Compound, curable composition, and cured product

Abstract

To provide a novel (meth)acrylic polymer having a silyl group, with a reduced content of halogen derived from an initiator, or to provide a novel (meth)acrylic polymer having a silyl group that can improve the stress at break of a cured product.SOLUTION: A compound A according to an aspect of the present invention is represented by the general formula in the figure, where: P1 and P2 are (meth)acrylic polymers having a silyl group; Ra1 and Ra2 are each independently a hydrogen atom or a methyl group; Rb1, Rb2, R1 and R2 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms and may contain heteroatoms; and R3 is an organic group having 1 to 20 carbon atoms and may contain heteroatoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel compound. The present invention also relates to a curable composition and a cured product containing the compound. [Background technology]

[0002] Polymer molecules having silyl groups form siloxane bonds with other polymer molecules through hydrolysis of the silyl groups. This crosslinking reaction results in a rubber-like cured product. Curable compositions containing such polymer molecules are used in sealants, adhesives, paints, etc.

[0003] Among such polymers having a silyl group, those having a poly(meth)acrylic acid ester as the main chain are known to be able to be produced by atom transfer radical polymerization (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2018-162394 Summary of the Invention [Problem to be solved by the invention]

[0005] In the method for producing a polymer by atom transfer radical polymerization as described in Patent Document 1, halogen atoms derived from the initiator remain at the terminals of the polymer molecules even after the elongation reaction of the polymer molecules is completed. In other words, the polymer obtained by atom transfer radical polymerization inevitably contains halogen atoms derived from the initiator. However, depending on the application of the curable composition, a lower halogen content may be preferred (e.g., application in electronic components).

[0006] Furthermore, the curable composition described in Patent Document 1 still leaves room for improvement in the stress at break of the resulting cured product.

[0007] An object of one aspect of the present invention is to provide a novel (meth)acrylic polymer having a silyl group, which has a reduced content of halogen derived from an initiator.An object of another aspect of the present invention is to provide a novel (meth)acrylic polymer having a silyl group, which can improve the stress at break of a cured product. [Means for solving the problem]

[0008] In order to solve the above problems, a compound A according to one embodiment of the present invention is represented by the following general formula: [ka] During the ceremony, P 1 and P 2 are both (meth)acrylic polymers having a silyl group, R a1 and R a2 are each independently a hydrogen atom or a methyl group, R b1 , R b2 , R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may contain a heteroatom, R 3 is an organic group having 1 to 20 carbon atoms, which may contain a heteroatom, Above P 1 and P 2 are both, The molecule has an XY diblock structure having an X block and a Y block or an XYX triblock structure, the X block contains an average of more than 2.0 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers, The molecular weight distribution (Mw / Mn) is 1.8 or less. [Effects of the Invention]

[0009] According to one aspect of the present invention, there is provided a novel (meth)acrylic polymer having a silyl group, which has a reduced content of halogen derived from an initiator. According to another aspect of the present invention, there is provided a novel (meth)acrylic polymer having a silyl group, which can improve the stress at break of a cured product. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a graph that supports the production of compound A in terms of an increase in molecular weight. DETAILED DESCRIPTION OF THE INVENTION

[0011] However, the present invention is not limited to the following embodiments and various modifications may be made within the scope of the claims. Embodiments that combine technical means described in different embodiments are also included in the technical scope of the present invention.

[0012] Unless otherwise specified herein, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic." Unless otherwise specified herein, "silyl group" means "hydrolyzable silyl group." In one embodiment, the silyl group is an alkoxysilyl group.

[0013] In this specification, the "content of polymer components" refers to the total content of components in the curable composition that will be involved in the formation of a crosslinked body in the cured product. For example, component A: compound A and component C: polyoxyalkylene polymer having a silyl group are polymer components. 1 and / or P 2 Compounds containing the above are also polymer components. Examples of such polymer components include an amine and an unreacted (meth)acrylic polymer, an amine and one P 1 or P 2 and compounds reacted with amines and three or more P 1 or P 2Examples of compounds include those obtained by reacting with

[0014] [1. Compound represented by formula (A)] Compound A according to one embodiment of the present invention is represented by the following general formula: 1 and P 2 The portion represented by -C(R a1 )(COOR b1 )-N(R 1 )-R 3 -N(R 2 )-C(R a2 )(COOR b2 The moiety represented by (3)- is a polyvalent amine crosslinking moiety, and the ends of the (meth)acrylic polymer are crosslinked via a polyvalent amine. Here, in the (meth)acrylic polymer (compound B represented by the following general formula) immediately after synthesis, a halogen derived from the initiator remains at the end of the molecular chain, and this halogen reacts with hydrogen of the amine to be eliminated, and dimerization occurs via the polyvalent amine to produce compound A. Below, the moieties constituting the compound will be explained individually. [ka]

[0015] [1.1. Polyamine bridging moiety] The polyamine bridging moiety is a -C(R a1 )(COOR b1 )-N(R 1 )-R 3 -N(R 2 )-C(R a2 )(COOR b2 )-. Of these, -C(R a1 )(COOR b1 ) and -C(R a2 )(COOR b2 -N(R) is a residue derived from a monomer that constitutes a (meth)acrylic polymer. 1 )-R 3 -N(R 2 )- is a residue derived from a polyamine.

[0016] R a1 and R a2 are each independently a hydrogen atom or a methyl group. a1 If is a hydrogen atom, then -C(R a1 )(COOR b1 ) is a residue derived from an acrylic monomer. a1 If is a methyl group, -C(R a1 )(COOR b1 ) is a residue derived from a methacrylic monomer. a2 The same is true for .

[0017] R b1 and R b2 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms. b1 and / or R b2 When each of the groups is an organic group, it may each independently have 1 to 19 carbon atoms or 1 to 18 carbon atoms.

