Method for producing curable resin composition

Abstract

To provide a method for producing a curable resin composition which is improved in curability, can give a cured product having high strength, and contains a polysilsesquioxane polymer and a reactive silyl group-containing organic polymer.SOLUTION: A raw material composition is stored at a temperature of 40°C or higher and 150°C or lower under a sealed condition, the raw material composition containing: a polysilsesquioxane polymer (A) having a reactive silyl group and a hydrocarbon group directly bonded to a silicon atom of a polysilsesquioxane skeleton; a poly(meth)acrylic polymer (B) having a reactive silyl group in a side chain and having no polysilsesquioxane skeleton; and a curing catalyst (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a curable resin composition containing a polysilsesquioxane polymer and an organic polymer having a reactive silyl group. [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 the silicon atom and can form a siloxane bond are known as moisture-reactive polymers, and are used in a wide range of industrial products such as adhesives, sealants, coating materials, paints, and pressure-sensitive adhesives. Widely used organic polymers containing such reactive silyl groups include those whose main chain skeleton is a polyalkylene oxide polymer or a (meth)acrylic polymer.

[0003] As a method for improving the mechanical properties exhibited after curing such organic polymers having reactive silyl groups, a technique of blending a polysilsesquioxane polymer with the organic polymer is known. A polysilsesquioxane polymer is a siloxane polymer formed by the hydrolysis and dehydration condensation reaction of organotrialkoxysilane, and has the composition formula: (RSiO 1.5 ) n In the 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] Special Publication No. 2020-521034 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventionally, curable resin compositions containing a polysilsesquioxane polymer and a reactive silyl group-containing organic polymer have sometimes been insufficient in curability and required a long time for curing. Furthermore, it is desirable that the cured product obtained by curing the curable resin composition exhibits high strength.

[0007] In view of the above-described current situation, an object of the present invention is to provide a method for producing a curable resin composition containing a polysilsesquioxane polymer and a reactive silyl group-containing organic polymer, which has improved curability and can give a cured product with high strength. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and have found that the above-mentioned problems can be solved by using, as the organic polymer, a poly(meth)acrylic polymer having at least a reactive silyl group in a side chain in a curable resin composition containing a polysilsesquioxane polymer, a reactive silyl group-containing organic polymer, and a curing catalyst, and by storing the composition under heated conditions, thereby completing the present invention.

[0009] That is, the present invention provides a polysilsesquioxane polymer (A) having a reactive silyl group and a hydrocarbon group directly bonded to a silicon atom of the polysilsesquioxane skeleton; A poly(meth)acrylic polymer (B) having a reactive silyl group in a side chain and not having a polysilsesquioxane skeleton, and The present invention relates to a method for producing a curable resin composition, which comprises a step of storing a raw material composition containing a curing catalyst (C) in a sealed state at a temperature of 40°C or higher and 150°C or lower. Preferably, the storage is carried out in a container having a moisture permeability of 60 mg / L or less for 24 hours under an atmosphere of 40°C and 90% RH. Preferably, the storage time is from 1 hour to 8 weeks. Preferably, the production method includes a step of mixing a polysilsesquioxane polymer (A) and a poly(meth)acrylic polymer (B) and dehydrating the mixture by heating to obtain a mixture; The method further includes a step of cooling the mixture and then adding a curing catalyst (C) to obtain the raw material composition. Preferably, the curing catalyst is a strong base catalyst. Preferably, the polysilsesquioxane polymer (A) further has a polyalkylene oxide polymer chain and / or a poly(meth)acrylic polymer chain bonded to the polysilsesquioxane skeleton. Preferably, the raw material composition further contains a polyalkylene oxide polymer (D) having a reactive silyl group and not having a polysilsesquioxane skeleton. Preferably, the proportion of the polysilsesquioxane polymer (A) is 1 to 30% by weight in the total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the optional polyalkylene oxide polymer (D). [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a method for producing a curable resin composition containing a polysilsesquioxane polymer and a reactive silyl group-containing organic polymer, which has improved curability and can give a cured product with high strength. According to the present invention, it is possible to produce a curable resin composition that has good workability when applied to a substrate, has improved curing properties, and can give a cured product with high strength. DETAILED DESCRIPTION OF THE INVENTION

[0011] The embodiments of the present invention will be specifically described below. The curable resin composition according to the present disclosure contains at least a polysilsesquioxane polymer (A) having a reactive silyl group and a hydrocarbon group, a poly(meth)acrylic polymer (B) having a reactive silyl group, and a curing catalyst (C). It may further contain a polyalkylene oxide polymer (D) having a reactive silyl group. The curable resin composition can be cured by hydrolysis and dehydration condensation of the reactive silyl groups contained in the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the optional polyalkylene oxide polymer (D), to form a cured product.

[0012] <<Polysilsesquioxane polymer (A)>> The polysilsesquioxane polymer (A) has at least a polysilsesquioxane skeleton, a reactive silyl group (a1), and a hydrocarbon group (a2), and may further have a polyalkylene oxide polymer chain and / or a poly(meth)acrylic polymer chain (a3).

[0013] The polysilsesquioxane skeleton has a composition formula of (RSiO 1.5 ) n It refers to a siloxane polymer skeleton represented by the formula: and is composed of a hydrolysis condensation product of alkoxysilane components containing at least organotrialkoxysilane.

[0014] 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. Examples of the organic group include organic groups other than alkoxy groups, such as alkyl groups, aryl groups, and alkenyl groups. The organic group preferably contains an alkyl group having 1 to 10 carbon atoms and / or an aryl group having 6 to 10 carbon atoms.

[0015] The alkoxy group OR' bonded to a silicon atom may specifically be an alkoxy group having 1 to 3 carbon atoms. More specifically, examples include a methoxy group, an ethoxy group, and a propoxy group, with a methoxy group and an ethoxy group being preferred, and a methoxy group being more preferred. The alkoxy group may be of one type, or two or more types may be mixed.

[0016] Specific examples of organotrialkoxysilanes in which the organic group is an alkyl group are not particularly limited, and include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, pentyltriisopropoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, etc. Among these, methyltrialkoxysilane is preferred, and methyltrimethoxysilane is particularly preferred.

[0017] Specific examples of organotrialkoxysilanes in which the organic group is an aryl group are not particularly limited, and include, for example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltrippropoxysilane, xylyltrimethoxysilane, xylyltriethoxysilane, xylyltrippropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, etc. Among these, phenyltrialkoxysilanes are preferred, and phenyltrimethoxysilane is particularly preferred.

[0018] In terms of the physical properties of the polysilsesquioxane polymer (A), the total proportion of organotrialkoxysilanes whose organic group is an alkyl group and organotrialkoxysilanes whose organic group is an aryl group in the alkoxysilane component is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, and particularly preferably 99 to 100 mol%. Examples of alkoxysilanes other than organotrialkoxysilanes whose organic group is an alkyl group and organotrialkoxysilanes whose organic group is an aryl group include organotrialkoxysilanes whose organic group does not fall under either of the alkyl group and aryl group groups, as well as diorganodialkoxysilanes, triorganomonoalkoxysilanes, and tetraalkoxysilanes.

