(Meth)acrylic acid ester copolymers and curable compositions

Abstract

This (meth)acrylic acid ester-based copolymer (A) has a reactive silicon group represented by formula (1). Monomer components forming the copolymer include a (meth)acrylic acid ester (a1), a polyoxyalkylene-based polymer (a2) having more than one (meth)acryloyl group per molecule, and a chain transfer agent (a3) having a mercapto group. The mol ratio (a2) / (a3) is 0.06 or more. The monomer components further include a monomer (a4) having a reactive silicon group and a polymerizable unsaturated group and / or (a3) further includes a reactive silicon group. (1): -SiR1 cX3-c. R1 represents a substituted or unsubstituted hydrocarbon group having 1-20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.

Description

[Technical Field]

[0001] The present invention relates to a (meth)acrylic acid ester copolymer having a reactive silicon group, a method for producing the same, and a curable composition containing the copolymer. [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] 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 Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 52-73998 [Patent Document 2] Japanese Unexamined Patent Publication No. 59-122541 [Patent Document 3] Patent No. 5082851 [Overview of the project] [Problems that the invention aims to solve]

[0007] Polymers containing reactive silicon groups are desirable to have low viscosity for easy handling before curing, while exhibiting good physical properties after curing. However, the reactive silicon group-containing graft copolymer described in Patent Document 3 did not have sufficient physical properties after curing and needed improvement.

[0008] In view of the above situation, the present invention aims to provide a reactive silicon group-containing (meth)acrylic acid ester copolymer that exhibits good physical properties after curing despite having low viscosity, and a curable composition containing the same. [Means for solving the problem]

[0009] As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by using specific monomers and chain transfer agents in specific ratios as monomer components constituting a reactive silicon group-containing (meth)acrylic acid ester polymer, and have completed the present invention.

[0010] That is, the first invention is a (meth)acrylic acid ester copolymer (A) having a reactive silicon group represented by the following formula (1), wherein the monomer components constituting the copolymer are (meth)acrylic acid ester (a1), a polyoxyalkylene polymer (a2) having more than one (meth)acryloyl group in the molecule, and a chain transfer agent (a3) having a mercapto group. The molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent (a3) having a mercapto group is 0.06 or more. Further, the monomer components further contain 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 has a reactive silicon group. The invention relates to a (meth)acrylic acid ester copolymer (A). -SiR c X 3-c (1) (In the formula, R 1 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.) Preferably, the value calculated by the formula: (weight average molecular weight of copolymer (A)) / (weight average molecular weight of polyoxyalkylene polymer (a2)) is 0.65 or more. Preferably, the polyoxyalkylene polymer (a2) occupies 0.08 mol% or more and 6.0 mol% or less in the monomer components. Preferably, the chain transfer agent (a3) having a mercapto group occupies 0.4 mol% or more and 15 mol% or less in the monomer components. Preferably, the number average molecular weight of the polyoxyalkylene polymer (a2) is 50,000 or less. Preferably, the content of the polyoxyalkylene polymer (a2) is 60% by weight or less in the monomer components. [[ID=​​​​​Preferably, the (meth)acrylate (a1) contains at least one monomer selected from the group consisting of a methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate. Preferably, among the total amount of the monomer components excluding the polyoxyalkylene polymer (a2), the proportion of the (meth)acrylate (a1) component, which is at least one monomer selected from the group consisting of a methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate, is 60% by weight or more. Preferably, the sulfur atom concentration in the (meth)acrylate copolymer (A) is 700 ppm or more and 20,000 ppm or less. The second invention is a (meth)acrylate copolymer (A) having a reactive silicon represented by the following formula (1), wherein the copolymer includes a structure in which two first molecular chains are bonded via one second molecular chain, and both ends of the second molecular chain are bonded to non-terminal sites of the first molecular chain, the first molecular chain is composed of a molecular chain of a (meth)acrylate polymer, the second molecular chain is composed of a molecular chain of a polyoxyalkylene polymer, the reactive silicon group is bonded to the first molecular chain, and the first molecular chain has, at either end, -S-R 3 (In the formula, S represents a sulfur atom, and R 3 represents a hydrocarbon group which may have the reactive silicon group), and the molar ratio of the polyoxyalkylene polymer to the -S-R 3 is 0.06 or more. The present invention relates to a (meth)acrylate copolymer (A). -SiR 1 c X 3-c (1) (In the formula, R 1 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.) The third of the present invention relates to a curable composition containing the (meth)acrylate copolymer (A) or a cured product of the curable composition. The fourth aspect of the present invention relates to a method for producing a (meth)acrylic acid ester copolymer (A) having a reactive silicon group shown in the following formula (1), comprising the step of copolymerizing monomer components, wherein the monomer components contain 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, the molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent (a3) ​​having a mercapto group is 0.06 or more, and the monomer components further contain 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.) [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a reactive silicon group-containing (meth)acrylic acid ester copolymer that exhibits good physical properties (e.g., elongation, strength, etc.) after curing, despite having low viscosity, and a curable composition containing the same. The reactive silicon group-containing (meth)acrylic acid ester copolymer according to the present invention includes a block copolymer, and even if it has a large weight-average molecular weight, its viscosity can be kept relatively low. [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.

