Curable composition and cured product

Abstract

To provide a curable composition that yields a cured product which readily elongates even under a small load, or a curable composition that exhibits little change in physical properties even after high-temperature storage.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, a hydrocarbon having a carbon-carbon double bond within the molecule; component C, a radical generator; and component D, a curing catalyst. Component A is a polymer meeting specific requirements.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Polymer molecules having silyl groups form siloxane bonds with other polymer molecules by hydrolysis of the silyl groups. A rubbery cured product is obtained by this crosslinking reaction. Curable compositions containing such polymer molecules are used in sealing materials, adhesives, paints, etc. (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Various physical properties are required for curable compositions and cured products depending on the application scenario. For example, a cured product used as a sealing material for a working joint is preferably easy to stretch even with a small force. Alternatively, for a curable composition stored in a warehouse without air conditioning equipment, it is preferable that the physical property changes are small even after storage at a high temperature of about 50°C.

[0005] One aspect of the present invention is to provide a curable composition that gives a cured product that is easy to stretch even with a small force. Another aspect of the present invention is to provide a curable composition in which the physical property changes are small even after storage at a high temperature.

Means for Solving the Problems

[0006] In order to solve the above problems, a curable composition according to one aspect of the present invention contains the following components A to D: Component A: (Meth)acrylic polymer having a silyl group; Component B: Hydrocarbon having a carbon-carbon double bond in the molecule; Component C: Radical generator; Component D: Curing catalyst; Here, the above Component A has an XY diblock structure or an XYX triblock structure having an X block and a Y block in the molecule, the repeating unit derived from the silyl group-containing (meth)acrylate monomer contained in the above X block is more than 2.0 on average, the repeating unit derived from the silyl group-containing (meth)acrylate monomer contained in the above Y block is 0 wt% or more and less than 5 wt% based on the weight of all the repeating units contained in the above 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, a curable composition is provided that gives a cured product that is easily stretchable even with a small force. According to another aspect of the present invention, a curable composition is provided that has little change in physical properties even after storage at high temperature.

Mode for Carrying Out the Invention

[0008] Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications may be made within the scope shown in the claims. Embodiments in which technical means described in different embodiments are combined are also included in the technical scope of the present invention.

[0009] Unless otherwise specified in this specification, "A~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 aspect of the present invention contains component A: a (meth)acrylic polymer having a silyl group, component B: a hydrocarbon having a carbon-carbon double bond in the molecule, component C: a radical generator, and component D: a curing catalyst. The curable composition may further contain, as an optional component, component E: a reducing agent. The curable composition may contain additives other than those described above. Each component may be blended alone or in combination of two or more.

[0011] [1.1. Component A: (meth)acrylic polymer having a 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 with a high frequency of appearance of the silyl group and a Y block with a low frequency of appearance of the silyl group. 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. Note that the overall structure 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 "XYX triblock structure" means the "ABA triblock structure" generally referred to among those skilled in the art. The ratio of X / Y in component A is preferably (5 / 95) to (60 / 40), more preferably (15 / 85) to (40 / 60).

[0014] In one embodiment, the molecule of component A has an XY diblock structure. In the 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 (assuming the total repeating units contained in the molecule is 100%). Here, the X block is the block where silyl groups are relatively more distributed.

[0015] In one embodiment, the molecule of component A has an XYX triblock structure. In the molecule with an XYX triblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from the ends of the molecule (assuming the total repeating units contained in the molecule is 100%). Here, the X blocks are the blocks located at both ends of the molecule.

[0016] Component A has repeating units derived from a silyl group-containing (meth)acrylate monomer. The repeating units derived from the silyl group-containing (meth)acrylate monomer are relatively more contained in the X block. The repeating units derived from the silyl group-containing (meth)acrylate 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 the repeating units derived from the silyl group-containing (meth)acrylate monomer contained in the plurality of X blocks is more than 2.0 on average. On the other hand, the repeating units derived from the silyl group-containing (meth)acrylate monomer contained in the Y block are 0 wt% or more and less than 5 wt% based on the weight of all the repeating units contained in the Y block.

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

[0018] The upper limit of the repeating units derived from the silyl group-containing (meth)acrylate 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, still more preferably 2% by weight or less, and particularly preferably 1% by weight or less, based on the weight of all the repeating units contained in the Y block. The lower limit of the repeating units derived from the silyl group-containing (meth)acrylate monomer contained in the Y block is preferably 0% by weight or more, and more preferably more than 0% by weight, based on the weight of all the 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, still more preferably 3.0 or more, and particularly preferably 3.4 or more, as a 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, still more preferably 6.0 or less, and particularly preferably 5.0 or less. When the number of silyl groups is within the above range, a curable composition and a cured product having good physical properties can be obtained.

