Curable composition and its cured product

Abstract

This curable composition contains: a (meth)acrylic acid ester-based copolymer (A) having a reactive silicon group represented by formula (1); and a polyoxyalkylene-based polymer (B) having a reactive silicon group represented by formula (1). A monomer component constituting (A) includes: a (meth)acrylic acid ester (a1); a polyoxyalkylene-based polymer (a2) having more than one (meth)acryloyl group in the molecule; and a chain transfer agent (a3) having a mercapto group. The monomer component further includes a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and / or (a3) further has a reactive silicon group. -SiR1 cX3-c (1) R1 represents a substituted or unsubstituted C1-C20 hydrocarbon group. X represents a hydroxyl group or a hydrolyzable group. c is 0 or 1.

Description

[Technical Field]

[0001] The present invention relates to a curable composition comprising a polymer having a reactive silicon group, and a cured product thereof. [Background technology]

[0002] Organic polymers having silicon groups (hereinafter also referred to as "reactive silicon groups") that have a hydroxyl group or a hydrolyzable group on a silicon atom and can form siloxane bonds through hydrolysis and condensation reactions react even at room temperature due to moisture and other factors. It is known that rubbery cured products can be obtained when such organic polymers are crosslinked by the siloxane condensation reaction of reactive silicon groups.

[0003] Among these organic polymers, polyoxyalkylene polymers having reactive silicon groups have relatively low viscosity, making them easy to work with when preparing and using compounded compositions. Furthermore, the resulting cured products have a good balance of mechanical properties, weather resistance, and dynamic durability, making them widely used in applications such as sealants, adhesives, and paints (see Patent Document 1).

[0004] To improve the weather resistance and adhesiveness of polyoxyalkylene polymers having reactive silicon groups, a curable composition is known that uses a reactive silicon group-containing polyoxyalkylene polymer in combination with a reactive silicon group-containing (meth)acrylic acid ester polymer (see Patent Document 2). This curable composition is used as a highly weather-resistant sealant and an industrial adhesive.

[0005] On the other hand, Patent Document 3 describes a reactive silicon group-containing graft copolymer synthesized by radical polymerization of an oligomer having a polyether skeleton and double bonds at both ends, a vinyl monomer such as a (meth)acrylic acid ester, and a chain transfer agent, with the aim of overcoming the drawback of the slow curing speed of one-component moisture-curing adhesives using modified silicone or acrylic-modified silicone. This copolymer has a fast curing speed and excellent adhesive properties. [Prior art documents]

Patent Document

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] Polymers having reactive silicon groups are required to have a low viscosity so as to be easily handled before curing. According to the curable composition described in Patent Document 2, the weather resistance and adhesiveness of a polyoxyalkylene polymer having reactive silicon groups are improved, but the viscosity is relatively high and the elongation at break tends to decrease. In addition, the curability in the thickness direction (i.e., deep part curability) also tends to be low, and there is room for improvement in these aspects.

[0008] In view of the above situation, the present invention aims to provide a curable composition containing a polyoxyalkylene polymer containing a reactive silicon group and a (meth)acrylate polymer containing a reactive silicon group, which has a low viscosity, good deep part curability, and gives a cured product excellent in elongation at break.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that in a curable composition containing a polyoxyalkylene polymer containing a reactive silicon group and a (meth)acrylate polymer containing a reactive silicon group, by using specific monomers and a chain transfer agent in the (meth)acrylate polymer containing a reactive silicon group, the above problems can be solved, and the present invention has been completed.

[0010] In other words, the present invention relates to a curable composition containing a (meth)acrylic acid ester copolymer (A) having a reactive silicon group shown in the following formula (1), and a polyoxyalkylene polymer (B) having a reactive silicon group shown in the following formula (1), wherein the monomer component constituting the (meth)acrylic acid ester copolymer (A) contains a (meth)acrylic acid ester (a1), a polyoxyalkylene polymer (a2) having one or more (meth)acryloyl groups in the molecule, and a chain transfer agent (a3) ​​having a mercapto group, and further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and / or the chain transfer agent (a3) ​​having a mercapto group further contains a reactive silicon group. -SiR 1 c X 3-c (1) (In the formula, R 1 (where represents a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; c is 0 or 1.) Preferably, the polyoxyalkylene polymer (a2) accounts for 0.08 mol% to 6.0 mol% of the monomer components. Preferably, a chain transfer agent (a3) ​​having a mercapto group accounts for 0.4 mol% to 15 mol% of the monomer component. Preferably, a chain transfer agent (a3) ​​having a mercapto group accounts for 2% to 9% by weight of the monomer component. Preferably, an alkyl ester (a1') of the (meth)acrylic acid ester (a1) having 7 to 30 C12 atoms in the alkyl group accounts for 2% to 9% by weight of the monomer component. Preferably, the molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent having a mercapto group (a3) ​​is 0.04 or higher. Preferably, the number-average molecular weight of the polyoxyalkylene polymer (a2) is 20,000 or more. Preferably, the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) is 20,000 or less. Preferably, the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is 3.0 or more and 11.0 or less. Preferably, the sulfur atom concentration in the (meth)acrylic acid ester copolymer (A) is 700 ppm or more and 20,000 ppm or less. Preferably, the weight ratio of (meth)acrylic acid ester copolymer (A) to polyoxyalkylene polymer (B) is 5:95 to 50:50. Preferably, the polyoxyalkylene polymer (B) is linear. Preferably, the number-average molecular weight of the polyoxyalkylene polymer (B) is 20,000 or more. The present invention also relates to cured products of the curable composition. [Effects of the Invention]

[0011] According to the present invention, a curable composition comprising a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester polymer can be provided, which yields a cured product with low viscosity, good deep curing properties, and excellent elongation at break. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments. The curable composition according to this embodiment contains a (meth)acrylic acid ester copolymer (A) having reactive silicon groups, and a polyoxyalkylene polymer (B) having reactive silicon groups.

[0013] <<(meth)acrylic acid ester copolymer (A)>> (Meth)acrylic acid ester copolymer (A) has reactive silicon groups represented by the following formula (1) at the molecular chain terminals and / or side chains (non-terminal regions). -SiR 1 c X 3-c (1) (In the formula, R 1represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c is 0 or 1. )

[0014] R 1 The hydrocarbon group of R preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. R 1 Specific examples of R include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, a N,N-diethylaminomethyl group, etc. Among them, a methyl group and an ethyl group are preferred.

[0015] Examples of X include a hydroxyl group, hydrogen, 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, an alkenyloxy group, etc. Among these, alkoxy groups such as a methoxy group and an ethoxy group are more preferred because of their mild hydrolyzability and easy handling, and a methoxy group and an ethoxy group are particularly preferred.

[0016] c is 0 or 1. 0 is preferred because a cured product having a high Young's modulus can be obtained.

[0017] The reactive silicon groups in the (meth)acrylic acid ester copolymer (A) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, the methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred because they exhibit high activity. The methyldimethoxysilyl group is preferred because it yields a cured product with high elongation. The trimethoxysilyl group and triethoxysilyl group are more preferred because they yield a cured product with high strength, and the trimethoxysilyl group is even more preferred.

[0018] The reactive silicon group equivalent of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but is preferably 0.2 mmol / g or more, more preferably 0.4 mmol / g or more, and even more preferably 0.5 mmol / g or more. Furthermore, the reactive silicon group equivalent is preferably 2.0 mmol / g or less, and more preferably 1.0 mmol / g or less in terms of suppressing a decrease in the elongation of the cured product.

[0019] The (meth)acrylic acid ester copolymer (A) is a polymer formed by copolymerizing monomer components containing at least a (meth)acrylic acid ester (a1), a polyoxyalkylene polymer (a2) having one or more (meth)acryloyl groups in its molecule, and a chain transfer agent (a3) ​​having a mercapto group. In this application, "(meth)acrylic" refers to "acrylic and / or methacrylic".

[0020] (Meth)acrylic acid ester copolymer (A) has reactive silicon groups if it satisfies one or both of the following two conditions. Condition 1: The monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group. Condition 2: The chain transfer agent (a3) ​​having a mercapto group further has a reactive silicon group.

[0021] To obtain a cured product with high elongation, it is preferable that the amount of reactive silicon groups introduced under condition 2 is greater than the amount introduced under condition 1. Specifically, the amount of reactive silicon groups introduced under condition 1 is preferably 0.01 mmol / g or more, more preferably 0.03 mmol / g or more, and even more preferably 0.05 mmol / g or more. Furthermore, the amount of reactive silicon groups introduced under condition 1 is preferably 1.0 mmol / g or less, and more preferably 0.5 mmol / g or less. On the other hand, the amount of reactive silicon groups introduced under condition 2 is preferably 0.2 mmol / g or more, more preferably 0.3 mmol / g or more, and even more preferably 0.5 mmol / g or more. Furthermore, the amount of reactive silicon groups introduced under condition 2 is preferably 1.5 mmol / g or less, and even more preferably 1.0 mmol / g or less.

[0022] To obtain a cured product with high strength, it is preferable to introduce reactive silicon groups by both Condition 1 and Condition 2. Specifically, the amount of reactive silicon group equivalent introduced under Condition 1 is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and even more preferably 0.3 mmol / g or more. Furthermore, the amount of reactive silicon group equivalent introduced under Condition 1 is preferably 1.8 mmol / g or less, and more preferably 1.0 mmol / g or less. On the other hand, the amount of reactive silicon group equivalent introduced under Condition 2 is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and even more preferably 0.3 mmol / g or more. Furthermore, the amount of reactive silicon group equivalent introduced under Condition 2 is preferably 1.5 mmol / g or less, and even more preferably 1.0 mmol / g or less.

[0023] <(meth)acrylic acid ester (a1)> (Meth)acrylate ester (a1) is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Examples include pills, ethylene oxide adducts of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, 3,3,4,4,4-pentafluorobutyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth)acrylate, trifluoromethyl (meth)acrylate, perfluoroethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth)acrylate, 2-perfluorohexyl ethyl (meth)acrylate, 2-perfluorodecyl ethyl (meth)acrylate, 2-perfluorohexadecyl ethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, and 2-aminoethyl (meth)acrylate. One type may be used alone, or two or more types may be used in combination. (Meth)acrylic acid ester (a1) is preferably an alkyl ester of (meth)acrylic acid.

[0024] From the viewpoint of obtaining a high-strength cured product, the content of (meth)acrylic acid ester (a1) is preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, even more preferably 50% by weight or more, and even more preferably 60% by weight or more, based on the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A). Furthermore, from the viewpoint of durable adhesion, the content is preferably 50% by weight or more, more preferably 55% by weight or more, and even more preferably 60% by weight or more, based on the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A).

[0025] Since a cured product with high strength can be obtained, it is preferable that the (meth)acrylic acid ester (a1) contains an alkyl (meth)acrylic acid ester having 1 to 4 carbon atoms in the alkyl group. It is preferable that the alkyl (meth)acrylic acid ester having 1 to 4 carbon atoms in the alkyl group is contained in an amount of 35% by weight or more, more preferably 40% by weight or more, and even more preferably 45% by weight or more, relative to the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A).