[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 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.)

[0014] R 1 The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1 Specific examples include methyl groups, ethyl groups, chloromethyl groups, methoxymethyl groups, and N,N-diethylaminomethyl groups, but methyl groups and ethyl groups are preferred.

[0015] Examples of X include hydroxyl groups, hydrogen, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups such as methoxy groups and ethoxy groups are more preferred due to their mild hydrolysis and ease of handling, with methoxy groups and ethoxy groups being particularly preferred.

[0016] c is either 0 or 1. 0 is preferred because it yields a cured product with a high Young's modulus.

[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 and yield cured products with good mechanical properties. The trimethoxysilyl group and triethoxysilyl group are more preferred because they yield cured products with a high Young's modulus, 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 0.06 mmol / g or more, more preferably 0.08 mmol / g or more, and even more preferably 0.1 mmol / g or more. Furthermore, the reactive silicon group equivalent is preferably 1.0 mmol / g or less, more preferably 0.5 mmol / g or less, and particularly preferably 0.3 mmol / g or less, from the viewpoint 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)acrylate(a1) is preferably an alkyl meth)acrylate.

[0024] From the viewpoint of achieving both flexibility and high rigidity, the content of (meth)acrylic acid ester (a1) is preferably 40% by weight or more, more preferably 45% by weight or more, even more preferably 50% by weight or more, even more preferably 55% by weight or more, and even more preferably 60% by weight or more, relative to 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, relative to 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, an alkyl (meth)acrylate ester having 1 to 4 carbon atoms in the alkyl group is preferred as the (meth)acrylic acid ester (a1). It is preferable that the alkyl (meth)acrylate ester having 1 to 4 carbon atoms in the alkyl group is contained in an amount of 40% by weight or more, more preferably 45% by weight or more, and even more preferably 50% 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 to contain at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate, as it can form a hard polymer chain and yield a highly strong cured product. In particular, of the total amount of the monomer components excluding the polyoxyalkylene polymer (a2), it is preferable that the proportion of at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate, which is the (meth)acrylic acid ester (a1) component, is 60% by weight or more, and more preferably 70% by weight or more.

[0027] <(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).

[0028] 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.

[0029] The main chain skeleton of the polyoxyalkylene polymer may be linear or branched, but it is preferable that it be linear.

[0030] 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).

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] The number-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 1,000 or more, and even more preferably 2,000 or more. Furthermore, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 40,000 or less, even more preferably 30,000 or less, particularly preferably 15,000 or less, and most preferably 10,000 or less.