[0020] Specific examples of the silyl group-containing (meth)acrylic acid ester monomer 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-chain side chain. In the present specification, the "(meth)acrylic monomer having a long-chain side chain" refers to the formula: CH 2 =C(R 1 )COOR 2 wherein the monomer represented by. In the formula, R 1 is a hydrogen atom or a methyl group. R 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-chain side chain is preferably 1% by weight or more based on all the constitutional units contained in Component A. Component A containing such a repeating unit may improve the compatibility with the polyoxyalkylene polymer or improve the physical properties of the resulting cured product. The upper limit of the content of the repeating unit derived from the (meth)acrylic monomer having a long-chain 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 can be kept from soaring extremely.

[0023] Examples of the (meth)acrylic monomer having a long-chain 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 preferable. These monomers are liquid at room temperature and have the advantage of high polymerization stability. Further, by blending these monomers, a (meth)acrylic acid-based polymer having high compatibility with a polyoxyalkylene-based polymer can be obtained.

[0025] In the present specification, the "(meth)acrylic monomer having a non-long-chain side chain" means, in the above formula, a monomer in which R 2 is a group 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 preferable. These monomers have low procurement costs and are suitable for the purpose of reducing the production cost of Component A.

[0027] Furthermore, from the perspective of the 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 the viscosity of the polymer becomes low. Therefore, a curable composition that is easy to use in a low-temperature environment can be obtained.

[0028] Component A may have a repeating unit derived from a monomer other than the (meth)acrylate monomer. In component A, the proportion of the repeating unit derived from the (meth)acrylate monomer 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] [1.1.2. Silyl groups possessed by (meth)acrylic polymers] The silyl group possessed by component A may be derived from a silyl group-containing (meth)acrylate 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’) 3 SiO-. R’ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. The three R’s present may be the same or different. R 3 or R 4When there are two or more of them, 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 plurality of X are contained in one silyl group, they may be the same or different. When a plurality of silyl groups are contained in one molecule of component A, 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 from 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. As an example, a monomer represented by the following general formula can be mentioned. H 2 C=C(R 5 )C(=O)-O-(CH 2 ) m -SiR 6 n (OR 7 ) 3-n

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

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

[0034] [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 still 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 still more preferably 20,000 or less. If the number average molecular weight of component A is within the above range, the viscosity of the curable composition will 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 decreases 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 the 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 the measurement is the molecular weight in terms of standard polystyrene.

[0037] [1.1.4. Method for Producing 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 preferable because component A can be obtained with little use of a polymerization solvent, a polymerization initiator, a chain transfer agent, etc. A living polymerization method is preferable because a functional group can be introduced near the terminal of the polymer molecule and component A with a small molecular weight distribution can be synthesized. Examples of the living polymerization method include a living radical polymerization method, a living cationic polymerization method, and a living anionic polymerization method. Among them, the living radical polymerization method is suitable for the polymerization of (meth)acrylic monomers. Examples of the living radical polymerization method 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 Organocatalysts", Polymer Journal, 68, 223-231 (2011); JP-A-2014-111798) · Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT polymerization) · Nitroxide 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 Method

[0038] Examples of methods for introducing a silyl group into Component A include the method described in JP-A-2018-162394. The method disclosed in this document introduces a silyl group into Component A by copolymerizing a (meth)acrylate monomer and a silyl group-containing (meth)acrylate monomer. More specifically, by controlling the amount of the silyl group-containing (meth)acrylate monomer added according to the progress stage of living polymerization, a silyl group is introduced near the terminal of the Component A molecule. 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: Hydrocarbon Having a Carbon-Carbon Double Bond in the Molecule] Component B is a hydrocarbon having a carbon-carbon double bond in the molecule. A "hydrocarbon" is a compound mainly composed of carbon and hydrogen. The lower limit of the number of carbon atoms that Component B has can be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more. The upper limit of the number of carbon atoms that Component B has can be 30 or less, 25 or less, 20 or less, or 15 or less.

[0040] Component B may have a small number of heteroatoms (such as oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, etc.). The number of heteroatoms that Component B has can be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. In one embodiment, Component B is composed of only carbon atoms and hydrogen atoms.

[0041] The number of carbon-carbon double bonds that Component B has is not particularly limited. The number of carbon-carbon double bonds that Component B has can be 5 or less, 4 or less, 3 or less, 2 or less, or 1. In one embodiment, Component B has only 1 carbon-carbon double bond.