[0026] (Meth)acrylic acid ester (a1) is preferable because it can form a hard polymer chain and yield a highly strong cured product. Therefore, it is preferable to contain at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate. In particular, of the total amount of the monomer components excluding the polyoxyalkylene polymer (a2), it is preferable that the proportion of (meth)acrylic acid ester (a1), which is at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate, is 60% by weight or more, and more preferably 70% by weight or more.

[0027] To improve compatibility with the polyoxyalkylene polymer (B), it is preferable that the (meth)acrylic acid ester (a1) contains an alkyl (meth)acrylic acid ester (a1') having 7 to 30 C atoms in the alkyl group. The content of the alkyl (meth)acrylic acid ester (a1') having 7 to 30 C atoms in the alkyl group is preferably 0.5% to 15% by weight, more preferably 0.7% to 13% by weight, even more preferably 1% to 11% by weight, even more preferably 1.5% to 10% by weight, and particularly preferably 2% to 9% by weight, based on the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A). When the content is 9% by weight or less, the tensile strength of the cured product can be improved.

[0028] <(a2) Polyoxyalkylene polymers having one or more (meth)acryloyl groups in the molecule> Polyoxyalkylene polymer (a2) is a polymer in itself, but it is one of the monomers that make up (meth)acrylic acid ester copolymer (A). Because polyoxyalkylene polymer (a2) has (meth)acryloyl groups, it can copolymerize with other monomers such as (meth)acrylic acid ester (a1). Moreover, because polyoxyalkylene polymer (a2) has more than one (meth)acryloyl group in one molecule, it can function as a so-called polyfunctional macromonomer. The main chain skeleton of polyoxyalkylene polymer (a2) (the second molecular chain described later) can form a structure that crosslinks two molecular chains (the first molecular chain described later) composed of polymers such as (meth)acrylic acid ester (a1) in (meth)acrylic acid ester copolymer (A). Hereinafter, polyoxyalkylene polymer (a2) will also be referred to as polyfunctional macromonomer (a2).

[0029] The main chain skeleton of the polyfunctional macromonomer (a2) is a polyoxyalkylene polymer. The main chain skeleton of the polyfunctional macromonomer (a2) is not particularly limited and includes, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Among these, polyoxypropylene is preferred.

[0030] The main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but it is preferable that it be linear.

[0031] The (meth)acryloyl group of the polyfunctional macromonomer (a2) is preferably represented by the following formula (2). CH2=C(R 2 )-COO-Z (2) (In the formula, R 2 represents a hydrogen or methyl group. Z represents the main chain skeleton of the polyfunctional macromonomer (a2).

[0032] The polyfunctional macromonomer (a2) has an average of more than one (meth)acryloyl group per molecule. The average number of (meth)acryloyl groups per molecule of the polyfunctional macromonomer (a2) is preferably 1.1 to 5, more preferably 1.3 to 4, even more preferably 1.6 to 2.5, and particularly preferably 1.8 to 2.0. The polyfunctional macromonomer (a2) may have only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups.

[0033] The polyfunctional macromonomer (a2) may have (meth)acryloyl groups at either the molecular chain ends and / or side chains of the polyoxyalkylene polymer. From the viewpoint of excellent mechanical properties, it is preferable to have them at the molecular chain ends. In particular, it is especially preferable that the polyfunctional macromonomer (a2) has a linear main chain skeleton and has (meth)acryloyl groups at both ends of its molecular chain.

[0034] There are no particular limitations on the method for synthesizing the polyfunctional macromonomer (a2), but one example is to prepare a polyoxyalkylene polymer having one or more hydroxyl groups in the molecule (preferably a linear polyoxyalkylene polymer having hydroxyl groups at both ends), and then introduce (meth)acryloyl groups using these hydroxyl groups.

[0035] As an example of a method for synthesizing polyfunctional macromonomers (a2), a compound having an isocyanate group and a (meth)acryloyl group can be reacted with a polyoxyalkylene polymer having a hydroxyl group to form a urethane bond and introduce a (meth)acryloyl group. Specific examples of compounds having the isocyanate group and (meth)acryloyl group include, for example, isocyanate ethyl (meth)acrylate, isocyanate propyl (meth)acrylate, isocyanate butyl (meth)acrylate, and isocyanate hexyl (meth)acrylate.

[0036] Another example of a method for synthesizing polyfunctional macromonomers (a2) is to introduce isocyanate groups into a polyoxyalkylene polymer having hydroxyl groups by reacting it with a diisocyanate compound, and then introduce (meth)acryloyl groups by reacting it with a compound having both hydroxyl groups and (meth)acryloyl groups. Specific examples of the diisocyanate compounds include, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-diphenylmethane diisocyanate. Specific examples of compounds having the hydroxyl group and (meth)acryloyl group include, for example, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0037] As yet another example of a method for synthesizing polyfunctional macromonomers (a2), a carboxyl group can be introduced into a polyoxyalkylene polymer having a hydroxyl group by reacting it with an acid anhydride, and then a (meth)acryloyl group can be introduced by reacting it with a compound having an epoxy group and a (meth)acryloyl group. Specific examples of the aforementioned acid anhydrides include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, trimellitic anhydride, methylnadic anhydride, and dodecyl succinic anhydride. Specific examples of compounds having the epoxy group and the (meth)acryloyl group include, for example, glycidyl (meth)acrylate.

[0038] Another example of a method for synthesizing polyfunctional macromonomers (a2) involves dehydration condensation of methacrylic acid and acrylic acid with a polyoxyalkylene polymer containing hydroxyl groups. Furthermore, to carry out the reaction under milder conditions, a method is used in which methacrylate chloride, methacrylate bromide, methacrylate iodide, acrylate chloride, acrylate bromide, and acrylate iodide are reacted with a polyoxyalkylene polymer containing hydroxyl groups.

[0039] The number-average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but from the viewpoint of achieving both the elongation at break and adhesion exhibited by the cured product and the ease of handling of (a2), it is preferably 500 or more, more preferably 2,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more, as this yields a cured product with high elongation at break. Furthermore, it is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, even more preferably 40,000 or less, and particularly preferably 30,000 or less.

[0040] The weight-average molecular weight of the polyfunctional macromonomer (a2) is not particularly limited, but from the viewpoint of achieving both the mechanical properties and adhesiveness exhibited by the cured product and the ease of handling of (a2), it is preferably 500 or more, more preferably 2,500 or more, more preferably 12,000 or more, and particularly preferably 24,000 or more. Furthermore, it is preferably 130,000 or less, more preferably 85,000 or less, even more preferably 60,000 or less, even more preferably 50,000 or less, and most preferably 40,000 or less.

[0041] The molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the polyfunctional macromonomer (a2) is not particularly limited, but is preferably narrow, specifically less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and particularly preferably 1.3 or less.

[0042] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polyfunctional macromonomer (a2) are values ​​measured by GPC (polystyrene equivalent), and the detailed measurement method is described in the examples.

[0043] The (meth)acrylic acid ester copolymer (A) has molecular chains of a (meth)acrylic acid ester polymer composed of polymers such as (meth)acrylic acid ester (a1), and molecular chains of a polyoxyalkylene polymer derived from a polyfunctional macromonomer (a2). Since the polyfunctional macromonomer (a2) has more than one polymerizable (meth)acryloyl group in one molecule, the (meth)acrylic acid ester copolymer (A) may have a structure in which more than one molecular chain of the (meth)acrylic acid ester polymer is bonded to one molecular chain of the polyoxyalkylene polymer. The molecular chains of the polyoxyalkylene polymer may be introduced to either the terminal or side chain (non-terminal portion) of the molecular chain of the (meth)acrylic acid ester polymer, but from the viewpoint of adhesion, it is preferable that they be introduced to the side chain.

[0044] In particular, when the polyfunctional macromonomer (a2) has (meth)acryloyl groups at both ends of the molecular chain of the polyoxyalkylene polymer, an H-type structure can be formed in which the molecular chain of the (meth)acrylic acid ester polymer is bonded to both ends of the molecular chain of the polyoxyalkylene polymer. Here, the molecular chain of the polyoxyalkylene polymer corresponds to the horizontal bar of H, and the molecular chain of the (meth)acrylic acid ester polymer corresponds to the two vertical bars contained in H. The H-type structure will be described later.

[0045] The content of the polyfunctional macromonomer (a2) is preferably 1% to 70% by weight, more preferably 5% to 60% by weight, and even more preferably 10% to 50% by weight, relative to the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A). In particular, when obtaining a cured product with high tensile strength, the content of the polyfunctional macromonomer (a2) is preferably less than 50% by weight, and more preferably less than 40% by weight. On the other hand, when obtaining a cured product with high elongation, the content of the polyfunctional macromonomer (a2) is preferably 35% by weight or more, and more preferably 40% by weight or more.

[0046] Furthermore, the content of the polyfunctional macromonomer (a2) is preferably 0.08 mol% to 6.0 mol%, more preferably 0.1 mol% to 5.0 mol%, and even more preferably 0.15 mol% to 2.3 mol% among the monomer components constituting the (meth)acrylic acid ester copolymer (A). Within this range, the effects of using the polyfunctional macromonomer (a2) can be achieved while suppressing gelation during the synthesis of the (meth)acrylic acid ester copolymer (A).

[0047] The average number of polyfunctional macromonomers (a2) per molecule of (meth)acrylic acid ester copolymer (A) is preferably 0.02 or more and 2.0 or less, from the viewpoint of the strength of the cured product obtained by curing the (meth)acrylic acid ester copolymer (A). The lower limit is more preferably 0.03 or more, even more preferably 0.04 or more, even more preferably 0.05 or more, particularly preferably 0.07 or more, and most preferably 0.08 or more. The upper limit is more preferably 1.5 or less, and even more preferably 1.0 or less. The above average number can be calculated by the following formula. Formula: Number average molecular weight of (meth)acrylic acid ester copolymer (A) (g / mol) / (Weight of (meth)acrylic acid ester copolymer (A) (g) / (Number of moles of polyoxyalkylene polymer (a2)))

[0048] <Chain transfer agent containing a mercapto group (a3)> By including a chain transfer agent (a3) ​​having a mercapto group in the monomer components constituting the (meth)acrylic acid ester copolymer (A), it is possible to narrow the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) and suppress gelation during the synthesis of the (meth)acrylic acid ester copolymer (A), even though a polyfunctional macromonomer (a2) is used. Furthermore, it becomes possible to preferentially synthesize polymer molecules in which one molecule of polyfunctional macromonomer (a2) is introduced into one molecule of the (meth)acrylic acid ester copolymer (A).

[0049] The chain transfer agent (a3) ​​having a mercapto group may not have a reactive silicon group, but it is preferable that it further has a reactive silicon group. By having a reactive silicon group in the chain transfer agent (a3) ​​having a mercapto group, a reactive silicon group can be introduced to the ends of the molecular chains of the (meth)acrylic acid ester polymer.

[0050] The chain transfer agent (a3) ​​having a mercapto group is not particularly limited, but examples include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane, n-dodecylmercaptan, tert-dodecylmercaptan, laurylmercaptan, and the like.