[0019] <Reactive silyl group (a1)> The polysilsesquioxane polymer (A) has a reactive silyl group (a1), which is bonded to the polysilsesquioxane skeleton. Here, the term "reactive silyl group" refers to a silyl group having a hydroxyl group or a hydrolyzable group on the silicon atom, which is capable of undergoing hydrolysis and dehydration condensation reactions in the presence of water and, if necessary, a condensation catalyst. Specific examples of the reactive silyl group (a1) include an alkoxysilyl group and a silanol group. The reactive silyl group (a1) may be an alkoxysilyl group or a silanol group. The reactive silyl group (a1) may also contain both an alkoxysilyl group and a silanol group. By containing the reactive silyl group (a1), the polysilsesquioxane polymer (A) can exhibit curability through hydrolysis and dehydration condensation reactions.

[0020] The alkoxysilyl group is a group represented by -SiOR', and is a portion of the alkoxy groups contained in the alkoxysilane raw material that remain 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. Specific examples include a methoxysilyl group, an ethoxysilyl group, and a propoxysilyl group. A methoxysilyl group or an ethoxysilyl group is preferred, and a methoxysilyl group is more preferred. The alkoxysilyl group may be of one type, or two or more types may be mixed.

[0021] The silanol group is a group represented by —SiOH, and is formed when some of the alkoxy groups contained in the alkoxysilane raw material undergo a hydrolysis reaction during the production of the polysilsesquioxane polymer (A), but do not undergo a dehydration condensation reaction, i.e., remain without forming a siloxane bond.

[0022] <Hydrocarbon group (a2)> The polysilsesquioxane polymer (A) further comprises a hydrocarbon group (a2). The hydrocarbon group (a2) is directly bonded to a silicon atom of the polysilsesquioxane skeleton and serves as a substituent on the silicon atom. The hydrocarbon group (a2) preferably comprises an alkyl group having 1 to 10 carbon atoms and / or an aryl group having 6 to 10 carbon atoms.

[0023] Examples of the hydrocarbon group (a2) include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3, even more preferably 1 or 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, or an acyl group as a substituent. The alkyl group may be of one type, or two or more types may be used in combination.

[0024] Examples of the aryl group having 6 to 10 carbon atoms, which is another example of the hydrocarbon group (a2), include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The number of carbon atoms in the aryl group is preferably 6 to 10, more preferably 6 to 8, even 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, or an acyl group as a substituent. The aryl group may be of one type, or two or more types may be used in combination.

[0025] With respect to the hydrocarbon group (a2), the molar ratio of the alkyl group to the aryl group (alkyl group:aryl group) may be 0:100 to 100:0 or 1:99 to 99:1. In particular, from the viewpoint of the appearance of the cured product, it is preferably 45:55 to 99:1.

[0026] <Polymer chain (a3)> The polysilsesquioxane polymer (A) preferably further comprises a polyalkylene oxide polymer chain and / or a poly(meth)acrylic polymer chain (a3). The presence of the polymer chain (a3) ​​can improve the storage stability of the polysilsesquioxane polymer (A). The polysilsesquioxane polymer (A) may comprise a polyalkylene oxide polymer chain but not a poly(meth)acrylic polymer chain as the polymer chain (a3), or conversely, may comprise a poly(meth)acrylic polymer chain but not a polyalkylene oxide polymer chain. Alternatively, the polysilsesquioxane polymer (A) may comprise both a polyalkylene oxide polymer chain and a poly(meth)acrylic polymer chain.

[0027] In the polysilsesquioxane polymer (A), the polymer chain (a3) ​​may be bonded to the polysilsesquioxane skeleton at multiple positions on the side chains and / or terminals, but is preferably bonded at one position. Among these, it is more preferred that only one terminal of the polymer chain (a3) ​​is bonded to the polysilsesquioxane skeleton. That is, it is preferred that, among the multiple terminals possessed by the polymer chain, only one specific terminal is bonded to the polysilsesquioxane skeleton, and the terminals other than the specific terminal are not bonded to the polysilsesquioxane skeleton and are free. In this case, the polymer chain (a3) ​​can be said to be a monovalent substituent in the polysilsesquioxane polymer (A).

[0028] In the polysilsesquioxane polymer (A), the polyalkylene oxide polymer chain and / or the poly(meth)acrylic polymer chain, which is the polymer chain (a3), preferably does not have a reactive silyl group.

[0029] The method by which the polysilsesquioxane skeleton and the polymer chain (a3) ​​are bonded is not particularly limited, but from the viewpoint of stability, it is preferable that they are bonded via a siloxane bond (-Si-O-). Such a siloxane bond can be formed, for example, by reacting an alkoxysilane component with a polyalkylene oxide polymer having a reactive silyl group at its terminal and / or a poly(meth)acrylic polymer having a reactive silyl group. This reaction will be described later.

[0030] The polymer skeleton of the polyalkylene oxide polymer chain, which is an example of the polymer chain (a3), is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Among these, polyoxypropylene is preferred.

[0031] The polyalkylene oxide polymer chain preferably has a linear polymer skeleton, and it is preferable that only one of the two terminals of the linear polymer skeleton is bonded to the polysilsesquioxane skeleton.

[0032] The polymer backbone of the poly(meth)acrylic polymer chain, which is another example of the polymer chain (a3), is preferably composed of a (meth)acrylic acid ester monomer. Specific examples of such a (meth)acrylic acid ester monomer are not particularly limited, and the (meth)acrylic acid ester monomers listed for the poly(meth)acrylic polymer (B) described below can be used. Among these, (meth)acrylic acid alkyl esters are preferred, acrylic acid alkyl esters are more preferred, and butyl acrylate is particularly preferred.

[0033] In addition, the (meth)acrylic acid ester monomer may be used in combination with other copolymerizable vinyl monomers. Specific examples of the vinyl monomer are not particularly limited, and the vinyl monomers listed for the poly(meth)acrylic polymer (B) described below can be used. However, the proportion of the (meth)acrylic acid ester monomers in all the monomers constituting the poly(meth)acrylic polymer chain is preferably 60% by weight or more and 100% by weight or less, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

[0034] The poly(meth)acrylic polymer chain preferably has a linear polymer skeleton, and only one of the two terminals of the linear polymer skeleton is preferably bonded to the polysilsesquioxane skeleton.

[0035] The proportion of polymer chains (a3) ​​that can be contained in the polysilsesquioxane polymer (A) is not particularly limited, but in order to fully enjoy the effects achieved by the polymer chains (a3), the weight ratio of the total hydrocarbon groups (a2) to the total polymer chains (a3) ​​is preferably 10:90 to 90:10, more preferably 15:85 to 85:15, and may also be 20:80 to 80:20, or 30 to 70:70:30.

[0036] The number average molecular weight of the polysilsesquioxane polymer (A) is not particularly limited, but 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.

[0037] <Production of Polysilsesquioxane Polymer (A)> The polysilsesquioxane polymer (A) can be produced by subjecting an alkoxysilane component containing the organotrialkoxysilane described above to hydrolysis and dehydration condensation reaction with water, if necessary, in the presence of a condensation catalyst. In an embodiment in which the polysilsesquioxane polymer (A) further contains a polymer chain (a3), the hydrolysis and dehydration condensation reaction may be carried out in the presence of a polyalkylene oxide polymer having a reactive silyl group at its terminal and / or a poly(meth)acrylic polymer having a reactive silyl group.

