Curable composition

Abstract

To provide a curable composition that contains a reactive silicon group-containing (meth)acrylic copolymer with a block structure, enabling provision of a cured product having improved strength or elongation.SOLUTION: A (meth)acrylic ester polymer (A) having a reactive silicon group has an X block and a Y block, and includes an XY diblock structure or an XYX triblock structure in a molecule. The average number of (meth)acrylic ester monomers having a reactive silicon group contained in the X block is 1.0 or more. A proportion of (meth)acrylic ester monomers having a reactive silicon group contained in the Y block is 0 to 3 wt.%. The polymer (A) has a molecular weight distribution (Mw / Mn) of 1.8 or less. A curing catalyst contains a titanium compound (B) represented by formula (R2-O)nTi-A4-n and ammonium hydroxide (C), or contains a reaction product of (B) and (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition containing a reactive silicon group-containing (meth)acrylic acid ester polymer. [Background technology]

[0002] Polymers containing reactive silicon groups are known as moisture-reactive polymers, and are found in many industrial products such as adhesives, sealants, coating materials, paints, and pressure-sensitive adhesives, and are used in a wide range of fields.

[0003] Known polymer components of such reactive silicon group-containing polymers include various polymers whose main chain skeletons include polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester copolymers.

[0004] Polymers with reactive silicon groups are stable over the long term, as the silicon groups do not react with water in the absence of a curing catalyst, and the curing reaction begins immediately when a curing catalyst is added. Tin catalysts are often used as curing catalysts, but catalysts other than tin are sometimes required.

[0005] For example, titanium catalysts have been developed as curing catalysts other than tin. For example, Patent Document 1 describes a curable composition containing a reactive silicon-containing polyoxyalkylene polymer having a specific structure, and a titanium compound having a specific structure and ammonium hydroxide as a curing catalyst.

[0006] On the other hand, Patent Document 2 discloses a (meth)acrylic copolymer having a specific diblock structure or triblock structure as a reactive silicon group-containing (meth)acrylic copolymer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2023 / 054701 [Patent Document 2] International Publication No. 2021 / 157583 Summary of the Invention [Problem to be solved by the invention]

[0008] The cured product obtained by curing a reactive silicon group-containing (meth)acrylic copolymer having a specific block structure as disclosed in Patent Document 2 with a general tin catalyst may not have sufficient strength or elongation, and there is a need to improve this.

[0009] An object of the present invention is to provide a curable composition that contains a reactive silicon group-containing (meth)acrylic copolymer having a block structure and that can give a cured product with improved strength or elongation. [Means for solving the problem]

[0010] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the use of a specific non-tin catalyst as a curing catalyst in a curable composition containing a reactive silicon group-containing (meth)acrylic copolymer having a block structure improves the strength or elongation of the resulting cured product, and have thus completed the present invention.

[0011] That is, the present invention relates to a compound represented by the general formula (1): -Si(R 1 ) 3-a X a (1) (R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. A curable composition containing a (meth)acrylic acid ester-based polymer (A) having a reactive silicon group represented by the formula: and a curing catalyst, The (meth)acrylic acid ester polymer (A) has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule, the number of monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group contained in the X block is 1.0 or more on average; the proportion of the monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group contained in the Y block is 0 to 3 wt % based on the total weight of all monomer units contained in the Y block; the (meth)acrylic acid ester polymer (A) has a molecular weight distribution (Mw / Mn) of 1.8 or less; The curing catalyst is represented by the general formula (2): (R 2 -O) n Ti-A 4-n (2) (R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; and A is a β-diketone group. and ammonium hydroxide (C), or a reaction product of the titanium compound (B) and the ammonium hydroxide (C). [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a curable composition that contains a reactive silicon group-containing (meth)acrylic copolymer having a block structure and that can give a cured product with improved strength or elongation. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. [1. Reactive silicon group-containing (meth)acrylic acid ester polymer (A)] The curable composition according to the present disclosure contains a reactive silicon group-containing (meth)acrylic ester polymer (A) (hereinafter also referred to as a (meth)acrylic ester polymer (A), a (meth)acrylic polymer (A), or a polymer (A)). In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic."

[0014] <Reactive silicon group> The (meth)acrylic acid ester polymer (A) is represented by the general formula (1): -Si(R 1 ) 3-a X a (1) (R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. It has a reactive silicon group represented by the following formula:

[0015] R 1 is a hydrocarbon group having 1 to 20 carbon atoms. 1 The number of carbon atoms in the hydrocarbon group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent.

[0016] R 1 The hetero-containing group that the hydrocarbon group may have as a substituent is a group containing a hetero atom, where an atom other than a carbon atom or a hydrogen atom is defined as a hetero atom.

[0017] Suitable examples of heteroatoms include N, O, S, P, Si, and halogen atoms. In the hetero-containing group, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0018] Suitable examples of hetero-containing groups include a hydroxyl group; a mercapto group; halogen atoms such as Cl, Br, I, and F; a nitro group; a cyano group; alkoxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, and an isopropyloxy group; alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, and an isopropylthio group; acyl groups such as an acetyl group, a propionyl group, and a butanoyl group; acyloxy groups such as an acetyloxy group, a propionyloxy group, and a butanoyloxy group; substituted or unsubstituted amino groups such as an amino group, a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group; substituted or unsubstituted aminocarbonyl groups such as an aminocarbonyl group, a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group; and a cyano group.

[0019] R 1 When R is a hydrocarbon group substituted with a hetero-containing group, 1 The total number of carbon atoms and hetero atoms in is preferably 2 to 30, more preferably 2 to 18, further preferably 2 to 10, and particularly preferably 2 to 6.

[0020] R 1Specific examples of the hydrocarbon group having 1 to 20 carbon atoms as the substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethyl-n-hexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; alkenyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, naphthalen-1-yl, naphthalen-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphthalen-1-ylmethyl, and naphthalen-2-ylmethyl.

[0021] These hydrocarbon groups substituted with the hetero-containing groups described above are also included in R 1 It is preferable as.

[0022] R 1 Suitable examples of R include alkyl groups such as methyl and ethyl groups; alkyl groups having hetero-containing groups such as chloromethyl and methoxymethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. 1 As the alkyl group, a methyl group, a methoxymethyl group, and a chloromethyl group are preferred, a methyl group and a methoxymethyl group are more preferred, and a methyl group is even more preferred.

[0023] a is 1, 2, or 3. a is preferably 2 or 3, and more preferably 2 from the viewpoints of the curability of the curable composition and the productivity of the polymer (A).

[0024] Examples of X include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group is more preferred because it is mildly hydrolyzable and easy to handle. Generally, the fewer the carbon atoms in an alkoxy group, the higher the reactivity. That is, the reactivity decreases in the order of methoxy, ethoxy, and propoxy groups. Utilizing this property, the specific structure of the reactive silicon group can be appropriately determined depending on the production method and application of the (meth)acrylic acid ester polymer (A).

[0025] Specific examples of the reactive silicon group 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. From the viewpoint of the curability of the curable composition, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, and the like are preferred, and a dimethoxymethylsilyl group is particularly preferred.

[0026] <(Meth)acrylic copolymer (A)> The (meth)acrylic copolymer (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 the (meth)acrylic copolymer (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.

[0027] The weight ratio of X / Y in the (meth)acrylic copolymer (A) is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0028] In one embodiment, the molecule of the (meth)acrylic copolymer (A) has an XY diblock structure. In a molecule of the XY diblock structure, the X block can be a region from one end of the molecule where 40% or less, 30% or less, or 25% or less of the monomer units are present, assuming that the total number of monomer units contained in the molecule is 100%. Here, the X block is the block on the side where reactive silicon groups are distributed in a relatively large amount.

[0029] In one embodiment, the molecule of the (meth)acrylic copolymer (A) has an XYX triblock structure. In a molecule with an XYX triblock structure, the X blocks can be regions where 40% or less, 30% or less, or 25% or less of the monomer units are present from both ends of the molecule, assuming that the total number of monomer units contained in the molecule is 100%. Here, the X blocks are blocks located at both ends of the molecule, and the Y block is a block located near the center of the molecule.

[0030] The (meth)acrylic copolymer (A) also contains monomer units derived from (meth)acrylic ester monomers having a reactive silicon group. These monomer units derived from (meth)acrylic ester monomers having a reactive silicon group are contained in a relatively large amount in the X block. Specifically, the number of monomer units derived from (meth)acrylic ester monomers having a reactive silicon group contained in the X block, calculated by adding up the number contained in the X block, is 1.0 or more on average. Meanwhile, the proportion of monomer units derived from (meth)acrylic ester monomers having a reactive silicon group contained in the Y block is 0 to 3 wt % based on the total weight of all monomer units contained in the Y block (100 wt %).

[0031] Therefore, the monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group are distributed in large quantities at least at one end of the (meth)acrylic copolymer (A). In particular, when the (meth)acrylic copolymer (A) has an XY diblock structure, the monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group are localized near one end of the molecule. In addition, when the (meth)acrylic copolymer (A) has an XYX triblock structure, the monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group are localized near both ends of the molecule.

[0032] The number of monomer units derived from (meth)acrylic acid ester monomers having a reactive silicon group contained in the X block is preferably 1.5 or more, more preferably 1.7 or more, on average, when the total number contained in the X block is counted. Similarly, the proportion of monomer units derived from (meth)acrylic acid ester monomers having a reactive silicon group contained in the X block is preferably more than 3% by weight, more preferably 4.5% by weight or more, and even more preferably 5% by weight or more, based on the total weight (100% by weight) of all monomer units contained in the X block.

