Curable composition and cured product

Abstract

To provide a curable composition which maintains the dispersion of hydrophobic silica even following storage.SOLUTION: A curable composition according to one aspect of the present invention includes: component A: a (meth)acrylic polymer having a silyl group; component B: an amine; component C: hydrophobic silica; and component D: a curing catalyst. Component A is a polymer that meets specific conditions.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition and a cured product. [Background technology]

[0002] Silica is widely and commonly used as a filler to be incorporated into hardenable compositions (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2010-65073 A Summary of the Invention [Problem to be solved by the invention]

[0004] In a curable composition containing silica (especially hydrophobic silica), it has been difficult to store the composition while maintaining the dispersion of the silica. That is, the curable composition containing silica has a problem that the silica and the resin component separate during storage, and the physical properties change after curing.

[0005] An object of one aspect of the present invention is to provide a curable composition in which the dispersion of hydrophobic silica is maintained even after storage. [Means for solving the problem]

[0006] In order to solve the above problems, a curable composition according to one embodiment of the present invention contains the following Components A to D: Component A: a (meth)acrylic polymer having a silyl group; Component B: amine; Component C: hydrophobic silica; Component D: Curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, or an XYX triblock structure, The number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is more than 2.0 on average, the content of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block, The molecular weight distribution (Mw / Mn) is 1.8 or less. Effect of the Invention

[0007] According to one aspect of the present invention, there is provided a curable composition in which the dispersion of hydrophobic silica is maintained even after storage. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] An example of an embodiment of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and may be modified in various ways within the scope of the claims. An embodiment that combines technical means described in different embodiments is also included in the technical scope of the present invention.

[0009] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic." Unless otherwise specified in this specification, "silyl group" means "hydrolyzable silyl group." In one embodiment, the silyl group is an alkoxysilyl group.

[0010] 1. Components of the Curable Composition The curable composition according to one embodiment of the present invention includes component A: a (meth)acrylic polymer having a silyl group, component B: an amine, component C: hydrophobic silica, and component D: a curing catalyst. The curable composition may further include component E: a polyoxyalkylene polymer having a silyl group as an optional component. The curable composition may include additives other than those described above. Only one type of each component may be blended, or two or more types may be blended.

[0011] [1.1. Component A: (meth)acrylic polymer having silyl group] Component A is a (meth)acrylic polymer having a silyl group. Component A has a silyl group derived from a silyl group-containing (meth)acrylic ester monomer. Component A has an X block having a high frequency of silyl groups and a Y block having a low frequency of silyl groups. Component A can be polymerized, for example, by changing the monomer composition during polymerization.

[0012] [1.1.1. Structure of component A] Component A has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule. The structure of the entire molecule of component A is not particularly limited as long as it contains an XY diblock structure or an XYX triblock structure, and may be, for example, an XYXY tetrablock structure.

[0013] Here, the term "XYX triblock structure" means the "ABA triblock structure" generally known among those skilled in the art. The ratio of X / Y in component A is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0014] In one embodiment, the molecule of component A has an XY diblock structure. In the molecule of the XY diblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from one end of the molecule (all repeating units contained in the molecule are taken as 100%). Here, the X block is the block on the side where silyl groups are distributed in a relatively large amount.

[0015] In one embodiment, the molecule of component A has an XYX triblock structure. In the molecule of the XYX triblock structure, the X blocks can be 40% or less, 30% or less, or 25% or less of the region from the ends of the molecule (all repeat units contained in the molecule are taken as 100%). Here, the X blocks are blocks located at both ends of the molecule.

[0016] Component A has a repeating unit derived from a silyl group-containing (meth)acrylic acid ester monomer. The repeating unit derived from the silyl group-containing (meth)acrylic acid ester monomer is contained relatively more in the X block. The repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block are more than 2.0 on average. When component A has two or more X blocks in one molecule, the total number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the multiple X blocks is more than 2.0 on average. On the other hand, the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block are 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block.

[0017] The repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block are more than 2.0 on average, preferably 2.1 or more, more preferably 2.2 or more, even more preferably 2.3 or more, and particularly preferably 2.5 or more. Similarly, the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block are preferably 0.5% by weight or more, more preferably 2.0% by weight or more, and even more preferably 3.0% by weight or more, based on the weight of all repeating units contained in the X block. The upper limit of the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is preferably 90% by weight or less, more preferably 60% by weight or less, and even more preferably 30% by weight or less.

[0018] The upper limit of the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block is less than 5% by weight, preferably 4% by weight or less, more preferably 3% by weight or less, even more preferably 2% by weight or less, and particularly preferably 1% by weight or less, based on the weight of all repeating units contained in the Y block. The lower limit of the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block is preferably 0% by weight or more, more preferably more than 0% by weight, based on the weight of all repeating units contained in the Y block.

[0019] The number of silyl groups introduced into component A is, on average, more than 2.0, preferably 2.2 or more, more preferably 2.6 or more, even more preferably 3.0 or more, and particularly preferably 3.4 or more, in the whole molecule. The upper limit of the number of silyl groups introduced into the (meth)acrylic polymer is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 5.0 or less. If the number of silyl groups is within the above range, a curable composition and a cured product with good physical properties can be obtained.

[0020] Specific examples of silyl group-containing (meth)acrylic acid ester monomers include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0021] Component A may contain a repeating unit derived from a (meth)acrylic monomer having a long side chain. In this specification, the term "(meth)acrylic monomer having a long side chain" refers to a repeating unit derived from a (meth)acrylic monomer having a long side chain, represented by the formula: CH2=C(R 1 )COOR 2 In the formula, R 1 R is a hydrogen atom or a methyl group. 2 is a group having 9 or more carbon atoms.

[0022] The content of the repeating unit derived from the (meth)acrylic monomer having a long side chain is preferably 1% by weight or more of all the constitutional units contained in Component A. Component A containing such a repeating unit may improve the compatibility with the polyoxyalkylene polymer and improve the physical properties of the obtained cured product. The upper limit of the content of the repeating unit derived from the (meth)acrylic monomer having a long side chain is preferably 5% by weight or less, more preferably 3% by weight or less. If the content is within the above range, the production cost of Component A does not increase excessively.

[0023] Examples of (meth)acrylic monomers having a long side chain include nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, docosyl (meth)acrylate, oleyl (meth)acrylate, linoleyl (meth)acrylate, and isobornyl (meth)acrylate.