[0051] The content of the chain transfer agent (a3) ​​having a mercapto group is preferably 0.5% to 12% by weight, more preferably 1% to 10% by weight, and more preferably 2% to 9% by weight, relative to the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A). If the content of the chain transfer agent (a3) ​​exceeds 10% by weight, low molecular weight (meth)acrylic acid ester copolymer component (A) may bleed onto the surface after curing.

[0052] Furthermore, the content of the chain transfer agent (a3) ​​having a mercapto group is preferably 0.1 mol% to 20 mol%, more preferably 0.4 mol% to 15 mol%, even more preferably 0.5 mol% to 10 mol%, and particularly preferably 0.6 mol% to 8 mol% in the monomer components constituting the (meth)acrylic acid ester copolymer (A). Within this range, the effects of using the chain transfer agent (a3) ​​having a mercapto group can be achieved.

[0053] The content of the polyfunctional macromonomer (a2) and the content of the chain transfer agent having a mercapto group (a3) ​​improves the strength of the cured product obtained by curing the (meth)acrylic acid ester copolymer (A). Therefore, it is preferable to adjust the molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent having a mercapto group (a3) ​​to 0.04 or higher. The molar ratio is more preferably 0.05 or higher, even more preferably 0.06 or higher, even more preferably 0.08 or higher, even more preferably 0.1 or higher, particularly preferably 0.12 or higher, and most preferably 0.15 or higher. There is no particular upper limit to the molar ratio, but it is preferably 1 or lower, and more preferably 0.5 or lower.

[0054] (Meth)acrylic acid ester copolymer (A) is a substituent (described later -SR) derived from a chain transfer agent (a3) ​​having a mercapto group. 3 Since it may have a structure represented by , it may contain sulfur atoms. The sulfur atom concentration in the (meth)acrylic acid ester copolymer (A) is preferably 700 ppm or more and 20,000 ppm or less, and more preferably 1,000 ppm or more and 15,000 ppm or less.

[0055] The method for measuring the sulfur atom concentration is not particularly limited. It can be measured by known elemental analysis methods such as organic elemental analysis and X-ray fluorescence analysis. Alternatively, the sulfur atom concentration may be a theoretical value calculated from the total amount of monomer components used in the production of the (meth)acrylic acid ester copolymer (A) and the amount of chain transfer agent having a mercapto group (a3).

[0056] <Monomers having reactive silicon groups and polymerizable unsaturated groups (a4)> The monomer (a4) having a reactive silicon group and a polymerizable unsaturated group can be any monomer and is not required, but its use is preferred. By using monomer (a4), a reactive silicon group can be introduced into the side chains (non-terminal parts) of the molecular chain of the (meth)acrylic acid ester polymer.

[0057] Examples of monomers (a4) having a reactive silicon group and a polymerizable unsaturated group include compounds having a (meth)acryloxy group and a reactive silicon group, such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyldimethoxymethylsilane; and compounds having a vinyl group and a reactive silicon group, such as vinyltrimethoxysilane and vinyltriethoxysilane. These compounds may be used individually or in combination of two or more.

[0058] When monomer (a4) is used, the content of monomer (a4) is preferably 0.1% to 50% by weight, more preferably 0.3% to 30% by weight, and even more preferably 0.5% to 20% by weight, relative to the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A). Furthermore, from the viewpoint of improving the thixotropy of the curable composition and obtaining a cured product with high elongation, the content of monomer (a4) is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less.

[0059] <Other monomers (a5)> The monomer components constituting the (meth)acrylic acid ester copolymer (A) may contain other monomers (a5) that do not fall under any of (a1) to (a4) described in detail above, or they may not contain any monomers. Other monomers (a5) include (meth)acrylic monomers that do not fall under (meth)acrylic acid esters (a1) or monomers having a reactive silicon group and a polymerizable unsaturated group (a4), and monomers other than said (meth)acrylic monomers. Specifically, these include (meth)acrylic acid; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl esters, and maleic acid dialkyl esters; fumaric acid and its derivatives such as fumaric acid monoalkyl esters and fumarate dialkyl esters; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, and butyl maleimide. Examples include maleimide monomers such as hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; olefin monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; (meth)acrylamide; (meth)acrylonitrile; and vinyl monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. These other monomers may be used individually or in combination of two or more.

[0060] The number average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but is preferably 500 to 50,000 in polystyrene equivalent molecular weight as measured by GPC, more preferably 500 to 30,000, and particularly preferably 1,000 to 10,000. In particular, since a low viscosity (meth)acrylic acid ester copolymer (A) can be obtained, the number average molecular weight is preferably 7,000 or less, more preferably 5,000 or less, and more preferably 4,000 or less. Furthermore, since it exhibits low viscosity and good adhesion when mixed with a polyoxyalkylene polymer (B), the number average molecular weight of the (meth)acrylic acid ester copolymer (A) is preferably 3,500 or less.

[0061] The weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but is preferably 500 to 80,000, more preferably 3,000 to 70,000, and particularly preferably 5,000 to 65,000, based on polystyrene-equivalent molecular weight measured by GPC. In particular, it is preferably 8,000 or more, and more preferably 13,000 or more, as it exhibits good mechanical properties. Furthermore, when mixed with the polyoxyalkylene polymer (B), a cured product with low viscosity and high strength is obtained, so the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) is preferably 30,000 or less, more preferably 25,000 or less, and even more preferably 20,000 or less.

[0062] With respect to the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) and the weight-average molecular weight of the polyoxyalkylene polymer (a2), it is preferable that the values ​​calculated by the following formula are 0.6 or greater. Formula: (Weight-average molecular weight of copolymer (A)) / (Weight-average molecular weight of polyoxyalkylene polymer (a2)) A value of 0.6 or higher calculated by the above formula means that the average number of polyoxyalkylene polymers (a2) introduced in one molecule of (meth)acrylic acid ester copolymer (A) is large, and the strength of the cured product obtained by curing the (meth)acrylic acid ester copolymer (A) can be further improved. From the viewpoint of the strength of the cured product, the value calculated by the above formula is more preferably 0.8 or higher, even more preferably 1.0 or higher, even more preferably 1.1 or higher, particularly preferably 1.2 or higher, and most preferably 1.3 or higher. There is no particular upper limit, but it is preferably 10 or lower, and more preferably 5 or lower.

[0063] The molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but from the viewpoint of making the (meth)acrylic acid ester copolymer (A) low viscosity, it is preferably 3.0 to 11.0, more preferably 3.2 to 10.0, and even more preferably 3.4 to 8.0. The molecular weight distribution of the (meth)acrylic acid ester copolymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0064] In a preferred embodiment, the (meth)acrylic acid ester copolymer (A) may include a triblock copolymer. The triblock copolymer has a structure in which two first molecular chains are linked via one second molecular chain. The first molecular chain consists of a molecular chain of the (meth)acrylic acid ester polymer, and the second molecular chain consists of a molecular chain of the polyoxyalkylene polymer.

[0065] The first molecular chain is formed by copolymerization of (a1), the (meth)acryloyl group in (a2), (a3), an arbitrary (a4), and any other monomer. A reactive silicon group is bonded to this first molecular chain. If the chain transfer agent (a3) ​​having a mercapto group has a reactive silicon group, the reactive silicon group is bonded to the end of the first molecular chain. If a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group is used, the reactive silicon group is bonded to the non-terminal portion of the first molecular chain. On the other hand, the second molecular chain constitutes the main chain skeleton of the polyoxyalkylene polymer in the polyfunctional macromonomer (a2).

[0066] Unlike typical ABA-type triblock copolymers, the bonding method between the two first molecular chains and one second molecular chain is such that both ends of the second molecular chain are bonded to the non-terminal portions of the first molecular chain. That is, the triblock copolymer contains an H-type structure, in which the two vertical bars in H correspond to the two first molecular chains, and the one horizontal bar in H corresponds to the one second molecular chain.

[0067] However, the (meth)acrylic acid ester copolymer (A) is not limited to a triblock copolymer with an H-type structure, and may also contain block copolymers having other structures in addition to the triblock copolymer with an H-type structure. Examples of such block copolymers having other structures include block copolymers having a structure in which three first molecular chains are linked via two second molecular chains.

[0068] The first and second molecular chains are linked via ester bonds derived from the (meth)acryloyl group in the polyfunctional macromonomer (a2) (i.e., ester bonds corresponding to the ester bonds in formula (2) above).

[0069] A (meth)acrylic acid ester copolymer (A) composed of a polyoxyalkylene polymer in which the first molecular chain is composed of a rigid polymer and the second molecular chain is composed of a flexible polymer is preferred because it yields a cured product with high strength and high elongation. Here, a rigid polymer refers to a polymer with a high glass transition temperature. A flexible polymer refers to a polymer with a low glass transition temperature. Specifically, the monomer components constituting the first molecular chain (monomer components excluding the polyoxyalkylene polymer (a2)) preferably contain at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate. The proportion of the monomers in the total amount of monomer components constituting the first molecular chain is preferably 60% by weight or more, and more preferably 70% by weight or more.

[0070] Since the first molecular chain is formed by reacting it with a chain transfer agent (a3) ​​having a mercapto group, one of the ends of the first molecular chain may have a substituent derived from (a3), -SR 3 It may have a structure represented by the above formula. In the above formula, S represents a sulfur atom, and R 3 R represents a hydrocarbon group which may have a reactive silicon group. Examples of the hydrocarbon group include alkyl groups, aryl groups, or aralkyl groups having 1 to 20 carbon atoms. The reactive silicon group is the reactive silicon group represented by formula (1) above. 3 Specific examples include, for instance, reactive silicon-containing methyl groups, reactive silicon-containing propyl groups, n-dodecyl groups, tert-dodecyl groups, and lauryl groups.

[0071] As described above, corresponding to the molar ratio of polyoxyalkylene polymer (a2) / chain transfer agent having a mercapto group (a3) ​​being 0.04 or higher, in the (meth)acrylic acid ester copolymer (A), the -SR 3The molar ratio of the polyoxyalkylene polymer to the (meth)acrylic acid ester copolymer (A) is preferably 0.04 or higher. When the molar ratio is 0.04 or higher, the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) increases, and the strength of the resulting cured product may improve. The molar ratio is more preferably 0.05 or higher, even more preferably 0.08 or higher, even more preferably 0.1 or higher, particularly preferably 0.12 or higher, and most preferably 0.15 or higher. There is no particular upper limit to the molar ratio, but it is preferably 1 or less, and more preferably 0.5 or less.

[0072] <<Meth)acrylic acid ester copolymer (A) production method>> The (meth)acrylic acid ester copolymer (A) can be produced by polymerizing the monomer components. The polymerization method is not particularly limited, but may be a general free radical polymerization. According to this embodiment, even though it is free radical polymerization, polymerization can be controlled, and a block copolymer (meth)acrylic acid ester copolymer (A) can be produced, and moreover, its molecular weight distribution can be made relatively narrow.