[0033] The upper limit of the proportion of monomer units derived from (meth)acrylic acid ester monomers having a reactive silicon group contained in the Y block is preferably 2% by weight or less, more preferably 1% by weight or less, based on the total weight of all monomer units contained in the Y block. The lower limit of the proportion of monomer units derived from (meth)acrylic acid ester monomers having a reactive silicon group contained in the Y block is preferably 0% by weight or more, more preferably more than 0% by weight, based on the total weight of all monomer units contained in the Y block.

[0034] When the (meth)acrylic copolymer (A) has an XY diblock structure, the number of reactive silicon groups contained in the (meth)acrylic copolymer (A) is preferably 1 or more, more preferably 1.1 or more, and even more preferably 1.2 or more on average per molecule. When the (meth)acrylic copolymer (A) has an XYX triblock structure or an XYXY tetrablock structure, the number of reactive silicon groups contained in the (meth)acrylic copolymer (A) is preferably 2 or more, more preferably 2.2 or more, and even more preferably 2.4 or more on average per molecule. The upper limit of the number of reactive silicon groups in the (meth)acrylic copolymer (A) is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 4.0 or less. When the number of reactive silicon groups is within the above range, the physical properties of the curable composition and the cured product can be good.

[0035] The number average molecular weight of the (meth)acrylic copolymer (A) is not particularly limited, but is preferably 4,000 to 80,000, more preferably 20,000 to 60,000. A number average molecular weight of 4,000 or more can improve the physical properties of the curable composition and the cured product. A number average molecular weight of 80,000 or less prevents the viscosity from becoming too high, ensuring sufficient workability. The number average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0036] The (meth)acrylic copolymer (A) is an acrylic copolymer having a small ratio (Mw / Mn; molecular weight distribution) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn). Specifically, the molecular weight distribution of the (meth)acrylic copolymer (A) is 1.8 or less. The molecular weight distribution of the (meth)acrylic copolymer (A) is preferably 1.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity of the polymer increases, which tends to reduce workability.

[0037] The weight-average molecular weight and number-average molecular weight can be measured, for example, by gel permeation chromatography (GPC). For GPC measurement, chloroform can be used as the mobile phase and a polystyrene gel column can be used as the stationary phase. These molecular weights can be calculated in terms of polystyrene.

[0038] The (meth)acrylic copolymer (A) having such a narrow molecular weight distribution can be suitably produced, for example, by a production method utilizing living radical polymerization, the details of which will be described later.

[0039] [1.1. (Meth)acrylic acid ester monomers] The (meth)acrylic copolymer (A) contains, in its main chain, monomer units derived from (meth)acrylic acid ester monomers. The (meth)acrylic acid ester monomers referred to here refer to monomers that do not have a reactive silicon group. Only one type of (meth)acrylic acid ester monomer may be used, or two or more types of (meth)acrylic acid ester monomers may be used in combination.

[0040] The (meth)acrylic acid ester monomer is not particularly limited, but examples thereof include the following. (Meth)acrylic acid ester monomer (α): A monomer having an alkyl group ester-bonded to (meth)acrylic acid, and the alkyl group having an alkoxy group having 1 to 5 carbon atoms. (Meth)acrylic acid ester monomer (β): A monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 1 to 5 carbon atoms. (Meth)acrylic acid ester monomer (γ): A monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 6 to 15 carbon atoms. (Meth)acrylic acid ester monomer (δ): A monomer in which the alkyl group ester-bonded to (meth)acrylic acid has 16 to 25 carbon atoms.

[0041] Next, the proportion of the monomer units derived from each monomer will be explained. Unless otherwise specified, the total weight of all the monomer units contained in the (meth)acrylic copolymer (A) is taken as 100% by weight. In the (meth)acrylic copolymer (A), the proportion of monomer units derived from the (meth)acrylic acid ester monomer (α) is preferably 0 to 20% by weight. The total proportion of monomer units derived from the (meth)acrylic acid ester monomer (β) and the (meth)acrylic acid ester monomer (γ) is preferably 45 to 96% by weight. The proportion of monomer units derived from the (meth)acrylic acid ester monomer (δ) is preferably 4 to 35% by weight. By containing each (meth)acrylic acid ester monomer in the above composition, the (meth)acrylic copolymer (A) can achieve good workability, mechanical properties, and weather resistance.

[0042] In one embodiment, the proportion of monomer units derived from the (meth)acrylic acid ester monomer (α) is preferably 5 to 20% by weight, more preferably 10 to 20% by weight. The proportion of monomer units derived from the (meth)acrylic acid ester monomer (β) is preferably 45 to 70% by weight, more preferably 50 to 70% by weight. The proportion of monomer units derived from the (meth)acrylic acid ester monomer (γ) is preferably 0 to 25% by weight, more preferably 10 to 25% by weight. The proportion of monomer units derived from the (meth)acrylic acid ester monomer (δ) is preferably 15 to 25% by weight, more preferably 15 to 20% by weight. By containing each (meth)acrylic acid ester monomer in the above composition, the (meth)acrylic copolymer (A) can achieve even better workability, mechanical properties, and weather resistance.

[0043] When the proportion of the monomer units derived from the (meth)acrylic acid ester monomer (β) is within the above range, a curable composition with low viscosity and good workability can be obtained. When the proportion of the monomer units derived from the (meth)acrylic acid ester monomer (γ) is within the above range, a cured product with excellent durability can be obtained. When the proportion of the monomer units derived from the (meth)acrylic acid ester monomer (δ) is within the above range, a cured product with excellent mechanical properties can be obtained.

[0044] The (meth)acrylic acid ester monomer is not particularly limited, and conventionally known ones can be used. Examples of the (meth)acrylic acid ester monomer (α) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (β) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (γ) include n-hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (δ) include pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, and docosyl (meth)acrylate.

[0045] Among the above-mentioned monomers, the (meth)acrylic acid ester monomer (α) is preferably one or more selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate, with 2-methoxyethyl acrylate being more preferred. The (meth)acrylic acid ester monomer (β) is preferably butyl acrylate. The (meth)acrylic acid ester monomer (γ) is preferably 2-ethylhexyl acrylate and dodecyl acrylate. The (meth)acrylic acid ester monomer (δ) is preferably one or more selected from the group consisting of pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, and docosyl (meth)acrylate, with octadecyl acrylate being more preferred. By selecting these monomers, the (meth)acrylic copolymer (A) can achieve a good balance of low viscosity, weather resistance, mechanical properties, and durability at high levels.

[0046] In one embodiment, the (meth)acrylic copolymer (A) does not contain any monomer units derived from the (meth)acrylic acid ester monomer (γ). Such a (meth)acrylic copolymer (A) has, for example, units derived from the above-mentioned preferred (meth)acrylic acid ester monomers (α), (β), and (δ). By not including the (meth)acrylic acid ester monomer (γ), the types of raw material monomers used can be reduced, thereby reducing production costs and labor.

[0047] The proportion of the monomer units derived from (meth)acrylic acid ester monomers contained in the (meth)acrylic copolymer (A) is preferably 70% by weight or more, and more preferably 90% by weight or more, based on the total weight of all monomer units contained in the (meth)acrylic copolymer (A) being 100% by weight. When the proportion of the monomer units derived from (meth)acrylic acid ester monomers is 70% or more, the (meth)acrylic copolymer (A) can achieve good weather resistance, mechanical properties, and durability.

[0048] [1.2. (Meth)acrylic acid ester monomers having reactive silicon groups] The (meth)acrylic copolymer (A) contains a monomer unit derived from a (meth)acrylic acid ester monomer having a reactive silicon group. The specific structure thereof is not particularly limited. An example thereof is a monomer represented by the following general formula (4): H2C=CR 3 C(=O)O-(CH2) m -Si(R 1 ) 3-a X a (4) In the formula, R 3 is hydrogen or a methyl group. m is an integer of 0 to 10. R 1 , X, and a are as defined above in general formula (1).

[0049] Specific examples of (meth)acrylic acid ester monomers having a reactive silicon group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane.

[0050] 2. Method for producing reactive silicon group-containing (meth)acrylic acid ester polymer (A) The (meth)acrylic copolymer (A) can be produced, for example, by a production method utilizing a living radical polymerization method. 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) ·Sigle Electron Transfer Polymerization; SET-LRP (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) Organotellurium Polymerization (TERP) method Polymerization method using organoantimony compounds (SBRP method) Organobismuth polymerization method (BIRP) -Iodine transfer polymerization method.

[0051] When the production method disclosed in JP 2018-162394 A is employed, halogen atoms may remain at one or both ends of the molecule of the (meth)acrylic copolymer (A) (the elongated ends of the molecular chain during polymerization). In one embodiment, the (meth)acrylic copolymer (A) has, on average, one or more halogen atoms per elongated end of the molecular chain during polymerization.

[0052] Among the living radical polymerization methods, atom transfer radical polymerization, single electron transfer polymerization, and reversible transfer catalyzed polymerization are preferred.

[0053] More preferred production methods include living radical polymerization of vinyl monomers using ATRP or SET-LRP with a transition metal or transition metal complex (composed of a transition metal compound and a ligand) as a catalyst, and RTCP, which does not use a transition metal as a catalyst.

[0054] Currently, there are two interpretations of the mechanism of living radical polymerization catalyzed by transition metal complexes: ATRP and SET-LRP. Based on ATRP, living radical polymerization consists of the equilibrium of the following two reactions (as an example, we will explain using a copper complex): (a) The monovalent copper complex abstracts the halogen at the end of the polymer to generate a radical, thereby becoming a divalent copper complex. (b) The divalent copper complex adds a halogen to the radical at the polymer end to form a monovalent copper complex.

