Curable composition and star polymer

Abstract

To provide a curable composition capable of yielding a cured product that elongates readily under small force and exhibits large elongation before rupture.SOLUTION: A curable composition according to one embodiment of the present invention comprises component A: a (meth)acrylic polymer having a silyl group, component B: polyethyleneimine, and component C: a curing catalyst. The component A is a polymer having a specific structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to curable compositions and star polymers. [Background technology]

[0002] Polymer molecules having silyl groups form siloxane bonds with other polymer molecules through hydrolysis of the silyl groups. This crosslinking reaction results in a rubber-like cured product. Curable compositions containing such polymer molecules are used in sealants, adhesives, paints, etc. (See, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023 / 048155 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned conventional techniques leave room for improvement in the elongation properties of the cured product.

[0005] An object of one aspect of the present invention is to provide a curable composition that can be easily stretched with a small force and can give a cured product that has a large elongation before breaking. [Means for solving the problem]

[0006] A curable composition according to one embodiment of the present invention contains the following components A to C: Component A: a (meth)acrylic polymer having a silyl group; Component B: Polyethyleneimine; Component C: Curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is more than 0.8 on average, The molecular weight distribution (Mw / Mn) is 1.8 or less.

[0007] Another aspect of the present invention provides a star polymer having a core that is polyethyleneimine and one or more arms that are (meth)acrylic polymers having silyl groups: Here, the arm is The molecule has an XY diblock structure having an X block and a Y block, The Y block is bonded to the core at the end thereof, the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is more than 0.8 on average, The molecular weight distribution (Mw / Mn) is 1.8 or less. [Effects of the Invention]

[0008] According to one aspect of the present invention, there is provided a curable composition that gives a cured product that is easily elongated with a small force and has a large elongation before breaking. DETAILED DESCRIPTION OF THE INVENTION

[0009] However, the present invention is not limited to the following embodiments and various modifications may be made within the scope of the claims. Embodiments that combine technical means described in different embodiments are also included in the technical scope of the present invention.

[0010] Unless otherwise specified herein, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic." Unless otherwise specified herein, "silyl group" means "hydrolyzable silyl group." In one embodiment, the silyl group is an alkoxysilyl group.

[0011] In this specification, the "content of polymer components" refers to the total content of components in a curable composition that will participate in the formation of a crosslinked body in the cured product. For example, component A: a (meth)acrylic polymer having a silyl group and component D: a polyoxyalkylene polymer having a silyl group are polymer components. In one embodiment, the "content of polymer components" refers to the total content of component A and component D.

[0012] 1. Components of the Curable Composition A curable composition according to one embodiment of the present invention comprises Component A: a (meth)acrylic polymer having a silyl group, Component B: polyethyleneimine, and Component C: a curing catalyst. The curable composition may optionally comprise Component D: a polyoxyalkylene polymer having a silyl group. The curable composition may optionally comprise components other than Components A to D. Each of these components may comprise only one type, or two or more types.

[0013] [1.1. Component A: (Meth)acrylic Polymer Having Silyl Groups] 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 acid ester monomer. Component A has an X block in which silyl groups appear frequently and a Y block in which silyl groups appear less frequently. Component A can be polymerized, for example, by changing the monomer composition during polymerization.

[0014] [1.1.1. Structure of (meth)acrylic polymer] The (meth)acrylic polymer has an X block and a Y block, and contains an XY diblock structure in the molecule. The overall molecular structure of the (meth)acrylic polymer is not particularly limited as long as it contains an XY diblock structure, and may be, for example, an XYXY tetrablock structure.

[0015] The ratio of X / Y in the (meth)acrylic polymer is preferably from (5 / 95) to (60 / 40), and more preferably from (15 / 85) to (40 / 60).

[0016] In one embodiment, the (meth)acrylic polymer molecule has an XY diblock structure. In a molecule with an 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 (where 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.

[0017] The (meth)acrylic polymer has repeating units derived from silyl group-containing (meth)acrylic ester monomers. The repeating units derived from silyl group-containing (meth)acrylic ester monomers are contained in a relatively large amount in the X block. The number of repeating units derived from silyl group-containing (meth)acrylic ester monomers contained in the X block is, on average, more than 0.8. When the (meth)acrylic polymer has two or more X blocks in one molecule, the total number of repeating units derived from silyl group-containing (meth)acrylic ester monomers contained in the multiple X blocks is, on average, more than 0.8. On the other hand, the number of repeating units derived from silyl group-containing (meth)acrylic ester monomers contained in the Y block may be 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block.

