Curable composition and cured product

Abstract

To provide a curable composition which gives a cured product improved in strength and elongation.SOLUTION: A curable composition according to one embodiment of the present invention contains a component A: a (meth)acrylic block copolymer having a silyl group, a component B: a (meth)acrylic random copolymer having a silyl group, a component C: a polyoxyalkylene-based polymer having a silyl group, a component D: an amine-modified silicone compound, and a component E: a curing catalyst. The component A and the component B are polymers satisfying specific conditions.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition and a cured product. [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] The curable compositions disclosed in the prior art such as Patent Document 1 leave room for improvement in the strength and elongation of the resulting cured products.

[0005] One aspect of the present invention is to provide a curable composition that provides a cured product with improved strength and elongation. [Means for solving the problem]

[0006] In order to solve the above problems, a curable composition according to one embodiment of the present invention contains the following components A to E: Component A: a (meth)acrylic block copolymer having a silyl group; Component B: a (meth)acrylic random copolymer having a silyl group; Component C: a polyoxyalkylene polymer having a silyl group; Component D: amine-modified silicone compound; Component E: Curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block or an XYX triblock structure, the X block contains an average of more than 2.0 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers, The molecular weight distribution (Mw / Mn) is 1.8 or less; Here, the component B is The polymer has an average of 1.0 or more silyl groups derived from silyl group-containing (meth)acrylic acid ester monomers per molecule, The molecular weight distribution (Mw / Mn) is greater than 1.8. [Effects of the Invention]

[0007] According to one aspect of the present invention, there is provided a curable composition that provides a cured product with improved strength and elongation. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] 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.

[0010] 1. Components of the Curable Composition A curable composition according to one embodiment of the present invention comprises Component A: a (meth)acrylic block copolymer having a silyl group, Component B: a (meth)acrylic random copolymer having a silyl group, Component C: a polyoxyalkylene polymer having a silyl group, Component D: an amine-modified silicone compound, and Component E: a curing catalyst. The curable composition may contain components other than Components A to E. Each of these components may contain only one type, or two or more types.

[0011] In the curable composition, it is believed that a bond is formed between component A and component D. That is, component A obtained by a production method such as that disclosed in JP 2018-162394 A has a halogen derived from the initiator at the reaction terminal, and it is presumed that this halogen reacts with an amine contained in component D, resulting in a bond between component A and component D. However, the above-mentioned mechanism of action is merely presumed and does not limit the scope of the present invention.

[0012] [1.1. Component A: (Meth)acrylic Block Copolymer Having Silyl Groups] Component A is a (meth)acrylic block copolymer 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.

[0013] [1.1.1. Structure of Component A] Component A has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule. The overall molecular 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.

[0014] Here, the term "XYX triblock structure" refers to what is commonly referred to by those skilled in the art as an "ABA triblock structure." The ratio of X / Y in component A is preferably from (5 / 95) to (60 / 40), and more preferably from (15 / 85) to (40 / 60).

[0015] In one embodiment, the molecule of component A 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.

[0016] In one embodiment, the molecule of component A has an XYX triblock structure. In a molecule with an XYX triblock structure, the X blocks can be 40% or less, 30% or less, or 25% or less of the region from the ends of the molecule (total repeating units contained in the molecule is taken as 100%). Here, the X blocks are blocks located at both ends of the molecule.

[0017] Component A has repeating units derived from silyl group-containing (meth)acrylic acid ester monomers. The repeating units derived from silyl group-containing (meth)acrylic acid 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 acid ester monomers contained in the X block is, on average, more than 2.0. When component A has two or more X blocks in one molecule, the total number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the multiple X blocks is, on average, more than 2.0. On the other hand, the number 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.

[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 2.0, preferably 2.1 or more, more preferably 2.2 or more, even more preferably 2.3 or more, and particularly preferably 2.5 or more. Similarly, the 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 Component A is, on average, more than 2.0, preferably 2.2 or more, more preferably 2.6 or more, even more preferably 3.0 or more, and particularly preferably 3.4 or more, per molecule. The upper limit of the number of silyl groups introduced into the (meth)acrylic polymer is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 5.0 or less. 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] Component A may contain a repeating unit derived from a (meth)acrylic monomer having a long side chain. In this specification, the term "(meth)acrylic monomer having a long side chain" refers to a repeating unit derived from a (meth)acrylic monomer having a long side chain, such as ... 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 Component A. Component A containing such repeating units may improve compatibility with polyoxyalkylene polymers and 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 Component A does 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 2 represents 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 Component A.