[0055] On the other hand, when interpreted based on SET LRP, living radical polymerization consists of the equilibrium of the following three reactions (as an example, we will explain using a copper complex): (a) Zero-valent metallic copper or a copper complex abstracts a halogen atom from the polymer terminal to generate a radical, thereby becoming a divalent copper complex. (b) The divalent copper complex adds a halogen to the radical at the polymer end to become a zero-valent copper complex. (c) The monovalent copper complex disproportionates to give zero- and divalent copper complexes.

[0056] Furthermore, a synthetic method called Activators Regenerated by Electron Transfer (ARGET), which is an improved version of ATRP, has also been reported (Macromolecules. 2006, 39, 39). This method uses a reducing agent to reduce highly oxidized transition metal complexes, which can cause polymerization delays or terminations, and allows the polymerization reaction to proceed rapidly to a high conversion rate even under low catalyst conditions with a small amount of transition metal complex. This ARGET method can also be used.

[0057] In one embodiment, the (meth)acrylic copolymer (A) can be produced by a production method including the following steps 1a and 2a, or the following steps 1b and 2b. In the following description, "containing 0% by weight of a (meth)acrylic acid ester monomer having a reactive silicon group" means "containing no (meth)acrylic acid ester monomer having a reactive silicon group." (Step 1a) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing more than 3% by weight of a (meth)acrylic acid ester monomer having a reactive silicon group using a living polymerization initiator. (Step 2a) A step of adding a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth)acrylic acid ester monomer having a reactive silicon group to the reaction system after Step 1a, and polymerizing the mixture. (Step 1b) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth)acrylic acid ester monomer having a reactive silicon group using a living polymerization initiator. (Step 2b) A step of adding a (meth)acrylic acid ester monomer mixture containing more than 3% by weight of a (meth)acrylic acid ester monomer having a reactive silicon group to the reaction system after Step 1b, and polymerizing the mixture.

[0058] In one embodiment, the living polymerization initiator is a living radical polymerization initiator. As the living radical polymerization initiator, a known substance can be used. Hereinafter, each step will be described in more detail for each structure of the (meth)acrylic copolymer (A).

[0059] (When the copolymer has an XY diblock structure) The (meth)acrylic acid copolymer (A) having an XY diblock structure can be produced by the above-mentioned steps 1a and 2a or steps 1b and 2b. In this case, steps 1a and 2b form an X block containing a relatively large amount of reactive silicon groups, while steps 2a and 1b form a Y block containing a relatively small amount of reactive silicon groups.

[0060] In step 1a, a (meth)acrylic acid ester monomer having a reactive silicon group is polymerized using a living polymerization initiator. For example, an initiator having one halogen group in the molecule can be used as the living polymerization initiator. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group can be 1 to 10 molar equivalents per molar equivalent of the initiator. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having a reactive silicon group may also be polymerized together. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group added to the reaction system in step 1a accounts for more than 3% by weight of the monomer mixture added to the reaction system in step 1a.

[0061] In step 2a, a (meth)acrylic acid ester monomer having no reactive silicon group is added to the reaction system after step 1a and polymerized. The amount of the (meth)acrylic acid ester monomer having no reactive silicon group added can be 2 to 600 molar equivalents per molar equivalent of the polymer obtained in step 1a. In step 2a, a (meth)acrylic acid ester monomer having a reactive silicon group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group added to the reaction system in step 2a accounts for 0 to 3 wt% of the monomer mixture added to the reaction system in step 2a.

[0062] In step 1b, a (meth)acrylic acid ester monomer having no reactive silicon group is polymerized using a living polymerization initiator. The same living polymerization initiator as in step 1a can be used. The amount of the (meth)acrylic acid ester monomer having no reactive silicon group can be 2 to 600 molar equivalents per molar equivalent of the initiator. In step 1b, a (meth)acrylic acid ester monomer having a reactive silicon group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group added to the reaction system in step 1b accounts for 0 to 3 wt % of the monomer mixture added to the reaction system in step 1b.

[0063] In step 2b, a (meth)acrylic acid ester monomer having a reactive silicon group is added to the reaction system after step 1b and polymerized. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group can be 1 to 10 molar equivalents per 1 molar equivalent of the polymer obtained in step 1b. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having a reactive silicon group may also be polymerized together. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group added to the reaction system in step 2b accounts for more than 3 wt% of the monomer mixture added to the reaction system in step 2b.

[0064] In the above process, examples of the "(meth)acrylic acid ester monomer having no reactive silicon group" include the (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) described in Section [1]. This also applies to the following description.

[0065] (When the copolymer has an XYX triblock structure) The (meth)acrylic acid copolymer (A) having an XYX triblock structure can be produced by carrying out the additional polymerization step (a) after the above-mentioned steps 1a and 2a, whereby an X block containing a relatively large amount of reactive silicon groups is formed by the steps 1a and 2a.

[0066] In the additional polymerization step (a), a (meth)acrylic acid ester monomer having a reactive silicon group is added to the reaction system after step 2a and polymerized. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group can be 1 to 10 molar equivalents per molar equivalent of the polymer obtained in step 2a. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having a reactive silicon group may also be polymerized together. The amount of the (meth)acrylic acid ester monomer having a reactive silicon group added to the reaction system in the additional polymerization step (a) accounts for more than 3% by weight of the monomer mixture added to the reaction system in that step.

[0067] (When the copolymer has four or more blocks) By appropriately combining the above-mentioned steps 1a, 2a, and the additional polymerization step (a), it is possible to produce a (meth)acrylic copolymer (A) having four or more blocks, such as a (meth)acrylic copolymer (A) having an XYXY tetrablock structure.

[0068] (Identification of the structure of the (meth)acrylic copolymer (A) by the production method) In one embodiment, the (meth)acrylic copolymer (A) is defined as a copolymer obtained by the above-mentioned production method, i.e., the (meth)acrylic copolymer (A) may be a copolymer obtained by a production method including steps 1a and 2a, or steps 1b and 2b.

[0069] In the above-mentioned production method, a (meth)acrylic acid ester monomer having a reactive silicon group is introduced by copolymerization, and therefore it is almost impractical to specifically specify the position of the reactive silicon group in the resulting copolymer molecule.

[0070] Furthermore, in the above-mentioned production method, when the same type of (meth)acrylic acid ester monomer not having a reactive silicon group is added to the reaction system in steps 1a and 2a (or steps 1b and 2b), the main chain structure of the resulting copolymer will be the same for both the X block and the Y block. In such a copolymer, it is almost impractical to specifically identify the boundary between the X block and the Y block.

[0071] Due to these circumstances, there are cases where it is necessary to define the (meth)acrylic copolymer (A) not as a specific structure of the copolymer molecule, but as a copolymer obtained by the above-mentioned production method.

[0072] Various chemicals that can be used in the production method according to one embodiment of the present invention will be described below. Each of these chemicals may be used alone or in combination of two or more. These chemicals may be added directly to the polymerization system, or may be generated within the polymerization system.

[0073] 2.1. Initiator As the initiator, a radical initiator having one halogen group in the molecule can be used. Examples of such initiators include ethyl 2-bromoisobutyrate, ethyl 2-bromobutyrate (also called ethyl α-bromobutyrate), ethyl bromoacetate, methyl bromoacetate, (1-bromoethyl)benzene, allyl bromide, methyl 2-bromopropionate, methyl chloroacetate, methyl 2-chloropropionate, and (1-chloroethyl)benzene. From the viewpoint of easy availability, ethyl 2-bromobutyrate, (1-bromoethyl)benzene, and methyl chloroacetate are preferred, and from the viewpoint of reactivity and safety, ethyl 2-bromobutyrate is preferred.

[0074] Alternatively, an initiator having a reactive silicon group may be used as the initiator. Alternatively, the reactive silicon group may be introduced into the initiator before or after the polymerization reaction. By such a method, a (meth)acrylic copolymer (A) having a reactive silicon group at least at the terminal can be produced.

[0075] [2.2. Polymerization catalyst] In the ATRP system, whether or not a reducing agent is used, a metal complex having a central metal of an element of Group 7, 8, 9, 10, or 11 of the periodic table can be used. Among these, metal complexes having a central metal of monovalent copper, divalent ruthenium, or divalent iron are particularly suitable.

[0076] Specific examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, and cuprous perchlorate. When using a copper compound as a polymerization catalyst, it is preferable to add an amine ligand to the polymerization system to enhance catalytic activity. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl2(PPh3)3) is also suitable as a catalyst. When using this catalyst, it is preferable to add an aluminum compound (such as trialkoxyaluminum) to the polymerization system to enhance catalytic activity. Furthermore, a tristriphenylphosphine complex of divalent iron chloride (FeCl2(PPh3)3) is also suitable as a catalyst. Among the above catalysts, copper catalysts are preferred because they are inexpensive. To enhance catalytic activity and productivity, it is more preferred to use a polydentate amine in combination with a copper catalyst.

[0077] [2.3. Polydentate amines] Examples of polydentate amines that can be used as ligands include: Bidentate and polydentate amines: 2,2-bipyridine, 4,4'-di-(5-nonyl)-2,2'-bipyridine, N-(n-propyl)pyridylmethanimine, N-(n-octyl)pyridylmethanimine Tridentate and multidentate amines: N,N,N',N'',N''-pentamethyldiethylenetriamine, N-propyl-N,N-di(2-pyridylmethyl)amine Tetradentate and polydentate amines: hexamethyltris(2-aminoethyl)amine (Me6TREN), N,N-bis(2-dimethylaminoethyl)-N,N'-dimethylethylenediamine, 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane, N',N''-dimethyl-N',N''-bis((pyridin-2-yl)methyl)ethane-1,2-diamine, tris[(2-pyridyl)methyl]amine, 2,5,8,12-tetramethyl-2,5,8,12-tetraazatetradecane Pentacoordinated polydentate amine: N,N,N',N'',N''',N'''',N''''-heptamethyltetraethylenetetramine Hexadentate polydentate amine: N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine · Polyamine: Polyethyleneimine.

