Sclerotic composition

Abstract

To provide a curable composition capable of giving a cured product improved in transparency while containing a polysilsesquioxane-based polymer and a reactive silyl group-containing polyether polymer.SOLUTION: There is provided a curable composition which comprising a polysilsesquioxane polymer (A), a polyalkylene oxide polymer having a reactive silyl group (B1) and / or a poly(meth)acrylic polymer having a reactive silyl group (B2) and a curing catalyst (C). (A) has a polysilsesquioxane skeleton, an alkoxysilyl group (a1) and / or a silanol group (a2), an alkyl group having 1 to 10 carbon atom (b1) and an aryl groups having 6 to 10 carbon atoms (b2), a polyalkylene oxide polymer chain (c1) and / or a linear poly(meth)acrylic polymer chain (c2). One end of (c1) and / or (c2) is bonded to the polysilsesquioxane skeleton. The molar ratio of (b1): (b2) is 45:55 to 99:1.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to curable compositions comprising polysilsesquioxane polymers. [Background technology]

[0002] Organic polymers having a silicon-containing group (hereinafter referred to as a "reactive silyl group") that has a hydroxyl group or a hydrolyzable group on a silicon atom and can form a siloxane bond are known as moisture-reactive polymers, and are included in many industrial products such as adhesives, sealing materials, coating materials, paints, and pressure sensitive adhesives, and are used in a wide range of fields. As such reactive silyl group-containing organic polymers, those whose main chain skeleton is a polyalkylene oxide polymer or a (meth)acrylic polymer are widely used.

[0003] As a method for improving the mechanical properties exhibited after curing such an organic polymer having a reactive silyl group, a technique of blending a polysilsesquioxane-based polymer with the organic polymer is known. A polysilsesquioxane-based polymer is a siloxane-based polymer formed by the hydrolysis and dehydration condensation reaction of an organotrialkoxysilane, and has the composition formula: (RSiO 1.5 ) n In the above formula, R represents a monovalent organic group such as a methyl group.

[0004] For example, Patent Document 1 discloses a crosslinked composition containing a polymer having a reactive silyl group and a silicone resin containing a silsesquioxane unit. Patent Document 2 discloses a composition containing a silsesquioxane containing a phenyl group and an alkoxy group, a silylated polymer containing an alkoxysilane group, and a carbonate filler. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2014-521819 [Patent Document 2] Japanese Patent Publication No. 2020-521034 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] In a conventional curable composition containing a polysilsesquioxane-based polymer and a reactive silyl group-containing organic polymer, the cured product obtained by curing this composition becomes cloudy, which may cause problems in the appearance of the cured product.

[0007] In view of the above situation, an object of the present invention is to provide a curable composition that contains a polysilsesquioxane-based polymer and a reactive silyl group-containing organic polymer and can provide a cured product with improved transparency. [Means for Solving the Problems]

[0008] As a result of intensive studies by the present inventors to solve the above problems, in a curable composition containing a polysilsesquioxane-based polymer and a reactive silyl group-containing organic polymer, a polyalkylene oxide polymer chain and / or a linear poly(meth)acrylic polymer chain is introduced into the polysilsesquioxane-based polymer, and as substituents on the silicon atom of the polysilsesquioxane-based polymer, an alkyl group and an aryl group are used in combination at a specific ratio, and it has been found that the above problems can be solved, leading to the present invention.

[0009] That is, the present invention relates to a curable composition containing a polysilsesquioxane polymer (A), a polyalkylene oxide polymer (B1) having a reactive silyl group and / or a poly(meth)acrylic polymer (B2) having a reactive silyl group, and a curing catalyst (C). The polysilsesquioxane polymer (A) has a polysilsesquioxane skeleton, an alkoxysilyl group (a1) and / or a silanol group (a2) bonded to the polysilsesquioxane skeleton, an alkyl group (b1) having 1 to 10 carbon atoms and an aryl group (b2) having 6 to 10 carbon atoms directly bonded to the silicon atom of the polysilsesquioxane skeleton, and a polyalkylene oxide polymer chain (c1) and / or a linear poly(meth)acrylic polymer chain (c2). One end of the polyalkylene oxide polymer chain (c1) and / or the linear poly(meth)acrylic polymer chain (c2) is bonded to the polysilsesquioxane skeleton, and the molar ratio of the alkyl group (b1) having 1 to 10 carbon atoms to the aryl group (b2) having 6 to 10 carbon atoms is 45:55 to 99:1. The present invention relates to a curable composition. Preferably, the weight ratio of the total of the alkyl group (b1) having 1 to 10 carbon atoms and the aryl group (b2) having 6 to 10 carbon atoms to the total of the polyalkylene oxide polymer chain (c1) and the linear poly(meth)acrylic polymer chain (c2) is 10:90 to 90:10. Preferably, the proportion of the polysilsesquioxane polymer (A) in the total of the polysilsesquioxane polymer (A) and the polyalkylene oxide polymer (B1) having a reactive silyl group and / or the poly(meth)acrylic polymer (B2) having a reactive silyl group is 1 to 90% by weight. The present invention may also be a sealing material or an adhesive containing the curable composition, or a cured product obtained by curing the curable composition.

Effects of the Invention

[0010] According to the present invention, it is possible to provide a curable composition that can give a cured product with improved transparency while containing a polysilsesquioxane-based polymer and a reactive silyl group-containing organic polymer.

Mode for Carrying Out the Invention

[0011] The embodiments of the present invention will be specifically described below.

[0012] The curable composition according to the present disclosure contains at least a polysilsesquioxane polymer (A), a polyalkylene oxide polymer (B1) having a reactive silyl group and / or a poly(meth)acrylic polymer (B2) having a reactive silyl group, and a curing catalyst (C). In this curable composition, the alkoxysilyl group (a1) and / or silanol group (a2) of the polysilsesquioxane polymer (A) and the reactive silyl group of the polyalkylene oxide polymer (B1) and / or poly(meth)acrylic polymer (B2) are hydrolyzed and dehydrated and condensed to cure, forming a cured product.

[0013] <<Polysilsesquioxane Polymer (A)>> The polysilsesquioxane polymer (A) according to the present disclosure has at least a polysilsesquioxane skeleton, an alkoxysilyl group (a1) and / or a silanol group (a2), an alkyl group (b1) having 1 to 10 carbon atoms and an aryl group (b2) having 6 to 10 carbon atoms, and a polyalkylene oxide polymer chain (c1) and / or a linear poly(meth)acrylic polymer chain (c2).