[0042] By blending Component B, the resulting cured product becomes easy to stretch even with a small force. In the examples of the present application, this is shown as a decrease in stress at 100% elongation. Also, by blending Component B, the change in physical properties is small even after storage at high temperature. In the examples of the present application, this is shown as a reduction in the change in viscosity, stress at 100% elongation, and stress at break after storage at high temperature.

[0043] The mechanism of action of this effect is presumed to be as follows (however, this presumption is for the purpose of facilitating the understanding of the present invention and is not intended to narrow the scope of the claims). That is, at the end of Component A synthesized by living polymerization, there is a halogen atom (such as a bromine atom) derived from the initiator. When Component B is present, the halogen atom at the end of Component A detaches, the carbon-carbon double bond of Component B cleaves, and a carbon-carbon single bond is formed between Component A and Component B. As a result, the above-described effects are brought about.

[0044] Component B is preferably an α-olefin. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icosene.

[0045] The number of carbon atoms of the α-olefin is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more. Examples of such α-olefins include 1-butene, 1-pentene, 1-hexene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icosene.

[0046] [1.3. Component C: Radical Generator] Component C is a radical generator. A radical generator refers to a compound that generates radicals by applying light energy and / or thermal energy. Examples of Component C include photo radical generators and thermal radical generators. Component C generates the reaction of the mechanism of action described in section [1.2.].

[0047] Examples of photoinitiators include carbonyl compounds, sulfur compounds, and acylphosphine oxides. Examples of carbonyl compounds include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methyl phenylglyoxylate, ethyl phenylglyoxylate, and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Examples of sulfur compounds include tetramethylthiuram monosulfide and tetramethylthiuram disulfide. An example of an acylphosphine oxide is 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0048] Examples of thermal initiators include peroxides. Among peroxides, organic peroxides are preferred. Examples of organic peroxides include t-butyl peroxy octoate, t-butyl peroxy isobutyrate, t-butyl peroxy laurate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butyl peroxy isophthalate, benzoyl peroxide, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, azobisisobutyronitrile, and peroxydicarbonate.

[0049] [1.4. Component D: Curing Catalyst] Component D is a curing catalyst. Examples of the curing catalyst include tin-based curing catalysts. Specific examples of the tin-based curing catalysts include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diisooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmaleate, dioctyltin diisooctylmaleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalic acid ester, etc.); reaction products of tetravalent tin compounds (dibutyltin oxide, dibutyltin diacetate, etc.) and silyl group-containing low molecular weight silicon compounds (tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, etc.); divalent tin compounds (tin octylate, tin naphthenate, tin stearate, etc.); monoalkyltins (monobutyltin compounds (monobutyltin trisoctoate, monobutyltin triisopropoxide, etc.), monooctyltin compounds, etc.); reaction products or mixtures of amine-based compounds and organotin compounds (reaction products or mixtures of laurylamine and tin octylate, etc.); chelate compounds (dibutyltin bisacetylacetonate, dioctyltin bisacetylcetonate, dibutyltin bisethylacetonate, dioctyltin bisethylacetonate, etc.); tin alcoholates (dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, dioctyltin diethylate, etc.).

[0050] Among these, chelate compounds (such as dibutyltin bisacetylacetonate) and tin alcoholates are preferably highly active as silanol condensation catalysts. Also, dibutyltin dilaurate is preferably less colored, inexpensive, and easily available even when added to the curable composition.

[0051] [1.5. Component E: Reducing Agent] Component E is a reducing agent. Since Component E is an optional component, it may or may not be included in the curable composition. Combining Component C, which is an oxidizing agent, and Component E can form a redox initiator system. As a result, radicals can be generated even at room temperature. Therefore, it is considered that the putative mechanism of action described in section [1.2.] can proceed at room temperature. Examples of Component D include sulfinic acid, amines, and transition metal salts. Among these, amines are preferred, and organic amines are more preferred.

[0052] Examples of organic amines include primary amines (such as paratoluidine, octylamine, laurylamine, etc.), secondary amines (such as dipropylamine, diethanolamine, morpholine, etc.), tertiary amines (such as diisopropyl-p-toluidine, dimethylaniline, dimethyl-p-toluidine, tris-(dimethylaminomethyl)phenol, trimethylamine, etc.), α-aminosulfones (such as bis-(toluenesulfonylmethyl)amine, bis-(toluenesulfonylmethyl)ethylamine, bis-(toluenesulfonylmethyl)-benzylamine, etc.), amine-aldehyde condensation products (such as condensation products of primary amines like aniline or butylamine and aliphatic aldehydes like butyraldehyde, etc.), and thiourea derivatives (such as 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylene thiourea, etc.).