[0018] The number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is, on average, more than 0.8, preferably 0.9 or more, more preferably 1.0 or more, even more preferably 1.1 or more, and particularly preferably 1.2 or more. Similarly, the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is preferably 0.5 wt% or more, more preferably 2.0 wt% or more, and even more preferably 3.0 wt% or more, based on the weight of all repeating units contained in the X block. The upper limit of the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is preferably 90 wt% or less, more preferably 60 wt% or less, and even more preferably 30 wt% or less.

[0019] The upper limit of the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block may be less than 5 wt %, preferably 4 wt % or less, more preferably 3 wt % or less, even more preferably 2 wt % or less, and particularly preferably 1 wt % or less, based on the weight of all repeating units contained in the Y block. The lower limit of the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is preferably 0 wt % or more, more preferably more than 0 wt %, based on the weight of all repeating units contained in the Y block.

[0020] The number of silyl groups introduced into the (meth)acrylic polymer is, on average, more than 0.8, preferably 0.9 or more, more preferably 1.0 or more, even more preferably 1.1 or more, and particularly preferably 1.2 or more, per molecule. The upper limit of the number of silyl groups introduced into the (meth)acrylic polymer is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 4.0 or less, and particularly preferably 2.0 or less. When the number of silyl groups is within the above range, a curable composition and a cured product with good physical properties can be obtained.

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

[0022] The content of repeating units derived from (meth)acrylic monomers with long side chains is preferably 1% by weight or more of all structural units contained in the (meth)acrylic polymer. A (meth)acrylic polymer containing such repeating units may improve the physical properties of the resulting cured product. The upper limit of the content of repeating units derived from (meth)acrylic monomers with long side chains 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 the (meth)acrylic polymer will not increase excessively.

[0023] Examples of (meth)acrylic monomers having long side chains 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 polymer having high compatibility with polyoxyalkylene polymers 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 in which the carbon number is 8 or less. 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 are inexpensive to procure and are suitable for the purpose of reducing the production cost of the (meth)acrylic polymer.

[0027] Furthermore, from the viewpoint of glass transition temperature, one or more types selected from n-butyl acrylate and 2-ethylhexyl acrylate are preferred. (Meth)acrylic polymers obtained from these monomers have low glass transition temperatures and low polymer viscosities. Therefore, a curable composition that can be easily used in low-temperature environments can be obtained.

[0028] The (meth)acrylic polymer may have repeating units derived from monomers other than (meth)acrylic acid ester monomers. In the (meth)acrylic polymer, the proportion of repeating units derived from (meth)acrylic acid ester monomers 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 the (meth)acrylic polymer.

[0029] [1.1.2. Silyl Groups in (Meth)acrylic Polymers] The silyl group contained in the (meth)acrylic polymer 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 (1): -[Si(R 3 ) 2-b (Y) b O] m -Si(R 4 ) 3-a (Y) a ···(1)

[0030] In formula (1), 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 4When 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 one silyl group contains multiple Xs, they may be the same or different. When one molecule of the (meth)acrylic polymer contains multiple 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, provided that 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, and an example thereof 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 one or more selected from the group consisting of hydrogen, a methyl group, and an ethyl group. 6 and / or R 7 When there are a plurality of m, 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-methacryloxypropylmethyldimethoxysilane, 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 at least 2,000, more preferably at least 10,000, and even more preferably at least 15,000. The upper limit of the number average molecular weight of Component A is preferably at most 50,000, more preferably at most 30,000, and even more preferably at most 20,000. 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, ensuring sufficient workability.

[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. When the molecular weight distribution is within the above range, the viscosity of the polymer tends to decrease and 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). GPC measurements use chloroform as the mobile phase and a polystyrene gel column as the stationary phase. The molecular weights obtained by measurement are molecular weights converted to standard polystyrene.

[0037] [1.1.4. Manufacturing method of component A] The polymerization method for component A is not particularly limited, and known polymerization methods can be used (radical polymerization, cationic polymerization, anionic polymerization, etc.). The polymerization method known as SGO (Solid Grade Oligomer; high-temperature continuous bulk polymerization) is preferred because it is a method for obtaining component A with almost no need for polymerization solvents, polymerization initiators, chain transfer agents, etc. Living polymerization is preferred because it allows for the introduction of functional groups near the ends of polymer molecules and enables the synthesis of component A with a narrow molecular weight distribution. Examples of living polymerization methods include living radical polymerization, living cationic polymerization, and living anionic polymerization, and among these, living radical polymerization is suitable for the 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 Review, Vol. 68, pp. 223-231 (2011); JP Patent Publication No. 2014-111798) Reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) Nitroxy radical method (NMP method) Polymerization method using organotellurium compounds (TERP method) Polymerization method using organoantimony compounds (SBRP method) Polymerization method using organobismuth compounds (BIRP method) Iodine transfer polymerization

[0038] An example of a method for introducing silyl groups into Component A is the method described in JP 2018-162394 A. The method disclosed in this document involves copolymerizing a (meth)acrylic acid ester monomer with a silyl group-containing (meth)acrylic acid ester monomer to introduce silyl groups into Component A. More specifically, the amount of silyl group-containing (meth)acrylic acid ester monomer added is controlled depending on the stage of progress of the living polymerization, thereby introducing silyl groups near the terminals of the Component A molecules. Component A obtained by these methods may have silyl groups locally at or near the terminals of the molecules.