[0014] The polysilsesquioxane skeleton refers to a siloxane-based polymer skeleton represented by the composition formula (RSiO 1.5 ) n and is composed of a hydrolysis condensate of an alkoxysilane component containing at least organotrialkoxysilane.

[0015] The organotrialkoxysilane refers to a silane compound having one organic group bonded to a silicon atom and three alkoxy groups bonded to the silicon atom, and is represented by the formula: RSi(OR')3. In the formula, R represents the organic group, and OR' represents an alkoxy group. The organic group refers to an organic group other than an alkoxy group, and includes at least both an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms.

[0016] The alkoxy group: OR' bonded to the silicon atom is the same group as the alkoxy group in the alkoxysilyl group (a1) that the polysilsesquioxane polymer (A) may have, and specifically, may be an alkoxy group having 1 to 3 carbon atoms. More specifically, a methoxy group, an ethoxy group, and a propoxy group can be mentioned, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable. The alkoxy group may be only one type, or two or more types may be mixed.

[0017] The organotrialkoxysilane includes at least an organotrialkoxysilane in which the organic group is an alkyl group and an organotrialkoxysilane in which the organic group is an aryl group.

[0018] Specific examples of the organotrialkoxysilane in which the organic group is an alkyl group are not particularly limited, and examples include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, pentyltriisopropoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, etc. Among them, methyltrialkoxysilane is preferable, and methyltrimethoxysilane is particularly preferable.

[0019] Specific examples of the organotrialkoxysilane in which the organic group is an aryl group are not particularly limited. For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltripropoxysilane, xylyltrimethoxysilane, xylyltriethoxysilane, xylyltripropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, etc. may be mentioned. Among them, phenyltrialkoxysilane is preferable, and phenyltrimethoxysilane is particularly preferable.

[0020] The molar ratio (alkyl group: aryl group) of the organotrialkoxysilane in which the organic group is an alkyl group to the organotrialkoxysilane in which the organic group is an aryl group is preferably 45:55 to 99:1 in order to improve the transparency of the cured product obtained by curing the curable composition. More preferably, it is 50:50 to 95:5, still more preferably 55:45 to 90:10, and even more preferably 60:40 to 85:15. Also, it may be 65:35 to 80:20. Further, in order to improve the strength of the cured product, it is preferably 70:30 to 99:1, and more preferably 75:25 to 95:5.

[0021] In the alkoxysilane component, the proportion occupied by the total of the organotrialkoxysilane in which the organic group is an alkyl group and the organotrialkoxysilane in which the organic group is an aryl group is preferably 80 to 100 mol% from the viewpoint of the physical properties exhibited by the polysilsesquioxane polymer (A), more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, and particularly preferably 99 to 100 mol%. Examples of the alkoxysilane other than the organotrialkoxysilane in which the organic group is an alkyl group and the organotrialkoxysilane in which the organic group is an aryl group include organotrialkoxysilane in which the organic group does not correspond to either the alkyl group or the aryl group, diorganodialkoxysilane, triorganomonoalkoxysilane, and tetraalkoxysilane.

[0022] <Alkoxysilyl group (a1) and / or silanol group (a2)> The polysilsesquioxane polymer (A) has an alkoxysilyl group (a1) and / or a silanol group (a2), and these groups are bonded to the polysilsesquioxane skeleton. By having these alkoxysilyl groups (a1) and / or silanol groups (a2), the polysilsesquioxane polymer (A) can exhibit curability by hydrolysis and dehydration condensation reactions.

[0023] The alkoxysilyl group (a1) is a group represented by -SiOR', and is a part of the alkoxy groups contained in the raw material alkoxysilane that remained unreacted during the production of the polysilsesquioxane polymer (A). The alkoxysilyl group may be, for example, an alkoxysilyl group having 1 to 3 carbon atoms. Specifically, a methoxysilyl group, an ethoxysilyl group, and a propoxysilyl group can be mentioned, with a methoxysilyl group and an ethoxysilyl group being preferred, and a methoxysilyl group being more preferred. The alkoxysilyl group may be only one type, or two or more types may be mixed.

[0024] The silanol group (a2) is a group represented by -SiOH, and is a part of the alkoxy groups contained in the raw material alkoxysilane that underwent a hydrolysis reaction during the production of the polysilsesquioxane polymer (A), but the dehydration condensation reaction did not proceed, that is, it remained without forming a siloxane bond.

[0025] <Alkyl group (b1) and aryl group (b2)> The polysilsesquioxane polymer (A) further has an alkyl group (b1) having 1 to 10 carbon atoms and an aryl group (b2) having 6 to 10 carbon atoms. These alkyl groups (b1) and aryl groups (b2) are directly bonded to the silicon atoms of the polysilsesquioxane skeleton and are substituents on the silicon atoms.

[0026] Examples of the alkyl group (b1) having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, etc. The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1. The alkyl group may have no substituent, or may have a hetero-containing group such as a halogen atom, an alkoxy group, an acyl group, etc. as a substituent. The alkyl group may be only one kind, or two or more kinds may be used in combination.

[0027] Examples of the aryl group (b2) having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. The number of carbon atoms of the aryl group is preferably 6 to 10, more preferably 6 to 8, still more preferably 6 to 7, and particularly preferably 6. The aryl group may have no substituent, or may have a hetero-containing group such as a halogen atom, an alkoxy group, an acyl group, etc. as a substituent. The aryl group may be only one kind, or two or more kinds may be used in combination.

[0028] When the alkyl group (b1) and the aryl group (b2) coexist in a specific ratio, the transparency of the cured product obtained by curing the curable composition can be improved. From this viewpoint, the molar ratio (alkyl group: aryl group) of the alkyl group (b1) and the aryl group (b2) is 45:55 to 99:1. Preferably it is 50:50 to 95:5, more preferably 55:45 to 90:10, still more preferably 60:40 to 85:15. Also, it may be 65:35 to 80:20. Further, since the strength of the cured product can be improved, it is preferably 70:30 to 99:1, and more preferably 75:25 to 95:5.

[0029] <Polyalkylene oxide polymer chain (c1) and / or linear poly(meth)acrylic polymer chain (c2)> The polysilsesquioxane polymer (A) further has a polyalkylene oxide polymer chain (c1) and / or a linear poly(meth)acrylic polymer chain (c2). Due to the presence of these polymer chains, the storage stability can be improved. The polysilsesquioxane polymer (A) may have a polyalkylene oxide polymer chain (c1) and not have a poly(meth)acrylic polymer chain (c2), or conversely, may have a poly(meth)acrylic polymer chain (c2) and not have a polyalkylene oxide polymer chain (c1). Also, it may have both a polyalkylene oxide polymer chain (c1) and a poly(meth)acrylic polymer chain (c2).