[0078] [2.4. Bases] A base may be added to the polymerization system to neutralize the acid present or generated in the polymerization system and prevent the accumulation of the acid. Examples of bases include: Monoamines: Monoamines are compounds that have one base moiety per molecule. Examples of monoamines include primary amines (methylamine, aniline, lysine, etc.), secondary amines (dimethylamine, piperidine, etc.), tertiary amines (trimethylamine, triethylamine, etc.), aromatic amines (pyridine, pyrrole, etc.), and ammonia. Polyamines: Examples of polyamines include diamines (ethylenediamine, tetramethylethylenediamine, etc.), triamines (diethylenetriamine, pentamethyldiethylenetriamine, etc.), tetramines (triethylenetetramine, hexamethyltriethylenetetramine, hexamethylenetetramine, etc.), polyethyleneimine, etc. Inorganic Bases: Inorganic bases are elements or compounds of Groups 1 and 2 of the periodic table. Examples of elements of Groups 1 and 2 of the periodic table include lithium, sodium, and calcium. Examples of compounds of elements of Groups 1 and 2 of the periodic table include sodium methoxide, potassium ethoxide, methyllithium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium phenoxy, potassium phenoxy, sodium ascorbate, and potassium ascorbate.

[0079] 2.5. Reducing Agents In living radical polymerization using a copper complex as a catalyst, it is known that polymerization activity can be improved by using a reducing agent in combination (ARGET ATRP). In ARGET ATRP, it is believed that polymerization activity is improved by reducing and reducing highly oxidized transition metal complexes (produced by coupling between radicals, etc.), which cause delays or terminations in the polymerization reaction. This allows the transition metal catalyst, which would normally require hundreds to thousands of ppm, to be reduced to tens to hundreds of ppm. In a production method according to one embodiment of the present invention, a reducing agent can be used to achieve a reaction mechanism similar to that of ARGET ATRP. Examples of reducing agents include the following:

[0080] (A reducing agent that does not generate acid when reducing copper complexes) Metals: Examples of metals include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (beryllium, magnesium, calcium, barium, etc.), main group metals (aluminum, zinc, etc.), and transition metals (copper, nickel, ruthenium, iron, etc.). These metals can also be used in the form of alloys (amalgams) with mercury. Metal Compounds: Examples of metal compounds include metal salts and metal complexes. Examples of ligands in metal complexes include carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds. More specific examples include compounds of metals with ammonia / amines, titanium trichloride, titanium alkoxides, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, carbonyl complexes (Ni(CO)4, Co2CO8, etc.), olefin complexes ([Ni(cod)2], [RuCl2(cod)], [PtCl2(cod)], etc.; cod represents cyclooctadiene), and phosphine complexes ([RhCl(P(CH5)3)3], [RuCl2(P(CH5)3)2], [PtCl2(P(CH5)3)2], etc.). ·Organotin compounds: Specific examples include tin octoate, tin 2-ethylhexylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate. Phosphorus or phosphorus compounds: Specific examples include phosphorus, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorastriamide, and hexaethylphosphorastriamide. Sulfur or sulfur compounds: Specific examples include sulfur, rongalites, hydrosulfites, and thiourea dioxide. Rongalite refers to formaldehyde derivatives of sulfoxylates, and is represented by the general formula: MSO2·CHO (where M is Na or Zn). Specific examples of rongalite include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite refers to sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.

[0081] (A reducing agent (hydride reducing agent) that generates acid when reducing a copper complex) Metal hydrides: Specific examples include sodium hydride, germanium hydride, tungsten hydride, aluminum hydrides (diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc.), and organotin hydrides (triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, trimethyltin hydride, etc.). Silicon hydrides: Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, and polymethylhydrosiloxane. Boron hydrides. Specific examples include borane, diborane, sodium borohydride, sodium trimethoxyborohydride, sodium borohydride sulfide, sodium cyanide borohydride, lithium cyanide borohydride, lithium borohydride, lithium triethylborohydride, lithium tri-s-butylborohydride, lithium tri-t-butylborohydride, calcium borohydride, potassium borohydride, zinc borohydride, and tetra-n-butylammonium borohydride. Nitrogen-hydrogen compounds: Examples include hydrazine and diimide. Phosphorus or phosphorus compounds: Specific examples include phosphines and diazaphospholenes. Sulfur or sulfur compounds: A specific example is hydrogen sulfide. Organic compounds that exhibit reducing properties: Specific examples include alcohols, aldehydes, phenols, and organic acid compounds. Examples of alcohols include methanol, ethanol, propanol, and isopropanol. Examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, and formic acid. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, and tocopherol. Examples of organic acid compounds include citric acid, oxalic acid, ascorbic acid, ascorbate, and ascorbic acid esters.

[0082] Alternatively, the reducing agent may be generated in the polymerization system by electrolytic reduction, in which electrons generated at the cathode directly (or after solvation) exert a reducing effect. In other words, the reducing agent may be generated by electrolysis.

[0083] 2.6. Solvents Examples of solvents include the following: However, ATRP can also be carried out without using a solvent. Highly polar aprotic solvents: dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone Carbonate solvents: ethylene carbonate, propylene carbonate Alcohol-based solvents: methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol Nitrile solvents: acetonitrile, propionitrile, benzonitrile Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone Ether solvents: diethyl ether, tetrahydrofuran Halogenated hydrocarbon solvents: methylene chloride, chloroform Ester solvents: ethyl acetate, butyl acetate Hydrocarbon solvents: pentane, hexane, heptane, cyclohexane, octane, decane, benzene, toluene, xylene ·Other solvents: ionic liquids, water, supercritical fluids.

[0084] In ATRP (ARGET) systems using a reducing agent, it is preferable that the transition metal or transition metal compound, polydentate amine, base, reducing agent, monomer, and initiator are uniformly contained in the polymerization system from the viewpoints of reaction control, polymerization reaction rate, ease of charging, and risk of scale-up. Therefore, it is preferable to select a solvent that can dissolve these substances.

[0085] <<Titanium Compounds (B)>> The curable composition according to one embodiment of the present disclosure may contain a titanium compound (B) represented by general formula (2). (R 2 -O) n Ti-A 4-n (2) (R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; and A is a β-diketone group. R 2The substituted or unsubstituted hydrocarbon group represented by the formula (I) is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, more preferably an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups. Examples of the saturated hydrocarbon group include linear or branched alkyl groups. The hydrocarbon group has 1 to 10 carbon atoms, preferably 1 to 6, and more preferably 1 to 4. Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl. Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxyl group, and an acetoxy group. R 2 When there are a plurality of groups, they may be the same or different.

[0086] The β-diketone group represented by A is not particularly limited as long as it is a β-diketone that can be incorporated into titanium, and examples thereof include 1-aryl-1,3-butanediones such as 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, and 1-(4-methoxyphenyl)-1,3-butanedione, and 1,3-diaryl-1,3-propanedione, such as 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione. Examples of suitable esters include diketones such as 1,3-propanedione and 3-benzyl-2,4-pentanedione, ketoesters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate and ethyl 3-oxohexanoate, ketoamides such as N,N-dimethyl acetoacetamide, N,N-diethyl acetoacetamide and acetoacetanilide, malonic acid esters such as dimethyl malonate, diethyl malonate and diphenyl malonate, and malonic acid amides such as N,N,N',N'-tetramethylmalonamide and N,N,N',N'-tetraethylmalonamide. Among these, diketones and ketoamides are preferred, and diketones are more preferred. Specifically, 2,4-pentanedione, 1-aryl-1,3-butanedione, 1,3-diaryl-1,3-propanedione, methyl acetoacetate, and ethyl acetoacetate are preferred, and methyl acetoacetate and ethyl acetoacetate are particularly preferred. When a plurality of A's are present, they may be the same or different.

[0087] n represents an integer of 1 to 4. n preferably represents 2, 3, or 4, and particularly preferably represents 4, since better curability can be achieved.

[0088] Specific examples of titanium compounds represented by general formula (2) include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, and diethoxydibutoxytitanium. Titanium dioxide, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, tetra(tert-butoxy)titanium, tetra(sec-butoxy)titanium, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethyl acetoacetate), diisobutoxytitanium bis(acetylacetonate), diisobutoxytitanium bis(ethyl acetoacetate), and the like. In terms of catalytic activity, compound stability, and handleability, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), diisobutoxytitanium bis(acetylacetonate), diisobutoxytitanium bis(ethylacetoacetate), tetraisopropoxytitanium, tetrabutoxytitanium, tetra(tert-butoxy)titanium, and tetra(sec-butoxy)titanium are preferred, and diisopropoxytitanium bis(ethylacetoacetate), diisobutoxytitanium bis(ethylacetoacetate), tetraisopropoxytitanium, and tetra(tert-butoxy)titanium are particularly preferred.

[0089] The above titanium compounds (B) may be used alone or in combination of two or more kinds.

[0090] When the titanium compound (B) is used without reacting it with the ammonium hydroxide (C) in advance, the amount of the titanium compound (B) used is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0091] <<Ammonium hydroxide (C)>> The curable composition according to one embodiment of the present disclosure may contain ammonium hydroxide (C). The ammonium hydroxide (C) is preferably represented by the following general formula (3).