[0039] 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, preferably 1,000 or more, and more preferably 2,500 or more. Furthermore, it is preferably 130,000 or less, more preferably 65,000 or less, even more preferably 60,000 or less, even more preferably 20,000 or less, and most preferably 13,000 or less.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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 a high Young's modulus, the content of the polyfunctional macromonomer (a2) is preferably 60% by weight or less, more preferably 50% by weight or less, and even more preferably 35% by weight or less. On the other hand, when obtaining a cured product with a low Young's modulus, the content of the polyfunctional macromonomer (a2) is preferably greater than 35% by weight.

[0045] 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).

[0046] The average number of polyfunctional macromonomers (a2) per molecule of (meth)acrylic acid ester copolymer (A) is preferably 0.03 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 0.04 or more, even more preferably 0.05 or more, even more preferably 0.07 or more, and particularly 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)))

[0047] <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).

[0048] 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.

[0049] 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.

[0050] The content of the chain transfer agent (a3) ​​having a mercapto group is preferably 0.1% by weight or more and 11% by weight or less, more preferably 0.1% by weight or more and 10% by weight or less, even more preferably 0.3% by weight or more and 7% by weight or less, and still more preferably 0.5% by weight or more and 5% by weight or less, based on the total amount of monomer components constituting the (meth)acrylic acid ester copolymer (A).

[0051] 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.

[0052] The content of the polyfunctional macromonomer (a2) and the content of the chain transfer agent (a3) ​​having a mercapto group are adjusted so as to improve the strength of the cured product obtained by curing the (meth)acrylic acid ester copolymer (A), that the molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent (a3) ​​having a mercapto group is 0.06 or higher. If the molar ratio is less than 0.06, the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) will not be sufficiently large, and the strength of the resulting cured product will be insufficient. The molar ratio is preferably 0.08 or higher, more preferably 0.1 or higher, even more preferably 0.12 or higher, and particularly 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.

[0053] (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.

[0054] 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).

[0055] <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 sites) of the molecular chain of the (meth)acrylic acid ester polymer.

[0056] 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.

[0057] 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.

[0058] <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.

[0059] 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, a number-average molecular weight of 7,000 or less is preferred because it yields a (meth)acrylic acid ester copolymer (A) with low viscosity.

[0060] The weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) is not particularly limited, but is preferably 500 to 80,000 in polystyrene equivalent molecular weight as measured by GPC, more preferably 3,000 to 70,000, and particularly preferably 5,000 to 65,000. Among these, it is preferable that it is 30,000 or more, as it exhibits good mechanical properties.

[0061] With regard 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 0.65 or higher. Formula: (Weight-average molecular weight of copolymer (A)) / (Weight-average molecular weight of polyoxyalkylene polymer (a2)) A value of 0.65 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.

[0062] 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.

[0063] 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.

[0064] 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).

[0065] 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.

[0066] 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.

[0067] 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).

[0068] 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.

[0069] 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), namely -SR 3 It may have a structure represented by the above formula. In the above formula, S represents a sulfur atom, and R 3R 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.

[0070] As described above, corresponding to the molar ratio of polyoxyalkylene polymer (a2) / chain transfer agent having a mercapto group (a3) ​​being 0.06 or higher, in the (meth)acrylic acid ester copolymer (A), the -SR 3 The molar ratio of the polyoxyalkylene polymer to is 0.06 or higher. If the molar ratio is less than 0.06, the weight-average molecular weight of the (meth)acrylic acid ester copolymer (A) will not be sufficiently large, and the strength of the resulting cured product will be insufficient. The molar ratio is preferably 0.08 or higher, more preferably 0.1 or higher, even more preferably 0.12 or higher, and particularly 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.

[0071] <<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.

[0072] 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.

[0073] 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 2% 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. To obtain a cured product with a high Young's modulus, it is preferable to use an aromatic hydrocarbon solvent as the solvent.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] <<Curable composition>> This embodiment also relates to a curable composition containing a (meth)acrylic acid ester copolymer (A). The curable composition may contain only the (meth)acrylic acid ester copolymer (A) as the reactive silicon group-containing polymer, or it may contain other reactive silicon group-containing polymers in addition to the (meth)acrylic acid ester copolymer (A).