[0030] In the polysilsesquioxane polymer (A), one end of these polyalkylene oxide polymer chains (c1) and / or linear poly(meth)acrylic polymer chains (c2) is bonded to the polysilsesquioxane skeleton. That is, among the plurality of ends that the polymer chain has, only one specific end is bonded to the polysilsesquioxane skeleton, and the ends other than the specific end are not bonded to the polysilsesquioxane skeleton and are in a free state. Therefore, the polyalkylene oxide polymer chain (c1) and / or the linear poly(meth)acrylic polymer chain (c2) can be said to be a monovalent substituent.

[0031] Those in which both ends of the polyalkylene oxide polymer chain or the linear poly(meth)acrylic polymer chain are bonded to the polysilsesquioxane skeleton and crosslink two polysilsesquioxane skeletons (for example, the structure shown in paragraph 0021 of JP-A-2013-49928) are excluded from the scope of the present disclosure.

[0032] The aforementioned free ends do not have a reactive silyl group. Therefore, polymer chains having a reactive silyl group at the end as described in paragraph 0131 of JP-A-2009-185169, for example, are excluded from the scope of the present disclosure. In addition, in the polysilsesquioxane polymer (A), it is preferable that the polyalkylene oxide polymer chain (c1) and the linear poly(meth)acrylic polymer chain (c2) do not have a reactive silyl group.

[0033] The manner in which the polysilsesquioxane skeleton binds to the polyalkylene oxide polymer chain (c1) and / or the linear poly(meth)acrylic polymer chain (c2) is not particularly limited, but from the viewpoint of stability, it is preferably bonded via a siloxane bond (-Si-O-). Such a siloxane bond can be formed by the reaction of an alkoxysilane component described later with a polyalkylene oxide polymer having a reactive silyl group at one end and / or a linear poly(meth)acrylic polymer having a reactive silyl group at one end.

[0034] The polymer skeleton of the polyalkylene oxide polymer chain (c1) is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, and the like. Among them, polyoxypropylene is preferable.

[0035] The polyalkylene oxide polymer chain (c1) preferably has a linear polymer skeleton. Further, among the two ends of the linear polymer skeleton, it is preferable that only one end is bonded to the polysilsesquioxane skeleton.

[0036] The polymer backbone of the poly(meth)acrylic polymer chain (c2) is preferably composed of a (meth)acrylic acid ester monomer. Such (meth)acrylic acid ester monomers are not particularly limited. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, etc. can be mentioned. Among these, (meth)acrylic acid alkyl esters are preferred, acrylic acid alkyl esters are more preferred, and butyl acrylate is particularly preferred.

[0037] In addition, a (meth)acrylic acid ester monomer and other copolymerizable monomers may be used in combination. However, the proportion of the (meth)acrylic acid ester monomer in the total monomers constituting the poly(meth)acrylic polymer chain (c2) is preferably 60% by weight or more and 100% by weight or less, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

[0038] The poly(meth)acrylic polymer chain (c2) has a linear polymer backbone, and only one of the two ends of the linear polymer backbone is bonded to the polysilsesquioxane backbone. For example, those in which the poly(meth)acrylic polymer chain is bonded to the polysilsesquioxane backbone at a portion other than the end of the polymer backbone (for example, in the middle of the polymer backbone) are excluded from the scope of the present disclosure.

[0039] The proportion of the polymer chains (c1) and / or (c2) contained in the polysilsesquioxane polymer (A) is not particularly limited. However, in order to sufficiently enjoy the effects achieved by the polymer chains (c1) and / or (c2), the total of the alkyl group (b1) having 1 to 10 carbon atoms and the aryl group (b2) having 6 to 10 carbon atoms: the total weight ratio of the polyalkylene oxide polymer chain (c1) and the linear poly(meth)acrylic polymer chain (c2) is preferably 10:90 to 90:10. More preferably, it is 15:85 to 85:15. Further, it may be 20:80 to 80:20, or may be 30 to 70:70:30.

[0040] The number average molecular weight of the polysilsesquioxane polymer (A) is preferably 400 to 10,000, and more preferably 500 to 5,000. The number average molecular weight of the polysilsesquioxane polymer (A) can be measured by GPC.

[0041] <Production of Polysilsesquioxane Polymer (A)> The polysilsesquioxane polymer (A) can be produced by subjecting an alkoxysilane component containing the organotrialkoxysilane described above, a polyalkylene oxide polymer having a reactive silyl group at one end, and / or a linear poly(meth)acrylic polymer having a reactive silyl group at one end, to hydrolysis and dehydration condensation reactions with water, optionally in the presence of a condensation catalyst.

[0042] When the reaction proceeds between the alkoxy groups in the alkoxysilane component, a polysilsesquioxane skeleton is formed. At the same time, when the reaction proceeds between the alkoxy group in the alkoxysilane component and the reactive silyl group of the polyalkylene oxide polymer or the poly(meth)acrylic polymer, a polyalkylene oxide polymer chain (c1) and / or a linear poly(meth)acrylic polymer chain (c2) is bonded to the polysilsesquioxane skeleton.

[0043] Also, during the reaction, some of the alkoxy groups contained in the alkoxysilane component remain unreacted, and / or after the alkoxy group undergoes a hydrolysis reaction, the dehydration condensation reaction does not proceed and remains, so that the produced polysilsesquioxane-based polymer (A) has an alkoxysilyl group (a1) and / or a silanol group (a2).

[0044] The hydrolysis and dehydration condensation reactions are preferably carried out by adding water. At this time, by adjusting the amount of water used, the amount of the alkoxysilyl group and / or the silanol group of the obtained polysilsesquioxane-based polymer and the molecular weight of the polysilsesquioxane-based polymer can be controlled. From this viewpoint, the amount of water used is preferably 20 mol% or more and 80 mol% or less, more preferably 25 mol% or more and 70 mol% or less, still more preferably 30 mol% or more and 60 mol% or less, and particularly preferably 35 mol% or more and 50 mol% or less, based on 100% of the total number of moles of the alkoxy groups on the silicon atoms contained in the alkoxysilane component.