[0038] An embodiment in which the polysilsesquioxane polymer (A) further contains a polymer chain (a3) ​​can also be produced by carrying out the hydrolysis and dehydration condensation reactions in the presence of an alkoxysilane having a radically polymerizable group or an alkoxysilane having a mercapto group, followed by adding the (meth)acrylic acid ester monomer and carrying out radical polymerization. The alkoxysilane having a radical polymerizable group is not particularly limited, and examples thereof include (3-trimethoxysilyl)propyl (meth)acrylate, (3-triethoxysilyl)propyl (meth)acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate, vinyltrimethoxysilane, p-styryltrimethoxysilane, etc. The alkoxysilane having a mercapto group is not particularly limited, and examples thereof include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane, etc.

[0039] A dehydration condensation reaction proceeds between the alkoxy groups in the alkoxysilane component to form a polysilsesquioxane skeleton. When the above-mentioned polyalkylene oxide polymer having a terminal reactive silyl group and / or poly(meth)acrylic polymer having a reactive silyl group is used, a dehydration condensation reaction also proceeds between the alkoxy group in the alkoxysilane component and the reactive silyl group possessed by the polyalkylene oxide polymer or the poly(meth)acrylic polymer, whereby the polymer chain (a3) ​​is bonded to the polysilsesquioxane skeleton.

[0040] Furthermore, during the reaction, some of the alkoxy groups contained in the alkoxysilane component remain unreacted, and / or after the alkoxy groups undergo a hydrolysis reaction, they remain without undergoing a dehydration condensation reaction, and therefore the produced polysilsesquioxane polymer (A) has alkoxysilyl groups and / or silanol groups as the reactive silyl groups (a1).

[0041] The hydrolysis and dehydration condensation reactions are preferably carried out with the addition of water. By adjusting the amount of water used, the amount of alkoxysilyl groups and / or silanol groups in the resulting polysilsesquioxane polymer and the molecular weight of the polysilsesquioxane polymer can be controlled. From this perspective, the amount of water used is preferably 20 mol% to 80 mol%, more preferably 25 mol% to 70 mol%, even more preferably 30 mol% to 60 mol%, and particularly preferably 35 mol% to 50 mol%, relative to the total number of moles of alkoxy groups on silicon atoms contained in the alkoxysilane component (100%).

[0042] The hydrolysis and dehydration condensation reactions are preferably carried out in the presence of a condensation catalyst to promote the reaction. Known condensation catalysts can be used. Specific examples include basic catalysts, acidic catalysts, and neutral salts. Since the storage stability of the resulting polysilsesquioxane polymer is improved, acidic catalysts and neutral salts are preferred as condensation catalysts, and neutral salts are more preferred.

[0043] As the acidic catalyst, organic acids are preferred in terms of compatibility with the alkoxysilane component, and phosphoric acid esters and carboxylic acids are more preferred. Specific examples of organic acids 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, and isobutyric acid.

[0044] Examples of basic catalysts include amine compounds such as N-ethylmorpholine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia; and metal hydroxides such as sodium hydroxide and potassium hydroxide.

[0045] A neutral salt is a positive salt composed of a strong acid and a strong base, such as a salt composed of a cation selected from the group consisting of a Group 1 element ion, a Group 2 element ion, a tetraalkylammonium ion, and a guanidium ion, and an anion selected from the group consisting of a Group 17 element ion (excluding fluoride ion), a sulfate ion, a nitrate ion, and a perchlorate ion. In particular, Group 17 element ions are preferred as anions because of their high nucleophilicity, and Group 1 element ions and Group 2 element ions are preferred as cations because they are not bulky and do not inhibit the nucleophilic action.

[0046] The specific compound of the neutral salt is not particularly limited, but preferred specific examples include lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, sodium bromide, potassium bromide, rabidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, lithium iodide, sodium iodide, potassium iodide, rabidium iodide, cesium iodide, magnesium iodide, calcium iodide, and strontium iodide.

[0047] The amount of the condensation catalyst added can be adjusted as appropriate, for example, about 50 ppm to 3% by weight of the alkoxysilane component. However, in order to improve the stability of the polysilsesquioxane polymer (A), it is preferable to use a smaller amount of the condensation catalyst within a range that achieves the effect of shortening the reaction time due to the condensation catalyst.

[0048] The reaction temperature when carrying out the hydrolysis and dehydration condensation steps can be appropriately determined by those skilled in the art, but for example, it is preferable to heat the reaction solution to a range of 50 to 110° C. Furthermore, the reaction time when carrying out the hydrolysis and dehydration condensation steps can be appropriately determined by those skilled in the art, but may be, for example, about 10 minutes to 12 hours.

[0049] A step of removing alcohol generated by hydrolysis of the alkoxysilane component during the production of the polysilsesquioxane polymer (A) may be carried out after the hydrolysis and dehydration condensation steps. This allows the content of volatile components, such as alcohol, contained in the polysilsesquioxane polymer (A) to be reduced. The alcohol removal step can be carried out by subjecting the mixed liquid to atmospheric or reduced pressure distillation to distill off the alcohol. The conditions for atmospheric or reduced pressure distillation can be appropriately set by those skilled in the art, and the temperature may be, for example, about 60 to 160°C.

[0050] <Polyalkylene oxide polymer having reactive silyl groups at the terminals> The polyalkylene oxide polymer that can be used to produce the polysilsesquioxane polymer (A) according to one embodiment of the present disclosure has a reactive silyl group at its terminal. In particular, it is preferable that the reactive silyl group is present at only one terminal of the polymer backbone. Details of the reactive silyl group are the same as those of the reactive silyl group (b1) present in the poly(meth)acrylic polymer (B) described below, and therefore will not be described here.

[0051] The polymer backbone of the polyalkylene oxide polymer is the same as the polymer backbone of the polyalkylene oxide polymer chain described above, and therefore a description thereof will be omitted.

[0052] Examples of a method for producing a polyalkylene oxide polymer having a reactive silyl group at its terminal include a method in which an epoxy compound is polymerized with an initiator having a hydroxyl group to produce a polyalkylene oxide polymer having a hydroxyl group at its terminal, and then the hydroxyl group is converted into a reactive silyl group-containing group using a known method.

[0053] When an initiator having one hydroxyl group is used as the initiator having a hydroxyl group, a polyalkylene oxide polymer having a reactive silyl group at only one end according to a preferred embodiment can be produced. The initiator having one hydroxyl group can be a monohydric alcohol, such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, etc. Further examples include low-molecular-weight polyoxypropylene monoalkyl ethers.

[0054] The number average molecular weight of the polyalkylene oxide polymer having a reactive silyl group at its terminal is not particularly limited, but is preferably 500 to 50,000, more preferably 500 to 30,000, and particularly preferably 1,000 to 10,000, in terms of polystyrene, as measured by GPC.

[0055] The weight average molecular weight of the polyalkylene oxide polymer having a reactive silyl group at its terminal is not particularly limited, but is preferably 500 to 80,000, more preferably 3,000 to 70,000, and particularly preferably 5,000 to 65,000, in terms of polystyrene, as measured by GPC.