[0079] <<Silanol Condensation Catalyst>> The curable composition according to this embodiment preferably contains a silanol condensation catalyst for the purpose of promoting the reaction that condenses the reactive silicon groups of the (meth)acrylic acid ester copolymer (A) and extending or crosslinking the polymer chain.

[0080] Examples of silanol condensation catalysts include organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, and alkoxy metals.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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).

[0086] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0087] 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.

[0088] 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 (meth)acrylic acid ester copolymer (A).

[0089] <<Other additives>> The curable composition according to this embodiment may contain, in addition to the (meth)acrylic acid ester copolymer (A) 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.

[0090] <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.

[0091] 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 (meth)acrylic acid ester copolymer (A).

[0092] Organic balloons and inorganic balloons may be added to reduce the weight (lower specific gravity) of the composition.

[0093] <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.

[0094] 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.

[0095] 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 (meth)acrylic acid ester copolymer (A).

[0096] <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.

[0097] 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.

[0098] 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 (meth)acrylic acid ester copolymer (A).

[0099] <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.

[0100] <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.

[0101] The amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of (meth)acrylic acid ester copolymer (A).

[0102] <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.

[0103] 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 (meth)acrylic acid ester copolymer (A).

[0104] <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.

[0105] 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 (meth)acrylic acid ester copolymer (A).

[0106] <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).

[0107] 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 (meth)acrylic acid ester copolymer (A).

[0108] <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.

[0109] 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.

[0110] 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 (meth)acrylic acid ester copolymer (A).

[0111] <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.

[0112] 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.

[0113] 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 (meth)acrylic acid ester copolymer (A).

[0114] <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 (meth)acrylic acid ester copolymer (A).

[0115] <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.

[0116] 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 (meth)acrylic acid ester copolymer (A).

[0117] <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.

[0118] 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 (meth)acrylic acid ester copolymer (A). As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0119] <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.

[0120] The ratio of epoxy resin to (meth)acrylic acid ester copolymer (A) is preferably in the range of (meth)acrylic acid ester copolymer (A) / epoxy resin = 100 / 1 to 1 / 100 by weight. If the ratio of (meth)acrylic acid ester copolymer (A) / 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) / epoxy resin exceeds 100 / 1, the strength of the polymer cured product becomes insufficient.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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 (meth)acrylic acid ester copolymer (A).

[0128] 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.

[0129] The curable composition according to this embodiment can be used as a sealing material, adhesive, molding agent, vibration damping material, soundproofing material, foaming material, paint, spray material, waterproof coating agent, etc. for buildings, ships, automobiles, roads, etc.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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]

[0134] The present invention will be specifically described below with reference to examples, but these examples are not intended to limit the present invention.

[0135] (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℃

[0136] (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.

[0137] (Synthesis Example 1) 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.

[0138] (Synthesis Example 2) 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 (a2-2) 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.

[0139] (Synthesis Example 3) 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.

[0140] (Synthesis Example 4) To a polyoxypropylene glycol with a number-average molecular weight of approximately 4,020 (end-group molecular weight of 2,980), 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups of the polyoxypropylene glycol. After removing the methanol by vacuum defloration, 1.79 molar equivalents of allyl chloride were added relative to the hydroxyl groups of the polyoxypropylene glycol 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, and the water was removed by centrifugation. Another 300 parts by weight of water were added to the resulting hexane solution and stirred, and the water was removed again by centrifugation, after which the hexane was removed by vacuum defloration. Thus, a polyoxyalkylene polymer (p-1) having allyl groups at the ends, a number-average molecular weight of 4,020, and a weight-average molecular weight of 4,860 was obtained.