[0045] The hydrolysis and dehydration condensation reactions are preferably carried out in the presence of a condensation catalyst for promoting the reactions. Known catalysts can be used as the condensation catalyst. Specifically, basic catalysts, acidic catalysts, neutral salts, etc. can be mentioned. Since the storage stability of the obtained polysilsesquioxane-based polymer is improved, acidic catalysts and neutral salts are preferred as the condensation catalyst, and neutral salts are more preferred.

[0046] As the acidic catalyst, organic acids are preferred due to their compatibility with the alkoxysilane component, and phosphate esters and carboxylic acids are more preferred. Specific examples of the organic acid include ethyl acid phosphate, butyl acid phosphate, dibutyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, dibutyl phosphate, bis(2-ethylhexyl) phosphate, formic acid, acetic acid, butyric acid, isobutyric acid, etc.

[0047] Examples of the basic catalyst include amine compounds such as N-ethylmorpholine, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-t-butyldiethanolamine, triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, ammonia, etc., and metal hydroxides such as sodium hydroxide, potassium hydroxide, etc.

[0048] The neutral salt is a normal salt composed of a strong acid and a strong base. For example, it is a salt composed of any one selected from the group consisting of Group I element ions, Group II element ions, tetraalkylammonium ions, and guanidinium ions as cations, and any one selected from the group consisting of Group XVII element ions excluding fluoride ions, sulfate ions, nitrate ions, and perchlorate ions as anions. In particular, as the anion, Group XVII element ions are preferred because of their high nucleophilicity, and as the cation, Group I element ions and Group II element ions are preferred as ions that are not bulky so as not to inhibit the nucleophilic action.

[0049] The specific compounds of the neutral salt are not particularly limited, but preferred specific examples include lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, and the like.

[0050] The addition amount of the condensation catalyst can be adjusted as appropriate. For example, it may be about 50 ppm to 3% by weight based on the alkoxysilane component. However, in order to improve the stability of the polysilsesquioxane polymer (A), within the range where the effect of shortening the reaction time by the condensation catalyst is achieved, the smaller the amount of the condensation catalyst used, the more preferable.

[0051] The reaction temperature when carrying out the hydrolysis and dehydration condensation step can be appropriately set by those skilled in the art. For example, it is preferable to heat the reaction solution in the range of 50 to 110 °C. Also, the reaction time when carrying out the hydrolysis and dehydration condensation step can be appropriately set by those skilled in the art. For example, it may be about 10 minutes to 12 hours.

[0052] The step of removing the alcohol generated by the hydrolysis of the alkoxysilane component during the production of the polysilsesquioxane polymer (A) may be carried out after the hydrolysis and dehydration condensation step. Thereby, the content of volatile components such as alcohol contained in the polysilsesquioxane polymer (A) can be reduced. The step of removing the alcohol can be carried out by subjecting the mixed solution to vacuum distillation to distill off the alcohol. The conditions of the vacuum distillation can be appropriately set by those skilled in the art. For example, the temperature may be about 60 to 160 °C.

[0053] <Polyalkylene oxide polymer having a reactive silyl group at one end> The polyalkylene oxide polymer that can be used for producing the polysilsesquioxane polymer (A) according to the present disclosure has a reactive silyl group only at one end of its polymer backbone.

[0054] The reactive silyl group is a silyl group having a hydroxyl group or a hydrolyzable group on a silicon atom, and is a group in which a hydrolysis and dehydration condensation reaction can proceed in the presence of water and, if necessary, a condensation catalyst. Examples of the hydrolyzable group include hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group, and the like. Among these, alkoxy groups such as methoxy group and ethoxy group are more preferable, and methoxy group and ethoxy group are particularly preferable because of their mild hydrolyzability and easy handling.

[0055] The reactive silyl group possessed by the polyalkylene oxide polymer is not particularly limited, and examples thereof include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like.

[0056] Since the polymer backbone of the polyalkylene oxide polymer is the same as the polymer backbone of the polyalkylene oxide polymer chain (c1) described above, the description thereof is omitted.

[0057] As a method for producing a polyalkylene oxide polymer having a reactive silyl group only at one end, a polyalkylene oxide polymer having a hydroxyl group only at one end is produced by polymerizing an epoxy compound with an initiator having one hydroxyl group, and then, using a known method, converting the hydroxyl group into a reactive silyl group-containing group.

[0058] As the initiator having one hydroxyl group, a monohydric alcohol can be used. For example, methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, etc. can be mentioned. Further, low molecular weight polyoxypropylene monoalkyl ether, etc. can also be mentioned.

[0059] The number average molecular weight of the polyalkylene oxide polymer having a reactive silyl group at one end is not particularly limited, but in terms of the polystyrene equivalent molecular weight by GPC measurement, 500 to 50,000 is preferable, 500 to 30,000 is more preferable, and 1,000 to 10,000 is particularly preferable.

[0060] The weight average molecular weight of the polyalkylene oxide polymer having a reactive silyl group at one end is not particularly limited, but in terms of the polystyrene equivalent molecular weight by GPC measurement, 500 to 80,000 is preferable, 3,000 to 70,000 is more preferable, and 5,000 to 65,000 is particularly preferable.

[0061] <Linear poly(meth)acrylic polymer having a reactive silyl group at one end> The poly(meth)acrylic polymer that can be used for producing the polysilsesquioxane polymer (A) according to the present disclosure is a polymer having a linear polymer skeleton, and has a reactive silyl group only at one end of the linear skeleton. The details of the reactive silyl group are the same as the reactive silyl group described above for the polyalkylene oxide polymer, so the description is omitted.

[0062] Since the monomers constituting the poly(meth)acrylic polymer are the same as the (meth)acrylate-based monomers described above with respect to the poly(meth)acrylic polymer chain (c2), the description thereof is omitted.

[0063] As a method for introducing a reactive silyl group only at one end of the polymer skeleton of the poly(meth)acrylic polymer, known methods can be used without particular limitation. As an example, a method of polymerizing a monomer in the presence of a chain transfer agent having a mercapto group and a reactive silyl group can be mentioned. By using such a chain transfer agent, a reactive silyl group can be introduced only at one end of the polymer skeleton of a linear poly(meth)acrylic polymer.

[0064] The chain transfer agent is not particularly limited, and examples thereof include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane, and the like.

[0065] The amount of the chain transfer agent used is preferably 0.1% by weight or more and 20% by weight or less, more preferably 0.3% by weight or more and 15% by weight or less, and still more preferably 0.5% by weight or more and 7% by weight or less, based on the total amount of the total monomers and the chain transfer agent constituting the poly(meth)acrylic polymer.