[0039] [1.2. Component B: Polyethyleneimine] Component B is polyethyleneimine. Polyethyleneimine is a polymer containing many repeating units of -(CH2-CH2-NH)- and is obtained by ring-opening polymerization of aziridine. From the imine contained in -(CH2-CH2-NH)-, further -(CH2-CH2-NH)- can be extended. Therefore, component B may be linear or branched.

[0040] The structure represented by -(CH2-CH2-NH)- (including a structure in which -(CH2-CH2-NH)- further branches from an imine) preferably accounts for 50% by weight or more of the total weight of component C, more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0041] The lower limit of the number average molecular weight of Component B is preferably at least 300, more preferably at least 400, and even more preferably at least 500. The upper limit of the number average molecular weight of Component B is preferably at most 30,000, more preferably at most 20,000, and even more preferably at most 10,000.

[0042] The lower limit of the amine value of Component B is preferably 10 or more, more preferably 15 or more, and even more preferably 18 or more. The upper limit of the amine value of Component B is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.

[0043] The lower limit of the pH of component B is preferably 8 or higher, more preferably 9 or higher, and even more preferably 10 or higher. The upper limit of the pH of component B is preferably 13.5 or lower, more preferably 12.5 or lower, and even more preferably 12 or lower. The pH of component B referred to here is the pH of a 5 wt % aqueous solution.

[0044] If component B satisfies the above parameter range, it can be said to have an appropriate size and secondary amines at an appropriate density. Therefore, when it becomes the core of the star polymer described below, the entire molecule can be made to an appropriate size and an appropriate number of arms can be bonded. This can improve the elongation performance of the cured product.

[0045] [1.3. Component C: Curing catalyst] Component C is a curing catalyst. Examples of the curing catalyst include organometallic catalysts such as tin-based curing catalysts. Specific examples of tin-based curing catalysts 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, mixtures of dibutyltin oxide and phthalate esters, 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); monoalkyltins (such as monobutyltin compounds (such as monobutyltin trisoctoate and monobutyltin triisopropoxide), and monooctyltin compounds); reaction products or mixtures of amine compounds and organotin 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).

[0046] Component C may be an organometallic catalyst other than a tin-based curing catalyst. Examples of such component C include titanium tetra(i-propoxide), titanium tetra(n-butoxide), titanium tetra(2-ethylhexoxide), titanium tetra(tert-butoxide), titanium tetra(stearylalkoxide), zirconium tetra(n-propoxide), zirconium tetra(n-butoxide), bismuth tris(2-ethylhexanoate), bismuth neodecanoate, bismuth tetramethylheptanedioate, and bismuth naphthenate.

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

[0048] [1.4. Component D: Polyoxyalkylene Polymer Having Silyl Groups] [1.4.1. Main chain of component D] The molecular structure of component D may be linear or branched. Alternatively, it may 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 diols and polyoxypropylene triols is particularly preferred.

[0049] Examples of the main chain structure of component D include structures represented by the following general formula: 8 is a divalent alkylene group. -R 8 -O-

[0050] The structure represented by the above general formula preferably accounts for 50% by weight or more of the total weight of component D, more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0051] 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.

[0052] Specific examples of the repeating unit represented by the above general formula include -CHO-, -CHCHO-, -CHCH(CH)O-, -CHCH(CH)O-, -CHC(CH)O-, and -CHCHCHCHO-. Of these, it is preferred that the main chain of component D is polypropylene oxide consisting of -CHCH(CH)O-.

[0053] [1.4.2. Silyl Group of Component D] Component D may have, for example, the silyl group described in Section [1.1.2]. In one embodiment, the silyl group contained in Component D is represented by the following general formula: -Si(R 9 ) 3-a (X) a

[0054] In the formula, R 9 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, and more preferably 1 to 5. R 9 may be substituted with a heteroatom-containing group. Examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, and halogen atoms (fluorine, chlorine, bromine, and iodine). In one embodiment, R 9 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. 9 When multiple R are included, they may be the same or different. 9 may be different for each silyl group contained in component D.

[0055] In the formula, X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an oxime group, and an acetoxy group. In one embodiment, X is a hydroxyl group, a methoxy group, an ethoxy group, or an isopropoxy group. When one silyl group contains multiple Xs, they may be the same or different. X may be different for each silyl group contained in component D.