[0018] R b1 and / or R b2 is an organic group, R b1 and / or R b2 may each independently have a heteroatom. The heteroatom may be one or more selected from the group consisting of oxygen, nitrogen, sulfur, silicon, and halogen atoms (fluorine, chlorine, bromine, and iodine atoms). b1 and / or R b2 The number of heteroatoms contained in each of R may independently be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. In one embodiment, the heteroatom is a silicon atom, and R b1 and / or R b2 In one embodiment, the heteroatoms are oxygen and silicon atoms, and R b In one embodiment, R b1 and / or R b2 does not contain halogen atoms.

[0019] R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms. 1 and / or R 2 When each of the groups is an organic group, it may each independently have 1 to 8, 1 to 10, 1 to 12, 1 to 14, 1 to 16, or 1 to 18 carbon atoms.

[0020] R 1 and / or R 2 is an organic group, R 1 and / or R 2 may each independently have a heteroatom. The heteroatom may be one or more selected from the group consisting of oxygen, nitrogen, sulfur, silicon, and halogen atoms (fluorine, chlorine, bromine, and iodine atoms). 1 and / or R 2 The number of heteroatoms contained in each of R may independently be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. 1 and / or R 2 does not contain halogen atoms. 1 and / or R 2 None of the above has a silyl group.

[0021] R 3 is an organic group having 1 to 20 carbon atoms. 3 may each independently have 1 to 8, 1 to 10, 1 to 12, 1 to 14, 1 to 16, or 1 to 18 carbon atoms.

[0022] R 3 R may have a heteroatom. The heteroatom may be one or more selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). 3 The number of heteroatoms contained in R may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less.3 does not contain halogen atoms. 3 does not have a silyl group.

[0023] In one embodiment, the amine attached to the (meth)acrylic copolymer in the polyamine crosslinking moiety is a diamine. 1 , R 2 and R 3 In one embodiment, R 1 and R 2 is a hydrogen atom.

[0024] [1.2. (Meth)acrylic polymer having silyl group] The (meth)acrylic polymer having a silyl group is a compound A having P 1 and P 2 The (meth)acrylic polymer has a silyl group derived from a silyl group-containing (meth)acrylic acid ester monomer. The (meth)acrylic polymer has an X block in which the silyl group appears frequently and a Y block in which the silyl group appears less frequently. The (meth)acrylic polymer can be polymerized, for example, by changing the monomer composition during the polymerization.

[0025] [1.2.1. Structure of (meth)acrylic polymer] The (meth)acrylic polymer 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 polymer 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.

[0026] Here, the "XYX triblock structure" refers to what is commonly referred to by those skilled in the art as an "ABA triblock structure." The X / Y ratio in the (meth)acrylic polymer is preferably from (5 / 95) to (60 / 40), and more preferably from (15 / 85) to (40 / 60).

[0027] In one embodiment, the (meth)acrylic polymer molecule has an XY diblock structure. In a molecule with an XY diblock structure, the X block can be a region of 40% or less, 30% or less, or 25% or less from one end of the molecule (where all repeating units contained in the molecule are taken as 100%). Here, the X block is the block on the side where silyl groups are distributed in a relatively large amount.

[0028] In one embodiment, the (meth)acrylic polymer molecule has an XYX triblock structure. In a molecule with an XYX triblock structure, the X blocks may be 40% or less, 30% or less, or 25% or less of the region from the ends of the molecule (all repeating units contained in the molecule are taken as 100%). Here, the X blocks are blocks located at both ends of the molecule.

[0029] The (meth)acrylic polymer has repeating units derived from silyl group-containing (meth)acrylic ester monomers. The repeating units derived from silyl group-containing (meth)acrylic ester monomers are contained in a relatively large amount in the X block. The number of repeating units derived from silyl group-containing (meth)acrylic ester monomers contained in the X block is, on average, more than 2.0. When the (meth)acrylic polymer has two or more X blocks in one molecule, the total number of repeating units derived from silyl group-containing (meth)acrylic ester monomers contained in the multiple X blocks is, on average, more than 2.0. On the other hand, the number of repeating units derived from silyl group-containing (meth)acrylic ester monomers contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block.

[0030] The number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is, on average, more than 2.0, preferably 2.1 or more, more preferably 2.2 or more, even more preferably 2.3 or more, and particularly preferably 2.5 or more. Similarly, the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is preferably 0.5 wt% or more, more preferably 2.0 wt% or more, and even more preferably 3.0 wt% or more, based on the weight of all repeating units contained in the X block. The upper limit of the number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block is preferably 90 wt% or less, more preferably 60 wt% or less, and even more preferably 30 wt% or less.

[0031] The upper limit of the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block may be less than 5 wt %, preferably 4 wt % or less, more preferably 3 wt % or less, even more preferably 2 wt % or less, and particularly preferably 1 wt % or less, based on the weight of all repeating units contained in the Y block. The lower limit of the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is preferably 0 wt % or more, more preferably more than 0 wt %, based on the weight of all repeating units contained in the Y block.

[0032] The number of silyl groups introduced into the (meth)acrylic polymer is, on average, more than 2.0, preferably 2.2 or more, more preferably 2.6 or more, even more preferably 3.0 or more, and particularly preferably 3.4 or more, per molecule. The upper limit of the number of silyl groups introduced into the (meth)acrylic polymer is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, and particularly preferably 5.0 or less. When the number of silyl groups is within the above range, a curable composition and a cured product with good physical properties can be obtained.

[0033] It should be noted that the number of silyl groups mentioned above is the same as that of one P 1 or P 2According to the production methods disclosed in Patent Document 1 and the production examples of the present application, it is not possible to accurately control the number of silyl groups introduced into each polymer molecule (it is, of course, possible to make the density of silyl groups different between the X block and the Y block by changing the monomer composition depending on the polymerization stage). Therefore, in the above explanation, for convenience, the number of silyl groups introduced into one P is used, rather than the number of silyl groups contained in compound A. 1 or P 2 The average number of silyl groups per unit area is given.