[0066] The polymerization method for producing a linear poly(meth)acrylic polymer having a reactive silyl group at one end is not particularly limited, and may be general free radical polymerization. In free radical polymerization, it is preferable to use a polymerization initiator such as an azo compound or a peroxide.

[0067] The number average molecular weight of the linear poly(meth)acrylic polymer having a reactive silyl group at one end is not particularly limited, but in terms of the polystyrene equivalent molecular weight measured by GPC, it is preferably 500 to 50,000, more preferably 500 to 30,000, and particularly preferably 1,000 to 10,000. Among them, since a polymer with low viscosity can be obtained, the number average molecular weight is preferably 7,000 or less.

[0068] The weight average molecular weight of the linear poly(meth)acrylic polymer having a reactive silyl group at one end is not particularly limited, but in terms of the polystyrene equivalent molecular weight measured by GPC, it is preferably 500 to 80,000, more preferably 3,000 to 70,000, and particularly preferably 5,000 to 65,000. Among them, since a polymer with low viscosity can be obtained, the weight average molecular weight is preferably 15,000 or less.

[0069] <<Polyalkylene oxide polymer (B1) having a reactive silyl group>> The polyalkylene oxide polymer (B1) has a reactive silyl group. The reactive silyl group refers to a silicon-containing group having a hydroxyl group or a hydrolyzable group on the silicon atom and capable of forming a siloxane bond by a hydrolysis / dehydration condensation reaction, and specifically can be represented by the following general formula (1). -Si(R 1 ) 3-a (X) a (1) In formula (1), R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a heteroatom-containing group. X each independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3.

[0070] R 1 is a hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.

[0071] R1 The heteroatom-containing group which may have a hydrocarbon group as a substituent is a group containing a heteroatom. Here, an atom other than a carbon atom and a hydrogen atom is defined as a heteroatom.

[0072] Preferable examples of the heteroatom include N, O, S, P, Si, and a halogen atom. For the heteroatom-containing group, the total of the number of carbon atoms and the number of heteroatoms is preferably from 1 to 10, more preferably from 1 to 6, and still more preferably from 1 to 4.

[0073] R 1 Preferable examples of R include, for example, an alkyl group such as a methyl group and an ethyl group; an alkyl group having a heteroatom-containing group such as a chloromethyl group and a methoxymethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and the like. R 1 is preferably a methyl group, a methoxymethyl group, and a chloromethyl group, more preferably a methyl group and a methoxymethyl group, and still more preferably a methyl group.

[0074] Examples of X include, for example, a hydroxyl group, hydrogen, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, and the like. Among these, an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable because of their mild hydrolyzability and easy handling.

[0075] a is 1, 2, or 3. As a, 2 or 3 is preferable, and 2 is particularly preferable from the viewpoints of curability and the strength of the cured product.

[0076] Specific examples of the reactive silyl group include, but are not limited to, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, a (N,N-diethylaminomethyl)diethoxysilyl group, and the like. Among these, a dimethoxymethylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are preferable because a cured product having good mechanical properties can be obtained. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are more preferable, and a trimethoxysilyl group and a (methoxymethyl)dimethoxysilyl group are particularly preferable. From the viewpoint of stability, a dimethoxymethylsilyl group and a triethoxysilyl group are more preferable, and a dimethoxymethylsilyl group is particularly preferable.

[0077] The average number of reactive silyl groups per molecule of the polyalkylene oxide polymer (B1) is preferably more than 1.0, more preferably 1.3 or more, and even more preferably 1.6 or more. The upper limit of the average number is not particularly limited, but is preferably 6 or less, and more preferably 5 or less. Incidentally, the average number of reactive silyl groups per molecule of the polymer (B1) can be calculated from the results of NMR measurement.

[0078] Examples of the polymer backbone of the polyalkylene oxide polymer (B1) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, and the like. Each polymer may be mixed in a block form, a graft form, or the like. Among these, polyoxypropylene is particularly preferred. The polyalkylene oxide polymer (B1) preferably contains 50% by weight or more, more preferably 70% by weight or more, of the repeating unit of the alkylene oxide in the polymer backbone.

[0079] The polyalkylene oxide polymer (B1) may be a polymer having any one type of polymer backbone, or a mixture of two or more polymers having different polymer backbones. Further, for the mixture, it may be a mixture of polymers produced separately, or a mixture produced simultaneously to have an arbitrary mixing composition.

[0080] The number average molecular weight of the polyalkylene oxide polymer (B1) is not particularly limited, but as the polystyrene-equivalent molecular weight in GPC, 3,000 to 100,000 is preferred, 3,000 to 50,000 is more preferred, and 3,000 to 30,000 is particularly preferred. When the number average molecular weight is within the above range, the amount of the reactive silyl group introduced is appropriate, so that a polyalkylene oxide polymer (B1) having an easy-to-handle viscosity and excellent workability can be relatively easily produced while keeping the production cost within an appropriate range.

[0081] The molecular weight of the polyalkylene oxide polymer (B1) can also be expressed as the molecular weight in terms of end groups determined by directly measuring the end group concentration by titration analysis based on the measurement method of hydroxyl value in JIS K 1557 and the principle of the iodine value measurement method defined in JIS K 0070 for the polymer precursor before the introduction of reactive silyl groups, taking into account the structure of the polymer (degree of branching determined by the polymerization initiator used). The molecular weight in terms of end groups of the polyalkylene oxide polymer (B1) can also be obtained by creating a calibration curve of the number average molecular weight determined by general GPC measurement of the polymer precursor and the molecular weight in terms of end groups, and converting the number average molecular weight determined by GPC of the polyalkylene oxide polymer (B1) to the molecular weight in terms of end groups.

[0082] The molecular weight distribution (Mw / Mn) of the polyalkylene oxide polymer (B1) is not particularly limited, but 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, particularly preferably 1.4 or less, even more particularly preferably 1.3 or less, and most particularly preferably 1.2 or less. The molecular weight distribution of the polyalkylene oxide polymer (B1) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

[0083] The production method of the polyalkylene oxide polymer (B1) is not particularly limited, and it can be produced by a known method, for example, as disclosed in International Publication No. WO 2016 / 03571.

[0084] <<Poly(meth)acrylic polymer (B2) having a reactive silyl group>> The (meth)acrylic acid ester monomer constituting the main chain of the poly(meth)acrylic polymer (B2) having a reactive silyl group is not particularly limited, and various ones can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, (3-trimethoxysilyl)propyl (meth)acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate and other (meth)acrylic acid monomers can be mentioned.