[0141] (Synthesis Example 5) 41.7 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 59.7 parts by weight of butyl acrylate, 10.1 parts by weight of stearyl methacrylate, 21.9 parts by weight of the polyfunctional macromonomer (a2-1) prepared in Synthesis Example 1, 1.0 part by weight of 3-methacryloxypropyltrimethoxysilane, 7.3 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.9 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 8.1 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-1) with a number average molecular weight of 2,470 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.070 mmol / g, the reactive silicon group equivalent was 0.42 mmol / g, and the sulfur atom concentration was 10,941 ppm.

[0142] (Synthesis Example 6) 78.4 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 41.0 parts by weight of butyl acrylate, 7.0 parts by weight of stearyl methacrylate, 44.4 parts by weight of the polyfunctional macromonomer (a2-1) prepared in Synthesis Example 1, 0.7 parts by weight of 3-methacryloxypropyltrimethoxysilane, 6.9 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.9 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 8.1 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-2) with a number average molecular weight of 3,000 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.12 mmol / g, the reactive silicon group equivalent was 0.34 mmol / g, and the sulfur atom concentration was 10,291 ppm.

[0143] (Synthesis Example 7) 58.9 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 prepared by dissolving 47.4 parts by weight of butyl acrylate, 8.0 parts by weight of stearyl methacrylate, 33.3 parts by weight of the polyfunctional macromonomer (a2-1) prepared in Synthesis Example 1, 0.8 parts by weight of 3-methacryloxypropyltrimethoxysilane, 10.5 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.9 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 8.1 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-3) with a number average molecular weight of 1,910 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.094 mmol / g, the reactive silicon group equivalent was 0.53 mmol / g, and the sulfur atom concentration was 15,961 ppm.

[0144] (Synthesis Example 8) 46.4 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 46.0 parts by weight of methyl methacrylate, 11.2 parts by weight of butyl acrylate, 7.6 parts by weight of stearyl methacrylate, 32.9 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 2, 1.0 part by weight of 3-methacryloxypropyltrimethoxysilane, 1.3 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 10.7 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 8.5 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 7,410 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.016 mmol / g, the reactive silicon group equivalent was 0.11 mmol / g, and the sulfur atom concentration was 2,149 ppm.

[0145] (Synthesis Example 9) 44.0 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 51.4 parts by weight of methyl methacrylate, 12.5 parts by weight of butyl acrylate, 8.5 parts by weight of stearyl methacrylate, 25.0 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 2, 1.1 parts by weight of 3-methacryloxypropyltrimethoxysilane, 1.5 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.9 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 9.5 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 8,120 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.012 mmol / g, the reactive silicon group equivalent was 0.12 mmol / g, and the sulfur atom concentration was 2,402 ppm.

[0146] (Synthesis Example 10) 44.0 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 51.5 parts by weight of methyl methacrylate, 13.5 parts by weight of butyl acrylate, 8.5 parts by weight of stearyl methacrylate, 25.0 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 2, 1.5 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 11.9 parts by weight of isobutanol was added dropwise over 5 hours. A mixed solution of 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 9.5 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) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-6) with a number average molecular weight of 7,930 (GPC molecular weight). The solution has a polyfunctional macromonomer equivalent of 0.012 mmol / g, a reactive silicon group equivalent of 0.075 mmol / g, and a sulfur atom concentration of 2,401 ppm.

[0147] (Synthesis Example 11) 44.2 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 50.9 parts by weight of methyl methacrylate, 12.3 parts by weight of butyl acrylate, 8.4 parts by weight of stearyl methacrylate, 24.7 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 2, 2.2 parts by weight of 3-methacryloxypropyltrimethoxysilane, 1.5 parts by weight of n-dodecyl mercaptan, and 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.8 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 9.4 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-7) with a number average molecular weight of 7,610 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.012 mmol / g, the reactive silicon group equivalent was 0.088 mmol / g, and the sulfur atom concentration was 2,417 ppm.