[0092] [ka]

[0093] (In the formula, R 4 , R 5 , R 6 , R 7 are the same or different and represent a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms. Y represents a hydroxyl group. R 4 , R 5 , R 6 , R 7 The substituted or unsubstituted hydrocarbon group represented by the formula (I) is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably a linear or branched alkyl group. The hydrocarbon group has 1 to 8 carbon atoms, preferably 1 to 6, and more preferably 1 to 4. Examples of the aliphatic hydrocarbon group include saturated hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, and octyl groups, and unsaturated hydrocarbon groups such as vinyl, allyl, prenyl, crotyl, and cyclopentadienyl groups, with methyl, ethyl, and butyl being preferred.

[0094] Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, and a benzyl group.

[0095] Substituents that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxy group, an acetoxy group, etc. Examples of the substituted hydrocarbon group include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, or an ethoxyethyl group, a hydroxyalkyl group such as a hydroxymethyl group, a hydroxyethyl group, or a 3-hydroxypropyl group, and a 2-acetoxyethyl group.

[0096] Specific examples of the ammonium hydroxide represented by general formula (3) include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, as well as trimethylbenzylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, and tris(2-hydroxyethyl)methylammonium hydroxide. In particular, tetraalkylammonium hydroxides are preferred, and tetrabutylammonium hydroxide is more preferred.

[0097] When the titanium compound (B) and the ammonium hydroxide (C) are used without reacting them in advance, the amount of the ammonium hydroxide (C) used is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0098] The molar ratio (B / C) of the titanium compound (B) to the ammonium hydroxide (C) is in the range of 0.1 / 1 to 10 / 1, and from the viewpoint of obtaining good curability, is preferably 1 / 1 to 10 / 1, and more preferably 2 / 1 to 5 / 1.

[0099] <Reaction product of titanium compound (B) and ammonium hydroxide (C)> The curable composition according to the present disclosure may contain both the titanium compound (B) and the ammonium hydroxide (C), or may contain a reaction product obtained by reacting the titanium compound (B) with the ammonium hydroxide (C). Either embodiment can improve the strength or elongation of the cured product, but the embodiment using the reaction product is preferred because it can result in better strength or elongation.

[0100] The reaction product can be obtained by reacting the mixture of the two at, for example, 40 to 100° C. Specifically, this temperature is preferably 40 to 100° C. In the mixture, the molar ratio of the titanium compound (B) to the ammonium hydroxide (C) may be, for example, 0.1 to 100, and more preferably 0.2 to 10.

[0101] The amount of the reaction product of the titanium compound (B) and the ammonium hydroxide (C) used is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0102] <<Polymer (D) Having Reactive Silicon Groups>> The curable composition according to the present disclosure may contain only the (meth)acrylic acid ester polymer (A) as the polymer having a reactive silicon group, or may further contain, in addition to the polymer (A), a polymer (D) other than the polymer (A) that has a reactive silicon group.

[0103] The reactive silicon group contained in polymer (D) can be represented by the above-mentioned general formula (1). The reactive silicon group contained in polymer (A) and the reactive silicon group contained in polymer (D) may be the same silicon group or different silicon groups.

[0104] Specific examples of the reactive silicon group that polymer (D) has include, but are not limited to, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group.Among these, dimethoxymethylsilyl group, trimethoxysilyl group, triethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are preferred because they can obtain a cured product with good mechanical properties. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are more preferred, and a trimethoxysilyl group is particularly preferred because it improves curability.

[0105] Specific examples of the polymer (D) include, but are not limited to, reactive silicon group-containing polyoxyalkylene polymers. The main chain structure of the polyoxyalkylene polymer may be linear or branched.

[0106] The main chain of the reactive silicon group-containing polyoxyalkylene polymer has a structure represented by the formula -R 13 -O-(wherein, R 13 is a linear or branched alkylene group having 1 to 14 carbon atoms), and R 13 is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. 13 Specific examples of repeating units represented by -O- include -CHO-, -CHCHO-, -CHCH(CH)O-, -CHC(CH)(CH)O-, and -CHCHCHCHO-, with -CHCHO- and -CHCH(CH)O- being preferred, and -CHCH(CH)O- being more preferred.

[0107] <Method for producing reactive silicon group-containing polyoxyalkylene polymer> Next, a method for producing a reactive silicon group-containing polyoxyalkylene polymer will be described.

[0108] The reactive silicon group-containing polyoxyalkylene polymer can be produced by introducing a reactive silicon group into a precursor polymer into which the reactive silicon group can be introduced. Specifically, the reactive silicon group-containing polyoxyalkylene polymer can be produced by introducing an olefin group into a polyoxyalkylene polymer (d1) having a terminal hydroxyl group by utilizing the reactivity of the hydroxyl group to obtain a precursor polymer having an olefin group, and then reacting the precursor polymer with a reactive silicon group-containing compound reactive with the olefin group to introduce the reactive silicon group.

[0109] (polymerization) The polymer backbone of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a polyoxyalkylene polymer (d1) having a hydroxyl group at its terminal. Although the specific polymerization method is not particularly limited, a polymerization method using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferred because it produces a hydroxyl-terminated polymer with a narrow molecular weight distribution (Mw / Mn).

[0110] The initiator having a hydroxyl group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low-molecular-weight polyoxypropylene glycol, low-molecular-weight polyoxypropylene triol, butanol, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, low-molecular-weight polyoxypropylene monoallyl ether, low-molecular-weight polyoxypropylene monoalkyl ether, etc. When obtaining a polymer having three or more main chain ends in one molecule, glycerin, pentaerythritol, low-molecular-weight polyoxypropylene triol, etc., having three or more hydroxyl groups can be used.

[0111] The epoxy compound is not particularly limited, but examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether, with propylene oxide being preferred.

[0112] (Reaction with alkali metal salts) When introducing olefin groups into a polyoxyalkylene polymer (d1) having terminal hydroxyl groups, it is preferable to first react the polyoxyalkylene polymer (d1) with an alkali metal salt to convert the terminal hydroxyl groups into metaloxy groups. Alternatively, a double metal cyanide complex catalyst can be used instead of the alkali metal salt. In this manner, a metaloxy-terminated polyoxyalkylene polymer (d2) is formed.

[0113] The alkali metal salt is not particularly limited, but examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoints of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and sodium tert-butoxide being more preferred. From the viewpoint of availability, sodium methoxide is preferred. The alkali metal salt may be subjected to the reaction in a state dissolved in a solvent.

[0114] (Reaction with electrophile (d3)) The metaloxy group-terminated polyoxyalkylene polymer (d2) obtained as described above can be reacted with an electrophilic agent (d3) having an olefin group to convert the metaloxy group into a structure containing an olefin group, thereby forming a polyoxyalkylene polymer (d4) having an olefin group in the terminal structure.

[0115] The electrophilic agent (d3) having an olefin group is not particularly limited as long as it is a compound that can react with the metaloxy group of the polyoxyalkylene polymer (d2) and introduce an olefin group into the polyoxyalkylene polymer. Examples of the electrophilic agent (d3) include an organic halide (d3-1) having an olefin group and an epoxy compound (d3-2) having an olefin group.

[0116] An organic halide (d3-1) having an olefin group, which is one embodiment of the electrophilic agent (d3), reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby introducing a structure containing an olefin group as a terminal structure of a polyoxyalkylene polymer.

[0117] Specific examples of the organic halide (d3-1) having an olefin group include, but are not limited to, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred because of ease of handling. Furthermore, methallyl chloride, methallyl bromide, and methallyl iodide are preferred because they improve the average ratio of the number of reactive silicon groups to the number of terminals of the polymer skeleton.

[0118] Alternatively, a halogenated hydrocarbon compound having a carbon-carbon triple bond can be used as the organic halide (d3-1) having an olefin group. The polyoxyalkylene polymer (d5) obtained by reacting such a compound has a carbon-carbon triple bond at the end of the polymer skeleton. When a reactive silicon group is introduced into such a polymer (d5), the atom adjacent to the reactive silicon group will have a carbon-carbon double bond.

[0119] Examples of the halogenated hydrocarbon compound having a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-2 ... Examples of the halogenated hydrocarbon compounds include 1-iodo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Among these, propargyl chloride, propargyl bromide, and propargyl iodide are more preferred. In addition to the halogenated hydrocarbon compounds having a carbon-carbon triple bond, halogenated hydrocarbon compounds having a carbon-carbon double bond may also be used.

[0120] An epoxy compound (d3-2) having an olefin group, which is another embodiment of the electrophile (d3), can react with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing an olefin group and a hydroxyl group as a terminal structure of the polyoxyalkylene polymer. In the ring-opening addition reaction, one or more epoxy compounds (d3-2) can be added to one metaloxy group by adjusting the amount of epoxy compound (d3-2) used relative to the metaloxy group and the reaction conditions.

[0121] Specific examples of the epoxy compound (d3-2) having an olefin group are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred in terms of reactivity, with allyl glycidyl ether being particularly preferred.

[0122] As described above, when the metaloxy group-terminated polyoxyalkylene polymer (d2) is reacted with the epoxy compound (d3-2) having an olefin group, new metaloxy groups are generated by ring-opening of the epoxy group. Therefore, after the reaction with the epoxy compound (d3-2), the polymer can be reacted with the organic halide (d3-1) having an olefin group.

[0123] (Introduction of reactive silicon groups) The polyoxyalkylene polymer (d4) having an olefin group in the terminal structure or the polyoxyalkylene polymer (d5) (precursor polymer) having a carbon-carbon triple bond in the terminal structure obtained as described above can be subjected to a hydrosilylation reaction with a hydrosilane compound (d6) having a reactive silicon group, thereby introducing a reactive silicon group into the polymer. This produces a polyoxyalkylene polymer containing a reactive silicon group. The hydrosilylation reaction has the advantages of being simple to carry out, easy to adjust the amount of reactive silicon group introduced, and stable physical properties of the resulting polymer.