[0024] Among the above-mentioned monomers, one or more selected from octadecyl (meth)acrylate, oleyl (meth)acrylate, and linoleyl (meth)acrylate are preferred. These monomers have the advantage of being liquid at room temperature and having high polymerization stability. In addition, by blending these monomers, a (meth)acrylic acid-based polymer having high compatibility with a polyoxyalkylene-based polymer can be obtained.

[0025] In this specification, the term "(meth)acrylic monomer having a non-long side chain" refers to a (meth)acrylic monomer having a non-long side chain in the above formula, R 2represents a monomer having 8 or less carbon atoms. Examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isopropoxyethyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, glycidyl (meth)acrylate, 1-ethylcyclopentyl ether (meth)acrylate, and dimethylaminoethyl (meth)acrylate.

[0026] Among the above-mentioned monomers, one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred. These monomers have low procurement costs and are suitable for the purpose of reducing the production cost of component A.

[0027] Furthermore, from the viewpoint of glass transition point, one or more selected from n-butyl acrylate and 2-ethylhexyl acrylate are preferred. Component A obtained from these monomers has a low glass transition point and a low polymer viscosity. Therefore, a curable composition that is easy to use in a low temperature environment is obtained.

[0028] Component A may have a repeating unit derived from a monomer other than a (meth)acrylic acid ester monomer. The proportion of the repeating unit derived from a (meth)acrylic acid ester monomer in Component A is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more of the total weight of Component A.

[0029] The silyl group contained in Component A may be derived from a silyl group-containing (meth)acrylic acid ester monomer. In one embodiment, the silyl group is represented by the following general formula: -[Si(R 3 ) 2-b (Y) b O] m -Si(R 4 ) 3-a (Y) a

[0030] In the formula, R 3 and R 4 are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or a triorganosiloxy group represented by (R')3SiO-. R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms. The three R's may be the same or different. R 3 or R 4 When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acetoxy group, and an oxime group. In one embodiment, Y is a hydroxyl group, a methoxy group, an ethoxy group, or an isopropoxy group. When a single silyl group contains a plurality of X's, they may be the same or different. When a single molecule of component A contains a plurality of silyl groups, Y may be different for each silyl group. a is 0, 1, 2, or 3. b is 0, 1, or 2. m is an integer of 0 to 19. However, the relationship a+mb≧1 is satisfied.

[0031] The specific structure of the silyl group-containing (meth)acrylic acid ester monomer is not particularly limited. An example is a monomer represented by the following general formula: H2C=C(R 5 )C(=O)-O-(CH2) m -SiR 6 n (OR 7 ) 3-n

[0032] In the formula, R 5 is hydrogen or a methyl group. 6 and R 7 R is at least one selected from the group consisting of hydrogen, a methyl group, and an ethyl group. 6 and / or R 7 When a plurality of are present, they may be the same or different. m is an integer of 0 to 10. n is an integer of 0 to 2.

[0033] Specific examples of silyl group-containing (meth)acrylic acid ester monomers include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0034] [1.1.3. Physical properties of component A] In one embodiment, the lower limit of the number average molecular weight of component A is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. The upper limit of the number average molecular weight of component A is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. When the number average molecular weight of component A is within the above range, the viscosity of the curable composition does not become too high, and sufficient workability can be ensured.

[0035] In one embodiment, the molecular weight distribution of component A is 1.8 or less, preferably 1.5 or less, 1.4 or less, 1.3 or less, or 1.2 or less. If the molecular weight distribution is within the above range, the viscosity of the polymer tends to decrease and the workability tends to improve. The molecular weight distribution is a value given by "weight average molecular weight ÷ number average molecular weight".

[0036] The weight average molecular weight and number average molecular weight are measured by gel permeation chromatography (GPC). For GPC measurement, chloroform is used as the mobile phase and a polystyrene gel column is used as the stationary phase. The molecular weight obtained by measurement is the molecular weight converted into standard polystyrene.

[0037] [1.1.4. Manufacturing method of component A] The polymerization method of component A is not particularly limited, and known polymerization methods can be used (radical polymerization method, cationic polymerization method, anionic polymerization method, etc.). The polymerization method called SGO (Solid Grade Oligomer; high temperature continuous bulk polymerization) is preferred because it is a method that can obtain component A without using a polymerization solvent, a polymerization initiator, a chain transfer agent, etc. A living polymerization method is preferred because it can introduce a functional group near the end of the polymer molecule and can synthesize component A with a small molecular weight distribution. Examples of living polymerization methods include living radical polymerization method, living cationic polymerization method, and living anionic polymerization method, and among them, living radical polymerization method is suitable for polymerization of (meth)acrylic monomers. Examples of living radical polymerization methods include the following. Atom Transfer Radical Polymerization (ATRP) (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721) Single Electron Transfer Polymerization (SET-LRP (see J. Am. Chem. Soc. 2006, 128, 14156; JPSChem 2007, 45, 1607)) Reversible Chain Transfer Catalyzed Polymerization (RTCP) (see "Living Radical Polymerization Controlled by Organic Catalysts" Polymer Journal Vol. 68, 223-231 (2011); JP Patent Publication No. 2014-111798) Reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) Nitroxy radical method (NMP method) Polymerization using organotellurium compounds (TERP method) · Polymerization method using organoantimony compounds (SBRP method) Polymerization method using organobismuth compounds (BIRP method) -Iodine transfer polymerization method

[0038] An example of a method for introducing a silyl group into component A is the method described in JP 2018-162394 A. The method disclosed in the document introduces a silyl group into component A by copolymerizing a (meth)acrylic acid ester monomer and a silyl group-containing (meth)acrylic acid ester monomer. More specifically, a silyl group is introduced near the terminal of the component A molecule by controlling the input amount of the silyl group-containing (meth)acrylic acid ester monomer according to the progress stage of the living polymerization. Component A obtained by these methods may have a silyl group locally at the terminal or near the terminal of the molecule.

[0039] [1.2. Component B: Amine] Component B is an amine. By amine is meant a compound having one or more amino groups or substituted amino groups. In one embodiment, component B has one or more amino groups.

[0040] Specific examples of component B include amines (octylamine, 2-ethylhexylamine, laurylamine, stearylamine, etc.); nitrogen-containing heterocyclic compounds (pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN)); guanidines (guanidine, phenylguanidine, diphenylguanidine, etc.); biguanides (butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide, etc.); amino group-containing silane coupling agents; and ketimine compounds. Component B is preferably a polyvalent amine having two or more amino groups or substituted amino groups.