[0053] [1.6. Other Components] In addition to the components described above, the curable composition may contain various additives. By containing these additives, various physical properties of the curable composition and the cured product can be adjusted. Examples of additives are as follows. These additives may be used alone or in combination of two or more.

[0054] (Adhesion Promoter) The curable composition may contain an adhesion promoter. By adding the adhesion promoter, the risk of the sealing material peeling off from an adherend such as a siding board can be reduced (this peeling occurs due to fluctuations in the joint width or the like caused by an external force). In addition, there may be no need to use a primer for improving adhesion. In this case, simplification of the construction work is expected.

[0055] Examples of the adhesion promoter include silane coupling agents. Specific examples of the silane coupling agents include isocyanate group-containing silanes (γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, 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, 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-acryloyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); isocyanurate silanes (tris(trimethoxysilyl)isocyanurate, etc.).In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated amino-silane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives obtained by modifying silane coupling agents, can also be used as silane coupling agents.

[0056] When the content of component A is 100 parts by weight, the content of the adhesion-imparting agent is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight.

[0057] (Filler) The curable composition may contain a filler. Examples of fillers include wood powder; reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), carbon black, 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, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate, shirasu balloon, etc.); fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0058] When the total content of component A is 100 parts by weight, 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.

[0059] (Physical property modifier) The curable composition may contain a physical property modifier for adjusting the tensile properties of the cured product. By using the physical property modifier, the hardness of the cured product can be increased, or conversely, the hardness of the cured product can be decreased and the elongation can be increased.

[0060] Examples of the physical property adjuster include alkylalkoxysilanes (such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilanes (such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, etc.); alkoxysilanes having functional groups (such as vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); silicone varnishes; polysiloxanes.

[0061] When the total content of component A is 100 parts by weight, the content of the physical property adjuster is preferably 0.1 to 80 parts by weight, and more preferably 0.1 to 50 parts by weight.

[0062] (Thixotropic agent (anti-sagging agent)) The curable composition may contain a thixotropic agent (anti-sagging agent) in order to prevent sagging and improve workability.

[0063] Examples of the thixotropic agent include polyamide waxes; hydrogenated castor oil derivatives; metal soaps (such as calcium stearate, aluminum stearate, barium stearate, etc.).

[0064] When the total content of component A is 100 parts by weight, the content of the thixotropic agent is preferably 0.1 to 50 parts by weight, and more preferably 0.2 to 25 parts by weight.

[0065] (Photocurable substance) The curable composition may contain a photocurable substance. A photocurable substance is a substance that undergoes a chemical change in a short time under the action of light and causes a physical property change (such as curing). By containing a photocurable substance, the adhesiveness (residual tack) of the cured product surface can be reduced. A typical photocurable substance can be cured, for example, by standing at room temperature for one day at a sunlit position indoors (near a window, etc.). Many photocurable substances are known, such as organic monomers, oligomers, resins, and compositions containing these, and the types thereof are not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, vinyl polycinnamates, and azide resins.

[0066] Specific examples of unsaturated acrylic compounds include (meth)acrylate esters of low molecular weight alcohols (such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, neopentyl alcohol, etc.); (meth)acrylate esters of alcohols modified with acids (such as bisphenol A, isocyanuric acid) or low molecular weight alcohols with ethylene oxide, propylene oxide, etc.; (meth)acrylate esters (such as polyether polyols having a polyether main chain and a hydroxyl group at the end, polymer polyols obtained by radical polymerization of vinyl monomers in polyols having a polyether main chain, polyester polyols having a polyester main chain and a hydroxyl group at the end, polyols having a vinyl-based or (meth)acrylic copolymer main chain and a hydroxyl group in the main chain, etc.); epoxy acrylate oligomers obtained by reacting epoxy resins (such as bisphenol A type, novolac type, etc.) with (meth)acrylic acid; urethane acrylate oligomers having a urethane bond and a (meth)acrylic group in the molecular chain obtained by reacting polyols, polyisocyanates, hydroxyl group-containing (meth)acrylates, etc.

[0067] When the total content of component A is 100 parts by weight, the content of the photocurable substance is preferably 0.01 to 30 parts by weight.

[0068] (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, substances described in [Kenichi Saruwatari et al., "Antioxidant Handbook", Taiseisha, 1976] and [Yoshijiro Oze, ed., "Deterioration and Stabilization of Polymer Materials", CMC, 1990, pages 235 - 242] can be mentioned.