[0073] Examples of polymerization initiators usable in the aforementioned free radical polymerization include azo compounds such as 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], and 1,1'-azobis(cyclohexane-1-carbonitride). Diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, and di(3,5,5-trimethylhexanoyl) peroxide; diisopropyl peroxide, di-sec-butyl peroxide, di-2-ethylhexyl peroxide, di-1-methylheptyl peroxide, and di-3-methoxybutyl peroxide; Examples include peroxydicarbonates such as di-dicarbonate and dicyclohexyl per-dicarbonate; peroxyesters such as tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, and cumyl perneodecanoate; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; dialkyl peroxides such as di-tert-butyl peroxide, diquyl peroxide, tert-butylquyl peroxide, and 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroxyperoxide and tert-butyl hydroperoxide; and peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane. These polymerization initiators may be used individually or in combination of two or more.

[0074] Examples of solvents usable in the free radical polymerization include aromatic solvents such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, and methylcyclohexane; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate, and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dialkyl carbonate compounds such as dimethyl carbonate and diethyl carbonate; and alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol. Among these, alcohol compounds are preferred because they result in a narrower molecular weight distribution. Aromatic solvents are preferred due to their high solubility. Aliphatic hydrocarbon solvents are preferred due to their low odor. The molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is affected by the amount of chain transfer agent (a3) ​​added and the solvent. When the amount of chain transfer agent (a3) ​​added is 3% by weight or less, the result is greatly affected by the type of solvent. When it is desired to obtain a (meth)acrylic acid ester copolymer (A) with a narrow molecular weight distribution, it is preferable to use isobutanol as the solvent.

[0075] As described above, the (meth)acrylic acid ester copolymer (A) can have reactive silicon groups by using a monomer (a4) having reactive silicon groups and polymerizable unsaturated groups, or by using a chain transfer agent (a3) ​​that further has reactive silicon groups in addition to mercapto groups. Both methods may be used in combination. By using a monomer (a4) having reactive silicon groups and polymerizable unsaturated groups, reactive silicon groups can be randomly introduced into the side chains of the molecular chains of the (meth)acrylic acid ester polymer. Alternatively, by using a chain transfer agent (a3) ​​that further has reactive silicon groups in addition to mercapto groups, reactive silicon groups can be introduced into the ends of the molecular chains of the (meth)acrylic acid ester polymer.

[0076] However, in order to further introduce reactive silicon groups into the (meth)acrylic acid ester copolymer (A), the following methods can also be used in combination. (i) A method of copolymerizing a monomer having a reactive functional group (V group) with a (meth)acrylic acid ester (a1) or the like, and then reacting the resulting copolymer with a compound having a functional group that reacts with the V group and a reactive silicon group. Specifically, examples include a method of copolymerizing 2-hydroxyethyl acrylate and then reacting it with an isocyanate silane compound having a reactive silicon group, or a method of copolymerizing glycidyl acrylate and then reacting it with an aminosilane compound having a reactive silicon group. (ii) A method for introducing reactive silicon groups by modifying the terminal functional groups of a (meth)acrylic acid ester copolymer synthesized by living radical polymerization. (meth)acrylic acid ester copolymers obtained by living radical polymerization readily have functional groups introduced at the polymer ends, and reactive silicon groups can be introduced at the polymer ends by modifying them.

[0077] Compounds having a functional group that reacts with the V group and a reactive silicon group used in method (i) include, for example, isocyanate silane compounds such as 3-isocyanate propyl dimethoxymethylsilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, isocyanate methyl dimethoxymethylsilane, isocyanate methyl trimethoxysilane, and isocyanate methyl triethoxysilane; 3-glycidoxypropyl dimethoxymethylsilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, and glycidoxymethyl Examples include epoxysilane compounds such as dimethoxymethylsilane, glycidoxymethyltrimethoxysilane, and glycidoxymethyltriethoxysilane; and aminosilane compounds such as 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyltriethoxysilane.

[0078] Method (ii) can utilize any modification reaction, but examples include a method using a compound having a reactive group and a reactive silicon group that can react with terminal functional groups obtained by living radical polymerization, or a method in which a double bond is introduced to the polymer terminal using a compound having a reactive group and a double bond that can react with terminal functional groups, and then a reactive silicon group is introduced using a hydrosilylation reaction or the like.

[0079] <<Polyoxyalkylene polymer (B)>> <Reactive silicon group> The polyoxyalkylene polymer (B) has a reactive silicon group represented by formula (1) above. However, the reactive silicon group of the polyoxyalkylene polymer (B) may be the same as or different from the reactive silicon group of the (meth)acrylic acid ester copolymer (A).

[0080] The reactive silicon groups possessed by the polyoxyalkylene polymer (B) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, the methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred because they exhibit high activity, the methyldimethoxysilyl group is preferred because it yields a cured product with high elongation, the trimethoxysilyl group and triethoxysilyl group are more preferred because they yield a cured product with high strength, and the trimethoxysilyl group is even more preferred.

[0081] The polyoxyalkylene polymer (B) may have an average of one or fewer reactive silicon groups at each terminal site, or it may have an average of more than one reactive silicon group at each terminal site. Having an average of more than one reactive silicon group at each terminal site means that the polyoxyalkylene polymer (B) contains polyoxyalkylene having two or more reactive silicon groups at each terminal site, as shown in formula (3) below.

[0082] [ka]

[0083] The polyoxyalkylene polymer (B) may contain only polyoxyalkylene molecules having two or more reactive silicon groups at one terminal site, or it may contain both polyoxyalkylene molecules having two or more reactive silicon groups at one terminal site and polyoxyalkylene molecules having one reactive silicon group at one terminal site. Furthermore, a single polyoxyalkylene molecule may have multiple terminal sites, some having two or more reactive silicon groups and others having one reactive silicon group. In addition, the polyoxyalkylene polymer (B) as a whole may contain polyoxyalkylene molecules that have an average of more than one reactive silicon group at each terminal site, but also have terminal sites that do not have reactive silicon groups.

[0084] In the above equation (3), R 4 and R 6 Each of these independently represents a divalent carbon-1 to carbon-6 bonding group, R 4 and R 6 The atom bonded to each adjacent carbon atom is either carbon, oxygen, or nitrogen. 5 and R 7 Each of these independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. 1 X and c are as described above with respect to equation (1).

[0085] R 4 and R 6 This may be a divalent organic group having 1 to 6 carbon atoms, and may also be a hydrocarbon group containing an oxygen atom. The hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and even more preferably 1 to 2. 4 Specific examples include, for instance, -CH2OCH2-, -CH2O-, and -CH2-, but -CH2OCH2- is preferred. 6 Specific examples include, for instance, -CH2- and -CH2CH2-, but -CH2- is preferred.

[0086] R 5 and R7 The number of carbon atoms in the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. 5 and R 7 Specific examples include, for instance, a hydrogen atom, a methyl group, and an ethyl group, but preferably a hydrogen atom and a methyl group, and more preferably a hydrogen atom.

[0087] The terminal portion represented by formula (3) is, in a particularly preferred embodiment, R 4 is -CH2OCH2-, and R 6 is -CH2-, and R 5 and R 7 Each of these is a hydrogen atom. n is preferably an integer between 1 and 5, more preferably an integer between 1 and 3, and even more preferably 1 or 2. However, n is not limited to a single value, and may be a mixture of multiple values.

[0088] The reactive silicon groups in the polyoxyalkylene polymer (B) preferably number more than 1.0 on average at each terminal site, more preferably 1.1 or more, even more preferably 1.5 or more, and even more preferably 2.0 or more. Furthermore, it is preferable that there be 5 or fewer, and more preferably 3 or fewer.

[0089] The number of terminal sites having more than one reactive silicon group in one molecule of polyoxyalkylene polymer (B) is preferably 0.5 or more on average, more preferably 1.0 or more, even more preferably 1.1 or more, and even more preferably 1.5 or more. It is also preferably 4 or less, and more preferably 3 or less.

[0090] The polyoxyalkylene polymer (B) may have reactive silicon groups in locations other than the terminals, but it is preferable to have reactive silicon groups only at the terminals, as this makes it easier to obtain a rubbery cured product with high elongation and low elastic modulus.

[0091] The average number of reactive silicon groups per molecule of polyoxyalkylene polymer (B) is preferably more than 1.0, more preferably 1.2 or more, even more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. Furthermore, it is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less. When the average number is greater than 1.0 and 6.0 or less, a cured product with high strength and high elongation can be obtained.

[0092] <Main chain structure> There are no particular restrictions on the main chain skeleton of the polyoxyalkylene polymer (B), and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Among these, polyoxypropylene is preferred. It is preferable that the polyoxyalkylene polymer (B) has only a polyoxyalkylene polymer skeleton as its polymer skeleton and does not have a (meth)acrylic acid ester polymer skeleton.

[0093] The number-average molecular weight of the polyoxyalkylene polymer (B) is preferably 3,000 or more, more preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, and particularly preferably 25,000 or more, in terms of polystyrene-equivalent molecular weight in GPC, from the viewpoint of the cured product exhibiting good mechanical properties. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 45,000 or less, and particularly preferably 40,000 or less.

[0094] The molecular weight of polyoxyalkylene polymer (B) can also be expressed as the end-group-reduced molecular weight, which is determined by directly measuring the end-group concentration of the organic polymer precursor before the introduction of reactive silicon groups by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and considering the structure of the organic polymer (degree of branching determined by the polymerization initiator used). Alternatively, the end-group-reduced molecular weight of polyoxyalkylene polymer (B) can be determined by creating a calibration curve between the number-average molecular weight obtained by general GPC measurement of the organic polymer precursor and the above-mentioned end-group-reduced molecular weight, and then converting the number-average molecular weight obtained by GPC of polyoxyalkylene polymer (B) to the end-group-reduced molecular weight.

[0095] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (B) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving various mechanical properties such as the durability and elongation of the cured product, 1.2 or less is preferred. The molecular weight distribution of the polyoxyalkylene polymer (B) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0096] Furthermore, the main chain structure of the polyoxyalkylene polymer (B) may be linear or branched, but a linear structure is preferable to obtain a cured product with high elongation.

[0097] <Method for synthesizing polyoxyalkylene polymer (B)> Next, we will explain the method for synthesizing polyoxyalkylene polymer (B). Polyoxyalkylene polymers (B) can be synthesized by conventional methods. However, polyoxyalkylene polymers (B) having an average of one or fewer reactive silicon groups at each terminal site can be obtained by introducing one carbon-carbon unsaturated bond per terminal to a hydroxyl-terminated polymer obtained by polymerization, and then reacting it with a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bond. When introducing a carbon-carbon unsaturated bond into the polymer, halogenated hydrocarbon compounds having carbon-carbon unsaturated bonds, as described later, can be used. As such halogenated hydrocarbon compounds, in addition to halogenated hydrocarbon compounds having carbon-carbon double bonds, such as allyl chloride, as described later, halogenated hydrocarbon compounds having carbon-carbon triple bonds, such as propargyl chloride, can also be used.

[0098] Furthermore, polyoxyalkylene polymers (B) having an average of more than one reactive silicon group at each terminal site are preferably obtained by introducing two or more carbon-carbon unsaturated bonds per terminal to a hydroxyl-terminated polymer obtained by polymerization, and then reacting it with a reactive silicon group-containing compound that reacts with carbon-carbon unsaturated bonds. The synthesis method is described below.