[0056] In the formula, a is 1, 2, or 3.

[0057] Examples of the silyl group contained in Component D 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 number of silyl groups introduced into Component D may be more than 1.0 on average for the entire molecule, and is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more. The upper limit of the number of silyl groups introduced into Component D is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and particularly preferably 2.0 or less. If the number of silyl groups is within the above range, a curable composition and cured product with good physical properties can be obtained.

[0059] The silyl group of Component D may be contained in the main chain or in a side chain. The silyl group of Component D may be located in the middle of the molecular chain or at the terminal of the molecular chain. Preferably, the silyl group is located at two or more terminals of the molecular chain.

[0060] Component D may be a commercially available product. Examples of commercially available Component D include Kaneka MS Polymer (registered trademark) SAT400, SAT350, S303H, S203H, and SAX220 (Kaneka Corporation).

[0061] [1.4.3. Physical properties of component D] The lower limit of the number average molecular weight of Component D is preferably 2,000 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 D is preferably 50,000 or less, and more preferably 30,000 or less.

[0062] The molecular weight distribution of component D may be 1.8 or less, 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 tends to increase, reducing workability.

[0063] [1.4.4. Manufacturing Method of Component D] Component D can be obtained by the methods described in

[0011] to

[0058] of JP 2021-55010 A.

[0064] [1.5. Other Ingredients] The curable composition may contain various additives in addition to the above-mentioned components. By adding these additives, various physical properties of the curable composition and the cured product can be adjusted. Examples of additives include the following. These additives may be used alone or in combination of two or more.

[0065] (adhesion imparting agent) The curable composition may contain an adhesion promoter. Addition of an adhesion promoter can reduce the risk of the sealant peeling off from an adherend such as a siding board (this peeling occurs when the joint width changes due to external forces). It may also eliminate the need to use a primer to improve adhesion. In this case, simplification of the application process is expected.

[0066] Examples of adhesion promoters include silane coupling agents. Specific examples of silane coupling agents include isocyanate group-containing silanes (γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, etc.); amino group-containing silanes (γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, 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.

[0067] The content of the adhesion promoter is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer component.

[0068] (filling material) The curable composition may contain a filler. Examples of fillers include wood flour, reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell flour, rice husk flour, graphite, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrated silicic acid, etc.), carbon black, etc.), fillers (ground 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 white, zinc powder, zinc carbonate, shirasu balloon, etc.), and fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0069] The content of the filler is preferably 5 to 5000 parts by weight, more preferably 10 to 2500 parts by weight, and particularly preferably 15 to 1500 parts by weight, based on 100 parts by weight of the content of the polymer component.

[0070] (Physical property adjuster) The curable composition may contain a physical property modifier that adjusts the tensile properties of the cured product. By using a 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.

[0071] 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.

[0072] The content of the physical property adjuster is preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the polymer component content.

[0073] (thixotropy imparting agent (anti-sagging agent)) The curable composition may contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability.

[0074] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps not included in the above-mentioned component F (calcium stearate, aluminum stearate, barium stearate, etc.).

[0075] 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, based on 100 parts by weight of the content of the polymer component.

[0076] (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 period of time due to the action of light, resulting in a change in physical properties (such as curing). By incorporating a photocurable substance, the stickiness (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 location indoors (such as near a window). Many photocurable substances are known, including organic monomers, oligomers, resins, and compositions containing these, and the type is not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azide resins.

[0077] 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 a polyether and has a hydroxyl group at the end, and polyols whose main chain is a polyether, obtained by radical polymerization of vinyl monomers in such polyols). polymer polyols obtained by reacting an epoxy resin (such as bisphenol A or novolac) with (meth)acrylic acid; and urethane acrylate oligomers having urethane bonds and (meth)acrylic groups in the molecular chain, which are obtained by reacting a polyol, polyisocyanate, hydroxyl group-containing (meth)acrylate, etc.

[0078] The content of the photocurable substance is preferably 0.01 to 30 parts by weight, assuming that the content of the polymer component is 100 parts by weight.

[0079] (antioxidants and light stabilizers) The curable composition may contain an antioxidant and / or a light stabilizer. Various antioxidants and light stabilizers are known. Examples include substances described in [Kenichi Saruwatari et al., "Antioxidant Handbook," Taiseisha, 1976] and [Zenjiro Osawa, editor, "Degradation and Stabilization of Polymer Materials," CMC, 1990, pp. 235-242].

[0080] Examples of antioxidants 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 Irgafos 38, Irgafos 168, and Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals); and hindered phenol-based antioxidants. Of the above, hindered phenol-based antioxidants are preferred.

[0081] Specific examples of hindered phenol 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 ethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)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) 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-butyl Examples of suitable hydroxybenzoates include 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and 2,4-di-t-butylphenyl-4-hydroxybenzoate.