[0056] <Poly(meth)acrylic polymer having reactive silyl groups> The poly(meth)acrylic polymer that can be used to produce the polysilsesquioxane polymer (A) according to one embodiment of the present disclosure has a reactive silyl group. Among these, a poly(meth)acrylic polymer having a linear polymer backbone and having a reactive silyl group at only one end of the linear backbone is preferred. Details of the reactive silyl group are the same as those of the reactive silyl group (b1) contained in the poly(meth)acrylic polymer (B) described below, and therefore will not be described here.

[0057] The monomers constituting the poly(meth)acrylic polymer are the same as the (meth)acrylic acid ester-based monomers described above in relation to the poly(meth)acrylic polymer chain, and therefore, description thereof will be omitted.

[0058] As a method for introducing a reactive silyl group into the polymer backbone of the poly(meth)acrylic polymer, any known method can be used without any particular limitation. In particular, one example of a method for introducing a reactive silyl group into only one end of the polymer backbone of the poly(meth)acrylic polymer is a method of polymerizing a monomer in the presence of a chain transfer agent having a mercapto group and a reactive silyl group. By using such a chain transfer agent, a reactive silyl group can be introduced into only one end of the polymer backbone of the linear poly(meth)acrylic polymer.

[0059] The chain transfer agent is not particularly limited, but examples thereof include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, and (mercaptomethyl)trimethoxysilane.

[0060] 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 even more preferably 0.5% by weight or more and 7% by weight or less, of the total amount of all monomers constituting the poly(meth)acrylic polymer and the chain transfer agent.

[0061] The polymerization method for producing the poly(meth)acrylic polymer having the reactive silyl group is not particularly limited, but may be a general free radical polymerization. In the free radical polymerization, it is preferable to use a polymerization initiator such as an azo compound or a peroxide.

[0062] The number average molecular weight of the poly(meth)acrylic polymer having a reactive silyl group is not particularly limited, but is preferably 500 to 50,000, more preferably 500 to 30,000, and particularly preferably 1,000 to 10,000, in terms of polystyrene, as measured by GPC. In particular, the number average molecular weight is preferably 7,000 or less, since a polymer having a low viscosity can be obtained.

[0063] The weight-average molecular weight of the poly(meth)acrylic polymer having a reactive silyl group is not particularly limited, but is preferably 500 to 80,000, more preferably 3,000 to 70,000, and particularly preferably 5,000 to 65,000, in terms of polystyrene, as measured by GPC. In particular, the weight-average molecular weight is preferably 15,000 or less, since a polymer having a low viscosity can be obtained.

[0064] <<Poly(meth)acrylic polymer (B)>> The curable resin composition according to the present disclosure contains a poly(meth)acrylic polymer (B) having a reactive silyl group (b1) in a side chain. The poly(meth)acrylic polymer (B) is a polymer that does not have a polysilsesquioxane skeleton. The absence of a polysilsesquioxane skeleton means, for example, 29 This can be confirmed by Si NMR. By using at least a poly(meth)acrylic polymer (B) having a reactive silyl group (b1) in a side chain as the organic polymer having a reactive silyl group, it is possible to achieve an improvement in the strength of the cured product by storage under heating, as described below.

[0065] The (meth)acrylic acid ester monomer constituting the main chain of the poly(meth)acrylic polymer (B) is not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and nonyl (meth)acrylate can be used. Nyl, (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-dimethylsilyl).

[0033] Examples of (meth)acrylic acid monomers include (meth)acrylic acid (2-trimethoxysilyl)propyl, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adducts 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, and 2-perfluorohexadecylethyl (meth)acrylate.

[0066] Examples of monomer units other than those mentioned 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; and monomers containing a nitrogen-containing group such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

[0067] The poly(meth)acrylic polymer (B) may be a polymer obtained by copolymerizing a (meth)acrylic acid ester monomer with 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, mono- and di-alkyl esters of maleic acid; fumaric acid, mono- and di-alkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, and octylmaleimide. Examples of suitable monomers include maleimide monomers such as ethylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol, and a plurality of these can also be used as copolymerization components.

[0068] As the poly(meth)acrylic polymer (B), a (co)polymer composed of a (meth)acrylic acid ester-based monomer or a copolymer composed of a (meth)acrylic acid ester-based monomer and a styrene-based monomer is preferred because of its excellent physical properties, a (co)polymer composed of a (meth)acrylic acid ester-based monomer is more preferred, and a (co)polymer composed of an acrylic acid ester-based monomer is particularly preferred.

[0069] The reactive silyl group (b1) contained in the poly(meth)acrylic polymer (B) can be specifically 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 hetero-containing group. Each X 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] R 1 The hetero-containing group that the hydrocarbon group may have as a substituent is a group containing a hetero atom, where an atom other than a carbon atom or a hydrogen atom is defined as a hetero atom.

[0072] Suitable examples of heteroatoms include N, O, S, P, Si, and halogen atoms. In the hetero-containing group, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0073] R 1Suitable examples of R include alkyl groups such as methyl and ethyl groups; alkyl groups having hetero-containing groups such as chloromethyl and methoxymethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. 1 As the alkyl group, a methyl group, a methoxymethyl group, and a chloromethyl group are preferred, a methyl group and a methoxymethyl group are more preferred, and a methyl group is even more preferred.

[0074] Examples of X include a hydroxyl group, hydrogen, halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. Among these, an alkoxy group is preferred because it is mildly hydrolyzable and easy to handle, and a methoxy group and an ethoxy group are more preferred.

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

[0076] Specific examples of the reactive silyl group (b1) include, but are not limited to, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group etc. Among these, dimethoxymethylsilyl group, trimethoxysilyl group, triethoxysilyl group and (methoxymethyl)dimethoxysilyl group are preferred because they can obtain cured products with good mechanical properties. From the viewpoint of activity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferred, and trimethoxysilyl group and (methoxymethyl)dimethoxysilyl group are particularly preferred. From the viewpoint of stability, dimethoxymethylsilyl group and triethoxysilyl group are more preferred, and dimethoxymethylsilyl group is particularly preferred.

[0077] The poly(meth)acrylic polymer (B) has a reactive silyl group (b1) in its side chain. Here, "having a reactive silyl group in its side chain" means that the reactive silyl group is bonded to a repeating unit other than the repeating units at both ends of the main chain among the repeating units constituting the main chain. This includes both cases where the reactive silyl group is directly bonded to the main chain and cases where it is indirectly bonded to the main chain via another molecular chain. By using a poly(meth)acrylic polymer having a reactive silyl group in its side chain rather than at the end of the main chain, it is possible to achieve an improvement in the strength of the cured product due to storage under heat, as described below.

[0078] The poly(meth)acrylic polymer (B) preferably has an average of 0.05 to 5.0 reactive silyl groups (b1) in the side chain per molecule, more preferably 0.1 to 3.0 reactive silyl groups (b1), and even more preferably 0.5 to 2.0 reactive silyl groups (b1).

[0079] The presence of reactive silyl groups (b1) in the side chains of the poly(meth)acrylic polymer (B) can be confirmed by NMR. The content of reactive silyl groups (b1) (or Si) in the side chains contained in one molecule of the poly(meth)acrylic polymer (B) can be measured by NMR.