[0034] One P 1 or P 2 The number of silyl groups that one P has can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. 1 or P 2 The number of silyl groups in the X block may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (when there are multiple X blocks, the total number of silyl groups contained in all the X blocks may be the above number). 1 or P 2 Among these, the number of silyl groups contained in the Y block may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (when there are multiple Y blocks, the total number of silyl groups contained in all the Y blocks may be the above-mentioned number).

[0035] The (meth)acrylic polymer may contain a repeating unit derived from a (meth)acrylic monomer having a long side chain. In this specification, the "(meth)acrylic monomer having a long side chain" refers to a (meth)acrylic monomer having the formula: CH2=C(R 4 )COOR 5 It is a monomer represented by the formula: 4 is a hydrogen atom or a methyl group. 5 is a group having 9 or more carbon atoms.

[0036] The content of repeating units derived from (meth)acrylic monomers with long side chains is preferably 1% by weight or more of all structural units contained in the (meth)acrylic polymer. A (meth)acrylic polymer containing such repeating units may improve the physical properties of the resulting cured product. The upper limit of the content of repeating units derived from (meth)acrylic monomers with long side chains is preferably 5% by weight or less, more preferably 3% by weight or less. If the content is within the above range, the production cost of the (meth)acrylic polymer will not increase excessively.

[0037] Examples of (meth)acrylic monomers having long side chains include nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, docosyl (meth)acrylate, oleyl (meth)acrylate, linoleyl (meth)acrylate, and isobornyl (meth)acrylate.

[0038] Among the above-mentioned monomers, one or more selected from octadecyl (meth)acrylate, oleyl (meth)acrylate, and linoleyl (meth)acrylate are preferred. These monomers have the advantage of being liquid at room temperature and having high polymerization stability. In addition, by blending these monomers, a (meth)acrylic acid-based polymer having high compatibility with a polyoxyalkylene-based polymer can be obtained.

[0039] In this specification, the term "(meth)acrylic monomer having a non-long side chain" refers to a (meth)acrylic monomer having a non-long side chain in the above formula, R 5represents a monomer in which the carbon number is 8 or less. Examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isopropoxyethyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, glycidyl (meth)acrylate, 1-ethylcyclopentyl ether (meth)acrylate, and dimethylaminoethyl (meth)acrylate.

[0040] Among the above-mentioned monomers, one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred. These monomers are inexpensive to procure and are suitable for the purpose of reducing the production cost of the (meth)acrylic polymer.

[0041] Furthermore, from the viewpoint of glass transition temperature, one or more types selected from n-butyl acrylate and 2-ethylhexyl acrylate are preferred. (Meth)acrylic polymers obtained from these monomers have low glass transition temperatures and low polymer viscosities. Therefore, a curable composition that can be easily used in low-temperature environments can be obtained.

[0042] The (meth)acrylic polymer may have repeating units derived from monomers other than (meth)acrylic acid ester monomers. In the (meth)acrylic polymer, the proportion of repeating units derived from (meth)acrylic acid ester monomers is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more, of the total weight of the (meth)acrylic polymer.

[0043] [1.2.2. Silyl Groups in (Meth)acrylic Polymers] The silyl group contained in the (meth)acrylic polymer may be derived from a silyl group-containing (meth)acrylic acid ester monomer. In one embodiment, the silyl group is represented by the following general formula (1): -[Si(R 5 ) 2-b (Y) b O] m -Si(R 6 ) 3-a (Y) a ···(1) In formula (1), R 5 and R 6 are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a methoxymethyl group, or a triorganosiloxy group represented by (R')3SiO-. R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms. The three R's may be the same or different. R 5 or R 6 When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acetoxy group, and an oxime group. In one embodiment, Y is a hydroxyl group, a methoxy group, an ethoxy group, or an isopropoxy group. When one silyl group contains multiple Xs, they may be the same or different. When one molecule of the (meth)acrylic polymer contains multiple silyl groups, Y may be different for each silyl group. a is 0, 1, 2, or 3. b is 0, 1, or 2. m is an integer of 0 to 19, provided that the relationship a+mb≧1 is satisfied.

[0044] The specific structure of the silyl group-containing (meth)acrylic acid ester monomer is not particularly limited, and an example thereof is a monomer represented by the following general formula: H2C=C(R 7 )C(=O)-O-(CH2) m -SiR 8 n (OR 9 ) 3-n In the formula, R 7 is hydrogen or a methyl group. 8 and R 9 R is one or more selected from the group consisting of hydrogen, a methyl group, and an ethyl group. 8 and / or R 9 When there are a plurality of m, they may be the same or different. m is an integer of 0 to 10. n is an integer of 0 to 2.

[0045] Specific examples of silyl group-containing (meth)acrylic acid ester monomers include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0046] [1.2.3. Physical properties of (meth)acrylic polymers] In one embodiment, P 1 or P 2 The lower limit of the number average molecular weight of the portion represented by P is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. 1 or P 2 The upper limit of the number average molecular weight of the portion represented by P is preferably 80,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. 1 or P 2 When the number average molecular weight of the part represented by the formula (I) is within the above range, the viscosity of the curable composition does not become too high, and sufficient workability can be ensured.

[0047] In one embodiment, P 1 or P 2 The molecular weight distribution of the portion represented by is 1.8 or less, preferably 1.5 or less, 1.4 or less, 1.3 or less, or 1.2 or less. If the molecular weight distribution is within the above range, the viscosity of the polymer tends to decrease and workability tends to improve. The molecular weight distribution is a value given by "weight average molecular weight / number average molecular weight".

[0048] The weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC). GPC measurements use chloroform as the mobile phase and a polystyrene gel column as the stationary phase. The molecular weights obtained by measurement are molecular weights converted to standard polystyrene.