[0082] 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-19. 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.).

[0083] 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.

[0084] 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 succinic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester.

[0085] 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 (all manufactured by ADEKA Corporation), and Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (all manufactured by Chiba Specialty Chemicals).

[0086] An antioxidant and a light stabilizer may be used in combination. By using these in combination, the effects of each agent may be further improved, and the heat resistance, weather resistance, etc. of the cured product may be improved. For example, to improve weather resistance, an ultraviolet absorber and a hindered amine-based compound (HALS) may be combined. This combination is preferable because it can further improve the effects of each agent.

[0087] The content of the antioxidant and / or light stabilizer is preferably 0.1 to 20 parts by weight, respectively, based on 100 parts by weight of the content of the polymer component.

[0088] [2. Star-shaped polymers] One aspect of the present invention is a star polymer having a core and one or more arms. The core is polyethyleneimine and corresponds to component B. The arms are (meth)acrylic polymers and correspond to component A.

[0089] When Component A is produced by the production method disclosed in JP 2018-162394 A (see also the Production Examples of the present application), halogens derived from the initiator remain at the reaction terminals of the polymer molecules. Therefore, in the curable composition, at least a portion of the terminal halogens of Component A react with at least a portion of the secondary amines of Component B, potentially forming bonds between them. Component B contains many secondary amines, each of which has the potential to react with the terminal halogens of Component A, so the reaction product as a whole becomes a star polymer.

[0090] In star polymers, the Y block ends of the arms are bonded to the core. In other words, the X block, which has a high density of silyl groups, is located distal to the core. This structure of star polymers can improve the elongation properties of the cured product.

[0091] To form a star polymer with such a structure, a halogen remains at the terminal of the Y block of Component A. To synthesize such Component A, the X block may be synthesized in the first half of the synthesis, and the Y block may be synthesized in the second half of the synthesis (see Production Example 1 of the present application for a more specific example).

[0092] 3. Composition of the curable composition In the curable composition, the lower limit of the content of component B may be 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more, relative to 100 parts by weight of the polymer component content. The upper limit of the content of component B may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less, relative to 100 parts by weight of the polymer component content.

[0093] In the curable composition, the lower limit of the content of component C may be 0.1 parts by weight or more or 0.5 parts by weight or more, based on 100 parts by weight of the polymer component. The upper limit of the content of component E may be 8 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less, based on 100 parts by weight of the polymer component.

[0094] In the curable composition, the lower limit of the content ratio (weight ratio) of Component A / Component D may be 10 / 90 or more, 20 / 80 or more, or 30 / 70 or more. The upper limit of the content ratio (weight ratio) of Component A / Component D may be 90 / 10 or less, 80 / 20 or less, or 70 / 30 or less.

[0095] 4. Form of curable composition The curable composition containing components A to D may be a one-component type or a multi-component type. A one-component curable composition is one in which all of the components are blended in advance and then sealed and stored. A one-component curable composition cures after use due to moisture in the environment. In a multi-component curable composition, the curing catalyst and the other components are prepared separately and then mixed together at the time of use. A multi-component curable composition may contain other optional agents (such as a colorant) in addition to the above components.

[0096] When the curable composition is prepared as a multi-component type, a colorant can be further added when mixing the 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.

[0097] Furthermore, in the case of multi-component curable compositions, a retarder can be added when mixing the base resin and curing agent, which allows fine adjustment of the curing speed at the work site.

[0098] [5. Cured product] A cured product can be obtained from the above-described curable composition by a known method. For example, the above-described curable composition can absorb ambient moisture and spontaneously change into a cured product. The uses of the cured product are not particularly limited. Examples include architectural and industrial sealants, electrical and electronic component materials (such as solar cell backside 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, sealants for can lids and the like, potting agents for electrical and electronic applications, films, gaskets, casting materials, various molding materials, artificial marble, anti-rust and waterproof sealants for cut portions of wire-reinforced glass or laminated glass, and waterproofing agents.

[0099] In one embodiment, the cured product is in the form of a film. The lower limit of the thickness of the produced film 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 produced film 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.

[0100] A 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 from the substrate, or in a state where the substrate and the film are integrated. Examples of uses of the film-like cured product include sealing materials, coating agents, and adhesives.