[0080] To produce the poly(meth)acrylic polymer (B) having the reactive silyl group (b1) in the side chain, a (meth)acrylic acid ester-based monomer containing a reactive silyl group and a (meth)acrylic acid ester-based monomer not containing a reactive silyl group may be copolymerized as monomers constituting the main chain. The method for producing the poly(meth)acrylic polymer (B) is not particularly limited, and the polymer can be produced by a known method such as that disclosed in WO 2016 / 03571.

[0081] The monomer composition of the poly(meth)acrylic polymer (B) can be selected depending on the application and purpose, and for applications requiring strength, a polymer having a relatively high glass transition temperature (Tg) is preferred, preferably 0° C. or higher and 200° C. or lower, and more preferably 20° C. or higher and 100° C. or lower. Tg can be calculated using the following Fox formula. Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (In the formula, Mi represents the weight fraction of the monomer i component constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of the monomer i.)

[0082] The number average molecular weight of the poly(meth)acrylic polymer (B) is not particularly limited, but is preferably 500 or more and 50,000 or less, more preferably 500 or more and 30,000 or less, in terms of polystyrene, as measured by GPC.

[0083] <<Curing catalyst (C)>> The curable resin composition according to the present disclosure contains a curing catalyst (C) for the purpose of promoting a reaction of hydrolysis and dehydration condensation of reactive silyl groups contained in the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the optional polyalkylene oxide polymer (D), i.e., a curing reaction.

[0084] As the curing catalyst, a conventionally known one can be used, and specific examples thereof include organic tin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, and the like.

[0085] Specific examples of organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin salt and orthosilicate ethyl, a reaction product of dibutyltin oxide and phthalic acid ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), a reaction product of dioctyltin salt and orthosilicate ethyl, etc. In view of the recent increase in environmental concern, dioctyltin compounds are preferred.

[0086] Specific examples of metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, cesium carboxylate, etc. The carboxylic acid group can be a combination of the following carboxylic acids with various metals.

[0087] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0088] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0089] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxytitanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0090] Other curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0091] The curing catalyst may be a combination of two or more different catalysts. For example, the combination of the amine compound and a carboxylic acid or the amine compound and an alkoxy metal may have the effect of improving reactivity.

[0092] From the viewpoint of improving curability and strength of the cured product, it is preferable to use a strong base catalyst as the curing catalyst (C).

[0093] Specific examples of the strong base catalyst include heterocyclic amine compounds, particularly compounds having an amidine skeleton, such as 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), guanidine, phenylguanidine, diphenylguanidine, butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide.

[0094] From the viewpoint of achieving both an improved curing reaction rate and workability during curing, the amount of the curing catalyst (C) added is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, even more preferably 0.1 to 10 parts by weight, still more preferably 0.2 to 7 parts by weight, and particularly preferably 0.5 to 5 parts by weight, relative to 100 parts by weight in total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the optional polyalkylene oxide polymer (D).

[0095] <<Polyalkylene oxide polymer (D)>> The curable resin composition according to the present disclosure preferably further contains a polyalkylene oxide polymer (D) having a reactive silyl group (d1). The polyalkylene oxide polymer (D) is a polymer that does not have a polysilsesquioxane skeleton. The absence of a polysilsesquioxane skeleton can be, for example, 29 This can be confirmed by Si NMR. The details of the reactive silyl group (d1) in the polyalkylene oxide polymer (D) are the same as those of the reactive silyl group (b1) in the poly(meth)acrylic polymer (B), and therefore will not be described here. However, the reactive silyl group (d1) in the polyalkylene oxide polymer (D) may have the same structure as or a different structure from the reactive silyl group (b1) in the poly(meth)acrylic polymer (B).

[0096] The average number of reactive silyl groups (d1) per molecule of polyalkylene oxide polymer (D) 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, more preferably 5 or less. The average number (d1) of reactive silyl groups per molecule of polymer (D) can be calculated from the results of NMR measurement.

[0097] Examples of the polymer skeleton of the polyalkylene oxide polymer (D) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Each polymer may be present in a mixture of block and graft forms. Among these, polyoxypropylene is particularly preferred. The polyalkylene oxide polymer (D) preferably contains 50% by weight or more, more preferably 70% by weight or more of the alkylene oxide repeating units in the polymer skeleton.

[0098] The polymer skeleton of the polyalkylene oxide polymer (D) may be a straight-chain polymer skeleton or a branched-chain polymer skeleton, or may be a mixture of a straight-chain polymer skeleton and a branched-chain polymer skeleton.

[0099] The polyalkylene oxide polymer (D) may be a polymer having any one kind of polymer backbone, or a mixture of two or more kinds of polymers having different polymer backbones. The mixture may be a mixture of polymers produced separately, or may be a mixture produced simultaneously to have any desired mixed composition.

[0100] The number average molecular weight of the polyalkylene oxide polymer (D) is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, as calculated as polystyrene by GPC. When the number average molecular weight is within the above range, the amount of reactive silyl groups introduced is appropriate, and thus a polyalkylene oxide polymer (D) having a manageable viscosity and excellent workability can be produced relatively easily while keeping production costs within an appropriate range.

[0101] The molecular weight of the polyalkylene oxide polymer (D) can also be expressed as an end-group-converted molecular weight, which is calculated by directly measuring the end-group concentration of a polymer precursor before the introduction of reactive silyl groups by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the polymer structure (the degree of branching determined by the polymerization initiator used).The end-group-converted molecular weight of the polyalkylene oxide polymer (D) can also be calculated by creating a calibration curve of the number average molecular weight determined by general GPC measurement of the polymer precursor and the end-group-converted molecular weight, and converting the number average molecular weight determined by GPC of the polyalkylene oxide polymer (D) into an end-group-converted molecular weight.

[0102] The molecular weight distribution (Mw / Mn) of the polyalkylene oxide polymer (D) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, 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 (D) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0103] The method for producing the polyalkylene oxide polymer (D) is not particularly limited, and the polymer can be produced by a known method such as that disclosed in WO 2016 / 03571.

[0104] In the curable resin composition according to the present disclosure, the amounts of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the optional polyalkylene oxide polymer (D) can be appropriately determined taking into consideration the curability of the composition, the strength of the resulting cured product, and the like. Specifically, the proportion of the polysilsesquioxane polymer (A) in the total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the polyalkylene oxide polymer (D) is preferably 1 to 50 wt%, more preferably 1 to 30 wt%, even more preferably 2 to 25 wt%, and particularly preferably 3 to 20 wt%. Furthermore, because of the significant effect of improving the strength of the cured product, the proportion of the polysilsesquioxane polymer (A) is preferably 18 wt% or more, more preferably 20 wt% or more.

[0105] Furthermore, the proportion of the poly(meth)acrylic polymer (B) and the polyalkylene oxide polymer (D) in the total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the polyalkylene oxide polymer (D) is preferably 50 to 99% by weight, more preferably 70 to 99% by weight, even more preferably 75 to 98% by weight, and particularly preferably 80 to 97% by weight.