[0085] Examples of monomer units other than those described above include acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylolacrylamide and N-methylolmethacrylamide; monomers containing an epoxy group such as glycidyl acrylate and glycidyl methacrylate; monomers containing a nitrogen-containing group such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate, and the like.

[0086] The poly(meth)acrylic polymer (B2) may be a polymer obtained by copolymerizing a (meth)acrylate monomer and a vinyl monomer copolymerizable therewith. The vinyl monomer is not particularly limited, and examples thereof include styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. These can also be used as a plurality of copolymerization components.

[0087] As the poly(meth)acrylic polymer (B2), a (co)polymer composed of a (meth)acrylate monomer or a copolymer composed of a (meth)acrylate monomer and a styrene monomer is preferred because of its excellent physical properties. A (co)polymer composed of a (meth)acrylate monomer is more preferred, and a (co)polymer composed of an acrylate monomer is particularly preferred.

[0088] The poly(meth)acrylic polymer (B2) has a reactive silyl group. Since the details of the reactive silyl group are the same as those of the reactive silyl group of the polyalkylene oxide polymer (B1), the description is omitted.

[0089] The production method of the poly(meth)acrylic polymer (B2) is not particularly limited, and it can be produced by a known method, for example, as disclosed in International Publication No. 2016 / 03571.

[0090] The monomer composition of the poly(meth)acrylic polymer (B2) can be selected according to the use and purpose. For applications that require strength, those with a relatively high glass transition temperature (Tg) are preferred, preferably 0°C or higher and 200°C or lower, and more preferably those with a Tg of 20°C or higher and 100°C or lower. The Tg is determined by the above-mentioned Fox's formula.

[0091] The number average molecular weight of the poly(meth)acrylic polymer (B2) is not particularly limited, but in terms of the polystyrene equivalent molecular weight measured by GPC, it is preferably 500 or more and 50,000 or less, and more preferably 500 or more and 30,000 or less.

[0092] In the curable composition according to the present disclosure, the content of the polysilsesquioxane polymer (A) can be appropriately determined in consideration of the curability of the composition, the strength of the resulting cured product, etc. However, among the total of the polysilsesquioxane polymer (A), the polyalkylene oxide polymer (B1) having a reactive silyl group, and / or the poly(meth)acrylic polymer (B2) having a reactive silyl group, the proportion of the polysilsesquioxane polymer (A) is preferably 1 to 90% by weight, more preferably 2 to 70% by weight, still more preferably 3 to 60% by weight, particularly preferably 4 to 50% by weight, and most preferably 5 to 40% by weight.

[0093] <<Curing catalyst (C)>> The curable composition according to the present disclosure preferably contains a curing catalyst (C) for the purpose of promoting the reaction of hydrolyzing and dehydrating and condensing the alkoxysilyl group (a1) and / or silanol group (a2) of the polysilsesquioxane polymer (A) with the reactive silyl group of the polyalkylene oxide polymer (B1) and / or poly(meth)acrylic polymer (B2), that is, the curing reaction.

[0094] As the curing catalyst, conventionally known ones can be used. Specifically, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. can be mentioned.

[0095] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), the reaction product of dibutyltin oxide and a silicate compound, the reaction product of dibutyltin oxide and a phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), the reaction product of dioctyltin oxide and a silicate compound, etc. Due to the increasing environmental concerns in recent years, dioctyltin compounds are preferred.

[0096] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, cesium carboxylate, and the like. As the carboxylic acid group, various metals can be combined with the following carboxylic acids.

[0097] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, etc.; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), etc.; guanidines such as guanidine, phenylguanidine, diphenylguanidine, etc.; biguanides such as butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide, etc.; an amino group-containing silane coupling agent; a ketimine compound, and the like.

[0098] Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, and the like.

[0099] Specific examples of the alkoxy metal include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), etc., aluminum compounds such as aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetoacetate, etc., and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0100] As other curing catalysts, fluoride anion-containing compounds, photoacid generators, and photobase generators can also be used.

[0101] Two or more different types of catalysts may be used in combination as the curing catalyst. For example, by using the above-mentioned amine compound in combination with a carboxylic acid or an amine compound in combination with an alkoxy metal, an effect of improving reactivity may be obtained.

[0102] From the viewpoint of the curing rate, it is preferable to use at least one selected from the group consisting of a tetravalent tin compound and an amine compound having an amidine skeleton as the curing catalyst (C).

[0103] From the viewpoint of achieving both an improvement in the curing reaction rate and workability during curing, the blending amount of the curing catalyst (C) is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, still more preferably 0.1 to 10 parts by weight, even more preferably 0.5 to 7 parts by weight, and particularly preferably 1 to 5 parts by weight, based on 100 parts by weight in total of the polysilsesquioxane polymer (A), the polyalkylene oxide polymer (B1), and / or the poly(meth)acrylic polymer (B2).

[0104] <<Curable Composition>> In addition to the polysilsesquioxane polymer (A), the polyalkylene oxide polymer (B1) and / or the poly(meth)acrylic polymer (B2), and the curing catalyst (C), the curable composition according to the present disclosure may contain various additives as necessary. Examples of such additives include fillers, adhesion-imparting agents, dehydrating agents, plasticizers, sag prevention agents, antioxidants, light stabilizers, ultraviolet absorbers, physical property modifiers, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, and organic resins other than the polyalkylene oxide polymer (B1) and / or the poly(meth)acrylic polymer (B2).

[0105] Further, for the purpose of adjusting various physical properties of the curable composition or the cured product, other additives other than those described above may be added to the curable composition as necessary. Examples of such other additives include, for example, tackifying resins, solvents, diluents, epoxy resins, surface property improvers, foaming agents, curing property adjusters, flame retardants, silicates, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.

[0106] The curable composition can be prepared as a one-component type in which all the compounding components are pre-compounded and stored in a sealed manner and cured by moisture in the air after construction. The one-component curable composition preferably does not substantially contain water, and the water content is preferably 5% by weight or less, more preferably 1% by weight or less. Also, as a curing agent, components such as a curing catalyst, a filler, a plasticizer, and water are compounded, and the curing agent and a main agent containing a polysilsesquioxane polymer (A), a polyalkylene oxide polymer (B1), and / or a poly(meth)acrylic polymer (B2) are mixed before use to prepare a two-component type. The main agent of the two-component type preferably does not substantially contain water, and the water content is preferably 5% by weight or less, more preferably 1% by weight or less. From the viewpoint of workability, the one-component type is preferred.