[0101] [6. Summary] The present invention includes the following aspects. <1> A curable composition comprising the following components A to C: Component A: a (meth)acrylic polymer having a silyl group; Component B: Polyethyleneimine; Component C: Curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is more than 0.8 on average, The molecular weight distribution (Mw / Mn) is 1.8 or less. <2> 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; <1> The curable composition according to claim 1. <3> 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> or <2> The curable composition according to claim 1. <4> The number average molecular weight of the component A is 2,000 to 50,000. <1> ~ <3> The curable composition according to any one of the preceding claims. <5> The number average molecular weight of the component B is 300 to 30,000. <1> ~ <4> The curable composition according to any one of the preceding claims. <6> Component C is an organometallic catalyst. <1> ~ <5> The curable composition according to any one of the preceding claims. <7> Further containing the following component D: <1> ~ <6> The curable composition according to any one of the preceding claims: Component D: a polyoxyalkylene polymer having a silyl group; Here, the component D is represented by the formula: -Si(R 9 ) 3-a (X) a and a silyl group represented by the formula: During the ceremony, R 9 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; R 9 may be substituted with a heteroatom-containing group; One silyl group has R 9If multiple are included, they may be the same or different; R 9 may be different for each silyl group; X represents a hydroxyl group or a hydrolyzable group; When one silyl group contains a plurality of Xs, they may be the same or different. X may be different for each silyl group; a is 1, 2 or 3. <8> <1> ~ <7> A cured product obtained by curing the curable composition according to any one of the above items. <9> A star polymer having a core which is polyethyleneimine and one or more arms which are (meth)acrylic polymers having silyl groups: Here, the arm is The molecule has an XY diblock structure having an X block and a Y block, The Y block is bonded to the core at the end thereof, the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is more than 0.8 on average, The molecular weight distribution (Mw / Mn) is 1.8 or less. [Example]

[0102] [Measurement method] [Number average molecular weight] The following apparatus was used to measure the number average molecular weight. The measured value is a molecular weight converted into polystyrene. Liquid delivery system: e2695 (Waters) Column: Shodex GPC K-804, K-802.5 (Showa Denko K.K.) Solvent: Chloroform ·Measurement temperature: 40℃

[0103] [Terminal silyl group introduction rate] 1 The introduction rate of terminal silyl groups was calculated from the results of H-NMR measurement. 1The following equipment was used for H-NMR measurements. Measuring instrument: JNM-LA400 (JEOL Ltd.) Solvent: CDCl3

[0104] [Tensile properties of cured product] The curable composition was cured at 23°C and 50% RH to obtain a cured product. According to JIS K 6251, a No. 3 dumbbell-shaped test piece was obtained from the cured product, and the tensile properties were measured. The tensile properties were measured using an autograph at 23°C and 55% RH. The evaluation items were the stress at 100% elongation and the stress at break.

[0105] 〔material〕 Ingredient A (Meth)acrylic polymer (A) having a silyl group (obtained in Production Example 1) Component A' (a (meth)acrylic polymer having a silyl group other than Component A) (Meth)acrylic polymer (A') having a silyl group (obtained in Comparative Production Example 1) ●Ingredient B Polyethyleneimine (B-1) (number average molecular weight: 600, pH: 10-12 (as a 5% by weight aqueous solution), amine value: 21) Polyethyleneimine (B-2) (number average molecular weight: 1800, pH: 10-12 (as a 5% by weight aqueous solution), amine value: 21) ●Component C Curing catalyst (Neostan U-220H, Nitto Kasei Co., Ltd., dibutyltin) ●Component D Silyl group-containing polyoxyalkylene polymer (D) (obtained in Production Example 2) Dehydrating agent Dehydrating agents (Silquest A-171, Momentive Performance Materials, vinyltrimethoxysilane) Adhesion promoter Adhesion promoters (Silquest A-187 Silane, Momentive Performance Materials, γ-glycidoxypropyltrimethoxysilane)