[0106] The weight ratio of poly(meth)acrylic polymer (B):polyalkylene oxide polymer (D) is preferably 100:0 to 10:90, more preferably 99:1 to 15:85, even more preferably 90:10 to 20:80, still more preferably 80:20 to 25:75, and particularly preferably 70:30 to 30:70.

[0107] <<Other Ingredients>> The curable resin composition according to the present disclosure may contain various additives as needed in addition to the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), the curing catalyst (C), and the optional polyalkylene oxide polymer (D). Examples of such additives include fillers, plasticizers, adhesion promoters, dehydrating agents, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, physical property adjusters, epoxy group-containing compounds, photocurable substances, oxygen-curable substances, and organic resins other than components (B) and (D).

[0108] Furthermore, for the purpose of adjusting various physical properties of the curable resin composition or the cured product, additives other than those described above may be added to the curable resin composition as necessary. Examples of such additives include tackifier resins, solvents, diluents, epoxy resins, surface property improvers, foaming agents, curability regulators, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0109] <Adhesion promoter> The curable resin composition according to the present disclosure may contain an adhesion promoter. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be added.

[0110] Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isopropyltriethoxysilane. Examples of suitable adhesives include isocyanate group-containing silanes such as cyanatepropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, and α-isocyanatemethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Reaction products of various silane coupling agents can also be used. Only one type of adhesion promoter may be used, or two or more types may be used in combination.

[0111] The amount of the adhesion promoter is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the polyalkylene oxide polymer (D).

[0112] <Dehydrating agent> The curable resin composition according to the present disclosure may contain a dehydrating agent. As the dehydrating agent, a compound capable of reacting with water preferentially over the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the polyalkylene oxide polymer (D) can be suitably used.

[0113] Specific examples of such dehydrating agents include methyltrimethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethoxydiphenylsilane, hexyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, vinylmethyldimethoxysilane, (methoxymethyl)trimethoxysilane, p-styryltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, bis(3-trimethoxysilylpropyl)amine, and ethyl groups thereof. Examples of the silicon compounds include oxysilane derivatives, mono- to octamer methyl silicates, mono- to octamer ethyl silicates, methyltriacetoxysilane, and vinyltris(2-methoxyethoxy)silane, and partial hydrolysis condensates of these silicon compounds; trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, and tributyl orthoformate; ester compounds such as trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, and tributyl orthoacetate; oxazolidine compounds such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine; carbamate compounds such as N-(trimethoxysilylmethyl)-O-methyl-carbamate, N-dimethoxy(methyl)silylmethyl-O-methyl-carbamate, and N-methyl[3-(trimethoxysilyl)-propyl]carbamate; and phosphorus pentoxide. Examples of the dehydrating agent include n-propyltrimethoxysilane, vinyltrimethoxysilane, and vinylmethyldimethoxysilane. Among these, silicon compounds having a trimethoxysilyl group are more preferred, and vinyltrimethoxysilane is particularly preferred. Only one type of dehydrating agent may be used, or two or more types may be used in combination.

[0114] The amount of the dehydrating agent to be added is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the polyalkylene oxide polymer (D).

[0115] <<Method for producing curable resin composition>> In producing the curable resin composition according to the present disclosure, the components are mixed to obtain a raw material composition, and then the raw material composition is stored in a sealed container under heating at a specific temperature. While the curability of raw material compositions prior to storage generally tends to be low, storage under heating significantly improves the curability and shortens the time required for curing while maintaining good workability, such as when applying the composition to a substrate. Furthermore, storage under heating can improve the strength of the cured product obtained by curing the curable resin composition.

[0116] The mechanism by which curability is improved by storage under heat is unclear, but it is thought that storage under heat causes the reactive silyl groups in the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the optional polyalkylene oxide polymer (D) to react with each other, bringing the molecules closer together and facilitating the curing reaction in the subsequent curing step. Furthermore, the mechanism by which the strength of the cured product is improved by storage under heat is also unclear, but it is thought that storage under heat improves the activity of the reactive silicon groups in component (B) and optional component (D).

[0117] The term "storage under a closed condition" refers to storage in a state in which the container filled with the raw material composition is prevented from allowing moisture to flow in from the outside. Specifically, the raw material composition may be filled into a container, and then the container may be sealed while being degassed, or may be sealed with a gas such as nitrogen.

[0118] The container is preferably moisture-proof, preventing moisture penetration so as to inhibit the hydrolysis reaction of the reactive silyl groups contained in each of the (A), (B), and (D) components. Specifically, the container preferably has a moisture permeability of 60 mg / L or less over 24 hours in an atmosphere of 40°C and 90% RH. The lower the moisture permeability, the more preferable it is, with 30 mg / L or less being preferred, 10 mg / L or less being more preferred, and 5 mg / L or less being even more preferred. A typical cartridge-type container used for storing moisture-curable resin compositions can be used as this container. The moisture permeability can be measured, for example, according to the method of JIS Z 0222:1959, and calculated by dividing the amount of water vapor passing through (g) over 24 hours by the volume (L) of the container.

[0119] When storing the raw material composition in a sealed container, the raw material composition may be stirred or shaken, but it is not necessary to stir the raw material composition, and the raw material composition may be left standing in the container.

[0120] The storage temperature is controlled within a range of 40°C to 150°C from the viewpoint of achieving a curability improvement effect while avoiding denaturation or decomposition of the blended components. The lower limit is preferably 45°C or higher, and more preferably 50°C or higher. The upper limit is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower.

[0121] The time for which the raw material composition is maintained under heating depends on the temperature during storage and cannot be uniformly determined, but may be appropriately set in consideration of the curability improving effect. The longer the storage time, the greater the curability improving effect tends to be. Specifically, the time is preferably 1 hour or more, more preferably 5 hours or more, even more preferably 12 hours or more, even more preferably 1 day or more, and particularly preferably 2 days or more.

[0122] The upper limit of the time is not particularly limited and may be determined appropriately from the viewpoint of the curability improvement effect and productivity, but may be 8 weeks or less, 6 weeks or less, or 4 weeks or less.

[0123] When mixing the components to obtain a raw material composition, all of the components may be mixed at once to obtain the raw material composition. However, in a preferred embodiment, components (A), (B), optional component (D), and other components (e.g., plasticizers, fillers, etc.) are first mixed and heated to dehydrate to obtain a mixture containing at least components (A) and (B), and then the mixture is cooled and the curing catalyst (C) and optional other components (e.g., dehydrating agents, adhesion promoters, etc.) are added to obtain the raw material composition. In this manner, the progress of the curing reaction during the preparation of the raw material composition can be effectively suppressed while the components are thoroughly mixed.

[0124] The conditions for the thermal dehydration are not particularly limited as long as they allow removal of moisture, and for example, the mixture may be heated to a temperature of about 40 to 150° C. and then cooled under normal pressure, or preferably under reduced pressure. The temperature at which the resulting mixture is cooled is also not particularly limited, and the temperature may be lower than the temperature at which the thermal dehydration was performed, and may be, for example, about room temperature to 60° C.

[0125] The curable resin composition produced by the method according to the present disclosure is prepared as a one-component composition in which all ingredients are premixed. The composition cures due to moisture in the air after application. Such a one-component curable resin composition is advantageous from the viewpoint of workability during application.