[0041] The lower limit of the functional group equivalent of the amino group in component B is preferably 100 g / mol or more, more preferably 120 g / mol or more, and even more preferably 150 g / mol or more. The upper limit of the functional group equivalent of the amino group in component B may be, for example, 300 g / mol or less. The functional group equivalent of the amino group is the weight of a compound containing 1 mol of amino groups. When the molecular weight of the compound is M and the number of amino groups contained in one molecule of the compound is X, the functional group equivalent of the amino group is calculated by M÷X.

[0042] [1.3. Component C: Hydrophobic Silica] Component C is hydrophobic silica. Hydrophobic silica refers to silica that has been subjected to a surface treatment to reduce the amount of silanol groups, which are hydrophilic groups exposed on the surface, and thus has reduced hydrophilicity. In general, hydrophobic silica is blended for the purpose of imparting thixotropy to the curable composition or reinforcing the cured product.

[0043] Examples of component C include fumed silica, precipitated silica, crystalline silica, fused silica, and sol-gel silica that have been hydrophobized by surface treatment. Among these, fumed silica is preferred because it is highly effective in imparting thixotropy to the curable composition and reinforcing the cured product.

[0044] Commercially available products may be used as component C. Examples include R972, RY200 (both of which are manufactured by EVONIK), X-30, and PM-20L (both of which are manufactured by Tokuyama Corporation).

[0045] The curable composition may contain hydrophilic silica in addition to component C. However, from the viewpoint of dispersibility, the content of hydrophilic silica is preferably small. In one embodiment, the content of hydrophilic silica may be 0.5 parts by weight or less, 0.3 parts by weight or less, or 0.1 parts by weight or less, assuming that the content of hydrophobic silica is 1 part by weight. In one embodiment, the curable composition does not contain hydrophilic silica.

[0046] [1.4. Component D: Curing catalyst] Examples of the curing catalyst include tin-based curing catalysts. Specific examples of the tin-based curing catalyst include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalic acid ester, etc.); tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and silyl group-containing low molecular weight silicon divalent tin compounds (such as tin octoate, tin naphthenate, and tin stearate); monoalkyltin compounds (such as monobutyltin compounds (such as monobutyltin tris-octoate and monobutyltin triisopropoxide), and monooctyltin compounds); reaction products or mixtures of amine compounds and organic tin compounds (such as reaction products or mixtures of laurylamine and tin octoate); chelate compounds (such as dibutyltin bisacetylacetonate, dioctyltin bisacetylcetonate, dibutyltin bisethylacetonate, and dioctyltin bisethylacetonate); and tin alcoholates (such as dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, and dioctyltin diethylate).

[0047] Among these, chelate compounds (such as dibutyltin bisacetylacetonate) and tin alcoholates are preferred because they have high activity as silanol condensation catalysts, and dibutyltin dilaurate is preferred because it causes little coloring when added to a curable composition, is inexpensive, and is easily available.

[0048] [1.5. Component E: Polyoxyalkylene polymer having silyl group] Component E is a polyoxyalkylene polymer having a silyl group. Component E is an optional component, and may or may not be included.

[0049] [1.5.1. Main chain of component E] The molecular structure of component E may be linear or branched. It may also be a mixture of molecules having these structures. Among these, a main chain derived from one or more selected from the group consisting of polyoxypropylene diol and polyoxypropylene triol is particularly preferred.

[0050] Examples of the main chain structure of component E include structures represented by the following general formula: 8 is a divalent alkylene group. -R 8 -O-

[0051] The structure represented by the above general formula preferably accounts for 50% by weight or more of the total weight of Component E, more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0052] R 8 The structure of R is not particularly limited as long as it is a divalent alkylene group. 8 is preferably an alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

[0053] Specific examples of the repeating unit represented by the above general formula include -CH2O-, -CH2CHO-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)2O-, and -CH2CH2CH2CH2O-. Among these, the main chain of component E is preferably polypropylene oxide consisting of -CH2CH(CH3)O-. Component E may contain a urethane bond or a urea bond in the main chain structure.

[0054] Commercially available products can also be used as component E. Examples of commercially available polyoxyalkylene polymers include Kaneka MS Polymer (registered trademark) S810, S257, and S327 (all manufactured by Kaneka Corporation); Silyl (registered trademark) SAX220, SAT400, SAX510, SAX520, SAX580, SAX750, and SAT145 (all manufactured by Kaneka Corporation); Exestar (registered trademark) ES-S2410, ES-S2420, and ES-S3630 (all manufactured by AGC Corporation); and HMS-1603 and HMS-1207 (all manufactured by Hua Ma Technology Co., Ltd.).

[0055] [1.5.2. Silyl group of component E] There is no particular limitation on the structure of the silyl group contained in Component E. The silyl group contained in Component E may be the silyl group contained in the (meth)acrylic polymer described in Section [1.1.2.].

[0056] In one embodiment, the structure of the silyl group contained in component E is represented by the following formula: -Si(R 9 ) 3-a (X) a In the formula, one silyl group is R 9 When multiple R are included, they may be the same or different. 9 R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 9 When R is substituted, it may be substituted with a heteroatom-containing group. When multiple silyl groups are present, R 9 may be different for each silyl group. 9 Examples of X include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. When one silyl group contains a plurality of Xs, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group. When a plurality of silyl groups are present, X may be different for each silyl group. An example of the hydrolyzable group is an alkoxy group. a is 1, 2, or 3.

[0057] Examples of the silyl group contained in Component E include a dimethoxysilyl group, a trimethoxysilyl group, a diethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.

[0058] The lower limit of the number of silyl groups introduced into component E is preferably 1.2 or more per molecule, more preferably more than 1.2, and even more preferably 1.5 or more. The upper limit of the number of silyl groups introduced into component E is preferably 4.0 or less per molecule, more preferably 2.5 or less. If the number of silyl groups is within the above range, the curable composition can be given good curability.

[0059] In addition, component E may be a polyoxyalkylene polymer having only one silyl group at the end. Such component E can function as a plasticizer. Component E obtained by the synthesis method described in JP 2021-75722 A may be used.

[0060] The silyl group of component E is preferably located at at least one terminal of the molecule, and more preferably located at both terminals of the molecule. If the silyl group is located at the terminal of the molecule, good elongation can be imparted to the cured product.