[0106] [Production Example 1: Synthesis of (meth)acrylic polymer (A)] The (meth)acrylic polymer (A) was synthesized by the following procedure. The (meth)acrylic polymer (A) is an XY diblock copolymer. In the (meth)acrylic polymer (A), a bromine atom is located at the reactive end at the end of the Y block. (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 a "(meth)acrylic acid ester monomer mixture." 2. Another stirring vessel was prepared. 18 mg of cupric bromide (CuBr2), 18 mg of hexamethyltris(2-aminoethyl)amine (Me6TREN), and 0.61 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 copper content of the copper solution was equivalent to 5 ppm relative to the total amount of the (meth)acrylic acid ester monomer mixture. 3. Another stirring vessel was prepared. 35 mL of methanol, 1 g of ascorbic acid, and 1.6 mL of triethylamine were placed in the stirring vessel and stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution." (1st step) 4. 5.8 g of ethyl α-bromobutyrate (initiator), 20 wt% of the total (meth)acrylic acid ester monomer mixture, 13.9 g of 3-methacryloxypropylmethyldimethoxysilane, 154 g of methanol, and the total copper solution were added to a mixer and stirred for 30 minutes to obtain a homogeneous solution. The mixer used here was a jacket temperature-controlled mixer, and the jacket temperature was set to 55°C. 5. When the temperature in the polymerization system reached 50°C or higher, the ascorbic acid solution was continuously added dropwise to initiate the polymerization reaction. The rate at which the ascorbic acid solution was added was set at 80 mg per hour. 6. When the temperature inside the polymerization system was monitored, it rose simultaneously with the start of the dropwise addition of ascorbic acid, reached its maximum temperature, and then gradually decreased. When the temperature difference between the temperature inside the polymerization system and the jacket temperature reached 2°C, a small amount of the reaction solution inside the polymerization system was sampled and analyzed by gas chromatography. The results showed that 81% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed. (2nd process) 7. The remainder of the (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. After the dropwise addition of the (meth)acrylic acid ester monomer mixture was completed, samples were taken sequentially and analyzed by gas chromatography. Polymerization was continued until 98% by weight of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. 8. The jacket temperature was changed to 80°C, and the solvent was then volatilized. A diaphragm pump was used first, followed by a vacuum pump. After volatilization was complete, the jacket temperature was cooled to 60°C or below. (purification) 9. 1000 g of butyl acetate was added to a jacket temperature-controlled stirrer and mixed with the polymer after devolatilization until a homogeneous solution was formed. An adsorbent was added to this homogeneous solution and stirred for 1 hour. The adsorbents used were 10 g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10 g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.). 10. After stirring, the resulting mixture was filtered through a filter equipped with a bag filter cloth. This resulted in a clear polymer solution. The solvent was then removed from the solution using a diaphragm pump and then a vacuum pump. Thus, a (meth)acrylic polymer (A) was obtained.

[0107] The (meth)acrylic polymer (A) had a number average molecular weight of 40,000 and a molecular weight distribution of 1.20. The number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block of the (meth)acrylic polymer (A) was 1.0 on average. The proportion of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block of the (meth)acrylic polymer (A) was 1.1% by weight, with the total weight of all repeating units contained in the Y block being 100% by weight.

[0108] Comparative Production Example 1: Synthesis of (meth)acrylic polymer (A') The (meth)acrylic polymer (A') was synthesized by the following procedure. The (meth)acrylic polymer (A') is an XYX diblock copolymer. In the (meth)acrylic polymer (A'), a bromine atom is located at the reactive end at the end of one of the X blocks. (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 a "(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 copper content of 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 placed in the stirring vessel and stirred under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution." (1st step) 4. 5.60 g of ethyl α-bromobutyrate (initiator; 0.029 mol), 20 wt% of the total (meth)acrylic acid ester monomer mixture, 10 g of 3-methacryloxypropylmethyldimethoxysilane (0.045 mol; 1.5 molar equivalents relative to the initiator), 107.68 g of methanol, and the total copper solution were added to a mixer, and stirred under a nitrogen stream for 30 minutes to obtain a homogeneous solution. The mixer used here was a jacket temperature-controlled mixer, 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 added dropwise to initiate the polymerization reaction. The rate at which the ascorbic acid solution was added was set to 144 mg per hour. 6. When the temperature inside the polymerization system was monitored, it rose simultaneously with the start of the dropwise addition of ascorbic acid, reached its maximum temperature, and then gradually decreased. When the temperature difference between the temperature inside the polymerization system and the jacket temperature reached 1°C, a small amount of the reaction solution inside the polymerization system was sampled and analyzed by gas chromatography. The results showed that 90% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed. (2nd process) 7. The remaining (80 wt. % of the total amount) of the (meth)acrylic acid ester monomer mixture not added in the first step 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 wt. % of the total amount of the (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 wt% of the total (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. The addition of the ascorbic acid solution was then stopped, and the polymerization was terminated. 9. The jacket temperature was changed to 80°C, and the solvent was then devolatilized. A diaphragm pump was used first, followed by a vacuum pump. After devolatilization was complete, the jacket temperature was cooled to 60°C or below. (purification) 10. 1000 g of butyl acetate was added to a jacket temperature-controlled stirrer and mixed with the polymer after devolatilization until a homogeneous solution was formed. An adsorbent was added to this homogeneous solution and stirred for 1 hour. The adsorbents used were 10 g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10 g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.). 11. After stirring, the resulting 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 homogeneous. The solvent was then removed from the solution using a diaphragm pump first and then a vacuum pump. In this way, a (meth)acrylic polymer (A') was obtained.

[0109] The (meth)acrylic polymer (A') had a number average molecular weight of 55,000 and a molecular weight distribution of 1.11. The number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block of the (meth)acrylic polymer (A'), calculated by adding up the numbers contained in both X blocks, was an average of 2.1. The proportion of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block of the (meth)acrylic polymer (A') was 1.1% by weight, with the total weight of all repeating units contained in the Y block being 100% by weight.