[0027] Furthermore, from the viewpoint of glass transition temperature, one or more types selected from n-butyl acrylate and 2-ethylhexyl acrylate are preferred. Component A obtained from these monomers has a low glass transition temperature, and the viscosity of the polymer is low. Therefore, a curable composition that can be easily used in low-temperature environments can be obtained.

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

[0029] [1.1.2. Silyl group contained in component A] The silyl group contained in Component A may be derived from a silyl group-containing (meth)acrylic acid ester monomer. In one embodiment, the silyl group is represented by the following general formula (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 4 When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acetoxy group, and an oxime group. In one embodiment, Y is a hydroxyl group, a methoxy group, an ethoxy group, or an isopropoxy group. When one silyl group contains multiple Xs, they may be the same or different. When one molecule of component A 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 from 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 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: Silyl Group-Containing (Meth)acrylic Random Copolymer] Component B is a (meth)acrylic random copolymer having a silyl group. Component B has a silyl group derived from a silyl group-containing (meth)acrylic acid ester monomer. Component B can be obtained, for example, by free radical polymerization of the monomer.

[0040] [1.2.1. Structure of Component B] Component B has a main chain derived from a (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomer contains a silyl group-containing (meth)acrylic acid ester monomer. Therefore, Component B has a silyl group derived from the silyl group-containing (meth)acrylic acid ester monomer.

[0041] Since component B is a random copolymer, the insertion sites of the silyl groups are also random. That is, in the polymer molecules that make up component B, the insertion sites of the silyl groups can be near the ends of the molecular chain or in the center of the molecular chain. On average, component B does not have regions where silyl groups are localized, as in the X blocks of component A.

[0042] Component B may contain a repeating unit derived from a (meth)acrylic monomer having a long side chain. In this specification, the term "(meth)acrylic monomer having a long side chain" refers to a repeating unit derived from a (meth)acrylic monomer having a long side chain, such as 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. Examples of such monomers and suitable types of monomers are as described in Section [1.1.1.]. A suitable content of the (meth)acrylic monomer having a long side chain is also as described in Section [1.1.1.].

[0043] Other examples and suitable types of (meth)acrylic acid ester monomers that can constitute Component B are as described in Section [1.1.1.].

[0044] [1.2.2. Silyl group contained in component B] In one embodiment, the silyl group contained in Component B is represented by the following general formula (2). -W-(CH2) n -Si(R 8 ) 3-a (X) a (2)

[0045] In formula (2), W is a divalent group other than CH2. The number of carbon atoms contained in W is, for example, 1 to 30, 1 to 20, 1 to 10, or 1 to 5.

[0046] In formula (2), n is an integer of 5 to 20. Preferably, n is an integer of 5 to 10. More preferably, n is an integer of 5 to 7.

[0047] In formula (2), R 8 represents a hydrogen atom or 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 8 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 8 is a hydrogen atom, a methyl group, or an ethyl group, preferably a methyl group. 8 When multiple silyl groups are contained in one molecule of component B, they may be the same or different. 8 may be different for each silyl group.

[0048] In formula (2), 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. Preferably, X is a hydroxyl group. When one silyl group contains multiple Xs, they may be the same or different. When one molecule of component A contains multiple silyl groups, X may be different for each silyl group.

[0049] In formula (2), a is 1, 2 or 3.

[0050] The number of silyl groups contained in Component B is, on average, 1.0 or more per molecule, preferably 1.5 or more, and more preferably 2.0 or more. The upper limit of the number of silyl groups contained in Component B can be, on average, 5.0 or less, 4.0 or less, 3.0 or less, or 2.0 or less per molecule. If the number of silyl groups is within the above range, the silyl groups are sufficiently crosslinked by moisture, resulting in a cured product with sufficient strength.

[0051] [1.2.3. Physical properties of component B] In one embodiment, the lower limit of the number average molecular weight of Component B 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 B 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 B is within the above range, the viscosity of the curable composition does not become too high, and sufficient workability can be ensured.