[0061] [1.5.3. Other physical properties of component E] The lower limit of the number average molecular weight of component E is preferably 3,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. The upper limit of the number average molecular weight of component E is preferably 70,000 or less, and more preferably 50,000 or less. By using a high molecular weight polymer having a number average molecular weight of 20,000 or more as component E, the elongation of the cured product can be improved.

[0062] The molecular weight distribution of component E is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.2 or less. If the molecular weight distribution is too large, the viscosity of the curable composition increases, and workability tends to decrease.

[0063] Such a component E can be obtained by the methods described in

[0011] to

[0058] of JP2021-55010A.

[0064] [1.6. Other ingredients] The curable composition may contain various additives in addition to the above-mentioned components. By including these additives, it is possible to adjust various physical properties of the curable composition and the cured product. Examples of additives include the following. These additives may be used alone or in combination of two or more.

[0065] (Dehydrating agent) The curable composition may contain a dehydrating agent. Examples of the dehydrating agent include alkoxysilane compounds, synthetic zeolites, activated alumina, silica gel, quicklime, and magnesium oxide. Examples of the alkoxysilane compounds include n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0066] Component E may be a commercially available product or a synthetic product. Commercially available examples of component E include SilQUEST A-171 (Momentive), VTMO (Evonik), and KBM-1003 (Shin-Etsu Chemical Co., Ltd.).

[0067] The content of the dehydrating agent is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total content of components A and E.

[0068] (Adhesion promoter) The curable composition may contain an adhesion promoter. By adding an adhesion promoter, the risk of the sealant peeling off from the adherend such as a siding board can be reduced (this peeling occurs when the joint width changes due to an external force). In addition, there may be cases where the need to use a primer to improve adhesion is eliminated. In this case, simplification of the construction work is expected.

[0069] An example of an adhesion promoter is a silane coupling agent. Specific examples of silane coupling agents include isocyanate group-containing silanes (γ-isocyanate propyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-isocyanate propyl methyl diethoxysilane, γ-isocyanate propyl methyl dimethoxysilane, etc.); amino group-containing silanes (γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyl diethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl diethoxysilane, γ-ureidopropyl trimethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, N-benzyl-γ-aminopropyl trimethoxysilane, silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.); mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-(β-carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, etc.); vinyl-type unsaturated group-containing silanes (vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); isocyanurate silanes (tris(trimethoxysilyl)isocyanurate, etc.).In addition, derivatives obtained by modifying silane coupling agents, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0070] The content of the adhesion promoter is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total content of Components A and E.

[0071] (filling material) The curable composition may contain a filler. Examples of the filler include wood flour, reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, white clay, etc.), fillers (heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red iron oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc oxide, zinc powder, zinc carbonate, shirasu balloon, etc.), and fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0072] The content of the filler is preferably from 5 to 5,000 parts by weight, more preferably from 10 to 2,500 parts by weight, and particularly preferably from 15 to 1,500 parts by weight, relative to 100 parts by weight of the total content of components A and E.

[0073] (Plasticizer) The curable composition may contain a plasticizer. The use of a plasticizer in combination with a filler increases the elongation of the cured product and allows the incorporation of a large amount of filler.

[0074] Examples of plasticizers include phthalates (dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc.); non-aromatic dibasic acid esters (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.); aliphatic esters (butyl oleate, methyl acetylricinoleate, etc.); esters of polyalkylene glycols (diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol esters, etc.); phosphate esters (tricresyl phosphate, tributyl phosphate, etc.); trimellitic acid esters, polystyrenes (polystyrene, poly-α-methylstyrene, etc.); polybutadiene; polybutene; polyisobutylene; butadiene-acrylonitrile; polychloroprene; chlorinated paraffins; hydrocarbon oils (alkyldiphenyls, partially hydrogenated terphenyls, etc.); process oils; polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), derivatives in which the hydroxyl groups of polyether polyols are converted to ester groups, ether groups, etc.); polyester plasticizers obtained from dibasic acids and dihydric alcohols (polyesters obtained from sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.); vinyl polymers (obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods).

[0075] Acrylic plasticizers can be produced by high-temperature continuous polymerization without using solvents and chain transfer agents (see U.S. Pat. No. 4,414,370, JP-A-59-6207, JP-B-5-58005, JP-A-1-313522, and U.S. Pat. No. 5,010,166). Specific examples of acrylic plasticizers include ARUFON UP-1000, UP-1020, and UP-1110 (all from Toagosei Co., Ltd.), JDX-P1000, JDX-P1010, and JDX-P1020 (all from Johnson Polymer Co., Ltd.).

[0076] The content of the plasticizer is preferably 5 to 800 parts by weight, more preferably 10 to 600 parts by weight, and further preferably 10 to 500 parts by weight, relative to 100 parts by weight of the total content of Components A and E.

[0077] (Physical property adjuster) The curable composition may contain a physical property modifier that adjusts the tensile properties of the cured product. By using the physical property modifier, it is possible to increase the hardness of the cured product, or conversely, to decrease the hardness of the cured product and increase the elongation.

[0078] Examples of physical property adjusters include alkylalkoxysilanes (methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilanes (dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, etc.); alkoxysilanes having functional groups (vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); silicone varnishes; and polysiloxanes.

[0079] The content of the physical property adjusting agent is preferably 0.1 to 80 parts by weight, and more preferably 0.1 to 50 parts by weight, relative to 100 parts by weight of the total content of Components A and E.

[0080] (Thixotropic agent (anti-sagging agent)) The curable composition may contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability.

[0081] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

[0082] The content of the thixotropy-imparting agent is preferably 0.1 to 50 parts by weight, and more preferably 0.2 to 25 parts by weight, relative to 100 parts by weight of the total content of Components A and E.

[0083] (light curing substance) The curable composition may contain a photocurable substance. A photocurable substance is a substance that undergoes a chemical change in a short time by the action of light, resulting in a change in physical properties (such as curing). By including a photocurable substance, the tackiness (residual tack) of the surface of the cured product can be reduced. A typical photocurable substance can be cured by leaving it at room temperature for one day in a sunny position indoors (such as near a window). Many photocurable substances are known, such as organic monomers, oligomers, resins, and compositions containing these, and the types are not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azido resins.