[0126] Prior to curing, the curable resin composition is formed into a desired shape by coating, casting, filling, or other methods. The curable resin composition that has been coated, cast, or filled and formed into a desired shape can be placed in a humid condition (generally in the air) and cured at room temperature or under heat. The conditions for curing under heat are not particularly limited, but a temperature of 60 to 220°C and a time of 1 to 120 minutes are preferred, and a temperature of 100 to 200°C and a time of 5 to 60 minutes are more preferred.

[0127] The curable resin composition according to the present disclosure can be used as an adhesive, a pressure-sensitive adhesive, a sealant for sealing in buildings, ships, automobiles, buses, roads, home appliances, etc., a mold release agent, a paint, a spray agent, etc. Furthermore, the cured product obtained by curing the curable resin composition can be suitably used as a waterproofing material, a waterproof coating material, an anti-vibration material, a vibration-damping material, a sound-proofing material, a foam material, etc. [Example]

[0128] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0129] The number average molecular weight and weight average molecular weight in each synthesis example are GPC molecular weights measured under the following conditions. Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0130] The end group-based molecular weight in each synthesis example is a molecular weight calculated by determining the hydroxyl value according to the measurement method of JIS K 1557 and the iodine value according to the measurement method of JIS K 0070, taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The average number of silyl groups introduced into each polymer shown in each synthesis example was calculated by NMR measurement.

[0131] (Synthesis Example 1) Propylene oxide was polymerized using butanol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene with a number average molecular weight of 7,800 (terminal molecular weight of 5,000) and a molecular weight distribution Mw / Mn of 1.48, which had a hydroxyl group at one end. Next, 1.2 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, 2.0 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer to convert the terminal hydroxyl groups to allyl groups, and unreacted allyl chloride was removed by devolatilization under reduced pressure. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polymer. This resulted in polyoxypropylene having an allyl group at only one end. To 500 g of the resulting polymer, 50 μl of platinum divinyldisiloxane complex (3 wt % platinum equivalent solution in 2-propanol) was added, and 9.5 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, after which unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (a3') bearing dimethoxymethylsilyl groups at only one end. The polymer was found to have an average of 0.8 dimethoxymethylsilyl groups at only one end.

[0132] (Synthesis Example 2) In a four-necked flask equipped with a stirrer, 10.1 parts by weight of polyoxypropylene (a3') having a dimethoxymethylsilyl group at only one end obtained in Synthesis Example 1, 88.3 parts by weight of methyltrimethoxysilane and 66.9 parts by weight of phenyltrimethoxysilane as silane monomers, 21.2 parts by weight of water (40 mol % relative to 100 mol % of the alkoxy groups in the alkoxysilane component), and 0.1 parts by weight of a 10% aqueous LiBr solution were added at room temperature, and the mixture was heated and reacted for 6 hours under reflux with the generated methanol. Methanol was removed from the resulting methanol solution under heating and reduced pressure to obtain a polysilsesquioxane polymer (A-1) having a polyalkylene oxide polymer chain (a3). It was confirmed that the polysilsesquioxane polymer (A-1) had a reactive silyl group. 1 This was confirmed by H NMR. Only one end of the polyalkylene oxide polymer chain (a3) ​​is bonded to the polysilsesquioxane skeleton.

[0133] (Synthesis Example 3) A mixture of 670 g of methyl methacrylate, 60 g of butyl acrylate, 134 g of stearyl methacrylate, 55 g of γ-methacryloxypropyldimethoxymethylsilane, 73 g of γ-mercaptopropyldimethoxymethylsilane, and 223 g of IBA was heated to 105°C. A solution of 24.8 g of azobis-2-methylbutyronitrile as a polymerization initiator was added dropwise to the mixture over 5 hours. A solution of 2.8 g of azobis-2-methylbutyronitrile as a polymerization initiator in 45 g of IBA was then added dropwise over 1 hour. After 2 hours of postpolymerization, a (meth)acrylate copolymer (B-1) with a solids concentration of 60% and a number-average molecular weight of 2,100 and containing dimethoxymethylsilyl groups in the side chains was obtained. Polymer (B-1) was found to contain an average of 1.34 dimethoxymethylsilyl groups per molecule. The polymer (B-1) does not have a polysilsesquioxane skeleton.

[0134] (Synthesis Example 4) A methanol solution of sodium methoxide was added to 900 g of polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 and 100 g of polyoxypropylene triol with a number-average molecular weight of approximately 4,500. The methanol was distilled off under heating and reduced pressure to convert the polypropylene oxide terminals to sodium alkoxide, followed by the addition of dichloromethane to increase the molecular weight. Allyl chloride was then added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. The resulting unpurified polyoxypropylene was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The hexane solution was then devolatilized under reduced pressure to remove metal salts from the polymer. This yielded polyoxypropylene with allyl groups at the terminals. To 500 g of this polymer, 50 μl of platinum divinyldisiloxane complex solution (3 wt. % platinum equivalent isopropanol solution) was added, and 8.9 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting for 2 hours at 100°C, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (D-1) with a number-average molecular weight of 16,800 and terminal dimethoxymethylsilyl groups. Polymer (D-1) was found to contain an average of 0.7 dimethoxymethylsilyl groups per terminal and an average of 1.4 dimethoxymethylsilyl groups per molecule. Polymer (D-1) does not have a polysilsesquioxane skeleton.

[0135] (Synthesis Example 5) Using polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene with terminal hydroxyl groups, a number-average molecular weight of 24,600 (terminal group equivalent molecular weight 17,400), and a molecular weight distribution Mw / Mn = 1.31. To the hydroxyl groups of the resulting hydroxyl-terminated polyoxypropylene, 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polymer. This resulted in the production of polyoxypropylene having allyl groups at its termini. To 500 g of this polymer, 50 μl of platinum divinyldisiloxane complex solution (3 wt. % platinum equivalent isopropanol solution) was added, and 6.4 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting for 2 hours at 100°C, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (D-2) with a number-average molecular weight of 26,200 and terminal dimethoxymethylsilyl groups. Polymer (D-2) was found to contain an average of 0.7 dimethoxymethylsilyl groups per terminal and an average of 2.2 dimethoxymethylsilyl groups per molecule. Polymer (D-2) does not have a polysilsesquioxane skeleton.

