends of linear polyoxypropylene.
• Both terminal components can correspond to the polyoxyalkylene-based polymer (A) when they satisfy the predetermined requirements.
• the one-terminal component can correspond to the polyoxyalkylene-based polymer (B) if it satisfies predetermined requirements.
• a number average molecular weight is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Tosoh HLC-8420GPC Column: TSKgel SuperH series manufactured by Tosoh Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C
• the viscosity is the viscosity measured at 23°C with an E-type viscometer (RE-85U manufactured by Tokyo Keiki, measurement cone: 3° x R14).
• a linear polyoxypropylene diol (commercially available product) having hydroxyl groups at both ends and having a number average molecular weight of about 4,500 is referred to as "polymer (E-1)".
• a linear polyoxypropylene diol (commercially available) having hydroxyl groups at both ends and having a number average molecular weight of about 3,000 is referred to as "Polymer (E-2)”.
• Each polymer contained in the polymer mixture can be separately referred to as polymer (A) and polymer (B). -1), etc.
• the polyoxyalkylene-based polymers (A) and (B) contained in the polyoxypropylene-based polymer mixture (AB-1) are simultaneously terminal-modified, the polymer (A) and (B)
• the "number of hydrolyzable silyl groups introduced to the ends of the molecular chains" can be considered to be the same. The same applies to the polymer mixture (AB-2) and polymer mixtures (CB-1) and (CB-2) shown later.
• a methyldimethoxysilyl group was also introduced at sites other than the ends of the molecular chain, and the number of groups was 0.75 when converted to one end of the molecular chain.
• rice field The average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain terminals was 1.50 when totaled with the number of hydrolyzable silyl groups introduced to the molecular chain terminals.
• a polymer (A-2) was obtained.
• the number of hydrolyzable silyl groups introduced to the molecular chain ends in the polyoxypropylene polymer (A-2) was 0.98.
• a plasticizer, a filler, titanium oxide, an anti-sagging agent, a light stabilizer, and an ultraviolet absorber were thoroughly mixed and thoroughly kneaded, and then passed through three paint rolls to disperse. Thereafter, the mixture was dehydrated under reduced pressure at 120° C. for 2 hours using a planetary mixer, cooled to 50° C. or less, added with a dehydrating agent, and kneaded in a substantially moisture-free state. After degassing under reduced pressure, it was sealed in a cartridge, which is a moisture-proof container, to obtain a masterbatch composition.
• each polymer or each polymer mixture, an adhesion imparting agent, and a silanol condensation catalyst are added to the masterbatch composition, thoroughly mixed, and uniformly kneaded and degassed using a rotation-revolution mixer. , to prepare each curable composition.
• various test specimens were prepared under a constant temperature and constant humidity atmosphere at 23° C. and a relative humidity of 50%, and various evaluations were performed.
• the following additives were used in the evaluation of the composition physical properties of all Examples, Comparative Examples, and Reference Examples.
• the blending amount is the number of parts by weight per 100 parts by weight of each polymer or each polymer mixture that is the base polymer.
• Plasticizer diisononyl phthalate (DINP, manufactured by J-Plus Co., Ltd.), 90 parts by weight Filler: (i) Fatty acid-treated precipitated calcium carbonate (Hakuenka CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 160 parts by weight (ii) Heavy calcium carbonate (Whiten SB Red, manufactured by Shiraishi Calcium Co., Ltd.), 54 parts by weight Titanium oxide: Typaque R-820, manufactured by Ishihara Sangyo Co., Ltd., 5 parts by weight Anti-sagging agent: Fatty acid amide wax (Disparon #6500, Kusumoto Kasei Co., Ltd.), 2 parts by weight Light stabilizer: Bis(2,2,6,6) -Tetramethyl-4-piperidyl) sebacate (tinuvin 770, manufactured by BASF), 1 part by weight UV absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (tinu
• the curable composition was filled into a 3 mm thick sheet form. After curing for 3 days at 23° C. and 50% relative humidity, it was aged for 4 days in a drier at 50° C. to obtain a sheet-like cured product. The obtained cured product was punched into a No. 3 dumbbell shape according to JIS K 6251 to obtain a test piece. Using the obtained test piece, a tensile test (tensile speed 200 mm / min) was performed using an autograph at 23 ° C. and a relative humidity of 50%, and the stress at 100% elongation, stress at break, and elongation at break were measured. It was measured.