[0099] (polymerization) In forming the main chain skeleton of the polyoxyalkylene polymer (B), a method is preferred in which an epoxy compound is polymerized on an initiator having a hydroxyl group, using a complex metal cyanide catalyst such as a zinc hexacyanocobaltate grime complex.

[0100] Examples of initiators having hydroxyl groups include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, and polypropylene monoalkyl ether, which have one or more hydroxyl groups.

[0101] Examples of epoxy compounds include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Among these, propylene oxide is preferred.

[0102] (Introduction of carbon-carbon unsaturated bonds) A preferred method for introducing two or more carbon-carbon unsaturated bonds to a single terminal is to first react an alkali metal salt with a hydroxyl-terminated polymer, then react it with an epoxy compound having carbon-carbon unsaturated bonds, and then react it with a halogenated hydrocarbon compound having carbon-carbon unsaturated bonds. This method allows for efficient and stable introduction of reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain by polymerization conditions.

[0103] Preferred alkali metal salts include sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide, with sodium methoxide and potassium methoxide being more preferred. Sodium methoxide is particularly preferred due to its availability.

[0104] The temperature for reacting with the alkali metal salt is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time for reacting with the alkali metal salt is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0105] Epoxy compounds having carbon-carbon unsaturated bonds, particularly those with the following formula:

[0106] [ka]

[0107] Compounds represented by the formula (3') can be suitably used. 4 and R 5The same applies as described above. Specific examples of epoxy compounds having carbon-carbon unsaturated bonds include, from the viewpoint of reaction activity, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide, with allyl glycidyl ether being particularly preferred.

[0108] The amount of epoxy compound having carbon-carbon unsaturated bonds added can be any amount, taking into consideration the amount of carbon-carbon unsaturated bonds introduced into the polymer and its reactivity. In particular, the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.2 or higher, more preferably 0.5 or higher. It is also preferably 5.0 or lower, and more preferably 2.0 or lower.

[0109] When an epoxy compound having a carbon-carbon unsaturated bond is subjected to a ring-opening addition reaction with a polymer containing a hydroxyl group, the reaction temperature is preferably 60°C to 150°C, and more preferably 110°C to 140°C.

[0110] Examples of halogenated hydrocarbon compounds having a carbon-carbon double bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Due to their ease of handling, allyl chloride and methlyl chloride are more preferred.

[0111] Examples of halogenated hydrocarbon compounds having a carbon-carbon triple bond include propargyl chloride, propargyl bromide, and propargyl iodide.

[0112] There are no particular restrictions on the amount of halogenated hydrocarbon compound having a carbon-carbon unsaturated bond added, but the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.7 or higher, more preferably 1.0 or higher. Furthermore, it is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0113] The reaction temperature for a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0114] (Introduction of reactive silicon groups) The method for introducing reactive silicon groups is not particularly limited, and known methods can be used. Examples of introduction methods are given below. (iii) A method for adding a hydrosilane compound to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction. (iv) A method of reacting a polymer having carbon-carbon unsaturated bonds with a compound (also called a silane coupling agent) having both a group capable of forming a bond in reaction with carbon-carbon unsaturated bonds and a reactive silicon group. Examples of groups capable of forming a bond in reaction with carbon-carbon unsaturated bonds include, but are not limited to, mercapto groups. (v) A method for reacting a reactive group-containing polymer with a silane coupling agent. Examples of reactive group combinations between the reactive group-containing polymer and the silane coupling agent include, but are not limited to, hydroxyl group and isocyanate group, hydroxyl group and epoxy group, amino group and isocyanate group, amino group and thioisocyanate group, amino group and epoxy group, amino group and α,β-unsaturated carbonyl group (reaction by Michael addition), carboxyl group and epoxy group, unsaturated bond and mercapto group, etc.

[0115] Method (iii) is preferred because the reaction is simple, the amount of reactive silicon groups introduced can be easily adjusted, and the physical properties of the resulting polyoxyalkylene polymer (B) are stable. Methods (iv) and (v) are preferred because they offer many reaction options and make it easy to increase the rate of reactive silicon group introduction.

[0116] The hydrosilane compounds that can be used by method (iii) are not particularly limited, but examples include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, and (N,N-diethylaminomethyl)diethoxysilane.

[0117] Regarding the amount of hydrosilane compound used, a molar ratio (moles of hydrosilane / moles of carbon-carbon unsaturated bonds) of 0.05 to 10 relative to the carbon-carbon unsaturated bonds in the precursor polymer is preferable from the viewpoint of reactivity, and 0.3 to 2 is more preferable from the viewpoint of economy.

[0118] Hydrosilylation reactions are accelerated by various catalysts. Known catalysts such as various complexes of cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium can be used as hydrosilylation catalysts. For example, platinum supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid with alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphite complexes [Pt{P(OPh)3}4] can be used. From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

[0119] Silane coupling agents that can be used by the method of (iv) or (v) above include, for example, mercaptosilanes that react with unsaturated bonds, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, and mercaptomethyldimethoxymethylsilane; and silane coupling agents that react with hydroxyl groups, such as 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyldimethoxymethylsilane, and isocyanate Isocyanate silanes such as methyltrimethoxysilane, isocyanate methyltriethoxysilane, and isocyanate methyldimethoxymethylsilane; epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, and glycidoxymethyldimethoxymethylsilane that react with hydroxyl groups, amino groups, or carboxyl groups; isocyanate group or thioisocyanate The following react with the group: 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)propyltrimethoxysilane, 3-(2-aminoethyl)propyldimethoxymethylsilane, 3-(2-aminoethyl)propyltriethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl Examples include aminosilanes such as -3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(3-(trimethoxysilyl)propyl)amine; and hydroxyalkylsilanes such as 3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane.

[0120] The main chain of the polyoxyalkylene polymer (B) is composed of ester bonds or the following formula (4), to the extent that the effects of the invention are not impaired: -NR 8 -C(=O)- (4) It may include an amide segment represented by . In formula (4), R 8 This represents an organic group with 1 to 10 carbon atoms or a hydrogen atom.

[0121] Cured products obtained from curable compositions containing a polyoxyalkylene polymer (B) containing ester bonds or amide segments may have high hardness and strength due to the action of hydrogen bonding, etc. However, polyoxyalkylene polymers (B) containing amide segments, etc., may cleave due to heat, etc. Also, curable compositions containing polyoxyalkylene polymers (B) containing amide segments, etc., tend to have high viscosity. Considering the above advantages and disadvantages, polyoxyalkylene polymers (B) may be made by using polyoxyalkylene containing amide segments, etc., or by using polyoxyalkylene without amide segments, etc.

[0122] Examples of amide segments represented by formula (4) include those formed by the reaction of an isocyanate group with a hydroxyl group, an amino group with a carbonate, an isocyanate group with an amino group, an isocyanate group with a mercapto group, and so on. Furthermore, amide segments formed by the reaction of an amide segment containing an active hydrogen atom with an isocyanate group are also included in the amide segments represented by formula (4).

[0123] A method for producing a polyoxyalkylene polymer (B) containing an amide segment is, for example, to react a polyoxyalkylene having an active hydrogen-containing group at its terminus with an excess polyisocyanate compound to synthesize a polymer having an isocyanate group at its terminus, or simultaneously with such synthesis, the following formula (5): ZR 9-SiR 1 c X 3-c (5) One method involves reacting the Z group of a silicon compound represented by with all or part of the isocyanate groups of a synthesized polymer. In formula (5), R 1 X and c are the same as above. 9 represents a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z represents a hydroxyl group, carboxyl group, mercapto group, primary amino group, or secondary amino group.

[0124] The silicon compound represented by formula (5) is not particularly limited, but examples include amino group-containing silanes such as γ-aminopropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, (N-phenyl)-γ-aminopropyltrimethoxysilane, and N-ethylaminoisobutyltrimethoxysilane; hydroxyl group-containing silanes such as γ-hydroxypropyltrimethoxysilane; and mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane. Furthermore, as described in Japanese Patent Publication No. 6-211879 (US Patent No. 5364955), Japanese Patent Publication No. 10-53637 (US Patent No. 5756751), Japanese Patent Publication No. 10-204144 (EP0831108), Japanese Patent Publication No. 2000-169544, and Japanese Patent Publication No. 2000-169545, Michael addition products of various α,β-unsaturated carbonyl compounds and primary amino group-containing silanes, or Michael addition products of various (meth)acryloyl group-containing silanes and primary amino group-containing compounds, can also be used as silicon compounds represented by formula (5).

[0125] Furthermore, as a method for producing the polyoxyalkylene polymer (B) containing the amide segment, for example, a polyoxyalkylene having an active hydrogen-containing group at its terminus is given the following formula (6): O=C=NR 9 -SiR 1c X 3-c (6) One method is to react a reactive silicon group-containing isocyanate compound represented by the formula (6). 9 , R 1 X and c are the same as described above.

[0126] The reactive silicon group-containing isocyanate compound represented by formula (6) is not particularly limited, but examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, γ-(methoxymethyl)dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl)dimethoxysilylmethyl isocyanate, and the like.

[0127] When the polyoxyalkylene polymer (B) contains amide segments, the number of amide segments per molecule of the polyoxyalkylene polymer (B) (average value) is preferably 1 to 10, more preferably 1.5 to 5, and particularly preferably 2 to 3, from the viewpoint of curability and viscosity. To lower the viscosity of the curable composition and improve workability, it is preferable that the polyoxyalkylene polymer (B) does not contain amide segments.

[0128] Methods for blending a (meth)acrylic acid ester copolymer (A) and a polyoxyalkylene polymer (B) have been proposed in Japanese Patent Publication Nos. 59-122541, 63-112642, 6-172631, and 11-116763, among others. Alternatively, a method can be used to synthesize the (meth)acrylic acid ester copolymer (A) by copolymerizing the monomer components constituting the (meth)acrylic acid ester copolymer (A) in the presence of the polyoxyalkylene polymer (B).

[0129] In the curable composition according to this embodiment, the weight ratio of (meth)acrylic acid ester copolymer (A) to polyoxyalkylene polymer (B) can be appropriately set considering the effects of the invention, but is preferably 5:95 to 50:50. Within this range, a cured product with high tensile strength and adhesive strength can be obtained. The weight ratio of polymer (A) to polymer (B) is more preferably 20:80 to 50:50, and even more preferably 30:70 to 50:50.

[0130] <<Curable composition>> This embodiment relates to a curable composition comprising a (meth)acrylic acid ester copolymer (A) and a polyoxyalkylene polymer (B). The curable composition may contain only the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B) as reactive silicon group-containing polymers, or it may contain other reactive silicon group-containing polymers in addition to the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0131] <<Silanol Condensation Catalyst>> The curable composition according to this embodiment preferably contains a silanol condensation catalyst for the purpose of promoting the reaction of condensing the reactive silicon groups of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B), thereby extending the chains or crosslinking the polymers.

[0132] Examples of silanol condensation catalysts include organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, and alkoxy metals.

[0133] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), reaction products of dibutyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalate esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, and reaction products of dioctyltin oxide and silicate compounds.