[0124] Specific examples of the hydrosilane compound (d6) having a reactive silicon group include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane; Tylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-triflic (chloropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trichloromethyl)dimethoxysilyloxy]dimethylsilane Examples of suitable alkoxysilanes include alkoxysilanes such as (fluoropropyl)dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0125] The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst to promote the reaction. Known hydrosilylation catalysts include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as complexes thereof, and these can be used. Specific examples include platinum supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [e.g., Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphite complexes [e.g., Pt{P(OPh)3}4]. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

[0126] As another method for producing the polymer (A), a compound (d7) having a reactive silicon group and an isocyanate group in one molecule may be reacted with a polyoxyalkylene polymer (d1) (precursor polymer) having a terminal hydroxyl group to form a urethane bond and introduce the reactive silicon group. The polymer (A) can also be produced by this method.

[0127] The compound (d7) having a reactive silicon group and an isocyanate group in one molecule is not particularly limited as long as it is a compound having both an isocyanate group capable of undergoing a urethane reaction with a hydroxyl group in the polyoxyalkylene polymer (d1) and a reactive silicon group in one molecule. Specific examples include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, (3-isocyanatepropyl)diethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, and (isocyanatemethyl)diethoxymethylsilane.

[0128] The urethanization reaction may be carried out without using a urethanization catalyst, or may be carried out in the presence of a urethanization catalyst for the purpose of improving the reaction rate or the reaction rate. Examples of such urethanization catalysts include conventionally known urethanization catalysts, such as those listed in "Polyurethanes: Chemistry and Technology," Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963. Specific examples include, but are not limited to, basic catalysts such as organotin compounds, bismuth compounds, and organic amines.

[0129] Another method for producing a reactive silicon group-containing polyoxyalkylene polymer is to react a polyoxyalkylene polymer (d1) having a terminal hydroxyl group with an excess of a polyisocyanate compound (d8) to form a polymer (precursor polymer) having an isocyanate group at its terminal, and then to react the precursor polymer with a compound (d9) having a group reactive with an isocyanate group (e.g., an amino group) and a reactive silicon group. This method also allows the production of a polyoxyalkylene polymer having a reactive silicon group at the terminal of the polymer backbone.

[0130] Examples of the polyisocyanate compound (d8) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0131] Examples of the compound (d9) having a group reactive with an isocyanate group and a reactive silicon group include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-(N-phenyl)aminopropyltrimethoxysilane, γ-(N-phenyl)aminopropyldi Examples thereof include amino group-containing silanes such as methoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; and mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxymethylsilane.

[0132] Another method for producing a reactive silicon group-containing polyoxyalkylene polymer is to react a polyoxyalkylene polymer (d4) (precursor polymer) having an olefin group in its terminal structure with a compound (d10) having a reactive silicon group and a mercaptan group in one molecule, and form a sulfide bond by addition of the mercaptan group to the olefin group, thereby introducing the reactive silicon group. This method also allows the production of a polyoxyalkylene polymer having a reactive silicon group at the end of the polymer backbone.

[0133] The compound (d10) having a reactive silicon group and a mercaptan group in one molecule is not particularly limited as long as it is a compound having both a mercaptan group capable of undergoing an addition reaction with an olefin group in the polyoxyalkylene polymer (d4) and a reactive silicon group in one molecule. Specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, and (mercaptomethyl)triethoxysilane.

[0134] The addition reaction of a mercaptan group to an olefin group may be carried out without using a radical initiator, but may be carried out in the presence of a radical initiator in order to improve the reaction rate or the reaction rate. As such a radical initiator, a conventionally known initiator can be used. Specific examples include, but are not limited to, azo-based initiators and peroxide-based initiators.

[0135] Among known radical initiators, catalysts with low activity toward reactive silicon groups are preferred. From this perspective, azo-based initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.

[0136] The content ratio of polymer (A) to polymer (D) is not particularly limited and can be set appropriately, but from the viewpoint of prioritizing the properties of the (meth)acrylic acid ester polymer (A) and improving the storage stability of the curable composition while maintaining good curability, it is preferable that the weight ratio of the (meth)acrylic acid ester polymer (A) is 50% or more of the total of the (meth)acrylic acid ester polymer (A) and polymer (D). The weight ratio of the (meth)acrylic acid ester polymer (A) may be more than 70%, more than 80%, or more than 95%. The upper limit may be 100%.

[0137] <<Curable composition>> In addition to the reactive silicon group-containing polymer (A), titanium compound (B), and ammonium hydroxide (C), the curable composition of the present disclosure may contain additives such as other silanol condensation catalysts, fillers, adhesion promoters, plasticizers, solvents, diluents, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, physical property modifiers, tackifier resins, epoxy group-containing compounds, photocurable substances, oxygen-curable substances, epoxy resins, and other resins. Furthermore, various additives may be added to the curable composition of the present disclosure as needed to adjust the physical properties of the curable composition or the cured product. Examples of such additives include surface modifiers, foaming agents, curability modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0138] <Silanol condensation catalyst> In the present invention, a titanium compound (B) and ammonium hydroxide (C), or a reaction product thereof, is used as a silanol condensation catalyst for hydrolyzing and condensing the reactive silicon groups of the polymer (A) having a reactive silicon group, but other silanol condensation catalysts may also be used in combination.

[0139] Other silanol condensation catalysts include, for example, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, and alkoxy metals.

[0140] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dioctyltin oxide with a silicate compound, and a reaction product of dibutyltin oxide with a phthalate ester.

[0141] Specific examples of metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, etc. The carboxylic acid group can be a combination of the following carboxylic acids with various metals. Specifically, iron 2-ethylhexanoate (divalent), iron 2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate (tetravalent), vanadium 2-ethylhexanoate (trivalent), calcium 2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent), barium 2-ethylhexanoate (divalent), manganese 2-ethylhexanoate (divalent), nickel 2-ethylhexanoate (divalent), cobalt 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate (tetravalent), iron neodecanoate (divalent), iron neodecanoate (trivalent), titanium neodecanoate (tetravalent), vanadium neodecanoate (trivalent), calcium neodecanoate (divalent), potassium neodecanoate (monovalent), barium neodecanoate (divalent), di-ethylhexanoate Examples of suitable oleates include zinc (tetravalent), iron oleate (divalent), iron oleate (trivalent), titanium oleate (tetravalent), vanadium oleate (trivalent), calcium oleate (divalent), potassium oleate (monovalent), barium oleate (divalent), manganese oleate (divalent), nickel oleate (divalent), cobalt oleate (divalent), zirconium oleate (tetravalent), iron naphthenate (divalent), iron naphthenate (trivalent), titanium naphthenate (tetravalent), vanadium naphthenate (trivalent), calcium naphthenate (divalent), potassium naphthenate (monovalent), barium naphthenate (divalent), manganese naphthenate (divalent), nickel naphthenate (divalent), cobalt naphthenate (divalent), and zirconium naphthenate (tetravalent).

[0142] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0143] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0144] Specific examples of alkoxy metals include aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0145] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0146] Two or more different silanol condensation catalysts may be used in combination.

[0147] The amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0148] <Filler> The curable composition according to the present disclosure can contain various fillers, such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic acid anhydride, hydrated silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament, etc.

[0149] The amount of filler used is preferably 1 to 600 parts by weight, particularly preferably 10 to 300 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0150] Organic or inorganic balloons may be added to reduce the weight (specific gravity) of the composition. Balloons are hollow spherical fillers, and examples of materials for these balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. The amount of balloons used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0151] <Adhesion promoter> An adhesion promoter may be added to the curable composition according to the present disclosure.

[0152] As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be added.

[0153] Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isopropyltriethoxysilane. Examples of suitable silanes include isocyanate group-containing silanes such as α-isocyanate propyl methyl dimethoxy silane, α-isocyanate methyl trimethoxy silane, and α-isocyanate methyl dimethoxy methyl silane; mercapto group-containing silanes such as γ-mercapto propyl trimethoxy silane, γ-mercapto propyl triethoxy silane, and γ-mercapto propyl methyl dimethoxy silane; and epoxy group-containing silanes such as γ-glycidoxy propyl trimethoxy silane and β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.

[0154] Also usable are condensates of various silane coupling agents, such as condensates of aminosilanes and condensates of aminosilanes with other alkoxysilanes; reaction products of aminosilanes and epoxysilanes, reaction products of aminosilanes and (meth)acrylic group-containing silanes, etc. Specific examples include Dynasylan 1146 and Dynasylan 1124 (manufactured by EVONIK).

[0155] The adhesion promoters may be used alone or in combination of two or more.

[0156] The amount of the adhesion promoter used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0157] Generally, when an adhesion promoter is incorporated into a curable composition containing a reactive silicon group-containing polymer, the strength of the cured product tends to improve, but the elongation tends to decrease significantly. However, when an adhesion promoter is incorporated into the curable composition according to the present embodiment, the strength of the cured product improves while preventing a significant decrease in elongation. Therefore, the curable composition according to the present embodiment can preferably contain an adhesion promoter, thereby enabling the production of a cured product that exhibits both high strength and high elongation. Among adhesion promoters, amino group-containing silane coupling agents are particularly preferred. In this case, the amount of the adhesion promoter, particularly the amino group-containing silane coupling agent, added is preferably 0.1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, and particularly preferably 0.5 to 2 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0158] <Plasticizer> A plasticizer can be added to the curable composition according to the present disclosure. Specific examples of the plasticizer include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; and 1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically, Hexamol®). Examples of suitable esters include non-phthalate ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamoll (manufactured by LANXESS)); phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; and epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate.