[0049] [1.3. Method for producing compound A] Among the constituent parts of compound A, a (meth)acrylic polymer having a silyl group can be produced, for example, by the method described in Patent Document 1. The method disclosed in this document involves copolymerizing a (meth)acrylic acid ester monomer with a silyl group-containing (meth)acrylic acid ester monomer to introduce a silyl group into the (meth)acrylic polymer. More specifically, by controlling the amount of silyl group-containing (meth)acrylic acid ester monomer added depending on the stage of progress of atom transfer radical polymerization, an X block with a high frequency of silyl group appearance and a Y block with a low frequency of silyl group appearance are produced separately.

[0050] The polymer obtained by this production method is compound B. In compound B, a halogen atom X derived from the initiator remains at the end of the polymer molecule. By reacting two units of compound B with a polyamine, the halogen atom X is eliminated, and compound B is dimerized via the polyamine to obtain compound A.

[0051] The type of polyamine to be reacted with compound B is not particularly limited. The polyamine may be one type or two types. In one embodiment, the polyamine is a primary amine and / or a secondary amine. In one embodiment, the polyamine is a diamine. The reaction temperature between compound B and the amine is preferably relatively high. In this way, hydrogen halide (such as hydrogen bromide) produced by the reaction is removed by vaporization. Therefore, the amount of hydrogen halide contained in the obtained compound A can be reduced, and the amount of halogen contained in the curable composition can be reduced. The reaction temperature is preferably 50 to 120°C or higher. If the reaction temperature is 50°C or higher, hydrogen halide can be sufficiently removed. If the reaction temperature is 120°C or lower, the occurrence of side reactions in compound B can be sufficiently suppressed.

[0052] The reaction time between compound B and the amine is preferably relatively long. Because the reaction rate between compound B and the amine is relatively slow, the reaction time is preferably 12 hours or more, more preferably 18 hours or more, and even more preferably 24 hours or more. If the reaction time is 10 hours or more, the elimination of halogen from compound B proceeds sufficiently, and the amount of halogen contained in the curable composition can be reduced to a desired level.

[0053] [2. Curable composition] The curable composition according to one embodiment of the present invention comprises Component A: Compound A and Component B: Curing catalyst. The curable composition may optionally comprise Component C: Polyoxyalkylene polymer having a silyl group. The curable composition may also comprise other components (additives, etc.). Each of these components may comprise only one type, or two or more types. Each component will be described in detail below. [ka]

[0054] [2.1. Component A: Compound A] Component A is compound A. Compound A has been described in Section [1], so a repeated explanation will be omitted.

[0055] [2.2. Component B: Curing catalyst] Examples of the curing catalyst include tin-based curing catalysts.Specific examples of the tin-based curing catalyst include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalic acid ester, etc.); tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and silyl group-containing low molecular weight silicon divalent tin compounds (such as tin octoate, tin naphthenate, and tin stearate); monoalkyltins (such as monobutyltin compounds (such as monobutyltin trisoctoate and monobutyltin triisopropoxide), and monooctyltin compounds); reaction products or mixtures of amine compounds and organotin compounds (such as reaction products or mixtures of laurylamine and tin octoate); chelate compounds (such as dibutyltin bisacetylacetonate, dioctyltin bisacetylcetonate, dibutyltin bisethylacetonate, and dioctyltin bisethylacetonate); and tin alcoholates (such as dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, and dioctyltin diethylate).

[0056] Among these, chelate compounds (such as dibutyltin bisacetylacetonate) and tin alcoholates are preferred because of their high activity as silanol condensation catalysts, and dibutyltin dilaurate is preferred because it causes little coloration when added to a curable composition, is inexpensive, and is easily available.

[0057] [2.3. Component C: Polyoxyalkylene Polymer Having Silyl Groups] [2.4.1. Main chain of component C] The molecular structure of component C may be linear or branched. Alternatively, it may be a mixture of molecules having these structures. Among these, a main chain derived from one or more selected from the group consisting of polyoxypropylene diols and polyoxypropylene triols is particularly preferred.

[0058] Examples of the main chain structure of component C include structures represented by the following general formula: 8 is a divalent alkylene group. -R 8 -O-

[0059] The structure represented by the above general formula preferably accounts for 50% by weight or more of the total weight of component C, more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0060] R 8 The structure of R is not particularly limited as long as it is a divalent alkylene group. 8 is preferably an alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

[0061] Specific examples of the repeating unit represented by the above general formula include -CHO-, -CHCHO-, -CHCH(CH)O-, -CHCH(CH)O-, -CHC(CH)O-, and -CHCHCHCHCHO-. Of these, it is preferred that the main chain of component C is polypropylene oxide consisting of -CHCH(CH)O-.

[0062] [2.4.2. Silyl Group of Component C] Component C may have, for example, the silyl group described in Section [1.2.2]. In one embodiment, the silyl group contained in Component C is represented by the following general formula: -Si(R 9 ) 3-a (X) a

[0063] In the formula, R 9 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, and more preferably 1 to 5. R 9 may be substituted with a heteroatom-containing group. Examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, and halogen atoms (fluorine, chlorine, bromine, and iodine). In one embodiment, R 9 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. 9 When a plurality of are included, they may be the same or different.

[0064] In the formula, X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an oxime group, and an acetoxy group. In one embodiment, X is a hydroxyl group, a methoxy group, an ethoxy group, or an isopropoxy group. When one silyl group contains multiple Xs, they may be the same or different.

[0065] In the formula, a is 1, 2, or 3.

[0066] Examples of the silyl group contained in component C include a dimethoxysilyl group, a trimethoxysilyl group, a diethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.

[0067] The number of silyl groups introduced into Component C is, on average, more than 1.0, preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more, on the whole molecule. The upper limit of the number of silyl groups introduced into Component C is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and particularly preferably 2.0 or less. If the number of silyl groups is within the above range, a curable composition and cured product with good physical properties can be obtained.

[0068] The silyl group of Component C may be contained in the main chain or in a side chain. The silyl group of Component C may be located in the middle of the molecular chain or at the terminal of the molecular chain. Preferably, the silyl group is located at two or more terminals of the molecular chain.