[0069] Examples of antioxidants include thioether - type antioxidants such as Adeka Stab PEP - 36 and Adeka Stab AO - 23 (all of the above are manufactured by ADEKA Corporation); phosphorus - type antioxidants such as Irgafos 38, Irgafos 168, and Irgafos P - EPQ (all of the above are manufactured by Ciba Specialty Chemicals); and hindered phenol - type antioxidants. Among those mentioned above, hindered phenol - type antioxidants are preferred.

[0070] Specific examples of the 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), 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-diethylenebis[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-hydroxybenzylphosphonic acid ethyl) 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 - 5 - (2H - benzotriazol - 2 - yl) - 4 - hydroxyphenyl] propionate - polyethylene glycol (molecular weight about 300) condensate, hydroxyphenylbenzotriazole derivative, 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 and the like.

[0071] Examples of commercially available antioxidants include Nocrack 200, Nocrack M - 17, Nocrack SP, Nocrack SP - N, Nocrack NS - 5, Nocrack NS - 6, Nocrack NS - 30, Nocrack 300, Nocrack NS - 7, Nocrack DAH (all of the above are from Ouchi Shinsei Chemical Industry Co., Ltd.); Adeka Stab AO - 30, Adeka Stab AO - 40, Adeka Stab AO - 50, Adeka Stab AO - 60, Adeka Stab AO - 616, Adeka Stab AO - 635, Adeka Stab AO - 658, Adeka Stab AO - 80, Adeka Stab AO - 15, Adeka Stab AO - 18, Adeka Stab 328, Adeka Stab AO - 37 (all of the above are from 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 of the above are from Ciba Specialty Chemicals); Sumilizer GM, Sumilizer GA - 80, Sumilizer GS (all of the above are from Sumitomo Chemical Co., Ltd.).

[0072] Examples of the light stabilizer include ultraviolet absorbers (benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of the above are from Ciba Specialty Chemicals)); triazine-based light stabilizers such as Tinuvin 1577; benzophenone compounds such as Chimassorb 81; benzoate compounds such as Tinuvin 120 (Ciba Specialty Chemicals); and hindered amine compounds). Among the above, hindered amine compounds are preferred.

[0073] Specific examples of the hindered amine compounds 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(3-aminopropyl)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 ester.

[0074] Examples of commercially available light stabilizers include Tinuvin 622LD, Tinuvin 144, Chimassorb 944LD, Chimassorb 119FL; (all of the above are from Ciba Specialty Chemicals), AdekaStab LA-52, AdekaStab LA-57, AdekaStab LA-62, AdekaStab LA-67, AdekaStab LA-63, AdekaStab LA-68, AdekaStab LA-82, AdekaStab LA-87 (all of the above are from ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, Sanol LS-440 (all of the above are from Ciba Specialty Chemicals).

[0075] The antioxidant and the light stabilizer may be used in combination. By using them in combination, the respective effects 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) can be combined. This combination can further improve the effects of the respective agents and is preferable.

[0076] When the total content of component A is 100 parts by weight, the content of the antioxidant and / or the light stabilizer is preferably 0.1 to 20 parts by weight, respectively.

[0077] [2. Composition of the curable composition] In the curable composition, when the total content of component A is 100 parts by weight, the lower limit of the content of component B is preferably 0.5 part by weight or more, more preferably 1 part by weight or more, and further preferably 2 parts by weight or more. The upper limit of the content of component B is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and further preferably 5 parts by weight or less.

[0078] In the curable composition, the lower limit of the number of carbon-carbon double bonds contained in the whole of component B is preferably 1 equivalent or more, more preferably 3 equivalents or more, when the reactive terminals (such as bromine terminals) contained in the whole of component A are taken as 1 equivalent. In the curable composition, the upper limit of the number of carbon-carbon double bonds contained in the whole of component B is preferably 10 equivalents or less, more preferably 8 equivalents or less, when the reactive terminals (such as bromine terminals) contained in the whole of component A are taken as 1 equivalent.

[0079] In the curable composition, the lower limit of the content of component C is preferably 0.1 part by weight or more, more preferably 0.3 part by weight or more, when the total content of component A is 100 parts by weight. The upper limit of the content of component C is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, still more preferably 1 part by weight or less, when the total content of component A is 100 parts by weight.

[0080] In the curable composition, the lower limit of the content of component D is preferably 0.1 part by weight or more, more preferably 0.5 part by weight or more, when the total content of component A is 100 parts by weight. The upper limit of the content of component D is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, when the total content of component A is 100 parts by weight.

[0081] In the curable composition, the lower limit of the content of component E is preferably 0.1 part by weight or more, more preferably 0.3 part by weight or more, when the total content of component A is 100 parts by weight. The upper limit of the content of component E is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, still more preferably 1 part by weight or less, when the total content of component A is 100 parts by weight.