[0159] Polymer plasticizers can also be used. Specific examples of polymer plasticizers include vinyl polymers, polyester plasticizers, polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxy groups of these polyether polyols are converted to ester groups, ether groups, etc., polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc.

[0160] The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group. If the amount is less than 5 parts by weight, the effect of the plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient. The plasticizer may be used alone or in combination of two or more types.

[0161] <Solvents, diluents> A solvent or diluent can be added to the curable composition according to the present disclosure. The solvent and diluent are not particularly limited, but examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When using a solvent or diluent, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher, in consideration of the problem of air pollution when the composition is used indoors. The above-mentioned solvents or diluents may be used alone or in combination of two or more thereof.

[0162] <Anti-sagging agent> If necessary, an anti-sagging agent may be added to the curable composition according to the present disclosure to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

[0163] The amount of the anti-sagging agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polymer (A) having a reactive silicon group.

[0164] <Antioxidants> An antioxidant (antiaging agent) can be used in the curable composition according to the present disclosure. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Examples include BHT, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520, and SONGNOX 1076. Similarly, hindered amine light stabilizers such as Tinuvin 622LD, Tinuvin 144, and Tinuvin 292; Chimassorb 944LD and Chimassorb 119FL (all manufactured by BASF); Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63, and Adekastab LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants that can be used include SONGNOX4120, Naugard 445, and OKABEST CLX050.

[0165] Specific examples of antioxidants are also described in Japanese Patent Application Laid-Open Nos. 4-283259 and 9-194731.

[0166] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0167] <Light stabilizer> A light stabilizer can be used in the curable composition according to the present disclosure. The use of a light stabilizer can prevent photooxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred. Hindered amine light stabilizers include Tinuvin 123, Tinuvin 144, Tinuvin 249, Tinuvin 292, Tinuvin 312, Tinuvin 622LD, Tinuvin 765, Tinuvin 770, Tinuvin 880, Tinuvin 5866, and Tinuvin B97; CHIMASSORB119FL and CHIMASSORB944LD (all manufactured by BASF); ADK STAB LA-57, LA-62, LA-63, LA-67, and LA-68 (all manufactured by ADEKA Corporation); SANOL LS-292, LS-2626, LS-765, LS-744, and LS-1114 (all manufactured by Sankyo Lifetech Co., Ltd.); SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, SONGSORB CS622, and SONGSORB Examples of light stabilizers include CS944 (both manufactured by SONGWON) and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.).

[0168] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0169] <UV absorber> An ultraviolet absorber can be used in the curable composition according to the present disclosure. The use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate-based compounds, with benzotriazole-based compounds being particularly preferred. Examples include Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, and Tinuvin 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON). Examples of triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1577ED (all manufactured by BASF), SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON), etc. Examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON).

[0170] The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0171] Addworks IBC760 (manufactured by Clariant) can also be used as a product containing antioxidants, light stabilizers, and UV absorbers.

[0172] <Physical property adjusters> The curable composition according to the present disclosure may optionally contain a physical property modifier to adjust the tensile properties of the resulting cured product. The physical property modifier is not particularly limited, but examples include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. The use of such a physical property modifier can increase the hardness of the curable composition according to the present disclosure upon curing, or, conversely, decrease the hardness and increase the elongation at break. The physical property modifiers may be used alone or in combination of two or more.

[0173] In particular, compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product. Compounds that form trimethylsilanol are particularly preferred. Examples of compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and that form silane monools on hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0174] The amount of the physical property adjuster used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0175] <Tackifying resin> In the present invention, a tackifying resin can be added for the purpose of improving adhesion or adhesion to a substrate or for other reasons. There are no particular limitations on the tackifying resin, and any commonly used resin can be used.

[0176] Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used alone or in combination of two or more.

[0177] The amount of tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group. If the amount is less than 2 parts by weight, it is difficult to obtain adhesion and bonding effects to the substrate, and if the amount exceeds 100 parts by weight, the viscosity of the composition becomes too high, which may make it difficult to handle.

[0178] <Compounds containing epoxy groups> A compound containing an epoxy group can be used in the curable composition according to the present disclosure. The use of a compound containing an epoxy group can improve the recovery of the cured product. Examples of compounds containing an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0179] <Photocurable substance> A photocurable material can be used in the curable composition according to the present disclosure. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many compounds of this type are known, including organic monomers, oligomers, resins, and compositions containing them. Representative examples include unsaturated acrylic compounds, which are monomers, oligomers, or mixtures thereof, having one or more acrylic or methacrylic unsaturated groups, polyvinyl cinnamates, and azido resins.

[0180] The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group; if it is used in an amount of 0.1 part by weight or less, there is no effect in improving weather resistance, and if it is used in an amount of 20 parts by weight or more, the cured product becomes too hard and tends to crack.

[0181] <Oxygen curing substance> An oxygen-curable substance can be used in the curable composition according to the present disclosure. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing surface stickiness and preventing the adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying such compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used alone or in combination of two or more.

[0182] The amount of oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group. If the amount used is less than 0.1 part by weight, the improvement in stain resistance will be insufficient, while if it exceeds 20 parts by weight, the tensile properties of the cured product will tend to be impaired. As described in JP-A-3-160053, it is recommended that the oxygen-curable substance be used in combination with a photocurable substance.

[0183] <Epoxy resin> The curable composition according to the present disclosure can be used in combination with an epoxy resin. Compositions containing an epoxy resin are particularly suitable as adhesives, especially adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A epoxy resins and novolac epoxy resins.

[0184] The ratio of these epoxy resins to the polymer (A) having a reactive silicon group is in the range of (A) / epoxy resin = 100 / 1 to 1 / 100 by weight. If the ratio of (A) / epoxy resin is less than 1 / 100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin product, and if the ratio of (A) / epoxy resin exceeds 100 / 1, the strength of the cured polymer product becomes insufficient.

[0185] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to the present disclosure. There are no particular limitations on the epoxy resin curing agent that can be used, and commonly used epoxy resin curing agents can be used.

[0186] When a curing agent for epoxy resin is used, the amount used is in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.

[0187] <<Preparation of Curable Composition>> The curable composition according to the present disclosure can be prepared as a one-component type in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application, or as a two-component type in which ingredients such as a curing catalyst, filler, plasticizer, and water are mixed separately as a curing agent, and then the ingredients are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

[0188] When the curable composition is a one-component type, all of the components are blended in advance, and therefore, it is preferable to dehydrate and dry the components containing water before use, or to dehydrate them by reducing the pressure during blending and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane.

[0189] The amount of the dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (A) having a reactive silicon group.

[0190] <<Applications>> The curable composition according to the present disclosure can be used for pressure-sensitive adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, waterproof coating materials, mold release agents, vibration-proofing materials, vibration-damping materials, soundproofing materials, foam materials, paints, spray materials, etc. The cured products obtained by curing the curable composition according to the present disclosure have excellent flexibility and adhesiveness, and therefore are more preferably used as sealants or adhesives.

[0191] The compound can also be used in a variety of applications, including electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for equipment, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, joint sealants for exterior materials such as sizing boards, coating materials, anti-slip coating materials, buffer materials, primers, conductive materials for electromagnetic wave shielding, thermally conductive materials, hot melt materials, potting agents for electrical and electronic applications, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and as a liquid sealant for rust prevention and waterproofing of the edges (cut parts) of wired glass and laminated glass, and for automobile parts, trucks, buses, and other large vehicle parts, train car parts, aircraft parts, ship parts, electrical parts, and various machine parts. Taking automobiles as an example, the curable compositions can be used in a wide variety of applications, including the adhesive attachment of plastic covers, trim, flanges, bumpers, window mountings, interior components, and exterior parts. Furthermore, because they can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer, they can also be used as various types of sealing and adhesive compositions. The curable compositions of the present disclosure can also be used as adhesives for interior panels, exterior panels, tiling adhesives, stonework adhesives, ceiling finish adhesives, floor finish adhesives, wall finish adhesives, vehicle panel adhesives, adhesives for assembling electrical, electronic, and precision equipment, adhesives for bonding leather, textiles, fabrics, paper, boards, and rubber, reactive post-crosslinking pressure-sensitive adhesives, sealants for direct glazing, sealants for double-glazing, sealants for SSG construction, sealants for working joints in buildings, and materials for civil engineering and bridge construction. They can also be used as adhesive materials, such as adhesive tapes and sheets.

[0192] The following items list preferred aspects of the present disclosure, but the present invention is not limited to the following items. [Item 1] General formula (1): -Si(R 1 ) 3-a X a (1) (R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. A curable composition containing a (meth)acrylic acid ester-based polymer (A) having a reactive silicon group represented by the formula: and a curing catalyst, The (meth)acrylic acid ester polymer (A) has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule, the number of monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group contained in the X block is 1.0 or more on average; the proportion of the monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group contained in the Y block is 0 to 3 wt % based on the total weight of all monomer units contained in the Y block; the (meth)acrylic acid ester polymer (A) has a molecular weight distribution (Mw / Mn) of 1.8 or less; The curing catalyst is represented by the general formula (2): (R 2 -O) n Ti-A 4-n (2) (R 2 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; and A is a β-diketone group. and ammonium hydroxide (C), or a reaction product of the titanium compound (B) and the ammonium hydroxide (C). [Item 2] Item 1. The curable composition according to item 1, further comprising an adhesion promoter. [Item 3] 3. The curable composition according to item 2, wherein the adhesion promoter comprises an amino group-containing silane coupling agent. [Item 4] 4. A cured product obtained by curing the curable composition according to claim 1. [Example]

[0193] The present invention will be specifically explained below with reference to examples, but the technical scope of the present invention is not limited to these examples.