• the curable composition was filled into a 3 mm thick sheet form. After curing for 3 days at 23° C. and 50% relative humidity, it was aged for 4 days in a drier at 50° C. to obtain a sheet-like cured product. The resulting cured product was punched into a dumbbell shape (JIS A type) for tearing test to obtain a test piece. Using the obtained test piece, a tear test (tensile speed of 200 mm/min) was performed using an autograph at 23° C. and a relative humidity of 50% to measure the stress at break.
• JIS A type dumbbell shape
• Table 2-1 shows the evaluation results divided into examples in which the stress during elongation of the cured product of the composition is about the same.
• Example 1 Comparative Example 1, and Reference Example 1 were compared for the results of systems exhibiting relatively high elongation stress.
• the polyoxyethylene that satisfies the predetermined requirements
• the cured product of the composition of Example 1 containing a mixture of alkylene polymers (A) and (B) can exhibit higher tear strength and elongation despite the low viscosity of the polymer mixture used. I understand.
• Example 2 Comparative Example 2, and Reference Example 2 compared the results of systems exhibiting relatively low elongation stress, which are also Example 1, Comparative Example 1, and Reference Example. It can be seen that the comparison between 1 shows equivalent results.
• Table 2-2 summarizes the results of Examples in which the structure of polymer (B) was mainly changed.
• the cured products of the compositions of Examples 1 and 3 to 8 using a polymer mixture having a lower viscosity than the polymer used in Reference Example 1 had a small number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• the cured product of the composition of Comparative Example 1 containing only the polyoxyalkylene polymer as the terminal component it can be seen that the cured product exhibits high tear strength and elongation while maintaining the same degree of viscosity.
• Example 11 even when a polymer (A-2) into which a hydrolyzable silyl group was introduced by a method different from that of the polymer (A-1) was used, the same results as in Example 1 were obtained. It can be seen that the results are shown.
• Table 2-3 shows a comparative example using a polyoxyalkylene-based polymer having both terminal components in which the number of hydrolyzable silyl groups introduced to the molecular chain terminal is less than 0.85, instead of the polymer (A).
• Table 2-4 shows the results of comparative examples using polyoxyalkylene-based polymers with both terminal components instead of polymer (B) while maintaining the same viscosity range, and the results of examples corresponding to the comparative examples.
• Comparative Example 10 has a viscosity comparable to that of Example 1, but at least elongation is greatly inferior, and it can be seen that tear strength and elongation are not compatible. The same applies to Comparative Example 11 and Example 12, Comparative Example 12 and Example 13.
• Example 13 achieves both high tear strength and elongation compared to Comparative Examples 13 and 14 showing similar viscosities. The same applies to Example 14 and Comparative Example 15.
• Table 2-6 shows the upper limit of the number average molecular weight of polymer (A).
• the polymer (A-1) or polymer (A-4) having a number average molecular weight of 25,000 or less It can be seen that when combined with coalescence (B-1), the elongation of the cured product of the composition is greatly improved, and the tear strength becomes equivalent or higher.
• Comparative Example 16 and Reference Example 5 when the polymer (C-9) having a number average molecular weight of more than 25,000 is used in combination with the polymer (B-1), the cured product of the composition It can be seen that although the elongation is slightly improved, the tear strength is greatly reduced.
• Table 2-7 shows the structure of the hydrolyzable silyl groups possessed by the polymer (A). Comparative Example 17 using a polyoxyalkylene-based polymer of both terminal components having hydrolyzable silyl groups with three hydroxyl groups or hydrolyzable groups on the silyl groups instead of the polymer (A) was carried out. It can be seen that compared with Example 1, the elongation and tear strength of the cured product of the composition are greatly reduced. The same applies to Comparative Example 18 and Example 6, Comparative Example 19 and Example 13.
• Table 2-8 shows that the number of hydrolyzable silyl groups introduced to the molecular chain ends in the polymer (A) is 0.85 or more.
• the polymer (A-1) and the polymer (B) were used in combination.
• Examples 1 and 6, or Example 16 in which the polymer (A-2) and the polymer (B) were used in combination the elongation of the cured product of the composition was greatly improved, and the tear strength was also improved to some extent. .
• the mixture of the polyoxyalkylene polymers (A) and (B) satisfying the above requirements has a low viscosity, and the cured product of the curable composition containing it has high elongation and tear strength.
• it can be seen that it can be suitably used as a base polymer for sealants and adhesives that require low viscosity and good mechanical properties after curing.

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