[0082] 〔3. Form of the curable composition〕 The curable composition may be of the one-component type or the multi-component type. The one-component curable composition is prepared by premixing all the compounding components and then storing them in a sealed manner. The one-component curable composition cures by moisture in the environment after use. In the multi-component curable composition, component D and the other components are prepared separately and mixed together at the time of use. The multi-component curable composition may include other agents (such as colorants) with optional configurations in addition to the above components.

[0083] When preparing the curable composition as a multi-component type, a colorant can be further added during the mixing of each component. For example, a colorant obtained by mixing a pigment, a plasticizer, and, if necessary, a filler and pasting it is preferable because of its high workability.

[0084] Also, a retarder can be added to the multi-component curable composition during the mixing of the main agent and the curing agent. Thereby, the curing rate can be finely adjusted at the work site.

[0085] [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 ambient moisture and spontaneously change into a cured product. The use of the cured product is not particularly limited. As an example, sealing agents for construction and industrial use, materials for electric and electronic parts (such as back-sealing agents for solar cells), electrical insulation materials (such as insulating coating materials for electric wires and cables), adhesives, bonding agents, elastic adhesives, contact adhesives, adhesives for tiles, paints, coating materials, sealing materials such as can lids, potting agents for electric and electronic use, films, gaskets, casting materials, various molding materials, artificial marble, rust-proof and waterproof sealing materials for the cut parts of wired glass or laminated glass, and waterproof agents can be mentioned.

[0086] In one embodiment, the cured product is in the form of a film. The lower limit of the thickness of the film to be manufactured can 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 to be manufactured can 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.

[0087] The film-like cured product can be produced, for example, by applying a curable composition to a substrate and then curing it. It may be used in a state where the film is peeled off from the substrate, or it may be used in a state where the substrate and the film are integrated. Examples of the uses of the film-like cured product include a sealing material, a coating agent, and an adhesive.

[0088] 〔5. Summary〕 The present invention includes the following aspects. <1> A curable composition containing the following components A to D: Component A: A (meth)acrylic polymer having a silyl group; Component B: A hydrocarbon having a carbon-carbon double bond in the molecule; Component C: A radical generator; Component D: A curing catalyst; Here, the above component A has an XY diblock structure or an XYX triblock structure having an X block and a Y block in the molecule, the repeating unit derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the above X block is more than 2.0 on average, the repeating unit derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the above Y block is 0 wt% or more and less than 5 wt% based on the weight of all the repeating units contained in the above 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 (wherein R 1 is a hydrogen atom or a methyl group, and R 2 is a group having 9 or more carbon atoms), and contains 1 wt% or more of the repeating unit derived therefrom, the curable composition according to <1>. <3> The number average molecular weight of the above component A is 2,000 to 50,000, the curable composition according to <1> or <2>. <4> The above-mentioned component B is an α-olefin, and the curable composition according to any one of <1> to <3>. <5> The curable composition according to <4>, wherein the α-olefin has 4 or more carbon atoms. <6> The above-mentioned component C is an organic peroxide, and the curable composition according to any one of <1> to <5>. <7> The curable composition according to any one of <1> to <6>, further comprising the following component E: Component E: Reducing agent. <8> The above-mentioned component E is an amine, and the curable composition according to <7>. <9> A cured product obtained by curing the curable composition according to any one of <1> to <8>.

Examples

[0089] 〔Measurement method〕 [Number average molecular weight] The following apparatus was used for measuring the number average molecular weight. The measured value is the molecular weight in terms of polystyrene. ·Liquid delivery system: HLC-8120GPC (manufactured by Tosoh Corporation) ·Column: TSK-GEL H type (manufactured by Tosoh Corporation) ·Solvent: THF

[0090] [Introduction rate of terminal silyl group] 1 From the results of 1H-NMR measurement, the introduction rate of the terminal silyl group was calculated. 1 The following apparatus was used for 1H-NMR measurement. ·Measuring instrument: JNM-LA400 (manufactured by JEOL Ltd.) ·Solvent: CDCl 3

[0091] [Viscosity] The viscosity of the prepared curable composition was measured using an E-type viscometer (VICOMETER TV-25type H, manufactured by Toki Sangyo Co., Ltd.). The measurement temperature was 23°C.

[0092] [Tensile properties] In accordance with JIS K 6251, a dumbbell-shaped No. 3 test piece was obtained from the cured product, and the tensile properties were measured. The measurement of the tensile properties was carried out at 23 °C and 55% RH using an autograph. The evaluation items were the stress at 100% elongation and the stress at break.