[0134] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. Various metals can be combined with the following carboxylic acids to form metal carboxylate salts.

[0135] Specific examples of amine compounds 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 butyl biguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0136] 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.

[0137] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), and diisopropoxytitanium bis (ethylacetoacetate), as well as aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0138] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0139] The silanol condensation catalyst may be used in combination with two or more different catalysts. For example, combining the amine compound with a carboxylic acid or with an alkoxy metal may improve reactivity.

[0140] When using a silanol condensation catalyst, the amount 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 total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0141] <<Other additives>> The curable composition according to this embodiment may contain, in addition to the (meth)acrylic acid ester copolymer (A), the polyoxyalkylene polymer (B), and an optional silanol condensation catalyst, as additives such as fillers, adhesion promoters, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, and other resins. Furthermore, the curable composition according to this embodiment may contain various additives as needed for the purpose of adjusting the physical properties of the composition or its cured product. Examples of such additives include, for example, plasticizers, solvents, diluents, photocurable substances, oxygen-curable substances, surface modifiers, silicates, curing modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, and foaming agents.

[0142] <Filler> The curable composition according to this embodiment may contain fillers. Examples of such fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, settling silica, crystalline silica, fused silica, wet silica, anhydrous silicic acid, hydrated silicic acid, alumina, carbon black, ferric oxide, aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fibers, filaments, and the like.

[0143] The amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0144] Organic balloons and inorganic balloons may be added to reduce the weight (lower specific gravity) of the composition.

[0145] <Adhesion-enhancing agent> The curable composition according to this embodiment may contain an adhesion promoter. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be used.

[0146] Specific examples of silane coupling agents 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; as well as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-iso Examples include isocyanate group-containing silanes such as cyanate-propylmethyldimethoxysilane, α-isocyanate-methyltrimethoxysilane, and α-isocyanate-methyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In addition, condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes and other alkoxysilanes, and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes, can also be used. The above adhesion-imparting agents may be used individually or in combination of two or more types.

[0147] The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0148] <Plasticizer> A plasticizer may be added to the curable composition according to this embodiment. Specific examples of plasticizers 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; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid 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; alkyl sulfonate phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

[0149] Furthermore, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc. Plasticizers may be used alone or in combination of two or more types.

[0150] The amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0151] <Solvents, Diluents> A solvent or diluent may be added to the curable composition according to this embodiment. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc., can be used. When a solvent or diluent is used, 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, due to concerns about air pollution when the composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more.

[0152] <Drip-preventing agent> The curable composition according to this embodiment may contain a drip inhibitor as needed to prevent dripping and improve workability. The drip inhibitor is not particularly limited, but examples include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These drip inhibitors may be used alone or in combination of two or more.

[0153] The amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0154] <Antioxidant> The curable composition according to this embodiment may contain an antioxidant (anti-aging agent). Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731.

[0155] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0156] <Light stabilizer> The curable composition according to this embodiment may contain a light stabilizer. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, but hindered amine-based compounds are particularly preferred.

[0157] The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0158] <UV absorber> The curable composition according to this embodiment may contain an ultraviolet absorber. Using an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate compounds. Benzotriazole-based compounds are particularly preferred. Specific examples include the commercially available products Chinuvin P, Chinuvin 213, Chinuvin 234, Chinuvin 326, Chinuvin 327, Chinuvin 328, Chinuvin 329, and Chinuvin 571 (all manufactured by BASF).

[0159] The amount of ultraviolet absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0160] <Physical property modifier> The curable composition according to this embodiment may contain a property modifier to adjust the tensile properties of the resulting cured product as needed. The 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; trialkylsilyl borates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using the above property modifier, the hardness of the curable composition according to this embodiment can be increased or decreased, resulting in increased elongation at break. The above property modifiers may be used alone or in combination of two or more.

[0161] In particular, compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis have the effect of reducing the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are especially preferred. Examples of compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and produce silane monool upon hydrolysis. Specifically, examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0162] The amount of property modifier used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0163] <Adhesive-granting resin> The curable composition according to this embodiment may contain a tackifying resin to enhance adhesion to the substrate or as needed. There are no particular restrictions on the tackifying resin; commonly used resins can be used.

[0164] Specific examples include terpene resins, aromatically 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 their hydrogenated products, 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 individually or in combination of two or more types.

[0165] The amount of tackifying 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 total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0166] <Compounds containing epoxy groups> In the curable composition according to this embodiment, compounds containing epoxy groups can be used. Using compounds with epoxy groups can improve the resilience of the cured product. Examples of compounds with epoxy groups include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, epoxybutyl stearate, and the like. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0167] <Photocurable substance> A photocurable substance can be used in the curable composition according to this embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many types of compounds of this kind are known, including organic monomers, oligomers, resins, or compositions containing them. Typical examples include unsaturated acrylic compounds, vinyl polycinnamates, or azidized resins, which are monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups.

[0168] The amount of photocurable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0169] <Oxygen curing substance> The curable composition according to this embodiment can use an oxygen-curable substance. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. These react with oxygen in the air to form a cured film near the surface of the cured product, preventing stickiness and 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 these 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 individually or in combination of two or more.

[0170] The amount of oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B). As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0171] <Epoxy resin> An epoxy resin can be used in combination with the curable composition according to this embodiment. Compositions with added epoxy resin are particularly preferred as adhesives, especially adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins or novolac type epoxy resins.

[0172] The ratio of epoxy resin to (meth)acrylic acid ester copolymer (A) and polyoxyalkylene polymer (B) is preferably in the range of 100 / 1 to 1 / 100 by weight, where (meth)acrylic acid ester copolymer (A) and polyoxyalkylene polymer (B) = total / epoxy resin. If the ratio of (meth)acrylic acid ester copolymer (A) and polyoxyalkylene polymer (B) = total / epoxy resin is less than 1 / 100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the epoxy resin cured product, and if the ratio of (meth)acrylic acid ester copolymer (A) and polyoxyalkylene polymer (B) = total / epoxy resin exceeds 100 / 1, the strength of the cured product will be insufficient.

[0173] 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 this embodiment. There are no particular restrictions on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be used.

[0174] When using a curing agent for epoxy resin, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

[0175] In this embodiment, it is preferable to prepare the curable composition as a one-component type that hardens upon contact with moisture in the air after application, by pre-mixing all the components and storing them in a sealed container.

[0176] In the case of a one-component curable composition, all components are pre-mixed. Therefore, it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them during mixing by reducing pressure or other means.

[0177] For dehydration and drying, suitable methods include heat drying for solid materials such as powders, and vacuum dehydration or dehydration using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc., for liquid materials. Alternatively, a small amount of isocyanate compound may be added and the isocyanate group may be reacted with water to dehydrate the material. Oxazolidine compounds such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may also be added and reacted with water to dehydrate the material.

[0178] In addition to these dehydration and drying methods, storage stability can be further improved by adding lower alcohols such as methanol and ethanol, or alkoxysilane compounds. Examples of such alkoxysilane compounds include methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0179] The amount of dehydrating agent, particularly the alkoxysilane compound, used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total of the (meth)acrylic acid ester copolymer (A) and the polyoxyalkylene polymer (B).

[0180] There are no particular limitations on the method for preparing the curable composition according to this embodiment. For example, conventional methods such as blending the above components and kneading them at room temperature or under heating using a mixer, rolls, or kneader, or dissolving and mixing the above components using a small amount of a suitable solvent, can be employed.

[0181] The curable composition according to this embodiment can be used as a sealant, adhesive, molding agent, vibration damping material, soundproofing material, foaming material, paint, spray material, waterproof coating agent, etc. for buildings, ships, automobiles, roads, etc.

[0182] Since the cured product obtained by curing the curable composition according to this embodiment has good adhesion to various substrates, it is more preferable to use the curable composition as a sealant or adhesive.

[0183] The curable composition according to this embodiment can be used in a variety of applications, such as electrical and electronic component materials like back-surface sealing materials for solar cells, electrical insulating materials like insulating coatings for electric wires and cables, elastic adhesives, contact adhesives, spray-type sealants, crack repair materials, tile adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical device sealants, food packaging materials, joint sealing materials for exterior materials such as sizing boards, coating materials, primers, conductive materials for electromagnetic shielding, thermal conductive materials, hot melt materials, potting agents for electrical and electronic applications, films, gaskets, various molding materials, rust-preventive and waterproof sealing materials for wired glass and laminated glass edges (cut sections), and liquid sealants used in automotive parts, electrical components, and various machine parts.

[0184] The cured product of the curable composition according to this embodiment can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin molded products, either alone or in combination with a primer. Therefore, the curable composition can also be used as a sealing composition or an adhesive composition.

[0185] The curable composition according to this embodiment can be used as an adhesive for interior panels, exterior panels, tile adhesives, stone cladding adhesives, ceiling finishing adhesives, floor finishing adhesives, wall finishing adhesives, vehicle panels, electrical / electronic / precision equipment assembly adhesives, direct glazing sealants, double-glazed glass sealants, SSG construction sealants, or working joint sealants for buildings. [Examples]

[0186] The present invention will be specifically described below with reference to examples, but these examples are not intended to limit the present invention.

[0187] (Number-average molecular weight and weight-average molecular weight) The number-average molecular weight and weight-average molecular weight in the examples are GPC molecular weights measured under the following conditions. Liquid delivery system: Tosoh HLC-8220GPC Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0188] (Sulfur atom concentration) The sulfur atom concentration is a theoretical value calculated from the total amount of monomer components used in the production of the (meth)acrylic acid ester copolymer (A) and the amount of chain transfer agent (a3) ​​containing a mercapto group.

[0189] (Synthesis Example 1) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 28,500 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and then 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. As a result, polyoxypropylene having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that this polymer has an average of 2.0 carbon-carbon unsaturated bonds introduced at each terminal site.

[0190] To 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, 36 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution based on platinum) was added, and 2.2 parts by weight of trimethoxysilane were slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted trimethoxysilane was removed by distillation under reduced pressure to obtain a linear reactive silicon-containing polyoxypropylene polymer (B-1) having an average of 1.6 trimethoxysilyl groups at one terminal site, an average of 3.2 silicon groups per molecule, and a number-average molecular weight of 28,500.

[0191] (Synthesis Example 2) Using a polyoxypropylene triol with a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 26,200 (end-group equivalent molecular weight of 17,440) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and then 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. As a result, polyoxypropylene having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that this polymer has an average of 2.0 carbon-carbon unsaturated bonds introduced at each terminal site. To 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, 72 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution based on platinum) was added, and 2.5 parts by weight of trimethoxysilane were slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted trimethoxysilane was removed by distillation under reduced pressure to obtain a branched-chain reactive silicon-containing polyoxypropylene polymer (B-2) having an average of 1.5 trimethoxysilyl groups at one terminal site, an average of 4.5 silicon groups per molecule, and a number-average molecular weight of 26,200.