[0052] In one embodiment, the molecular weight distribution of Component B is greater than 1.8, preferably 1.9 or greater, or 2.0 or greater. The upper limit of the molecular weight distribution of Component B can be 4 or less, or 3 or less. The molecular weight distribution is a value given by "weight average molecular weight / number average molecular weight."

[0053] In the present invention, when comparing the molecular weight distributions of Component A and Component B, Component A has a smaller value. This is mainly due to the difference in the polymerization method. Component A is generally synthesized by living radical polymerization. Therefore, a polymer product with a relatively narrow molecular weight distribution tends to be obtained. On the other hand, Component B is generally synthesized by free radical polymerization. Therefore, a polymer product with a wide molecular weight distribution tends to be obtained.

[0054] 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.

[0055] [1.2.4. Manufacturing method of component B] The method for producing component B is not particularly limited, and known methods can be used. For example, free radical polymerization can be used. Specific examples of free radical polymerization include solution polymerization, in which a polymerization initiator, a chain transfer agent, a solvent, and the like are added to a polymerization system and polymerization is carried out at 50 to 150°C; and continuous bulk polymerization, in which an acrylic acid ester monomer is polymerized at high temperature and high pressure (see JP 2001-207157 A).

[0056] Examples of the polymerization initiator include azo compounds (2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1,1'-azobis(cyclohexane-1-carbonitrile), etc.); diacyl peroxides (benzo peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, etc.); peroxydicarbonates (diisopropyl percarbonate, di-sec-butyl percarbonate, di-2-ethylhexyl percarbonate, di-1-methylheptyl percarbonate, di-3-methoxybutyl percarbonate, dicyclohexyl percarbonate, etc.); peroxyesters (tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecanoate, etc.); ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.); dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, etc.); hydroperoxides (cumene hydroxyperoxide, tert-butyl hydroperoxide, etc.); and other peroxides (1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, etc.). The polymerization initiator may be used alone or in combination of two or more.

[0057] Examples of chain transfer agents include mercapto group-containing compounds. Examples of compounds containing a mercapto group include n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan. Furthermore, by using a compound containing a mercapto group and a silyl group, a silyl group can be introduced into the molecular chain terminal of component B. Examples of such compounds include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, and (mercaptomethyl)dimethoxymethylsilane. Only one type of chain transfer agent may be used, or two or more types may be used. Chain transfer agents can adversely affect weather resistance. Therefore, the amount of chain transfer agent used is preferably 2% by weight or less of the total amount of monomers, and it is more preferable to not use any chain transfer agent at all.

[0058] Examples of solvents include aromatic compounds (toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, di-n-butyl phthalate, etc.); hydrocarbon compounds (hexane, heptane, octane, cyclohexane, methylcyclohexane, etc.); carboxylic acid ester compounds (butyl acetate, n-propyl acetate, isopropyl acetate, etc.); ketone compounds (methyl isobutyl ketone, methyl ethyl ketone, etc.); dialkyl carbonate compounds (dimethyl carbonate, diethyl carbonate, etc.); and alcohol compounds (1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol, etc.). Among these, one or more selected from dialkyl carbonate compounds and alcohol compounds are preferred. These substances are not substances for which the Ministry of Health, Labor and Welfare has established guideline values, have low odor, and have a low environmental impact. Among these, dimethyl carbonate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butyl alcohol are more preferable, and 2-propanol and isobutyl alcohol are even more preferable. These substances have high boiling points and can reduce the emission of all volatile organic compounds.

[0059] [1.3. Component C: Silyl Group-Containing Polyoxyalkylene Polymer] [1.3.1. Main chain of component C] The molecular structure of component C 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.

[0060] Examples of the main chain structure of component C include structures represented by the following general formula: 6 is a divalent alkylene group. -R 6 -O-

[0061] The structure represented by the above general formula 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.

[0062] R 6 The structure of R is not particularly limited as long as it is a divalent alkylene group. 6 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.

[0063] 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 -CHCHCHCHCHO-. Of these, it is preferred that the main chain of component C is polypropylene oxide consisting of -CHCH(CH)O-.

[0064] [1.3.2. Silyl group contained in component C] In one embodiment, the structure of the silyl group contained in Component C is represented by the following general formula (3). -Si(R 9 ) 3-a (X)a (3)

[0065] In formula (3), R 9 represents a hydrogen atom or 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 silyl groups are contained in one molecule of component C, they may be the same or different. 9 may be different for each silyl group.