[0107] Prior to curing, the curable composition is shaped into a desired shape by a method such as coating, casting, or filling. The curable composition that has been coated, cast, or filled and shaped can be cured at room temperature or can also be cured under heating. The heat curing conditions are not particularly limited, but preferably the temperature is 60 to 220°C and the time is 1 to 120 minutes, more preferably the temperature is 100 to 200°C and the time is 5 to 60 minutes.

[0108] The curable composition according to the present disclosure can be used as an adhesive, an adhesive agent, a sealing material for sealing construction in buildings, ships, automobiles, buses, roads, household appliances, etc., a mold release agent, a paint, a spraying agent, etc. Further, the cured product obtained by curing the curable composition is suitably used as a waterproof material, a coating film waterproof material, a vibration-proof material, a vibration damping material, a sound-proof material, a foaming material, etc.

Examples

[0109] The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

[0110] The number average molecular weight and the weight average molecular weight in each synthesis example are GPC molecular weights measured under the following conditions. Liquid delivery system: HLC-8420GPC manufactured by Tosoh Corporation Column: TSKgel SuperH series manufactured by Tosoh Corporation Solvent: THF Molecular weight: Polystyrene conversion Measurement temperature: 40 °C

[0111] The molecular weight in terms of terminal groups in each synthesis example was determined by measuring the hydroxyl value according to the method specified in JIS K 1557 and the iodine value according to the method specified in JIS K 0070, taking into account the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).

[0112] The average number of silyl groups introduced into each polymer shown in each synthesis example was calculated by NMR measurement.

[0113] (Synthesis Example 1) Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a hydroxyl group at one end, a number average molecular weight of 7800 (molecular weight in terms of terminal groups: 5000), and a molecular weight distribution Mw / Mn = 1.48. Subsequently, 1.2 molar equivalents of sodium methoxide as a 28% methanol solution was added to the hydroxyl group of this hydroxyl-terminated polyoxypropylene. After distilling off methanol by vacuum devolatilization, 2.0 molar equivalents of allyl chloride was added to the hydroxyl group of the polymer to convert the terminal hydroxyl group to an allyl group, and unreacted allyl chloride was removed by vacuum devolatilization under reduced pressure. The resulting unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and then water was removed by centrifugation. The hexane in the resulting hexane solution was removed by vacuum devolatilization under reduced pressure to remove the metal salts in the polymer. Thus, polyoxypropylene having an allyl group only at one end was obtained. To 500 g of the obtained polymer, 50 μl of a platinum divinyldisiloxane complex (a 2-propanol solution containing 3 wt% platinum in terms of platinum) was added, and while stirring, 9.5 g of dimethoxymethylsilane was slowly added dropwise. After reacting the mixed solution at 100 °C for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (c1’-1) having a dimethoxymethylsilyl group only at one end. It was found that the polymer had an average of 0.8 dimethoxymethylsilyl groups only at one end.

[0114] (Synthesis Example 2) 22 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105 °C under a nitrogen atmosphere. A mixed solution prepared by dissolving 96.6 parts by weight of butyl acrylate, 3.4 parts by weight of γ-mercaptopropyldimethoxymethylsilane, and 0.35 parts by weight of 2,2’-azobis(2-methylbutyronitrile) in 17.5 parts by weight of isobutanol was added dropwise over 5 hours, and polymerization was further carried out at 105 °C for 1.5 hours. By removing isobutanol from the obtained poly(meth)acrylic polymer in the isobutanol solution under heating and reduced pressure, a (meth)acrylic polymer (c2’-1) having a dimethoxymethylsilyl group only at one end of the molecular chain was obtained. It was found that the polymer had an average of 0.7 dimethoxymethylsilyl groups per molecule, a number average molecular weight of 3,900, and a weight average molecular weight of 8,000.

[0115] (Synthesis Example 3) Into a four-necked flask equipped with a stirrer, at room temperature, 10.0 parts by weight of polyoxypropylene (c1’-1) having a dimethoxymethylsilyl group only at one end obtained in Synthesis Example 1, 88.3 parts by weight of methyltrimethoxysilane as a silane monomer and 66.9 parts by weight of phenyltrimethoxysilane, 21.2 parts by weight of water (40 mol% based on 100 mol% of the alkoxy groups in the alkoxysilane component), and 0.1 part by weight of a 10% aqueous LiBr solution were added, and then the mixture was heated and reacted for 6 hours under reflux with the generated methanol. Methanol was removed from the obtained methanol solution under heating and reduced pressure to obtain a polysilsesquioxane polymer (A-1) having a polyalkylene oxide polymer chain (c1-1). It was 1 confirmed by 1H NMR that the polysilsesquioxane polymer (A-1) has an alkoxysilyl group (a1) and / or a silanol group (a2). Only one end of the polyalkylene oxide polymer chain (c1-1) is bonded to the polysilsesquioxane skeleton. The abbreviations of the silane monomers in Table 1 are as follows. MeTMS: Methyltrimethoxysilane PhTMS: Phenyltrimethoxysilane

[0116] (Synthesis Example 4, Comparative Synthesis Examples 1 to 3, 5) Polysilsesquioxane polymers (A-2), (A’-1) to (A’-3), and (A’-5) having a polyalkylene oxide polymer chain (c1-1) were obtained in the same manner as in Synthesis Example 3 except that the blending amounts of the respective components were changed as shown in Table 1.

[0117] (Comparative Synthesis Example 4) Using the (meth)acrylic polymer (c2’-1) having a dimethoxymethylsilyl group only at one end obtained in Synthesis Example 2, a polysilsesquioxane polymer (A’-4) having a linear poly(meth)acrylic polymer chain (c2-1) was obtained in the same manner as in Synthesis Example 3 except that the blending amounts of the respective components were changed as shown in Table 1.