[0069] Component C may be a commercially available product. Examples of commercially available Component C include Kaneka MS Polymer (registered trademark) SAT400, SAT350, S303H, S203H, and SAX220 (Kaneka Corporation).

[0070] [2.4.3. Physical properties of component C] The lower limit of the number average molecular weight of component C is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more.The upper limit of the number average molecular weight of component C is preferably 50,000 or less, and more preferably 30,000 or less.

[0071] The molecular weight distribution of component C may be 1.8 or less, preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.2 or less. If the molecular weight distribution is too large, the viscosity of the curable composition tends to increase, and workability tends to decrease.

[0072] [2.4.4. Manufacturing method of component C] Component C can be obtained by the methods described in

[0011] to

[0058] of JP 2021-55010 A.

[0073] [2.4. Other Ingredients] The curable composition may contain various additives in addition to the above-mentioned components. By adding these additives, various physical properties of the curable composition and the cured product can be adjusted. Examples of additives include the following. These additives may be used alone or in combination of two or more.

[0074] (adhesion imparting agent) The curable composition may contain an adhesion promoter. Addition of an adhesion promoter can reduce the risk of the sealant peeling off from an adherend such as a siding board (this peeling occurs when the joint width changes due to external forces). It may also eliminate the need to use a primer to improve adhesion. In this case, simplification of the application process is expected.

[0075] Examples of adhesion promoters include silane coupling agents. Specific examples of silane coupling agents include isocyanate group-containing silanes (γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, etc.); amino group-containing silanes (γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.; mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-(β-carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, etc.); vinyl-type unsaturated group-containing silanes (vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); isocyanurate silanes (tris(trimethoxysilyl)isocyanurate, etc.).In addition, derivatives obtained by modifying silane coupling agents, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0076] The content of the adhesion promoter is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer component.

[0077] (filling material) The curable composition may contain a filler. Examples of fillers include wood flour, reinforcing fillers (pulp, cotton chips, asbestos, mica, walnut shell flour, rice husk flour, graphite, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrated silicic acid, etc.), carbon black, etc.), fillers (ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red iron oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate, shirasu balloon, etc.), and fibrous fillers (asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc.).

[0078] The content of the filler is preferably 5 to 5000 parts by weight, more preferably 10 to 2500 parts by weight, and particularly preferably 15 to 1500 parts by weight, based on 100 parts by weight of the content of the polymer component.

[0079] (Physical property adjuster) The curable composition may contain a physical property modifier that adjusts the tensile properties of the cured product. By using a physical property modifier, it is possible to increase the hardness of the cured product, or conversely, to decrease the hardness of the cured product and increase the elongation.

[0080] Examples of physical property adjusters include alkylalkoxysilanes (methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, etc.); alkylisopropenoxysilanes (dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, etc.); alkoxysilanes having functional groups (vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.); silicone varnishes; and polysiloxanes.

[0081] The content of the physical property adjuster is preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the polymer component content.

[0082] (thixotropy imparting agent (anti-sagging agent)) The curable composition may contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability.

[0083] Examples of the thixotropy-imparting agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps not included in the above-mentioned component F (calcium stearate, aluminum stearate, barium stearate, etc.).

[0084] The content of the thixotropy-imparting agent is preferably 0.1 to 50 parts by weight, and more preferably 0.2 to 25 parts by weight, based on 100 parts by weight of the content of the polymer component.

[0085] (light curing substance) The curable composition may contain a photocurable substance. A photocurable substance is a substance that undergoes a chemical change in a short period of time due to the action of light, resulting in a change in physical properties (such as curing). By incorporating a photocurable substance, the stickiness (residual tack) of the surface of the cured product can be reduced. A typical photocurable substance can be cured by leaving it at room temperature for one day in a sunny location indoors (such as near a window). Many photocurable substances are known, including organic monomers, oligomers, resins, and compositions containing these, and the type is not particularly limited. Examples of photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, and azide resins.

[0086] Specific examples of unsaturated acrylic compounds include (meth)acrylic acid esters of low molecular weight alcohols (ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, neopentyl alcohol, etc.); (meth)acrylic acid esters of alcohols obtained by modifying acids (bisphenol A, isocyanuric acid) or low molecular weight alcohols with ethylene oxide, propylene oxide, etc.; (meth)acrylic acid esters (polyether polyols whose main chain is a polyether and has a hydroxyl group at the end, and polyols whose main chain is a polyether, obtained by radical polymerization of vinyl monomers in such polyols). polymer polyols obtained by reacting an epoxy resin (such as bisphenol A or novolac) with (meth)acrylic acid; and urethane acrylate oligomers having urethane bonds and (meth)acrylic groups in the molecular chain, which are obtained by reacting a polyol, polyisocyanate, hydroxyl group-containing (meth)acrylate, etc.

[0087] The content of the photocurable substance is preferably 0.01 to 30 parts by weight, assuming that the content of the polymer component is 100 parts by weight.

[0088] (antioxidants and light stabilizers) The curable composition may contain an antioxidant and / or a light stabilizer. Various antioxidants and light stabilizers are known. Examples include substances described in [Kenichi Saruwatari et al., "Antioxidant Handbook," Taiseisha, 1976] and [Zenjiro Osawa, editor, "Degradation and Stabilization of Polymer Materials," CMC, 1990, pp. 235-242].

[0089] Examples of antioxidants include thioether-based antioxidants such as ADK STAB PEP-36 and ADK STAB AO-23 (all manufactured by ADEKA Corporation); phosphorus-based antioxidants such as Irgafos 38, Irgafos 168, and Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals); and hindered phenol-based antioxidants. Of the above, hindered phenol-based antioxidants are preferred.