[0066] In formula (3), 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. When one molecule of component C contains multiple silyl groups, X may be different for each silyl group.

[0067] In formula (3), a is 1, 2 or 3.

[0068] Examples of the silyl group contained in component C 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.

[0069] The lower limit of the number of silyl groups introduced into Component C per molecule can be 1.2 or more, or 1.5 or more. The upper limit of the number of silyl groups introduced into Component C per molecule can be 4.0 or less, or 2.5 or less. If the number of silyl groups is within the above range, the curable composition can be imparted with good curability.

[0070] As component C, a polyoxyalkylene polymer having only one silyl group at the terminal may be used. Such a polymer can replace the plasticizer component. As component C, a polyoxyalkylene polymer obtained by the synthesis method described in JP 2021-75722 A may be used.

[0071] The silyl groups in component C are preferably located at one or more molecular terminals, and more preferably at two or more molecular terminals. If the silyl groups are located at the molecular terminals, good elongation can be imparted to the cured product.

[0072] Component C may be a commercially available product. Examples of commercially available component C include Kaneka MS Polymer (registered trademark) S810, S257, and S327 (all manufactured by Kaneka Corporation); Silyl (registered trademark) SAX220, SAT400, SAX510, SAX520, SAX580, SAX750, and SAT145 (all manufactured by Kaneka Corporation); Exestar (registered trademark) ES-S2410, ES-S2420, and ES-S3630 (all manufactured by AGC Corporation); and HMS-1603 and HMS-1207 (manufactured by Huangma Technology Co., Ltd.).

[0073] [1.3.3. Physical properties of component C] The lower limit of the number average molecular weight of component C 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 C is preferably 50,000 or less, and preferably 30,000 or less.

[0074] The molecular weight distribution of Component C is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.2 or less. If the molecular weight distribution is too large, the viscosity of the curable composition tends to increase, reducing workability.

[0075] Such component C can be obtained by the method described in

[0011] to

[0058] of JP 2021-55010 A.

[0076] [1.4. Component D: Amine-modified silicone compound] Component D is an amine-modified silicone compound. A curable composition containing component D has improved compatibility between the components, which tends to result in improved strength and elongation of the cured product.

[0077] The silicone compound refers to a compound having an organosiloxane skeleton. The organosiloxane skeleton is defined as -(Si-O) n -, where Si has two carbon-containing groups bonded thereto. Typically, the organosiloxane skeleton is a dimethylsiloxane skeleton. In one embodiment, component D has an organopolysiloxane skeleton in which organosiloxane skeletons are linked together (e.g., n in the above formula can be 10 or more, 50 or more, or 100 or more). In one embodiment, component D may have another main chain skeleton in addition to the organosiloxane skeleton (such as a polyol skeleton).

[0078] Component D has one or more amines in its molecule. The amines are preferably primary amines or secondary amines, and more preferably primary amines. In one embodiment, component D has one or more amino groups in its molecule. The amines may be contained in the organosiloxane skeleton or in other moieties. In one embodiment, component D has a structure in which one or more carbon-containing groups (such as methyl groups) at the end or side chain of the organosiloxane skeleton are substituted with groups having an amine.

[0079] In one embodiment, component D has two or more amines in its molecule. As explained at the beginning of Section [1], it is presumed that the amines in component D react with the halogens normally contained in component A to form bonds. If component D has two or more amines, two or more molecules of component A will polymerize via component D. It is believed that such polymerized component A can contribute to improving the strength of the cured product.

[0080] The upper limit of the amine functional group equivalent weight in component D may be 2000 g / mol or less, 1500 g / mol or less, or 500 g / mol or less. The lower limit of the amine functional group equivalent weight in component D may be 30 g / mol or more, or 100 g / mol or more. The amine functional group equivalent weight is the weight of a compound containing 1 mole of amine. When the molecular weight of the compound is M and the number of amines contained per molecule of the compound is X, the amine functional group equivalent weight is calculated by M / X. In one embodiment, the amine functional group equivalent weight is the functional group equivalent weight of primary amines and secondary amines, and tertiary amines are not included in the calculation of the equivalent weight.

[0081] Component D having an amine functional group equivalent weight within the above range can be said to have a sufficiently large number of organosiloxane skeletons relative to the number of amines. Therefore, effects attributable to the organosiloxane skeleton can be expected. For example, the surfactant effect due to the balance between the amines and the organosiloxane skeleton is high, and the compatibility of each component contained in the curable composition is improved, which can result in improved strength and elongation of the cured product.