[0194] [Synthesis Example 1: Synthesis of (meth)acrylic copolymer (A-1)] (preparation) 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 mixed therein. This mixture is referred to as a "(meth)acrylic acid ester monomer mixture."

[0195] Next, 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 vessel, and the mixture was stirred under a nitrogen stream until a homogeneous solution was obtained. This homogeneous solution is referred to as the "copper solution." The copper content in the copper solution was equivalent to 15 ppm relative to the total amount of the (meth)acrylic acid ester monomer mixture.

[0196] In addition, another stirring vessel was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid, and 1.6 mL of triethylamine were charged into this vessel and stirred under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution."

[0197] (Step 1: Formation of the first X block) 5.60 g of ethyl α-bromobutyrate (initiator; 0.029 mol), 20 wt% (200 g) 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 (manufactured by Wako Pure Chemical Industries, Ltd.), and the total amount of copper solution were charged into a stirrer, and stirred under a nitrogen gas flow for 30 minutes to obtain a homogeneous solution. The stirrer used here was a jacket temperature-controlled stirrer, and the jacket temperature was set to 45°C.

[0198] Next, 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 ascorbic acid solution was added dropwise at a rate of 144 mg of ascorbic acid per hour.

[0199] When the temperature in the polymerization system was monitored, it rose simultaneously with the start of the dropwise addition of ascorbic acid, reached a maximum temperature, and then gradually decreased. When the temperature difference between the temperature in the polymerization system and the jacket temperature reached 1°C, a small amount of the reaction solution in the polymerization system was sampled and analyzed by gas chromatography. The results showed that 90% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed.

[0200] (Second step: Formation of Y-block) Next, the remainder of the (meth)acrylic acid ester monomer mixture not added in the first step (800 g, 80% by weight of the total amount) was continuously added dropwise to the polymerization system over a period of 90 minutes. The ascorbic acid solution was added dropwise at a rate of 48 mg of ascorbic acid per hour. Sampling was also performed sequentially and analyzed by gas chromatography. The polymerization was continued until 88% by weight of the total (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed.

[0201] (Third step: Formation of second X block) Next, 11 g (0.049 mol; 1.6 molar equivalents relative to the initiator) of 3-methacryloxypropylmethyldimethoxysilane was added to the polymerization system. The continuous dropwise addition of the ascorbic acid solution was continued until 98 wt% of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. Thereafter, the dropwise addition of the ascorbic acid solution was stopped, and the polymerization was terminated.

[0202] The jacket temperature was changed to 80°C, and the solvent was then devolatilized. A diaphragm pump was used first, and then a vacuum pump was used. After devolatilization was completed, the jacket temperature was cooled to 60°C or lower.

[0203] (purification) 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 obtained. An adsorbent was added to the 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.).

[0204] 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; manufactured by Sumitomo Chemical) was added to the solution and mixed until homogeneous. The solvent was then removed from the solution to obtain a (meth)acrylic copolymer (A-1). A diaphragm pump was used first to remove the volatiles, followed by a vacuum pump.

[0205] The (meth)acrylic polymer (A-1) produced in Synthesis Example 1 corresponds to the (meth)acrylic acid ester polymer (A), and had a number average molecular weight of 55,000 and a molecular weight distribution of 1.11. The number of monomer units derived from a (meth)acrylic acid ester monomer having a reactive silicon group contained in the X block of the (meth)acrylic polymer (A-1) was 2.1 on average, when the total number of units contained in the X blocks at both ends was calculated. Furthermore, the proportion of monomer units derived from a (meth)acrylic acid ester monomer having a reactive silicon group contained in the Y block of the (meth)acrylic polymer (A-1) was 1.1% by weight, with the total weight of all monomer units contained in the Y block being 100% by weight.

[0206] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions. Solution delivery system: Waters e2695 Column: Showa Denko Shodex GPC K-804, K-802.5 Solvent: Chloroform Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0207] The average number of reactive silicon groups per polymer molecule was calculated from the polymer structure and the results of NMR measurement.

[0208] [Synthesis Example 2: Synthesis of curing catalyst (B-1)] A 500 mL four-necked round-bottom flask equipped with a nitrogen inlet tube was charged with 85.2 g (0.3 mol) of tetraisopropoxytitanium (manufactured by Tokyo Chemical Industry Co., Ltd.), and while stirring, 70 g (0.1 mol) of a 37% tetrabutylammonium hydroxide (hereinafter referred to as "TBAH") methanol solution (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes at an internal temperature of 60°C, and the mixture was stirred for 1 hour. The mixture was then concentrated under reduced pressure (final vacuum of 10 mmHg) to distill off isopropanol and methanol, yielding 80 g of the reaction product. 25 g of isopropanol was then added, yielding 105 g of curing catalyst (B-1) as a transparent liquid.

[0209] [Example 1, Comparative Examples 1-2] (Viscosity evaluation) The viscosity of the curable composition was measured at 23°C using a viscometer (Toki Sangyo VISCOMETER TV-25, 3° x R14 cone rotor, 1 rpm) in accordance with JIS K 7117-2. The amount of sample used for the measurement was 0.4 mL.

[0210] (Evaluation of the cured product) The curing catalyst shown in Table 1 was added to 100 parts by weight of the (meth)acrylic copolymer (A-1) and mixed thoroughly. The resulting mixture was poured into a mold and degassed under reduced pressure. It was then heated and cured at 50°C for 20 hours to obtain a sheet-like cured product with rubber elasticity. In Table 1, U220H is a tin catalyst: dibutyltin diacetoacetonate manufactured by Nitto Kasei Co., Ltd. From the resulting sheet-like cured product, No. 3 dumbbell-shaped test pieces as specified in JIS K 7113 were punched out. These test pieces were subjected to a tensile test to measure their mechanical properties. Specifically, the stress at 50% elongation, the stress at break, and the elongation at break (elongation relative to the distance between chucks) were measured. The results are shown in Table 1. An autograph (Shimadzu) was used for the measurement, and the measurement temperature was 23°C and the tensile speed was 200 mm / min. The gel fraction of the resulting sheet-like cured product was measured by immersing the sheet-like cured product in toluene and keeping it at 23° C. for 24 hours. Thereafter, the gel fraction was calculated by the following method. Gel fraction (%) = (weight of undissolved solid component ÷ weight of cured sheet before immersion in toluene) × 100

[0211] [Table 1]

[0212] Table 1 shows that Example 1, which uses a curing catalyst (B-1), which is a reaction product of a titanium compound (B) and ammonium hydroxide (C), for a reactive silicon group-containing (meth)acrylic acid ester polymer (A) having a block structure, has improved breaking strength (Tb) and elongation at break (Eb) compared to Comparative Examples 1 and 2, which use a tin-based curing catalyst.

[0213] Examples 2 to 5 According to the formulation shown in Table 2, a filler and a plasticizer were added to the (meth)acrylic copolymer (A-1) and mixed with a spatula, and then the mixture was dispersed by passing it through a three-roll mill three times. Then, a dehydrating agent, an adhesion promoter, and a curing catalyst were added and mixed thoroughly. The resulting mixture was poured into a mold and degassed under reduced pressure, after which it was cured by heating at 50°C for 20 hours to obtain a sheet-like cured product with rubber elasticity.

[0214] The following additives were used: Filler: Colloidal calcium carbonate (Shiraishi Kogyo Co., Ltd., Hakuenka CCR) Plasticizer: (Diisodecyl phthalate (manufactured by J-Plus Corporation, trade name: DIDP) Dehydrating agent: vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM1003) Adhesion promoter (amino group-containing silane coupling agent): (N-(β-aminomethyl)-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM603) The mechanical properties were measured in the same manner as above, and the results are shown in Table 2. [Table 2]

[0215] Table 2 shows that in Examples 2 to 5, in which a curing catalyst (B-1), which is a reaction product of a titanium compound (B) and ammonium hydroxide (C), was used with a reactive silicon group-containing (meth)acrylic acid ester polymer (A) having a block structure, the breaking strength (Tb) and elongation at break (Eb) of the cured product were both good.

[0216] Furthermore, compared to Example 2, in which no amino group-containing silane coupling agent was added, Examples 3 to 5, in which an amino group-containing silane coupling agent was added, showed an improvement in breaking strength (Tb) of more than two times. In addition, the elongation at break (Eb) also improved (Examples 3 and 4), or only decreased slightly by about 15% (Example 5), and it was found that there was no significant decrease in elongation at break.

Claims

1. General formula (1): -Si(R １ ) ３－ａ X ａ (1) (R １ each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. and a curing catalyst, The (meth)acrylic acid ester-based polymer (A) has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule, the number of monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group contained in the X block is 1.0 or more on average; the proportion of the monomer units derived from the (meth)acrylic acid ester monomer having a reactive silicon group contained in the Y block is 0 to 3 wt % based on the total weight of all monomer units contained in the Y block; the (meth)acrylic acid ester polymer (A) has a molecular weight distribution (Mw / Mn) of 1.8 or less; The curing catalyst is represented by the general formula (2): (R ２ -O) ｎ Ti-A ４－ｎ (2) (R ２ is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; n is an integer of 1 to 4; and A is a β-diketone group. and ammonium hydroxide (C), or a reaction product of the titanium compound (B) and the ammonium hydroxide (C).

2. The curable composition of claim 1 further comprising an adhesion promoter.

3. The curable composition of claim 2 , wherein the adhesion promoter comprises an amino group-containing silane coupling agent.

4. A cured product obtained by curing the curable composition according to any one of claims 1 to 3.

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