[0090] Specific examples of hindered phenol antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl) phenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 2,5-di-t-butylhydroquinone. , 2,5-di-t-amylhydroquinone, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4 hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene ethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzyl) Ethyl benzylphosphonate) calcium, tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis[(octylthio)methyl]o-cresol, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-t-butylphenyl)phosphite, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, methyl-3-[3-t-butyl Examples of suitable hydroxybenzoates include 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and 2,4-di-t-butylphenyl-4-hydroxybenzoate.

[0091] Examples of commercially available antioxidants include Nocrac 200, Nocrac M-17, Nocrac SP, Nocrac SP-N, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Nocrac 300, Nocrac NS-7, and Nocrac DAH (all manufactured by Ouchi Shinko Chemical Industry Co., Ltd.); ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, and ADK STAB AO-19. AO-37 (all manufactured by ADEKA Corporation); IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all manufactured by Chiba Specialty Chemicals); Sumilizer GM, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical Co., Ltd.).

[0092] Examples of light stabilizers include ultraviolet absorbers (benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, and Tinuvin 213 (all manufactured by Ciba Specialty Chemicals); triazine light stabilizers such as Tinuvin 1577; benzophenone compounds such as CHIMASSORB81; benzoate compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals); and hindered amine compounds. Of the above, hindered amine compounds are preferred.

[0093] Specific examples of the hindered amine compound include dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}], N,N'-bis(3aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and succinic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester.

[0094] Examples of commercially available light stabilizers include Tinuvin 622LD, Tinuvin 144, CHIMASSORB944LD, and CHIMASSORB119FL (all manufactured by Chiba Specialty Chemicals), Adeka STAB LA-52, Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, Adeka STAB LA-68, Adeka STAB LA-82, and Adeka STAB LA-87 (all manufactured by ADEKA Corporation), and Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744, and Sanol LS-440 (all manufactured by Chiba Specialty Chemicals).

[0095] An antioxidant and a light stabilizer may be used in combination. By using these in combination, the effects of each agent may be further improved, and the heat resistance, weather resistance, etc. of the cured product may be improved. For example, to improve weather resistance, an ultraviolet absorber and a hindered amine-based compound (HALS) may be combined. This combination is preferable because it can further improve the effects of each agent.

[0096] The content of the antioxidant and / or light stabilizer is preferably 0.1 to 20 parts by weight, respectively, based on 100 parts by weight of the content of the polymer component.

[0097] 3. Composition of the curable composition In the curable composition, the lower limit of the content of Component B is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, based on 100 parts by weight of the polymer component, and the upper limit of the content of Component B is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of the polymer component.

[0098] In the curable composition, the lower limit of the weight ratio of Component A / Component C can be 1 / 99 or more, 5 / 95 or more, 10 / 90 or more, 20 / 80 or more, 30 / 70 or more, 40 / 60 or more, or 50 / 50 or more. The lower limit of the weight ratio of Component A / Component C can be 99 / 1 or less, 95 / 5 or less, 90 / 10 or less, 80 / 20 or less, 70 / 30 or less, 60 / 40 or less, or 50 / 50 or less.

[0099] 4. Form of curable composition The curable composition containing components A to C may be a one-component type or a multi-component type. A one-component curable composition is one in which all of the components are blended in advance and then sealed and stored. A one-component curable composition cures after use due to moisture in the environment. In a multi-component curable composition, the curing catalyst and the other components are prepared separately and then mixed together at the time of use. A multi-component curable composition may contain other optional agents (such as a colorant) in addition to the above components.

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

[0101] Furthermore, in the case of multi-component curable compositions, a retarder can be added when mixing the base resin and curing agent, which allows fine adjustment of the curing speed at the work site.

[0102] [5. Cured product] A cured product can be obtained from the above-described curable composition by a known method. For example, the above-described curable composition can absorb ambient moisture and spontaneously change into a cured product. The uses of the cured product are not particularly limited. Examples include architectural and industrial sealants, electrical and electronic component materials (such as solar cell backside sealants), electrical insulating materials (such as insulating coating materials for electric wires and cables), pressure-sensitive adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, paints, coating materials, sealants for can lids and the like, potting agents for electrical and electronic applications, films, gaskets, casting materials, various molding materials, artificial marble, anti-rust and waterproof sealants for cut portions of wire-reinforced glass or laminated glass, and waterproofing agents.

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

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

[0105] [6. Summary] The present invention includes the following aspects. <1> Compound A represented by the following general formula: [ka] During the ceremony, P 1 and P 2 are both (meth)acrylic polymers having a silyl group, R a1 and R a2 are each independently a hydrogen atom or a methyl group, Rb1 , R b2 , R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may contain a heteroatom, R 3 is an organic group having 1 to 20 carbon atoms, which may contain a heteroatom, Above P 1 and P 2 are both, The molecule has an XY diblock structure having an X block and a Y block or an XYX triblock structure, the X block contains an average of more than 2.0 repeating units derived from silyl group-containing (meth)acrylic acid ester monomers, The molecular weight distribution (Mw / Mn) is 1.8 or less. <2> the content of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block is 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block; <1> Compound A described in <3> A curable composition comprising the following components A and B: Component A: <1> or <2> Compound A described in Component B: Curing catalyst. <4> Further containing the following ingredient C: <3> A curable composition according to any one of claims 1 to 4, Component C: A polyoxyalkylene polymer having a silyl group. <5> <3> or <4> A cured product obtained by curing the curable composition described in 1. [Example]

[0106] [Measurement method] [Average molecular weight] The average molecular weight was measured using the following equipment. The measured value is a molecular weight converted into polystyrene. Liquid delivery system: e2695 (Waters) Column: Shodex GPC K-804, K-802.5 (Showa Denko K.K.) Solvent: Chloroform ·Measurement temperature: 40℃

[0107] [Remaining rate of terminal bromine atoms] 1 The residual rate of terminal bromine atoms was calculated from the results of H-NMR measurement. 1 The following equipment was used for H-NMR measurements. Measuring instrument: JNM-LA400 (JEOL Ltd.) Solvent: CDCl3

[0108] Specifically, the uncured (meth)acrylic polymer dissolved in CDCl3 1 In the H-NMR spectrum, the residual rate of terminal bromine atoms was calculated based on the peak shift ratio of the hydrogen atoms located on the carbon atoms bonded to the Br groups.