[0082] Specific examples of component D include amine-modified silicone oil. Commercially available amine-modified silicone oils may be used. Examples of such commercially available products include DOWSIL BY 16-205, BY 16-213, BY 16-849 Fluid, BY 16-853 U, BY 16-871, BY 16-872, BY 16-879 B, BY 16-891, BY 16-892, FZ-3705, FZ-3710 Fluid, FZ-3760, FZ-3785, FZ-3789, and SF 8417. Fluid (all Dow Toray Industries, Inc.); KF-393, KF-857, KF-858, KF-859, KF-860, KF-861, KF-862, KF-864, KF-865, KF-867, KF-868, KF-869, KF-877, KF-880, KF-8002, KF-8004, KF-8005, KF-8008, KF-8010, KF-8012, K F-8021, PAM-E, X-22-161A, X-22-161B, X-22-1660B-3, X-22-3939A, X-22-9409 (all manufactured by Shin-Etsu Chemical Co., Ltd.); TSF4700, TSF4701, TSF4703, TSF4704, TSF4705, TSF4706, TSF4707, TSF4708, TSF4709 (all manufactured by Momentive Performance Materials Inc.).

[0083] [1.5. Component E: Curing catalyst] Examples of the curing catalyst include tin-based curing catalysts.Specific examples of the tin-based curing catalyst include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalic acid ester, etc.); tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and silyl group-containing low molecular weight silicon divalent tin compounds (such as tin octoate, tin naphthenate, and tin stearate); 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).

[0084] 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.

[0085] [1.6. 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.

[0086] (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.

[0087] 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.

[0088] The content of the adhesion promoter is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, when the total content of Components A to C is 100 parts by weight.

[0089] (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.).

[0090] 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, assuming that the total content of components A to C is 100 parts by weight.

[0091] (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.

[0092] 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.

[0093] 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, when the total content of Components A to C is 100 parts by weight.

[0094] (thixotropy imparting agent (anti-sagging agent)) The curable composition may contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability.

[0095] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps (calcium stearate, aluminum stearate, barium stearate, etc.).

[0096] 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, assuming that the total content of Components A to C is 100 parts by weight.

[0097] (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.

[0098] 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 a urethane bond and a (meth)acrylic group in the molecular chain obtained by reacting a polyol, a polyisocyanate, a hydroxyl group-containing (meth)acrylate, etc.

[0099] The content of the photocurable substance is preferably 0.01 to 30 parts by weight, assuming that the total content of components A to C is 100 parts by weight.

[0100] (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].

[0101] 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.

[0102] 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.

[0103] 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.).

[0104] 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.

[0105] 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.

[0106] 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).

[0107] 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.

[0108] The content of the antioxidant and / or light stabilizer is preferably 0.1 to 20 parts by weight, respectively, when the total content of Components A to C is 100 parts by weight.

[0109] (strong base) The hardenable composition may include a strong base. It is believed that the strong base provides favorable reaction conditions for the bonding of component A and component D. In one embodiment, the strong base may have a base dissociation constant pKb of 1 or less, 0.5 or less, or 0 or less.

[0110] The strong base may be an inorganic or organic compound, hi one embodiment, the strong base is an inorganic salt or a tertiary amine. Examples of inorganic salts include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.); alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.); alkali metal oxides (sodium oxide, etc.); alkaline earth metal oxides (calcium oxide, etc.). Examples of tertiary amines include diazabicycloundecene (1,8-diazabicyclo[5.4.0]-7-undecene), diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene), N,N,N',N',tetramethylguanidine, triethylamine, and tris-(dimethylaminomethyl)phenol.

[0111] Among the strong bases mentioned above, sodium hydroxide, calcium oxide, and diazabicycloundecene are preferred because they have high basicity and are easy to handle in liquid form. Furthermore, in terms of improving the storage stability of the curable composition, the strong base is preferably diazabicycloundecene.

[0112] The content of the amino group-introducing catalyst is preferably 0.1 to 10 parts by weight, assuming that the total content of Components A to C is 100 parts by weight.

[0113] 2. Composition of the curable composition In the curable composition, the lower limit of the content ratio (weight ratio) of Component A / Component B 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 B may be 90 / 10 or less, 80 / 20 or less, or 70 / 30 or less.