[0084] Specific examples of unsaturated acrylic compounds include (meth)acrylic acid esters of low molecular weight alcohols (ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, neopentyl alcohol, etc.); (meth)acrylic acid esters of alcohols obtained by modifying acids (bisphenol A, isocyanuric acid) or low molecular weight alcohols with ethylene oxide, propylene oxide, etc.; (meth)acrylic acid esters (polyether polyols whose main chain is polyether and has hydroxyl groups at the terminals, and vinyl monomers radically polymerized in polyols whose main chain is polyether). polymer polyols obtained by reacting an epoxy resin (such as bisphenol A type or novolak type) with (meth)acrylic acid, polyester polyols having a polyester main chain and hydroxyl groups at the terminals, and polyols having a vinyl or (meth)acrylic polymer main chain and hydroxyl groups in the main chain; epoxy acrylate oligomers obtained by reacting an epoxy resin (such as bisphenol A type or novolak type) with (meth)acrylic acid; and urethane acrylate oligomers having urethane bonds and (meth)acrylic groups in the molecular chain obtained by reacting a polyol, a polyisocyanate, a hydroxyl group-containing (meth)acrylate, etc.

[0085] The content of the photocurable substance is preferably 0.01 to 30 parts by weight, assuming the total content of components A and E to be 100 parts by weight.

[0086] (Antioxidants and Light Stabilizers) The curable composition may contain an antioxidant and / or a light stabilizer. Various antioxidants and light stabilizers are known. For example, the substances described in [Kenichi Saruwatari et al., "Antioxidant Handbook," Taiseisha, 1976] and [Zenjiro Osawa, editor, "Deterioration and Stabilization of Polymer Materials," CMC, 1990, pp. 235-242] can be mentioned.

[0087] Examples of the antioxidant include thioether-based antioxidants such as ADK STAB PEP-36 and ADK STAB AO-23 (all manufactured by ADEKA Corporation); phosphorus-based antioxidants such as Irgafos38, Irgafos168, and IrgafosP-EPQ (all manufactured by Ciba Specialty Chemicals); and hindered phenol-based antioxidants. Among the above, hindered phenol-based antioxidants are preferred.

[0088] Specific examples of hindered phenol-based antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 2,5-di-t-butylhydroquinone. , 2,5-di-t-amylhydroquinone, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl)propionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl)propionate ethyl benzylphosphonate) calcium, tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis[(octylthio)methyl]o-cresol, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-t-butylphenyl)phosphite, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, methyl-3-[3-t-bu ethyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol (molecular weight about 300) condensate, hydroxyphenylbenzotriazole derivatives, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

[0089] Examples of commercially available antioxidants include Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, Nocrac NS-7, and Nocrac DAH (all manufactured by Ouchi Shinko Chemical Industry Co., Ltd.); ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, and ADK STAB AO-37 (all manufactured by ADEKA Corporation); IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Chiba Specialty Chemicals); Sumilizer GM, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical Co., Ltd.).

[0090] Examples of light stabilizers include ultraviolet absorbers (benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, and Tinuvin 213 (all manufactured by Ciba Specialty Chemicals); triazine light stabilizers such as Tinuvin 1577; benzophenone compounds such as CHIMASSORB81; benzoate compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals); and hindered amine compounds). Of the above, hindered amine compounds are preferred.

[0091] Specific examples of the hindered amine compound include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}], N,N'-bis(3aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate.

[0092] Examples of commercially available light stabilizers include Tinuvin 622LD, Tinuvin 144, CHIMASSORB944LD, and CHIMASSORB119FL (all manufactured by Chiba Specialty Chemicals), Adeka STAB LA-52, Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, Adeka STAB LA-68, Adeka STAB LA-82, and Adeka STAB LA-87 (manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (manufactured by Chiba Specialty Chemicals).

[0093] An antioxidant and a light stabilizer may be used in combination. By using them in combination, the effect of each agent may be further improved, and the heat resistance, weather resistance, etc. of the cured product may be improved. For example, in order to improve weather resistance, an ultraviolet absorber and a hindered amine compound (HALS) may be combined. This combination is preferable because it can further improve the effect of each agent.

[0094] The content of the antioxidant and / or light stabilizer is preferably 0.1 to 20 parts by weight, respectively, when the total content of Components A and E is 100 parts by weight.

[0095] 2. Composition of the Curable Composition In the curable composition, the content ratio (weight ratio) of Component A to Component E is preferably Component A:Component E=(1:99) to (99:1), more preferably (10:90) to (90:10), and even more preferably (20:80) to (80:20). By blending the two components in the above range, it is easy to obtain a cured product that has both strength and elongation.

[0096] In the curable composition, the lower limit of the content of Component B is preferably 0.1 parts by weight or more, and more preferably 0.5 parts by weight or more, relative to 100 parts by weight of the total content of Components A and E. The upper limit of the content of Component B is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less, relative to 100 parts by weight of the total content of Components A and E.

[0097] In the curable composition, the lower limit of the content of component C is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1 part by weight or more, relative to 100 parts by weight of the total content of components A and E. The upper limit of the content of component C is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, relative to 100 parts by weight of the total content of components A and E.

[0098] In the curable composition, the lower limit of the content of Component D is preferably 0.1 parts by weight or more, and more preferably 0.5 parts by weight or more, relative to 100 parts by weight of the total content of Components A and E. The upper limit of the content of Component D is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less, relative to 100 parts by weight of the total content of Components A and E.

[0099] 3. Form of the curable composition The curable composition may be one-component or multi-component. A one-component curable composition is one in which all the components are mixed in advance and then sealed and stored. A one-component curable composition is cured by moisture in the environment after use. In a multi-component curable composition, component D and the other components are prepared separately, and the two are mixed at the time of use. A multi-component curable composition may contain other optional agents (such as colorants) in addition to the above components.

[0100] When the curable composition is prepared as a multi-component type, a colorant can be further added when mixing the respective components. The colorant is preferably a paste obtained by mixing, for example, a pigment, a plasticizer, and, if necessary, a filler, from the viewpoint of workability.

[0101] In addition, for multi-component curable compositions, a retarder can be added when mixing the base agent and the curing agent, allowing fine adjustment of the curing speed at the work site.

[0102] [4. Cured product] A cured product can be obtained from the above-mentioned curable composition by a known method. For example, the above-mentioned curable composition can absorb moisture in the surroundings and spontaneously change into a cured product. The use of the cured product is not particularly limited. Examples include architectural and industrial sealants, electrical and electronic component materials (such as solar cell back sealants), electrical insulating materials (such as insulating coating materials for electric wires and cables), pressure sensitive adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, paints, coating materials, sealing materials for can lids, etc., potting agents for electrical and electronic use, films, gaskets, casting materials, various molding materials, artificial marble, rust-proofing and waterproofing sealants for cut parts of wire-reinforced glass or laminated glass, and waterproofing agents.