[0136] (Synthesis Example 6) 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 stirred at 70-80°C for approximately 30 minutes. Pentamethyldiethylenetriamine was added to the mixture to initiate the reaction. 30 minutes after the start of the reaction, 80.0 g of n-butyl acrylate was continuously added over a period of 2 hours. Pentamethyldiethylenetriamine was added appropriately during the reaction to maintain the internal temperature at 70-90°C. The total amount of pentamethyldiethylenetriamine used during polymerization was 0.15 g. Four hours after the start of the reaction, the mixture was heated and stirred under reduced pressure at 80°C to remove volatiles. 35.0 g of acetonitrile, 21.0 g of 1,7-octadiene, and 0.34 g of pentamethyldiethylenetriamine were added to the mixture and stirred for 8 hours. The mixture was heated and stirred under reduced pressure at 80°C to remove volatiles. Butyl acetate was added to this concentrate to dissolve the polymer, and then diatomaceous earth was added as a filter aid, and aluminum silicate and hydrotalcite as adsorbents, and the mixture was heated and stirred in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) at an internal temperature of 100°C. The solid content in the mixture was removed by filtration, and the filtrate was heated and stirred under reduced pressure at an internal temperature of 100°C to remove volatiles. To this concentrate, aluminum silicate as an adsorbent, hydrotalcite, and a heat deterioration inhibitor were added, and the mixture was heated and stirred under reduced pressure (average temperature: about 175°C, reduced pressure: 10 Torr or less). Further, aluminum silicate and hydrotalcite were added as adsorbents, and an antioxidant was added, followed by heating and stirring 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 mixture was removed by filtration. The filtrate was heated and stirred under reduced pressure to remove the volatiles, yielding a polymer having alkenyl groups. This alkenyl-containing polymer, dimethoxymethylsilane (2.0 molar equivalents relative to the alkenyl groups), methyl orthoformate (1.0 molar equivalent relative to the alkenyl groups), and a platinum catalyst [a xylene solution of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst; hereafter referred to as platinum catalyst] (10 mg of platinum per kg of polymer) were mixed and heated with stirring at 100°C under a nitrogen atmosphere. After confirming the disappearance of the alkenyl groups, the reaction mixture was concentrated to obtain an acrylic polymer (B'-1) bearing terminal dimethoxymethylsilyl groups. The number-average molecular weight of the acrylic polymer was 24,700, the molecular weight distribution was 1.3, and the average number of terminal dimethoxymethylsilyl groups per molecule was 1.9.

[0137] Example 1 As the component (B), 50 parts by weight (32 parts by weight as solids) of the (meth)acrylic acid ester copolymer (B-1) obtained in Synthesis Example 3 and 48 parts by weight of the polyoxypropylene (D-1) obtained in Synthesis Example 4 were mixed together, and the isobutyl alcohol was removed under heating and reduced pressure. Then, as the component (A), 20 parts by weight of the polysilsesquioxane polymer (A-1) obtained in Synthesis Example 2 and 50 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Hakuenka CCR) were mixed and thoroughly kneaded, and the mixture was passed once through a small triple paint roll. The mixture was then dehydrated under reduced pressure at 120°C for 2 hours and cooled to below 50°C. After that, 3 parts by weight of vinyltrimethoxysilane (manufactured by Momentive Performance Materials, Inc., trade name: Silquest A-171) as a dehydrating agent, 2 parts by weight of γ-(2-aminoethyl)aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials, Inc., trade name: Silquest A-1120) as an adhesion promoter, and 3.0 parts by weight of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a curing catalyst (C) were added and kneaded. The mixture was then filled into a moisture-proof cartridge-type container (330 cc capacity) with a moisture permeability of 1 mg / 330 cc for 24 hours at 40°C and 90% RH and sealed to obtain a curable resin composition. The resulting curable resin composition was stored under the conditions (temperature, time) listed in Table 1, and the viscosity, curability, and tensile properties were measured initially (before storage) and after storage as described below.

[0138] (viscosity) The initial (before storage) or stored curable resin composition was left overnight in a thermostatic chamber at 23°C and 50% RH, and the viscosity at 2 rpm was measured using a rotor H5 with a TVB10U viscometer manufactured by Toki Sangyo Co., Ltd. The viscosity value at 2 rpm after storage divided by the initial viscosity value at 2 rpm was used as the viscosity increase rate.

[0139] (curable) The time when each curable resin composition was spread with a spatula was defined as the starting time, and the surface of the composition was confirmed by touching it with the spatula, and the time until the composition no longer stuck to the spatula (skinning time) was measured.

[0140] (tensile properties) Each curable resin composition was molded into a 3 mm thick sheet specimen, which was then completely cured by placing it at 23°C and 50% RH for 3 days and then in a dryer at 50°C for 4 days. After punching out into a No. 3 dumbbell shape, a tensile test was performed using an autograph manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min to measure the breaking strength (referred to as TB).

[0141] (Examples 2 and 3, Comparative Examples 1 to 3) Curable resin compositions were obtained and evaluated in the same manner as in Example 1, except that the blending amounts of each component were changed as shown in Table 1. The results are shown in Table 1.

[0142] [Table 1]

[0143] Table 1 shows that in Example 1, which contained components (A) and (B), the initial skinning time (before heated storage) was 9 minutes, but after 4 weeks of storage at 50°C the skinning time was 1 minute, and after 3 days of storage at 80°C the skinning time was less than 3 minutes, indicating that storage under heat improved curing. Furthermore, the initial breaking strength was 3.50 MPa, but after 4 weeks of storage at 50°C the breaking strength was 4.29 MPa, and after 3 days of storage at 80°C the breaking strength was 3.93 MPa, indicating that storage under heat improved the breaking strength of the cured product, resulting in a cured product with high strength. The same can be said for Examples 2 and 3. Furthermore, it can be seen that no significant increase in viscosity due to heated storage was observed in any of Examples 1 to 3, and good workability was maintained. In other words, in each Example, although no significant increase in viscosity was observed due to heated storage, the curability was improved.

[0144] On the other hand, Comparative Example 1, which did not contain component (A), showed a slow curing rate both initially and after heat storage. Comparative Example 2, which did not contain components (B) and (D) but instead contained a poly(meth)acrylic polymer having a reactive silyl group at its terminal, and Comparative Example 3, which did not contain component (B) but contained only component (D), showed an improvement in curability after heat storage, but the breaking strength of the cured product decreased.

Claims

1. a polysilsesquioxane polymer (A) having a reactive silyl group and a hydrocarbon group directly bonded to a silicon atom of the polysilsesquioxane skeleton; a poly(meth)acrylic polymer (B) having a reactive silyl group in a side chain and not having a polysilsesquioxane skeleton; a curing catalyst (C), and Polyalkylene oxide polymer (D) having a reactive silyl group and no polysilsesquioxane skeleton and storing a raw material composition containing the compound (I) in a sealed state at a temperature of 40°C or higher and 150°C or lower.

2. 2. The method according to claim 1, wherein the storage is carried out in a container having a moisture permeability of 60 mg / L or less for 24 hours under an atmosphere of 40° C. and 90% RH.

3. The method according to claim 1 or 2, wherein the storage time is from 1 hour to 8 weeks.

4. a step of mixing the polysilsesquioxane polymer (A) and the poly(meth)acrylic polymer (B) and dehydrating the mixture by heating to obtain a mixture; The method according to any one of claims 1 to 3, further comprising the step of cooling the mixture and then adding a curing catalyst (C) to obtain the raw material composition.

5. The method according to any one of claims 1 to 4, wherein the curing catalyst is a strong base catalyst.

6. The method according to any one of claims 1 to 5, wherein the polysilsesquioxane polymer (A) further has a polyalkylene oxide polymer chain and / or a poly(meth)acrylic polymer chain bonded to the polysilsesquioxane skeleton.

7. The production method according to any one of claims 1 to 6, wherein a proportion of the polysilsesquioxane polymer (A) is 1 to 30 wt% of the total of the polysilsesquioxane polymer (A), the poly(meth)acrylic polymer (B), and the polyalkylene oxide polymer (D).

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