[0114] In the curable composition, the lower limit of the content of component C is preferably 50% by weight or more, more preferably 60% by weight or more, and even more preferably 70% by weight or more, when the total content of components A to C is 100% by weight. The upper limit of the content of component C can be 90 parts by weight or less, 80 parts by weight or less, or 75 parts by weight or less. When the content of component C is within the above range, the mechanical properties of the cured product are excellent.

[0115] In the curable composition, the lower limit of the content of Component D may be 0.05 parts by weight or more, or 0.1 parts by weight or more, relative to 100 parts by weight of the total content of Components A to C. The upper limit of the content of Component D may be 5 parts by weight or less, or 3 parts by weight or less, relative to 100 parts by weight of the total content of Components A to C.

[0116] In the curable composition, the lower limit of the content of Component E may be 0.1 parts by weight or more, or 0.5 parts by weight or more, relative to 100 parts by weight of the contents of Components A to C. 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, relative to 100 parts by weight of the contents of Components A to C.

[0117] 3. Form of curable composition The curable composition containing components A to E 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.

[0118] 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.

[0119] 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.

[0120] [4. 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.

[0121] 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.

[0122] 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.

[0123] [5. Summary] <1> A curable composition comprising the following components A to E: Component A: a (meth)acrylic block copolymer having a silyl group; Component B: a (meth)acrylic random copolymer having a silyl group; Component C: a polyoxyalkylene polymer having a silyl group; Component D: amine-modified silicone compound; Component E: Curing catalyst; Here, the component A is The molecule has an XY diblock structure having an X block and a Y block or an XYX triblock structure, the X block contains an average of more than 2.0 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers, The molecular weight distribution (Mw / Mn) is 1.8 or less; Here, the component B is The polymer has an average of 1.0 or more silyl groups derived from silyl group-containing (meth)acrylic acid ester monomers per molecule, The molecular weight distribution (Mw / Mn) is greater than 1.8. <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> 5. The curable composition according to any one of claims 4 to 4. <5> The amine functional group equivalent weight of the component D is 30 g / mol or more. <1> ~ <4> The curable composition according to any one of the preceding claims. <6> When the total of the components A to C is 100% by weight, the content of component C is 50% by weight or more. <1> ~ <5> The curable composition according to any one of the preceding claims. <7> <1> ~ <6> A cured product obtained by curing the curable composition according to any one of the above items. [Example]

[0124] [Measurement method] [Number average molecular weight] The average molecular weight was measured using the following equipment. 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℃

[0125] [Terminal silyl group introduction rate] 1 The introduction rate of terminal silyl groups was calculated from the results of H-NMR measurement. 1 The following equipment was used for H-NMR measurements. Measuring instrument: JNM-LA400 (JEOL Ltd.) Solvent: CDCl3

[0126] [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 break and the elongation at break.

[0127] [Tear strength] The curable composition was cured at 23°C and 50% RH to obtain a cured product. Measurement was carried out using a crescent-shaped test piece in accordance with the method of JIS K6252-1.

[0128] [Appearance of the curable composition] The prepared curable composition was placed in 100 g (volume: 140 mL) and allowed to stand at 23° C. for 24 hours. After standing, the appearance of the curable composition was visually evaluated. The evaluation criteria were as follows: A: Transparent and not phase separated. B: Cloudy but no phase separation. C: Phase separation occurs.

[0129] 〔material〕 ●Ingredient A The (meth)acrylic block copolymer (A) having a silyl group obtained in Production Example 1 ●Ingredient B The (meth)acrylic random copolymer (B) having silyl groups obtained in Production Example 2 ●Component C Silyl group-containing polyoxyalkylene polymer (C) obtained in Production Example 3 ●Component D Amine-modified silicone compound (D-1) (DOWSIL BY 16-871, Dow-Toray Industries, Inc., amine functional group equivalent: 130 g / mol, monoamines introduced at both ends) Amine-modified silicone compound (D-2) (DOWSIL BY 16-853 U, Dow Toray Industries, Inc., amine functional group equivalent: 450 g / mol, monoamines introduced at both ends) Amine-modified silicone compound (D-3) (DOWSIL FZ-3789, Dow Toray Industries, Inc., amine functional group equivalent: 1300 g / mol, (AB) n (polyether modified, amino group introduced into the side chain) ●Ingredient E Curing catalyst (Neostan U-220H, Nitto Kasei Co., Ltd., dibutyltin) Dehydrating agent Dehydrating agents (Silquest A-171, Momentive Performance Materials, vinyltrimethoxysilane) Adhesion promoter Adhesion promoter (KBM-603, Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) Strong base (potassium hydroxide)