[0118]

Table 1

[0119] (Synthesis Example 5) 0.84 g of cuprous bromide, 8.79 g of acetonitrile, 20.0 g of n-butyl acrylate and 1.76 g of diethyl 2,5-dibromoadipate were added, and the mixture was stirred at 70 to 80 °C for about 30 minutes. Pentamethyldiethylenetriamine was added thereto to initiate the reaction. From 30 minutes after the start of the reaction to 2 hours, 80.0 g of n-butyl acrylate was continuously added. Pentamethyldiethylenetriamine was appropriately added during the reaction so that the internal temperature was 70 °C to 90 °C. The total amount of pentamethyldiethylenetriamine used during the polymerization was 0.15 g. Four hours after the start of the reaction, the volatile components were removed by heating and stirring under reduced pressure at 80 °C. 35.0 g of acetonitrile, 21.0 g of 1,7-octadiene and 0.34 g of pentamethyldiethylenetriamine were added thereto, and stirring was continued for 8 hours. The mixture was heated and stirred under reduced pressure at 80 °C to remove the volatile components. Butyl acetate was added to this concentrate to dissolve the polymer, and then diatomaceous earth as a filter aid, aluminum silicate as an adsorbent, and hydrotalcite were added, and the mixture was heated and stirred at an internal temperature of 100 °C in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred under reduced pressure at an internal temperature of 100 °C to remove the volatile components. Furthermore, aluminum silicate, hydrotalcite as adsorbents, and a thermal degradation inhibitor were added to this concentrate, and the mixture was heated and stirred under reduced pressure (average temperature about 175 °C, degree of vacuum 10 Torr or less). Furthermore, aluminum silicate and hydrotalcite were added as adsorbents, and an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150 °C in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). Butyl acetate was added to this concentrate to dissolve the polymer, and then the solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred under reduced pressure to remove the volatile components, thereby obtaining a polymer having an alkenyl group. A polymer having this alkenyl group, dimethoxymethylsilane (2.0 molar equivalents relative to the alkenyl group), methyl orthoformate (1.0 molar equivalent relative to the alkenyl group), and a platinum catalyst [a xylene solution of a bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane)platinum complex catalyst: hereinafter referred to as the platinum catalyst] (10 mg per 1 kg of the polymer as platinum) were mixed and heated with stirring at 100 °C under a nitrogen atmosphere. It was confirmed that the alkenyl group had disappeared, and the reaction mixture was concentrated to obtain an acrylic polymer (B2-1) having a dimethoxymethylsilyl group at the terminal. The number average molecular weight of the acrylic polymer was 24,700, the molecular weight distribution was 1.3, and the average number of dimethoxymethylsilyl groups at the terminal per molecule was 1.9.

[0120] (Example 1) As the component (A), 30 parts by weight of the polysilsesquioxane polymer (A-1) obtained in Synthesis Example 3, as the component (B), 70 parts by weight of the acrylic polymer (B2-1) obtained in Synthesis Example 5, vinyltrimethoxysilane (manufactured by Momentive Performance Materials, trade name: Silquest A-171) 3 parts by weight as a dehydrating agent, γ-(2-aminoethyl)aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials, trade name: Silquest A-1120) 2 parts by weight as an adhesion promoter, tin(II) octylate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-28) 1.5 parts by weight as a curing catalyst (C), and laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 parts by weight were added and kneaded to obtain a curable composition.

[0121] (Example 2, Comparative Examples 1 to 6) A curable composition was obtained in the same manner as in Example 1 except that the blending amounts of the respective components were changed as shown in Table 2.

[0122] (Tensile physical properties) Each curable composition was formed into a sheet-like specimen with a thickness of 3 mm, and was completely cured by placing it under the conditions of 23°C and 50% RH for 3 days and then in a dryer at 50°C for 4 days. After punching out with a No. 3 dumbbell shape, a tensile test was performed at a tensile speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation, and the breaking strength (denoted as TB) was measured. The results are shown in Table 2.

[0123] (Sheet appearance) The sheet-like specimen obtained above was visually confirmed to determine whether it was transparent or turbid.

[0124]

Table 2

[0125] From Table 2, it can be seen that in Examples 1 and 2 in which the (A) component was blended with the (B) component, the breaking strength of the cured product was significantly improved compared with Comparative Example 6 in which the (B) component was alone, and furthermore, a transparent cured product was obtained. Also, in Comparative Examples 1 to 4 in which polysilsesquioxane polymers (A'-1) to (A'-4) having only an alkyl group as a substituent on the silicon atom were blended with the (B) component, although the breaking strength of the cured product was improved compared with Comparative Example 6, the degree of improvement was small, and it can be seen that the cured product was turbid. Furthermore, in Comparative Example 5 in which a polysilsesquioxane polymer (A'-5) having an alkyl group and an aryl group as substituents on the silicon atom and a high aryl group ratio of 61 mol% was blended with the (B) component, although the breaking strength of the cured product was improved compared with Comparative Example 6, it can be seen that the cured product was turbid and inferior in appearance.

Claims

1. A curable composition comprising: a polysilsesquioxane polymer (A); a poly(meth)acrylic polymer (B2) having a reactive silyl group; and a curing catalyst (C), optionally containing a polyalkylene oxide polymer (B1) having a reactive silyl group, wherein the polysilsesquioxane polymer (A) has a polysilsesquioxane skeleton, an alkoxysilyl group (a1) and / or a silanol group (a2) bonded to the polysilsesquioxane skeleton, an alkyl group (b1) having 1 to 10 carbon atoms and an aryl group (b2) having 6 to 10 carbon atoms directly bonded to the silicon atom of the polysilsesquioxane skeleton, a polyalkylene oxide polymer chain (c1) and / or a linear poly(meth)acrylic polymer chain (c2), wherein only one end of the polyalkylene oxide polymer chain (c1) and / or the linear poly(meth)acrylic polymer chain (c2) is bonded to the polysilsesquioxane skeleton, and the molar ratio of the alkyl group (b1) having 1 to 10 carbon atoms to the aryl group (b2) having 6 to 10 carbon atoms is from 45:55 to 99:

1.

2. The curable composition according to claim 1, wherein the weight ratio of the total of the alkyl group (b1) having 1 to 10 carbon atoms and the aryl group (b2) having 6 to 10 carbon atoms to the total of the polyalkylene oxide polymer chain (c1) and the linear poly(meth)acrylic polymer chain (c2) is from 10:90 to 90:

10.

3. The curable composition according to claim 1 or 2, wherein the proportion of the polysilsesquioxane polymer (A) in the total of the polysilsesquioxane polymer (A), the polyalkylene oxide polymer (B1) having a reactive silyl group, and the poly(meth)acrylic polymer (B2) having a reactive silyl group is from 1 to 90% by weight.

4. A sealing material containing the curable composition according to any one of claims 1 to 3.

5. An adhesive containing the curable composition according to any one of claims 1 to 3.

6. A cured product obtained by curing the curable composition according to any one of claims 1 to 3.

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