[0192] (Synthesis Example 3) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 14,600 (end-group equivalent molecular weight of 9,130) and a molecular weight distribution Mw / Mn = 1.16, with hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and then 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. As a result, polyoxypropylene having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that this polymer has an average of 2.0 carbon-carbon unsaturated bonds introduced at each terminal site. To 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, 36 ppm of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 3.2 parts by weight of dimethoxymethylsilane were slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a linear reactive silicon-containing polyoxypropylene polymer (B-3) having an average of 1.5 dimethoxymethylsilyl groups at one terminal site, an average of 3.0 silicon groups per molecule, and a number-average molecular weight of 14,600.

[0193] (Synthesis Example 4) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 14,600 (end-group equivalent molecular weight of 9,130) and a molecular weight distribution Mw / Mn = 1.16, with hydroxyl groups at both ends. 60 ppm of U-360 (dibutyltin bis(isooctyl mercaptopropionate, Nitto Kasei Co., Ltd.)) was added to the obtained polyoxypropylene and heated to 90°C. One equivalent of A-LINK35 (3-isocyanatetopropyltrimethoxysilane Momentive) was added dropwise to the hydroxyl groups of the polyoxypropylene and the reaction was carried out at 90°C for 1 hour to obtain a linear reactive silicon group-containing polyoxypropylene polymer (B-4) having trimethoxysilyl groups at both ends, an average of 2.0 silicon groups per molecule, and a number-average molecular weight of 14,600.

[0194] (Synthesis Example 5) Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain polyoxypropylene oxide with a number-average molecular weight of 7,750 (end-group molecular weight of 5,000). Subsequently, a methanol solution of NaOMe equivalent to 1.2 times the hydroxyl group of this hydroxyl-terminated polyoxypropylene oxide was added, and the methanol was removed by distillation. Further, 3-chloro-1-propene was added to convert the terminal hydroxyl groups to allyl groups. Next, 36 ppm of platinum divinyldisiloxane complex (isopropanol solution equivalent to 3% by mass of platinum) was added to 100 parts by mass of the obtained allyl-terminated polyoxypropylene polymer, and while stirring, 1.72 parts by mass of dimethoxymethylsilane was slowly added dropwise. By reacting the mixed solution at 90°C for 2 hours, a linear reactive silicon-containing polyoxypropylene polymer (B-5) was obtained, having dimethoxymethylsilyl groups at the ends, an average of 0.7 silicon groups per molecule, and a number-average molecular weight of 7,750.

[0195] (Synthesis Example 6) To a polyoxypropylene glycol with a number-average molecular weight of approximately 4,020 (end-group equivalent molecular weight of 2,980), 60 ppm of U-360 (dibutyltin bis(isooctyl mercaptopropionate, Nitto Kasei Co., Ltd.)) was added. 0.93 equivalents of Karenz AOI (2-isocyanate ethyl acrylate, Showa Denko K.K.) were added dropwise to the hydroxyl groups of the polyoxypropylene glycol, and the reaction was carried out at 80°C for 1 hour in a nitrogen atmosphere containing 5.5% oxygen to obtain a polyoxyalkylene polymer (a2-1) having acryloyl groups at both ends (i.e., approximately 2 acryloyl groups per polymer molecule), a number-average molecular weight of 4,020, and a weight-average molecular weight of 4,860.

[0196] (Synthesis Example 7) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,020 (end-group molecular weight of 2,980) as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with hydroxyl groups at both ends, a number-average molecular weight of 28,340 (end-group molecular weight of 17,700), and a molecular weight distribution Mw / Mn = 1.24. 60 ppm of U-360 was added to the obtained polyoxypropylene, and 0.93 equivalents of Karenz AOI were added dropwise to the hydroxyl groups of the polyoxypropylene. The reaction was carried out at 80°C for 1 hour in a nitrogen atmosphere containing 5.5% oxygen to obtain a polyoxyalkylene polymer (a2-3) with acryloyl groups at both ends (i.e., approximately 2 acryloyl groups per polymer molecule), a number-average molecular weight of 28,340, and a weight-average molecular weight of 35,170.

[0197] (Synthesis Example 8) Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,020 (end-group molecular weight of 2,980) as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with hydroxyl groups at both ends, a number-average molecular weight of 21,100 (end-group molecular weight of 13,600), and a molecular weight distribution Mw / Mn = 1.21. 60 ppm of U-360 was added to the obtained polyoxypropylene, and 0.93 equivalents of Karenz AOI were added dropwise to the hydroxyl groups of the polyoxypropylene. The reaction was carried out at 80°C for 1 hour in a nitrogen atmosphere containing 5.5% oxygen to obtain a polyoxyalkylene polymer (a2-4) with acryloyl groups at both ends (i.e., approximately 2 acryloyl groups per polymer molecule), a number-average molecular weight of 21,100, and a weight-average molecular weight of 24,930.

[0198] (Synthesis Example 9) 58.4 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 39.0 parts by weight of methyl methacrylate, 0.2 parts by weight of butyl acrylate, 0.2 parts by weight of 2-ethylhexyl acrylate, 9.9 parts by weight of stearyl methacrylate, 36.7 parts by weight of the polyfunctional macromonomer (a2-1) prepared in Synthesis Example 6, 8.1 parts by weight of 3-methacryloxypropyltrimethoxysilane, 5.9 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.3 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-1) with a number average molecular weight of 2,820 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.091 mmol / g, the reactive silicon group equivalent was 0.63 mmol / g, and the sulfur atom concentration was 9,640 ppm.

[0199] (Synthesis Example 10) 48.0 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 46.7 parts by weight of methyl methacrylate, 18.7 parts by weight of butyl acrylate, 9.3 parts by weight of stearyl methacrylate, 9.3 parts by weight of polyfunctional macromonomer (trade name: APG-700, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (a2-2), 9.3 parts by weight of 3-methacryloxypropyltrimethoxysilane, 6.7 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.3 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-2) with a number average molecular weight of 2,770 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.13 mmol / g, the reactive silicon group equivalent was 0.72 mmol / g, and the sulfur atom concentration was 10,940 ppm.

[0200] (Synthesis Example 11) 48.0 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 46.7 parts by weight of methyl methacrylate, 11.2 parts by weight of butyl acrylate, 12.1 parts by weight of stearyl methacrylate, 14.0 parts by weight of polyfunctional macromonomer (trade name: APG-700, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (a2-2), 9.3 parts by weight of 3-methacryloxypropyltrimethoxysilane, 6.7 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution prepared by dissolving 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 6.3 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-3) with a number average molecular weight of 2,790 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.20 mmol / g, the reactive silicon group equivalent was 0.72 mmol / g, and the sulfur atom concentration was 10,941 ppm.

[0201] (Synthesis Example 12) 45.5 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 49.0 parts by weight of methyl methacrylate, 1.0 part by weight of butyl acrylate, 0.5 parts by weight of 2-ethylhexyl acrylate, 6.0 parts by weight of stearyl methacrylate, 36.0 parts by weight of the polyfunctional macromonomer (a2-4) prepared in Synthesis Example 8, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 12.0 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 7.2 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-4) with a number average molecular weight of 2,130 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.017 mmol / g, the reactive silicon group equivalent was 0.36 mmol / g, and the sulfur atom concentration was 11,410 ppm. (Synthesis Example 13) 40.6 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 37.8 parts by weight of methyl methacrylate, 0.5 parts by weight of butyl acrylate, 0.5 parts by weight of 2-ethylhexyl acrylate, 10.3 parts by weight of stearyl methacrylate, 36.5 parts by weight of the polyfunctional macromonomer (a2-3) prepared in Synthesis Example 7, 8.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 5.9 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.4 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 5.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-5) with a number average molecular weight of 2,370 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.013 mmol / g, the reactive silicon group equivalent was 0.64 mmol / g, and the sulfur atom concentration was 9,618 ppm.

[0202] (Synthesis Example 14) 39.8 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 50.0 parts by weight of methyl methacrylate, 1.0 part by weight of butyl acrylate, 4.0 parts by weight of stearyl methacrylate, 36.0 parts by weight of the polyfunctional macromonomer (a2-4) prepared in Synthesis Example 8, 2.0 parts by weight of 3-methacryloxypropyl dimethoxymethylsilane, 7.0 parts by weight of 3-mercaptopropyl dimethoxymethylsilane, and 1.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.7 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 4.9 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-6) with a number average molecular weight of 1,820 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.017 mmol / g, the reactive silicon group equivalent was 0.47 mmol / g, and the sulfur atom concentration was 12,424 ppm.

[0203] (Synthesis Example 15) 48.0 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution of 46.7 parts by weight of methyl methacrylate, 28.0 parts by weight of butyl acrylate, 9.3 parts by weight of stearyl methacrylate, 9.3 parts by weight of 3-methacryloxypropyltrimethoxysilane, 6.7 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. A mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.3 parts by weight of isobutanol was then added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-1) with a number average molecular weight of 2,230 (GPC molecular weight). The reactive silicon group equivalent of the solid content of the solution is 0.72 mmol / g, and the sulfur atom concentration is 10,941 ppm.

[0204] (Synthesis Example 16) 46.9 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution of 49.1 parts by weight of methyl methacrylate, 29.5 parts by weight of butyl acrylate, 9.8 parts by weight of stearyl methacrylate, 9.8 parts by weight of 3-methacryloxypropyltrimethoxysilane, 1.8 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. A mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.3 parts by weight of isobutanol was then added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solids content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-2) with a number average molecular weight of 4,100 (GPC molecular weight). The reactive silicon group equivalent of the solid content of the solution is 0.49 mmol / g, and the sulfur atom concentration is 2,939 ppm.

[0205] (Synthesis Example 17) 46.9 parts by weight of isobutanol were placed in a four-necked flask equipped with a stirrer and heated to 105°C under a nitrogen atmosphere. A mixed solution of 55.0 parts by weight of methyl methacrylate, 31.0 parts by weight of butyl acrylate, 0.5 parts by weight of 2-ethylhexyl acrylate, 6.0 parts by weight of stearyl methacrylate, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.3 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) with a number average molecular weight of 2,200 (GPC molecular weight). The reactive silicon group equivalent in the solid content of this solution was 0.36 mmol / g, and the sulfur atom concentration was 11,410 ppm.

[0206] Sixty parts by weight of the polyoxypropylene polymer (B-1) obtained in Synthesis Example 1 and isobutanol solutions of (meth)acrylic acid ester copolymers (A-1) to (A-6) or (P-1) to (P-3) obtained in Synthesis Examples 9 to 17 were mixed to a solid content concentration of 40 parts by weight. The isobutanol was then devolved by heating, and the viscosity of each mixture was measured by the method described below. The results are shown in Table 1.

[0207] (viscosity) A 25mm diameter cone plate (2°) was used as a jig, with a gap set to 60μm and a rotation speed of 0.1sec. -1 The viscosity of each mixture was measured at that time. A rheometer (ARES-G2) manufactured by TA Instruments was used. The results are shown in Table 1.

[0208] [Table 1]

[0209] (1) Methyl methacrylate (2) n-butyl acrylate (3) 2-ethylhexyl acrylate (4) Stearyl methacrylate (5) 3-Methacryloxypropyldimethoxymethylsilane (6) 3-Methacryloxypropyltrimethoxysilane (7) 3-mercaptopropyldimethoxymethylsilane (8) 3-mercaptopropyltrimethoxysilane (9) Polypropylene glycol diacrylate, number average molecular weight 700 (Shin Nakamura Chemical Industry Co., Ltd.)