[0093] [Stability after high-temperature storage] The prepared curable composition was placed in a storage container and stored at 50 °C for 4 weeks. The viscosity of the curable composition after storage and the tensile properties of the obtained cured product were measured by the above-mentioned method.

[0094] [Materials] The materials used in the examples and comparative examples are as follows. ● Component A · (Meth)acrylic polymer (A) having a silyl group obtained in the production example ● Component B · Hydrocarbon (B-1) having a carbon-carbon double bond in the molecule (1-hexene, Tokyo Chemical Industry Co., Ltd.) · Hydrocarbon (B-2) having a carbon-carbon double bond in the molecule (1-octene, Tokyo Chemical Industry Co., Ltd.) · Hydrocarbon (B-3) having a carbon-carbon double bond in the molecule (1-decene, Tokyo Chemical Industry Co., Ltd.) ● Component C · Radical generator (Perbutyl O, NOF Corporation, t-butylperoxy-2-ethylhexanoate) ● Component D · Curing catalyst (Neostann U-220H, Nitto Kasei Co., Ltd., dibutyltin) ● Component E · Reducing agent (toluidine, Tokyo Chemical Industry Co., Ltd.) ● Dehydrating agent · Dehydrating agent (Silquest A-171, Momentive Performance Materials, vinyltrimethoxysilane) ● Adhesion promoter ·(KBM-603, Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane)

[0095] [Production Example: Synthesis of (meth)acrylic polymer (A) having a silyl group] The (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-necked 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 the “(meth)acrylic ester monomer mixture”. 2. Another stirring container was prepared. 52.7 mg of cupric bromide (CuBr 2 ), 54.4 mg of hexamethyltris(2-aminoethyl)amine (Me 6 TREN) and 1.82 g of methanol were charged into the stirring container and stirred under a nitrogen stream until a homogeneous solution was obtained. This homogeneous solution is referred to as the “copper solution”. The copper contained in the copper solution corresponds to 15 ppm based on the total amount of the (meth)acrylic ester monomer mixture. 3. Still another stirring container was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid and 1.6 mL of triethylamine were charged into the stirring container and stirred under a nitrogen stream to form a homogeneous solution. This homogeneous solution is referred to as the “ascorbic acid solution”. [First Step] 4. To a stirrer were added 5.60 g of ethyl α-bromobutyrate (initiator; 0.029 mol), 20 wt% of the total amount of the (meth)acrylic 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 amount of the copper solution, and the mixture was stirred for 30 minutes under a nitrogen stream to form a homogeneous solution. The stirrer used at this time was a jacket temperature-controlled stirrer, and the jacket temperature was set to 45°C. 5. When the temperature in the polymerization system reached 40 °C or higher, the polymerization reaction was initiated by continuously dropping an ascorbic acid solution. The dropping rate of the ascorbic acid solution at this time was set such that 144 mg of ascorbic acid was introduced into the polymerization system per hour. 6. When the temperature in the polymerization system was monitored, the temperature increased simultaneously with the start of the dropping of ascorbic acid, and after reaching the maximum temperature, the temperature gradually decreased. When the temperature difference obtained by subtracting the jacket temperature from the temperature in the polymerization system 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 initially charged (meth)acrylic acid ester monomer mixture had been consumed. (Second step) 7. The remainder of the (meth)acrylic acid ester monomer mixture that was not introduced in the first step (80% by weight of the total amount) was continuously dropped into the polymerization system over 90 minutes. The dropping rate of the ascorbic acid solution at this time was set such that 48 mg of ascorbic acid was introduced into the polymerization system per hour. Also, sampling was performed sequentially and analyzed by gas chromatography. Then, the polymerization was continued until 88% by weight of the total amount of the (meth)acrylic acid ester monomer mixture introduced into the polymerization system was consumed. (Third step) 8. 11 g of 3-methacryloxypropylmethyldimethoxysilane (0.049 mol; 1.6 molar equivalents relative to the initiator) was introduced into the polymerization system. The continuous dropping of the ascorbic acid solution was continued until 98% by weight of the total amount of the (meth)acrylic acid ester monomer mixture introduced into the polymerization system was consumed. Thereafter, the dropping of the ascorbic acid solution was terminated and the polymerization was terminated. 9. After changing the jacket temperature to 80 °C, the solvent was devolatilized. For devolatilization, first a diaphragm pump was used, and then a vacuum pump was used. After completion of devolatilization, it was cooled until the jacket temperature reached 60 °C or lower. (Purification) 10. 1000 g of butyl acetate was charged into the jacket temperature-controlled stirring device, and the mixture was stirred until it became a homogeneous solution with the polymer after devolatilization. An adsorbent was added to this homogeneous solution and stirred for 1 hour. As the adsorbent, 10 g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10 g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.) were used. 11. After completion of the stirring, the resulting mixture was filtered through a filter lined with a bag filter cloth. As a result, a clear polymer solution was obtained. 1.5 g of an antioxidant (Sumilizer GS; Sumitomo Chemical Co., Ltd.) was added to this solution and mixed until homogeneous. Then, the solvent was removed from the solution using a diaphragm pump first and then a vacuum pump. In this way, the (meth)acrylic polymer (A) was obtained.