[0110] [Production Example 3: Synthesis of polyoxyalkylene polymer (C) having silyl groups] 1. Propylene oxide was polymerized to obtain polyoxypropylene with hydroxyl groups at both ends. This polyoxypropylene had a number-average molecular weight of 20,900 and a molecular weight distribution of 1.23. Polyoxypropylene glycol (number-average molecular weight: approximately 4,500) was used as the initiator. Zinc hexacyanocobaltate glyme complex was used as the catalyst. 2. 1.0 molar equivalent of NaOMe relative to the hydroxyl groups of polyoxypropylene was added as a 28% methanol solution. The mixture was devolatilized under vacuum at 140°C to distill off the methanol. 3. 0.3 molar equivalents of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the mixture was reacted at 140°C for 2 hours. 4. 1.5 molar equivalents of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups at 130° C. Unreacted allyl chloride was removed by volatilization under reduced pressure. 5. After removing remaining impurities such as metal salts, polyoxypropylene with multiple allyl groups at both ends was obtained. The allyl-terminated polyoxypropylene had an average of 1.3 allyl groups per end. 6. 1.4 parts by weight of dimethoxymethylsilane and 50 ppm of catalyst were added to 100 parts by weight of allyl-terminated polyoxypropylene, and the mixture was reacted at 90°C for 2 hours. Unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxyalkylene polymer (C). An isopropanol solution of platinum divinyldisiloxane complex (platinum content: 3% by weight) was used as the catalyst.

[0111] The polyoxyalkylene polymer (C) was a polyoxypropylene having a plurality of dimethoxymethylsilyl groups at both ends, and had a number average molecular weight of about 22,000. 1 When measured by 1 H-NMR, the number of silyl groups possessed by the polyoxyalkylene polymer (C) was found to be 1.4 on average per molecule.

[0112] [Examples 1 to 6, Comparative Examples 1 and 2] Samples for evaluating physical properties were prepared according to the following procedure. 1. Each component was prepared in the amount (unit: g) shown in Table 1. 2. Each ingredient was placed in a 150cc plastic cup and stirred with a spoon. 3. Using a planetary stirring and degassing device (ARE-310, Thinky Corporation), the mixture was stirred (1600 rpm x 90 seconds) and degassed (2200 rpm x 300 seconds) to obtain a curable composition. 4. The obtained curable composition was cured under conditions of 23°C and 55% RH to obtain a cured product.

[0113] 〔result〕 The results are shown in Table 1. [Table 1]

[0114] As can be seen from Table 1, the cured products according to the examples (containing component B) had significantly different tensile properties compared to the cured products according to the comparative examples (not containing component B). Specifically, the stress at 100% elongation was significantly smaller, and the elongation at break was significantly larger. This suggests that the curable composition according to one aspect of the present invention provides a cured product that is easily elongated with a small force and has a large elongation before breaking. [Industrial Applicability]

[0115] The present invention can be used for curable compositions and the like.

Claims

1. A curable composition comprising the following components A to C: Component A: a (meth)acrylic polymer having a silyl group; Component B: polyethyleneimine; Component C: curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block, the X block contains an average of more than 0.8 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers, The molecular weight distribution (Mw / Mn) is 1.8 or less.

2. 2. The curable composition according to claim 1, wherein 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.

3. The component A is CH ２ = C(R １ ) COOR ２ (In the formula, R １ is a hydrogen atom or a methyl group, and R ２ The curable composition according to claim 1 , wherein the repeating units derived from the group consisting of 1 to 10 carbon atoms are 1 to 10 carbon atoms.

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

5. 2. The curable composition according to claim 1, wherein the number average molecular weight of component B is 300 to 30,000.

6. The curable composition of claim 1 , wherein component C is an organometallic catalyst.

7. The curable composition of claim 1 further comprising the following component D: Component D: a polyoxyalkylene polymer having a silyl group; Here, the component D is a compound represented by the formula: -Si(R ９ ) ３－ａ (X) ａ The silyl group has the formula: During the ceremony, R ９ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; R ９ may be substituted with a heteroatom-containing group; One silyl group has R ９ When multiple are included, they may be the same or different; R ９ may be different for each silyl group; X represents a hydroxyl group or a hydrolyzable group; When one silyl group contains a plurality of Xs, they may be the same or different. X may be different for each silyl group; a is 1, 2 or 3.

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

9. A star polymer having a core which is polyethyleneimine and one or more arms which are (meth)acrylic polymers having silyl groups: Here, the arm is The molecule has an XY diblock structure having an X block and a Y block, the Y block is bonded to the core at an end thereof, the X block contains an average of more than 0.8 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers, The molecular weight distribution (Mw / Mn) is 1.8 or less.

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