[0103] In one embodiment, the cured product is in the form of a film. The lower limit of the thickness of the film produced may be 0.1 mm or more, 0.5 mm or more, 1 mm or more, 5 mm or more, or 10 mm or more. The upper limit of the thickness of the film produced may be 100 mm or less, 90 mm or less, 80 mm or less, 70 mm or less, 60 mm or less, or 50 mm or less.

[0104] The film-like cured product can be produced, for example, by applying the curable composition to a substrate and then curing it. The film may be used in a state where it is peeled off from the substrate, or in a state where the substrate and the film are integrated. Examples of applications of the film-like cured product include sealing materials, coating agents, and adhesives.

[0105] [5. Summary] The present invention includes the following aspects. <1> A curable composition comprising the following components A to D: Component A: a (meth)acrylic polymer having a silyl group; Component B: amine; Component C: hydrophobic silica; Component D: Curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, or an XYX triblock structure, The number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is more than 2.0 on average, the content of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block, The molecular weight distribution (Mw / Mn) is 1.8 or less. <2> The above component A is CH2=C(R 1 )COOR 2 (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a group having 9 or more carbon atoms), <1> The curable composition according to claim 1. <3> The number average molecular weight of the component A is 2,000 to 50,000. <1> or <2> The curable composition according to claim 1. <4> The functional group equivalent of the amino group in the component B is 100 g / mol or more. <1> ~ <3> 2. The curable composition according to claim 1 . <5> The component C is fumed silica. <1> ~ <4> 2. The curable composition according to claim 1 . <6> The following component E is further contained. <1> ~ <5> The curable composition according to any one of the preceding claims, Component E: A polyoxyalkylene polymer having a silyl group. <7> <1> ~ <6> 2. A cured product obtained by curing the curable composition according to claim 1. EXAMPLES

[0106] [Measurement method] [Number average molecular weight] The following device was used to measure the number average molecular weight. The measured value is a polystyrene-equivalent molecular weight. Liquid delivery system: HLC-8120GPC (Tosoh Corporation) Column: TSK-GEL H type (Tosoh Corporation) Solvent: THF

[0107] [Terminal silyl group introduction rate] 1 The introduction rate of terminal silyl groups was calculated from the results of H-NMR measurement. 1 The following equipment was used for H-NMR measurements. Measuring instrument: JNM-LA400 (manufactured by JEOL Ltd.) Solvent: CDCl3

[0108] [Tensile properties] A dumbbell-shaped test piece No. 3 was cut from the cured product and the tensile properties were measured in accordance with JIS K 6251. The tensile properties were measured at 23°C and 55% RH using an autograph. The evaluation item was the breaking elongation.

[0109] [Tear strength] A crescent-shaped test piece was obtained from the cured product, and the tear strength was measured in accordance with JIS K 6252. The tear strength was measured using an autograph at 23°C and 55% RH.

[0110] [Silica dispersibility] After storage at 50° C. for 4 weeks, the curable composition was visually inspected to evaluate the dispersibility of silica. The evaluation criteria were as follows: A: No solid-liquid separation has occurred, or even if it has occurred, it is within the acceptable range. B: Unacceptably large solid-liquid separation has occurred.

[0111] [Surface roughness] The surface of the cured product was touched with a finger to evaluate whether it was rough or not. This roughness was considered to be due to insufficient dispersion of the silica. The evaluation criteria were as follows: A: There is no or very little roughness. B: There is a strong feeling of roughness.

[0112] 〔material〕 The following materials were used: Ingredient A The (meth)acrylic polymer (A) having a silyl group obtained in Production Example 1 Component A' ((meth)acrylic polymer having a silyl group other than Component A) Silyl group-containing (meth)acrylic polymer (A') obtained in Comparative Production Example 1 ●Ingredient B Amine (B-1) (DOWSIL BY 16-871, Dow Chemical Company, amino-modified disiloxane, amino functional group equivalent: 130 g / mol) Amine (B-2) (FXJ-8074-D, T&K TOKA Corporation, polymeric polyamine, amino functional group equivalent: 445g / mol) Amine (B-3) (D0473, Tokyo Chemical Industry Co., Ltd., 3-diethylaminopropylamine, amino functional group equivalent: 130g / mol) ●Component C Hydrophobic silica (AEROSIL R972, Nippon Aerosil Co., Ltd., dimethylsilylated silica) ●Component D Curing catalyst (Neostan U-220H, Nitto Kasei Co., Ltd., dibutyltin) ●Ingredient E Polyoxyalkylene polymer having silyl groups (E-1) obtained in Production Example 2 Polyoxyalkylene polymer having silyl groups (E-2) obtained in Production Example 3 Dehydrating agent Dehydrating agents (Silquest A-171, Momentive Performance Materials, vinyltrimethoxysilane) Adhesion promoter Adhesion promoter (KBM-603, Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane)