[0096] The (meth)acrylic polymer (A) was an XYX type block copolymer, with a number average molecular weight of 55,000, a molecular weight distribution of 1.11, and the number of silyl groups introduced per molecule being 2.1. Also, the X block of the (meth)acrylic polymer (A) had an average of 2.1 repeating units derived from a silyl group-containing (meth)acrylic acid ester monomer per copolymer molecule. The Y block of the (meth)acrylic polymer (A) had 1.1% by weight of repeating units derived from a silyl group-containing (meth)acrylic acid ester monomer (based on the weight of all repeating units contained in the Y block). Note that the number of repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the Y block was extremely small. Therefore, when calculated to two significant figures, both the repeating units derived from the silyl group-containing (meth)acrylic acid ester monomer contained in the whole molecule and those contained in the whole X block were 2.1.

[0097] [Examples 1 to 3] A curable composition and a cured product were prepared according to the following procedure. 1. Each component was prepared in the amounts (unit: g) shown in Table 1. 2. Components A to C and E were put into a 150 cc plastic cup and stirred with a spatula. 3. The resulting composition was allowed to stand at 80 °C for 40 minutes. 4. A dehydrating agent, an adhesion-imparting agent, and Component D were further added to the plastic cup and stirred with a spatula. 5. Using a planetary stirring and defoaming device (ARE-310, Shinky Co., Ltd.), stirring (1600 rpm × 90 seconds) and defoaming (2200 rpm × 300 seconds) were carried out to obtain a curable composition. 6. The obtained curable composition was cured under the conditions of 23 °C and 50% RH to obtain a cured product. The physical properties of the obtained cured product were measured.

[0098] [Comparative Example 1] A curable composition and a cured product were prepared according to the following procedure. 1. Each component was prepared in the amounts (unit: g) shown in Table 1. 2. All the components were put into a plastic cup and stirred with a spatula. 3. Using a planetary stirring and defoaming device (ARE-310, Shinky Co., Ltd.), stirring (1600 rpm × 90 seconds) and defoaming (2200 rpm × 300 seconds) were carried out to obtain a curable composition. 4. The obtained curable composition was cured under the conditions of 23 °C and 50% RH to obtain a cured product. The physical properties of the obtained cured product were measured.

[0099] [Results] The results are shown in Table 1. [Table 1]

[0100] As can be seen from Table 1, the cured product according to the example had a smaller stress at 100% elongation immediately after production than the cured product according to the comparative example. From this, it is suggested that the curable composition according to the example gives a cured product that is easily stretched even with a small force.

[0101] As can be seen from Table 1 as well, the curable composition according to the examples had smaller changes in physical properties after storage at high temperatures than the curable composition according to the comparative examples. Specifically, the change in the viscosity of the curable composition was relatively small, and the changes in the stress at 100% elongation and the stress at break of the cured product were relatively small. From this, it is suggested that the curable composition according to the examples has high storage stability and small changes in physical properties even after storage at high temperatures.

Industrial Applicability

[0102] The curable composition according to one embodiment of the present invention can be suitably used for adhesives, sealing materials, adhesives, mold release agents, vibration isolators, vibration damping materials, soundproofing materials, foaming materials, paints, spraying materials, and the like.

Claims

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

2. The above-mentioned component A is CH ２ =C(R １ )COOR ２ (wherein R １ is a hydrogen atom or a methyl group, and R ２ is a group having 9 or more carbon atoms), and contains 1% by weight or more of a repeating unit derived therefrom. The curable composition according to claim 1.

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

4. The curable composition according to Claim 1, wherein the above Component B is an α-olefin.

5. The curable composition according to Claim 4, wherein the number of carbon atoms of the above α-olefin is 4 or more.

6. The curable composition according to Claim 1, wherein the above Component C is an organic peroxide.

7. The curable composition according to Claim 1, further containing the following Component E: Component E: A reducing agent.

8. The curable composition according to Claim 7, wherein the above Component E is an amine.

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

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