[0130] [Production Example 1: Synthesis of (meth)acrylic block copolymer (A) having silyl groups] A (meth)acrylic block copolymer (A) having a silyl group was synthesized by the following procedure. (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 and then a vacuum pump. In this way, a (meth)acrylic block copolymer (A) was obtained.

[0131] The (meth)acrylic block copolymer (A) produced in Production Example 1 was an XYX type block copolymer, with 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 was 2.1. The amount of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block was 1.1 wt % based on the weight of all repeating units contained in the Y block.

[0132] [Production Example 2: (Meth)acrylic random copolymer (B)] 1. 50g of toluene was heated to 110°C. 2. A solution prepared by dissolving 68 g of butyl acrylate, 10 g of methyl methacrylate, 20 g of stearyl methacrylate, 2 g of γ-methacryloxypropylmethyldimethoxysilane, and 0.5 g of 2,2′-azobis(2-methylbutyronitrile) (V-59, Wako Pure Chemical Industries, Ltd.) in 20 g of toluene was added dropwise to the toluene from step 1 over 4 hours. 3. Toluene was removed using an evaporator to obtain a (meth)acrylic random copolymer (B). A toluene solution of a (meth)acrylic random copolymer (B) having a number average molecular weight of about 18,000 was obtained.

[0133] The (meth)acrylic random copolymer has a structure in which dimethoxymethylsilyl groups are randomly introduced into the main chain of poly(meth)acrylic ester. The (meth)acrylic random copolymer (B) had a number average molecular weight of approximately 18,000 and a molecular weight distribution of 1.8. The number of silyl groups contained in the (meth)acrylic random copolymer (B) was an average of 0.94 per molecule.

[0134] [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 was added to 100 parts by weight of allyl-terminated polyoxypropylene, and the mixture was allowed to react 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.

[0135] 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.

[0136] [Examples 1 to 3, Comparative Example 1] 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.

[0137] 〔result〕 The results are shown in Table 1. [Table 1]

[0138] The curable compositions according to the examples contain components A to E. The curable compositions according to the comparative examples do not contain component D. As can be seen from Table 1, the cured products according to the examples had higher stress at break, elongation at break, and tear strength than the cured products according to the comparative examples. This suggests that the cured products according to one embodiment of the present invention have excellent strength and elongation.

[0139] When comparing the appearances of the curable compositions, no phase separation was observed in the curable compositions of the Examples, whereas phase separation was observed in the curable compositions of the Comparative Examples. From this, it is believed that the curable compositions of the Examples contain all of components A to E, and therefore have high compatibility, resulting in improved strength of the cured product. [Industrial Applicability]

[0140] The curable composition according to one embodiment of the present invention can be suitably used for pressure sensitive adhesives, sealants, adhesives, molding agents, vibration isolators, vibration dampers, soundproofing materials, foam materials, paints, spray materials, and the like.

Claims

1. A curable composition comprising the following components A to E: Component A: a (meth)acrylic block copolymer having a silyl group; Component B: a (meth)acrylic random copolymer having a silyl group; Component C: a polyoxyalkylene polymer having a silyl group; Component D: amine-modified silicone compound; Component E: curing catalyst; Here, the component A is The molecule has an XY diblock structure or an XYX triblock structure having an X block and a Y block, the X block contains an average of more than 2.0 repeating units derived from a silyl group-containing (meth)acrylic acid ester monomer, The molecular weight distribution (Mw / Mn) is 1.8 or less; Here, the component B is The (meth)acrylic acid ester monomer has an average of 1.0 or more silyl groups derived from the silyl group-containing (meth)acrylic acid ester monomer per molecule, The molecular weight distribution (Mw / Mn) is greater than 1.

8.

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. The curable composition according to claim 1, wherein the amine functional group equivalent of component D is 30 g / mol or more.

6. 2. The curable composition according to claim 1, wherein the content of component C is 50% by weight or more when the total of components A to C is 100% by weight.

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

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