[0113] [Production Example 1: Synthesis of (meth)acrylic polymer (A) having silyl group] A (meth)acrylic polymer (A) having a silyl group was synthesized according to the following procedure. This polymer corresponds to component A. (preparation) 1. A 2000 mL three-neck flask was prepared. 108 g of ethyl acrylate, 707 g of n-butyl acrylate, and 186 g of octadecyl acrylate were charged into the flask and mixed. This mixture is referred to as "(meth)acrylic acid ester monomer mixture." 2. Another stirring vessel was prepared. 52.7 mg of cupric bromide (CuBr2), 54.4 mg of hexamethyltris(2-aminoethyl)amine (Me6TREN) and 1.82 g of methanol were charged into the stirring vessel and stirred under a nitrogen stream until a homogeneous solution was obtained. This homogeneous solution is referred to as the "copper solution." The amount of copper contained in the copper solution was equivalent to 15 ppm relative to the total amount of the (meth)acrylic acid ester monomer mixture. 3. Another stirring vessel was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid, and 1.6 mL of triethylamine were charged into the stirring vessel and stirred under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is called "ascorbic acid solution." (1st step) 4. 5.60g of ethyl α-bromobutyrate (initiator; 0.029 mol), 20% by weight of the total (meth)acrylic acid ester monomer mixture, 10g of 3-methacryloxypropylmethyldimethoxysilane (0.045 mol; 1.5 molar equivalent to the initiator), 107.68g of methanol, and the total amount of copper solution were added to the stirrer, and stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. The stirrer used at this time was a jacket temperature-adjustable stirrer, and the jacket temperature was set to 45°C. 5. When the temperature in the polymerization system reached 40°C or higher, the ascorbic acid solution was continuously dripped to start the polymerization reaction. The dripping rate of the ascorbic acid solution was set to a rate at which 144 mg of ascorbic acid was added to the polymerization system per hour. 6. The temperature in the polymerization system was monitored and it rose as soon as the dropping of ascorbic acid started, reached a maximum temperature, and then gradually decreased. When the temperature difference between the temperature in the polymerization system and the jacket temperature reached 1°C, a small amount of the reaction solution in the polymerization system was sampled and analyzed by gas chromatography. As a result, 90% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed. (2nd process) 7. The remaining (meth)acrylic acid ester monomer mixture that was not added in the first step (80% by weight of the total amount) was continuously added dropwise to the polymerization system over a period of 90 minutes. The ascorbic acid solution was added dropwise at a rate of 48 mg of ascorbic acid per hour to the polymerization system. Sampling was also carried out sequentially and analyzed by gas chromatography. The polymerization was continued until 88% by weight of the total (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. (3rd step) 8. 11 g of 3-methacryloxypropylmethyldimethoxysilane (0.049 mol; 1.6 molar equivalents relative to the initiator) was added to the polymerization system. The ascorbic acid solution was continuously added dropwise until 98% by weight of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. Thereafter, the addition of the ascorbic acid solution was stopped to terminate the polymerization. 9. The jacket temperature was changed to 80°C, and the solvent was then volatilized. A diaphragm pump was used first, and then a vacuum pump was used. After volatilization was completed, the jacket temperature was cooled to 60°C or less. (purification) 10. 1000g of butyl acetate was added to a jacket temperature-controlled stirrer and mixed with the polymer after devolatilization until a homogeneous solution was obtained. An adsorbent was added to this homogeneous solution and stirred for 1 hour. As the adsorbent, 10g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.) were used. 11. After the stirring was completed, the mixture was filtered through a filter equipped with a bag filter cloth. This resulted in a clear polymer solution. 1.5 g of an antioxidant (Sumilizer GS; Sumitomo Chemical Co., Ltd.) was added to the solution and mixed until homogenous. Thereafter, the solvent was removed from the solution using a diaphragm pump first and then a vacuum pump. In this manner, a (meth)acrylic polymer (A) was obtained.

[0114] The (meth)acrylic polymer (A) was an XYX type block copolymer, with a number average molecular weight of 5,5000, a molecular weight distribution of 1.11, and a number of silyl groups introduced per molecule of 2.1. The X block of the (meth)acrylic polymer (A) had an average of 2.1 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers per copolymer molecule. The Y block of the (meth)acrylic polymer (A) had 1.1% by weight of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers (based on the weight of all repeating units contained in the Y block). The repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block were extremely small. Therefore, when calculated with two significant digits, the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the entire molecule and the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the entire X block were both 2.1.

[0115] Comparative Production Example 1: Synthesis of (meth)acrylic polymer (A') having silyl group A (meth)acrylic polymer having a methyldimethoxysilyl group introduced at the molecular end was synthesized by the following procedure. This polymer does not have a block copolymer structure, so it does not fall under component A. 1. The inside of a stainless steel reaction vessel equipped with a stirrer was deoxidized. 7.7 g of cuprous bromide and 200 g of butyl acrylate were charged into the reaction vessel and stirred while heating. 2. 90g of acetonitrile and 17.6g of diethyl 2,5-dibromoadipate (initiator) were added to a reaction vessel and mixed. The temperature of the mixture was adjusted to about 80°C, and then pentamethyldiethylenetriamine was added to initiate the polymerization reaction. 3. 800 g of butyl acrylate was gradually added to the reaction vessel to proceed with the polymerization reaction. During the polymerization, pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used during the polymerization was 1.4 g. During the polymerization reaction, the internal temperature of the reaction vessel was adjusted to about 80 to about 90°C. 4. When the monomer conversion rate (polymerization reaction rate) reached about 95% or more, the volatile matter was removed by devolatilization under reduced pressure to obtain a concentrated (meth)acrylic polymer. 5. To the polymer concentrate obtained in step 4 was added 200 g of 1,7-octadiene, 260 g of acetonitrile and 3.1 g of pentamethyldiethylenetriamine. 6. The mixture was heated and stirred for several hours while adjusting the internal temperature of the reaction vessel to about 80 to about 90° C. This caused the polymer terminals to react with 1,7-octadiene, and introduced alkenyl groups into the polymer terminals. 7. Acetonitrile and unreacted 1,7-octadiene were removed by volatilization under reduced pressure to obtain a concentrated polymer having alkenyl groups at its ends. 8. The concentrate obtained in step 7 was diluted with butyl acetate, and a filter aid and an adsorbent (Kyoward 700SEN and Kyoward 500SH, Kyowa Chemical Industry Co., Ltd.) were added. 9. The mixture obtained in step 8 was heated and stirred at about 80 to 100° C., and the solid components were filtered off. The filtrate was then concentrated to obtain a crude polymer. 10. A heat stabilizer (Sumilizer GS, Sumitomo Chemical Co., Ltd.) and an adsorbent (Kyoward 700SEN and Kyoward 500SH) were added to the crude polymer. 11. The temperature of the system was increased while removing volatilization under reduced pressure and heating with stirring, and the removal of volatilization under reduced pressure and heating with stirring were continued at about 170 to about 200° C. for several hours. 12. Adsorbents (Kyoward 700SEN and Kyoward 500SH) and butyl acetate in an amount about 10 times by weight relative to the crude polymer product were added, and the mixture was heated and stirred at about 170 to about 200° C. for several hours. 13. The treated liquid obtained in step 12 was further diluted with butyl acetate, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends. 14. 500 g of the polymer obtained in step 13 was mixed with 7.7 g of methyldimethoxysilane, 2.5 g of methyl orthoformate, and 50 mg of platinum catalyst, and heated and stirred at about 100° C. for about 1 hour. As the platinum catalyst, an isopropanol solution of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst was used. 15. Volatile components (unreacted methyldimethoxysilane, etc.) were distilled off under reduced pressure to obtain a (meth)acrylic polymer (A') having methyldimethoxysilyl groups introduced at the molecular terminals.