[0109] [Tensile properties of cured product] The curable composition was first cured and aged at 23°C for 3 days, and then at 50°C for 4 days to obtain a cured product. In accordance with JIS K 6251, No. 3 dumbbell-shaped test pieces were obtained from the cured product and the tensile properties were measured. The tensile properties were measured using an autograph at 23°C and 55% RH. The evaluation items were stress at 50% elongation, stress at 100% elongation, stress at break, and elongation at break.

[0110] [Gel fraction] The cured product was immersed in toluene for 24 hours, then removed and dried by heating. The gel fraction (%) was calculated from the change in weight of the cured product before and after immersion in toluene.

[0111] [Production Example: Synthesis of Compound B] Compound B was synthesized by the following procedure. Compound B synthesized in this production example is a (meth)acrylic polymer having a silyl group. In compound B, a bromine atom is located at the reactive end of the polymer chain, which is present at one position per molecule. (preparation) 1. A 2000 mL three-neck flask was prepared. 108 g of ethyl acrylate, 707 g of n-butyl acrylate, and 186 g of octadecyl acrylate were charged into the flask and mixed. This mixture is referred to as a "(meth)acrylic acid ester monomer mixture." 2. Another stirring vessel was prepared. 52.7 mg of cupric bromide (CuBr2), 54.4 mg of hexamethyltris(2-aminoethyl)amine (Me6TREN), and 1.82 g of methanol were charged into the stirring vessel and stirred under a nitrogen stream until a homogeneous solution was obtained. This homogeneous solution is referred to as the "copper solution." The copper content of the copper solution was equivalent to 15 ppm relative to the total amount of the (meth)acrylic acid ester monomer mixture. 3. Another stirring vessel was prepared. 30.8 mL of methanol, 1.0 g of ascorbic acid, and 1.6 mL of triethylamine were placed in the stirring vessel and stirred under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution." (1st step) 4. 5.60 g of ethyl α-bromobutyrate (initiator; 0.029 mol), 20 wt% of the total (meth)acrylic acid ester monomer mixture, 10 g of 3-methacryloxypropylmethyldimethoxysilane (0.045 mol; 1.5 molar equivalents relative to the initiator), 107.68 g of methanol, and the total copper solution were added to a mixer, and stirred under a nitrogen stream for 30 minutes to obtain a homogeneous solution. The mixer used here was a jacket temperature-controlled mixer, and the jacket temperature was set to 45°C. 5. When the temperature in the polymerization system reached 40°C or higher, the ascorbic acid solution was continuously added dropwise to initiate the polymerization reaction. The rate at which the ascorbic acid solution was added was set to 144 mg per hour. 6. When the temperature inside the polymerization system was monitored, it rose simultaneously with the start of the dropwise addition of ascorbic acid, reached its maximum temperature, and then gradually decreased. When the temperature difference between the temperature inside the polymerization system and the jacket temperature reached 1°C, a small amount of the reaction solution inside the polymerization system was sampled and analyzed by gas chromatography. The results showed that 90% by weight of the (meth)acrylic acid ester monomer mixture initially charged had been consumed. (2nd process) 7. The remaining (80 wt. % of the total amount) of the (meth)acrylic acid ester monomer mixture not added in the first step was continuously added dropwise to the polymerization system over a period of 90 minutes. The ascorbic acid solution was added dropwise at a rate of 48 mg of ascorbic acid per hour to the polymerization system. Sampling was also carried out sequentially and analyzed by gas chromatography. The polymerization was continued until 88 wt. % of the total amount of the (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. (3rd step) 8. 11 g of 3-methacryloxypropylmethyldimethoxysilane (0.049 mol; 1.6 molar equivalents relative to the initiator) was added to the polymerization system. The ascorbic acid solution was continuously added dropwise until 98 wt% of the total (meth)acrylic acid ester monomer mixture added to the polymerization system was consumed. The addition of the ascorbic acid solution was then stopped, and the polymerization was terminated. 9. The jacket temperature was changed to 80°C, and the solvent was then devolatilized. A diaphragm pump was used first, followed by a vacuum pump. After devolatilization was complete, the jacket temperature was cooled to 60°C or below. (purification) 10. 1000 g of butyl acetate was added to a jacket temperature-controlled stirrer and mixed with the polymer after devolatilization until a homogeneous solution was formed. An adsorbent was added to this homogeneous solution and stirred for 1 hour. The adsorbents used were 10 g of Kyoward 500SH (Kyowa Chemical Industry Co., Ltd.) and 10 g of Kyoward 700SEN-S (Kyowa Chemical Industry Co., Ltd.). 11. After stirring, the resulting mixture was filtered through a filter equipped with a bag filter cloth. This resulted in a clear polymer solution. 1.5 g of an antioxidant (Sumilizer GS; Sumitomo Chemical Co., Ltd.) was added to the solution and mixed until homogeneous. The solvent was then removed from the solution using a diaphragm pump and then a vacuum pump. In this way, Compound B was obtained.

[0112] Compound B had a number average molecular weight of 55,000 and a molecular weight distribution of 1.11. The number of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the X block of compound B, the total number of repeating units contained in both X blocks, was 2.1 on average. The proportion of repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block of compound B was 1.1 wt% when the total weight of all repeating units contained in the Y block was 100 wt%.

[0113] [Reference example] It was confirmed that the reaction of compound B with an amine resulted in the elimination of a halogen atom present at the polymer chain end of compound B. Note that the amine used in the Reference Example was a monovalent amine, and therefore the compound produced was different from compound A. However, it would be obvious to one skilled in the art that a similar reaction would occur when compound B was reacted with a polyvalent amine.