[0210] As shown in Table 1, the mixture containing (meth)acrylic acid ester copolymer (A) and polyoxyalkylene polymer (B) has a lower viscosity relative to its weight-average molecular weight (Mw) compared to the mixture containing (meth)acrylic acid ester copolymer (P) instead of (meth)acrylic acid ester copolymer (A).

[0211] The mixture containing (meth)acrylic acid ester copolymers (A-1) to (A-5) exhibits significantly lower viscosity compared to the mixture containing (meth)acrylic acid ester copolymer (P-2) formed without the use of polyfunctional macromonomer (a2), despite having a similar or even higher weight-average molecular weight. Furthermore, it was found that the (meth)acrylic acid ester copolymer (P-3), which does not use a polyfunctional macromonomer (a2) and has a monomer (a1') of 9% by weight or less, is incompatible with the polyoxyalkylene polymer (B-1), while the (meth)acrylic acid ester copolymer (A-4) is compatible with the polyoxyalkylene polymer (B-1) even when the monomer (a1') is 9% by weight or less.

[0212] (Example 1) 60 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (B-1) obtained in Synthesis Example 1 and the isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 9 were mixed to a solid content of 40 parts by weight, and then the isobutanol was heated and defoliated. To the obtained mixture, 40 parts by weight of Nanox #30 (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) and 30 parts by weight of CCR-S10 (synthetic calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.) were added as fillers, 20 parts by weight of Actcol P-23 (polypropylene glycol, manufactured by Mitsui Chemicals, Inc.) were added as a plasticizer, 2.5 parts by weight of Disparon 6500 (fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.) were added as a thixotropic agent, 1 part by weight of Nocrack CD (4,4'-bis(α,α-dimethylbenzyl)diphenylamine, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) was added as an antioxidant, and 1 part by weight of Adekastab AO-60 (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by ADEKA Corporation) was added and mixed using a planetary mixer, and the mixture was heated under reduced pressure at 120°C for 1 hour to dehydrate it. The obtained composition was cooled, and 3 parts by weight of A-171 (vinyltrimethoxysilane, Momentive Co., Ltd.) as a dehydrating agent, 3 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter, and 0.3 parts by weight of Neostan U-810 (dioctyl tin dilaurate, manufactured by Nitto Chemical Co., Ltd.) as a curing catalyst were mixed to obtain a one-component curable composition.

[0213] (deep hardening) The obtained one-component curable composition was filled into a 10 mm diameter polyethylene tube and cured under conditions of 23°C and 50% RH. After 1 day and 7 days, the gelled portion was removed using a spatula and its thickness was measured. The results are shown in Table 2.

[0214] (Tensile properties) A sheet approximately 2 mm thick was prepared using the obtained one-component curable composition and cured for 3 days at 23°C and 50% RH, followed by 4 days at 50°C. The obtained sheet was punched out into a No. 3 dumbbell shape (JIS K 6251), and a tensile strength test was performed at 23°C and 50% RH to measure the stress at 50% elongation (M50), strength at fracture (TB), and elongation at fracture (%). Tensile properties were measured using a Shimadzu Autograph (AGS-X) at a tensile speed of 200 mm / min. The results are shown in Table 2.

[0215] (Example 2) A one-component curable composition was obtained and evaluated in the same manner as in Example 1, except that the isobutanol solution of the (meth)acrylic acid ester copolymer (A-3) obtained in Synthesis Example 11 was used instead of the isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 9. The results are shown in Table 2.

[0216] (Example 3) A one-component curable composition was obtained and evaluated in the same manner as in Example 1, except that the isobutanol solution of the (meth)acrylic acid ester copolymer (A-5) obtained in Synthesis Example 13 was used instead of the isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 9. The results are shown in Table 2.

[0217] (Example 4) Except for using an isobutanol solution of the (meth)acrylic acid ester copolymer (A-5) obtained in Synthesis Example 13 instead of an isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 9, using a reactive silicon group-containing polyoxypropylene polymer (B-2) obtained in Synthesis Example 2 instead of the reactive silicon group-containing polyoxypropylene polymer (B-1) obtained in Synthesis Example 1, and using 0.8 parts by weight of DBU (1,8-diazabicyclo[5.4.0]undecene-7 Sunapro Co., Ltd.) as a curing catalyst, a one-component curable composition was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0218] (Example 5) Except for using an isobutanol solution of the (meth)acrylic acid ester copolymer (A-5) obtained in Synthesis Example 13 instead of an isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 9, and using a reactive silicon group-containing polyoxypropylene polymer (B-4) obtained in Synthesis Example 4 instead of the reactive silicon group-containing polyoxypropylene polymer (B-1) obtained in Synthesis Example 1, a one-component curable composition was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0219] (Comparative Example 1) A one-component curable composition was obtained and evaluated in the same manner as in Example 1, except that the isobutanol solution of the (meth)acrylic acid ester copolymer (P-1) obtained in Synthesis Example 15 was used instead of the isobutanol solution of the (meth)acrylic acid ester copolymer (A-1) obtained in Synthesis Example 9. The results are shown in Table 2.

[0220] [Table 2]

[0221] (1): Heavy calcium carbonate, primary particle size 1 μm (Maruo Calcium Co., Ltd.) (2): Synthetic calcium carbonate (Shiraishi Calcium Co., Ltd.) (3): Polypropylene glycol (Mitsui Chemicals, Inc.) (4): Fatty acid amide wax (Kusumoto Chemical Co., Ltd.) (5): Antioxidant (Ouchi Shinko Chemical Industry Co., Ltd.) (6): Antioxidant (ADEKA Corporation) (7): Vinyltrimethoxysilane (Momentive Co., Ltd.) (8): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) (9): Dioctyl tin dilaurate (Nitto Chemical Co., Ltd.) (10): 1,8-Diazabicyclo[5.4.0]undecene-7 (SunApro Co., Ltd.)

[0222] As shown in Table 2, it can be seen that in Examples 1 to 5, compared with Comparative Example 1, the thickness of the gelled part is large and the deep part sclerosis is good both 1 day later and 7 days later. Further, it can be seen that in Examples 1 and 2, in addition to the good deep part sclerosis compared with Comparative Example 1, a cured product with high tensile strength and large elongation at break can be obtained. It can be seen that in Examples 3 to 5 having a (meth)acrylate copolymer (A-5) having a polyfunctional macromonomer (a2) with a number average molecular weight of 20,000 or more, the elongation at break is significantly larger compared with Comparative Example 1.

[0223] (Example 6) Instead of the isobutanol solution of the (meth)acrylate copolymer (A-1) obtained in Synthesis Example 9, an isobutanol solution of the (meth)acrylate copolymer (A-6) obtained in Synthesis Example 14 was used, and instead of the reactive silicon group-containing polyoxypropylene polymer (B-1) obtained in Synthesis Example 1, the reactive silicon group-containing polyoxypropylene polymer (B-3) obtained in Synthesis Example 3 was used. Further, 20 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (B-5) obtained in Synthesis Example 5 was blended, and no plasticizer Actocol P-23 was blended. A one-component curable composition was obtained and each evaluation was carried out in the same manner as in Example 1 except that 1.5 parts by weight of Neostan S-1 (a reaction product of dioctyltin oxide and a silicate compound, Nitto Kasei Co., Ltd.) was used as a curing catalyst. The results are shown in Table 3.

[0224]

Table 3

[0225] (1): Heavy calcium carbonate, primary particle size 1 μm (Maruo Calcium Co., Ltd.) (2): Synthetic calcium carbonate (Shiraishi Calcium Co., Ltd.) (4): Fatty acid amide wax (Kusumoto Chemicals, Ltd.) (5): Antioxidant (Ouchi Shinsei Chemical Industry Co., Ltd.) (6): Antioxidant (ADEKA Corporation) (7): Vinyltrimethoxysilane (Momentive Co., Ltd.) (8): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) (11): Reaction product of dioctyl tin oxide and silicate compound (Nitto Chemical Co., Ltd.)

[0226] As shown in Table 3, Example 6 exhibits good deep hardening properties, and in terms of tensile properties, it yields a hardened product with high fracture strength and large elongation at fracture.

Claims

1. (A) A (meth)acrylic acid ester copolymer having a reactive silicon group as shown in the following formula (1), and A curable composition containing a polyoxyalkylene polymer (B) having a reactive silicon group as shown in the following formula (1), The monomer components constituting the (meth)acrylic acid ester copolymer (A) are (meth)acrylic acid ester (a1), A polyoxyalkylene polymer (a2) having one or more (meth)acryloyl groups in its molecule, It contains a chain transfer agent (a3) ​​having a mercapto group, and A curable composition wherein the monomer component further contains a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group, and / or a chain transfer agent (a3) ​​having a mercapto group further has a reactive silicon group. -SiR １ ｃ X ３－ｃ (1) (In the formula, R １ (where represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; c is 0 or 1.)

2. The curable composition according to Claim 1, wherein (meth)acrylate alkyl ester (a1'), in which the alkyl group has 7 to 30 carbon atoms, accounts for 2% by weight or more and 9% by weight or less of the monomer component.

3. The curable composition according to claim 1 or 2, wherein the polyoxyalkylene polymer (a2) accounts for 0.08 mol% or more and 6.0 mol% or less of the monomer component.

4. The curable composition according to any one of claims 1 to 3, wherein a chain transfer agent having a mercapto group (a3) ​​accounts for 0.4 mol% to 15 mol% of the monomer component.

5. The curable composition according to any one of claims 1 to 4, wherein a chain transfer agent (a3) ​​having a mercapto group accounts for 2% by weight or more and 9% by weight or less of the monomer component.

6. A curable composition according to any one of claims 1 to 5, wherein the molar ratio of polyoxyalkylene polymer (a2) to chain transfer agent having a mercapto group (a3) ​​is 0.04 or more.

7. The curable composition according to any one of claims 1 to 6, wherein the number average molecular weight of the polyoxyalkylene polymer (a2) is 20,000 or more.

8. The curable composition according to any one of claims 1 to 7, wherein the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) is 20,000 or less.

9. The curable composition according to any one of claims 1 to 8, wherein the molecular weight distribution of the (meth)acrylic acid ester copolymer (A) is 3.0 or more and 11.0 or less.

10. The curable composition according to any one of claims 1 to 9, wherein the sulfur atom concentration in the (meth)acrylic acid ester copolymer (A) is 700 ppm or more and 20,000 ppm or less.

11. The curable composition according to any one of claims 1 to 10, wherein the weight ratio of (meth)acrylic acid ester copolymer (A) to polyoxyalkylene polymer (B) is 5:95 to 50:

50.

12. The curable composition according to any one of claims 1 to 11, wherein the polyoxyalkylene polymer (B) is linear.

13. The curable composition according to any one of claims 1 to 12, wherein the number average molecular weight of the polyoxyalkylene polymer (B) is 20,000 or more.

14. A cured product of a curable composition according to any one of claims 1 to 13.

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