[0116] The (meth)acrylic polymer (A') had a number average molecular weight of 27,000, a molecular weight distribution of 1.2, and the number of silyl groups introduced per molecule of 2.0.

[0117] [Production Example 2: Synthesis of polyoxyalkylene polymer (E-1) having silyl group] A polyoxyalkylene polymer (E-1) having a methyldimethoxysilyl group introduced at the molecular terminal was synthesized according to the following procedure. 1. 1.2 equivalents of NaOMe relative to the hydroxyl groups at the ends of the polypropylene oxide molecules were added as a methanol solution. The methanol was distilled off. 2. Allyl chloride was added to convert the hydroxyl groups at the ends of the polypropylene oxide molecules to allyl groups, yielding crude allyl-terminated polypropylene oxide. 3. 100 parts by weight of unpurified allyl-terminated polypropylene oxide was mixed with 300 parts by weight of n-hexane and 300 parts by weight of water and stirred. Then, the water was removed by centrifugation. 4. The resulting solution was mixed with 300 parts by weight of water again and stirred. Then, the water was removed by centrifugation. 5. The n-hexane was removed by volatilization under reduced pressure to obtain purified allyl-terminated polypropylene oxide. 6. 1.80 parts by weight of methyldimethoxysilane was added to 100 parts by weight of the purified allyl-terminated polypropylene oxide, and the mixture was reacted at 90°C for 2 hours. As a catalyst, an isopropanol solution of platinum vinylsiloxane complex (platinum content: 3 wt%) was used. The catalyst concentration in the system was 150 ppm. In this way, a polyoxyalkylene polymer (E-1) having a silyl group was obtained.

[0118] The polyoxyalkylene polymer (E-1) was a polypropylene oxide having a methyldimethoxysilyl group introduced at the end, and had a number average molecular weight of about 4,800. 1 When measured by 1 H-NMR, the introduction rate of methyldimethoxysilyl groups at the molecular terminals of the polyoxyalkylene polymer (E-1) was 75%.

[0119] [Production Example 3: Synthesis of polyoxyalkylene polymer (E-2) having silyl group] A polyoxyalkylene polymer (E-2) having a methyldimethoxysilyl group introduced at the molecular terminal was synthesized according to the following procedure. 1. Propylene oxide was polymerized to obtain polypropylene oxide with a number average molecular weight of about 16,400. Polyoxypropylene triol was used as the initiator (molecular weight: about 3,000). Zinc hexacyanocobaltate glyme complex was used as the catalyst. The resulting polypropylene oxide has three hydroxyl groups at the ends of the molecule. 2. The polypropylene oxide obtained in step 1 was treated in accordance with steps 1 to 6 of Production Example 2 to introduce a silyl group, thereby obtaining a polyoxyalkylene polymer (E-2) having a silyl group.

[0120] The resulting polyoxyalkylene polymer (E-2) was a polypropylene oxide having a methyldimethoxysilyl group introduced at the end, and had a number average molecular weight of about 16,400. 1 When measured by 1 H-NMR, the introduction rate of methyldimethoxysilyl groups at the molecular terminals of the polyoxyalkylene polymer (E-2) was 70%.

[0121] [Examples 1 to 4, Comparative Examples 1 and 2] A sample for evaluating physical properties was prepared according to the following procedure. 1. Prepare each ingredient in the amount (unit: g) shown in Table 1. 2. Component A, component B, component C, dehydrating agent, and adhesive agent were placed in a 150cc plastic cup in this order and stirred with a spoon. 3. Components E and D were then added to a plastic cup in that order and stirred with a spoon. 4. Using a planetary stirring / defoaming device (ARE-310, Thinky Corporation), the mixture was stirred (1600 rpm×90 seconds) and degassed (2200 rpm×300 seconds) to obtain a curable composition. 5. The obtained curable composition was cured under conditions of 23°C and 55% RH to obtain a cured product. The physical properties of the obtained cured product were measured. In addition, the obtained curable composition was stored at 50°C for 4 weeks, and then cured in the same manner to obtain a cured product.

[0122] 〔result〕 The results are shown in Table 1. [Table 1]

[0123] As can be seen from Table 1, the curable compositions according to the Examples did not show solid-liquid separation either immediately after production or after storage. On the other hand, the curable compositions according to the Comparative Examples showed solid-liquid separation after storage. In addition, the curable compositions according to the Examples did not show roughness on the surface of the cured product, whether cured immediately after production or after storage. On the other hand, the curable compositions according to the Comparative Examples showed roughness on the surface of the cured product, even when cured immediately after production. From this, it was found that the curable compositions according to the Examples have excellent dispersibility of component C.

[0124] In addition, when comparing the curable compositions according to Examples 2 to 4 immediately after production with those after storage, the changes in the elongation at break and tear strength of the cured products were small (the rate of change was close to 1). On the other hand, when comparing the curable composition according to Comparative Example 1 immediately after production with those after storage, the changes in the elongation at break and tear strength of the cured products were large (the rate of change was far from 1). This shows that the curable composition according to one embodiment of the present invention has excellent stability. [Industrial Applicability]

[0125] The curable composition according to one embodiment of the present invention can be suitably used for pressure sensitive adhesives, sealing materials, adhesives, molding agents, vibration isolators, vibration dampers, soundproofing materials, foam materials, paints, spray materials, and the like.

Claims

1. A curable composition comprising the following components A to D: Component A: a (meth)acrylic polymer having a silyl group; Component B: Amine; Component C: hydrophobic silica; Component D: curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block or an XYX triblock structure, the number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the X block is more than 2.0 on average, a repeating unit derived from a silyl group-containing (meth)acrylic acid ester monomer contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block, The molecular weight distribution (Mw / Mn) is 1.8 or less.

2. The above component A is CH ２ = C(R １ ) COOR ２ (In the formula, R １ is a hydrogen atom or a methyl group, R ２ The curable composition according to claim 1 , comprising 1% by weight or more of repeating units derived from

3. The curable composition according to claim 1, wherein the number average molecular weight of component A is 2,000 to 50,000.

4. The curable composition according to claim 1, wherein the functional group equivalent of the amino group in component B is 100 g / mol or more.

5. The curable composition of claim 1 , wherein component C is a fumed silica.

6. The curable composition of claim 1 further comprising the following component E: Component E: A polyoxyalkylene polymer having a silyl group.

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

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