[0114] [Reference example 1] Compound B was reacted with an amine to produce a (meth)acrylic polymer with amine-modified terminals. The production of this polymer was confirmed by the elimination of bromine atoms from the polymer chain terminals. The specific procedure is as follows. 1. The bromine atoms located at the polymer chain ends of compound B were quantified. 2. 100 parts by weight of compound B, 0.61 parts by weight of n-hexylamine, 3 parts by weight of vinyltrimethoxysilane (dehydrating agent, KBM-1003, Shin-Etsu Chemical Co., Ltd.), and 1 part by weight of dibutyltin diacetylacetonate (curing catalyst (component B), Neostan U220H, Nitto Kasei Kogyo Co., Ltd.) were mixed to obtain a curable composition. 3. The curable composition was allowed to stand for 24 hours in an oven at 50° C. Since the curable composition contained a dehydrating agent, it remained uncured even after standing. 4. In the curable composition, the amount of bromine atoms located at the polymer chain terminals of the (meth)acrylic polymer is 1 Quantitative analysis was performed using H-NMR.

[0115] [Reference example 2] We verified that the bromine atom at the end of the polymer chain is eliminated by the reaction with amine. The specific procedure is as follows. 1. The bromine atoms located at the polymer chain ends of compound B were quantified. 2. A curable composition was obtained in the same manner as in Example 1, except that n-hexylamine was not added. In the curable composition, the amount of bromine atoms located at the polymer chain terminals of the (meth)acrylic polymer was 1 Quantitative analysis was performed using H-NMR.

[0116] (result) In the curable composition of Reference Example 1, the number of bromine atoms located at the polymer chain terminals of the (meth)acrylic polymer was reduced by about 70% compared to before the reaction with the amine. On the other hand, in the curable composition of Reference Example 2, the number of bromine atoms located at the polymer chain terminals of the (meth)acrylic polymer was the same as the number of bromine atoms located at the polymer chain terminals of compound B.

[0117] From this, it is considered that in the curable composition of Reference Example 1, about 70% of compound B reacted with amine to produce a (meth)acrylic polymer with amine-modified terminals. This is because in this production reaction, the bromine atom located at the polymer chain terminal of compound B is released from the polymer chain as hydrogen bromide.

[0118] Example 1 It was confirmed that the reaction between compound B and a polyamine (diamine) produces compound A. Specifically, the production of compound A was confirmed from the viewpoint of the average molecular weight and changes in the physical properties of the cured product.

[0119] The change in average molecular weight before and after the reaction of Compound B with a polyamine was examined. The specific procedure was as follows. 1. 100 parts by weight of compound B, 1 part by weight of diamine (a silicone oil modified at both ends with amino, DOWSIL BY 16-853-U, The Dow Chemical Company), and 3 parts by weight of vinyltrimethoxysilane (a dehydrating agent, KBM-1003, Shin-Etsu Chemical Co., Ltd.) were mixed. 2. The mixture was allowed to stand at 50°C for a predetermined period of time, which was either 4 days or 7 days. 3. After a specified period of time, the number average molecular weight (M n ), weight average molecular weight (M w ), Z average molecular weight (M z ) and Z+1 average molecular weight (M z+1 ) was sought.

[0120] (result) The results are shown in Figure 1. As shown in the figure, the average molecular weight increased over time, with particularly notable increases in the Z-average molecular weight and Z+1-average molecular weight, which are prone to show the effects of high-molecular-weight components. These results suggest that compound B reacted with polyamine to produce dimerized compound A.

[0121] [Example 2, Comparative Example 1] A curable composition was prepared by mixing 100 parts by weight of compound B, 1 part by weight of diamine (amino-modified silicone oil at both ends, DOWSIL BY 16-853-U, The Dow Chemical Company), 3 parts by weight of vinyltrimethoxysilane (dehydrating agent, KBM-1003, Shin-Etsu Chemical Co., Ltd.), and 1 part by weight of dibutyltin diacetylacetonate (curing catalyst, Neostan U220H, Nitto Kasei Kogyo Co., Ltd.). The time from mixing compound B and the diamine until adding the curing catalyst was as shown in Table 1.

[0122] The tensile properties and gel fraction of the cured product obtained by curing the curable composition were measured. The results are shown in Table 1. [Table 1]

[0123] (result) From the results of Example 1, it is considered that the curable compositions according to the Examples contain Compound A, while the curable compositions according to the Comparative Examples do not contain Compound A. As can be seen from Table 1, the cured products according to the Examples have improved stress at break without significant changes in other physical properties. This suggests that the mechanical strength of the cured product can be improved by incorporating Compound A into the curable composition. [Industrial Applicability]

[0124] The present invention can be used for curable compositions and the like.

Claims

1. Compound A represented by the following general formula: 【Chemical 1】 During the ceremony, P １ and P ２ are both (meth)acrylic polymers having a silyl group, R ａ１ and R ａ２ are each independently a hydrogen atom or a methyl group, R ｂ１ , R ｂ２ , R １ and R ２ are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may contain a heteroatom; R ３ is an organic group having 1 to 20 carbon atoms, which may contain a heteroatom; Above P １ and P ２ are both, The molecule has an XY diblock structure or an XYX triblock structure having an X block and a Y block, the X block contains an average of more than 2.0 repeating units derived from a silyl group-containing (meth)acrylic acid ester monomer, The molecular weight distribution (Mw / Mn) is 1.8 or less.

2. 2. Compound A according to claim 1, wherein the repeating units derived from silyl group-containing (meth)acrylic acid ester monomers contained in the Y block are 0% by weight or more and less than 5% by weight based on the weight of all repeating units contained in the Y block.

3. A curable composition comprising the following components A and B: Component A: Compound A according to claim 1; Component B: Curing catalyst.

4. The curable composition of claim 3, further comprising the following component C: Component C: a polyoxyalkylene polymer having a silyl group.

5. A cured product obtained by curing the curable composition according to claim 3 or 4.

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