[0148] (Synthesis Example 12) 25.6 parts by weight of SOLVESSO100 (manufactured by Ando Parachemy Co., Ltd.) and 25.6 parts by weight of Mineral Spirit (manufactured by Daishin Chemical Co., Ltd.) were placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 110°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 55.1 parts by weight of methyl methacrylate, 8.8 parts by weight of butyl acrylate, 8.1 parts by weight of stearyl methacrylate, 25.0 parts by weight of the polyfunctional macromonomer (a2-3) prepared in Synthesis Example 3, 1.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 1.5 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 8.8 parts by weight of SOLVESSO100 was added dropwise over 5 hours. Furthermore, a mixed solution prepared by dissolving 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 5.3 parts by weight of SOLVESSO100 was added, and polymerization was carried out at 110°C for 2 hours to obtain a solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-8) with a number average molecular weight of 4,860 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.0092 mmol / g, the reactive silicon group equivalent was 0.14 mmol / g, and the sulfur atom concentration was 2,396 ppm.

[0149] (Synthesis Example 13) 25.6 parts by weight of SOLVESSO100 (manufactured by Ando Parachemy Co., Ltd.) and 25.6 parts by weight of mineral spirits (manufactured by Daishin Chemical Co., Ltd.) were placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 110°C under a nitrogen atmosphere. A mixed solution prepared by dissolving 54.6 parts by weight of methyl methacrylate, 8.7 parts by weight of butyl acrylate, 8.0 parts by weight of stearyl methacrylate, 24.8 parts by weight of the polyfunctional macromonomer (a2-3) prepared in Synthesis Example 3, 1.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 2.4 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 8.8 parts by weight of SOLVESSO100 was added dropwise over 5 hours. Furthermore, a mixed solution prepared by dissolving 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 5.3 parts by weight of SOLVESSO100 was added, and polymerization was carried out at 110°C for 2 hours to obtain a solution (60% solids) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (A-9) with a number average molecular weight of 5,360 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.0091 mmol / g, the reactive silicon group equivalent was 0.18 mmol / g, and the sulfur atom concentration was 3,912 ppm.

[0150] (Synthesis Example 14) 36.9 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 prepared by dissolving 63.1 parts by weight of butyl acrylate, 12.6 parts by weight of stearyl methacrylate, 23.1 parts by weight of the polyfunctional macromonomer (a2-1) prepared in Synthesis Example 1, 1.2 parts by weight of 3-methacryloxypropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.9 parts by weight of isobutanol was added dropwise over 5 hours. Gelation occurred during the reaction, and a polymer solution could not be obtained. This Synthesis Example 14 is shown as Comparative Example 1 in Table 1.

[0151] (Synthesis Example 15) 38.1 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 87.4 parts by weight of butyl acrylate, 9.8 parts by weight of stearyl methacrylate, 1.0 part 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 20.9 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 8.1 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) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-2) with a number average molecular weight of 3,730 (GPC molecular weight). The reactive silicon group equivalent of the solid content of the solution is 0.13 mmol / g, and the sulfur atom concentration is 2,939 ppm.

[0152] (Synthesis Example 16) 41.7 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 49.7 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 23.1 parts by weight of allyl-terminated polyoxyalkylene polymer (p-1) prepared in Synthesis Example 4, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 1.8 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 20.9 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 8.1 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (60% solid content) of a reactive silicon group-containing (meth)acrylic acid ester copolymer (P-3) with a number average molecular weight of 1,980 (GPC molecular weight). The reactive silicon group equivalent in the solid content of this solution was 0.72 mmol / g, and the sulfur atom concentration was 10,948 ppm.

[0153] (Synthesis Example 17) 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 42.4 parts by weight of methyl methacrylate, 10.3 parts by weight of butyl acrylate, 7.0 parts by weight of stearyl methacrylate, 30.3 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 2, 0.9 parts by weight of 3-methacryloxypropyltrimethoxysilane, 9.1 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 9.8 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 7.9 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 (P-4) with a number average molecular weight of 1,830 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.014 mmol / g, the reactive silicon group equivalent was 0.50 mmol / g, and the sulfur atom concentration was 14,846 ppm.

[0154] (Synthesis Example 18) 49.1 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 40.1 parts by weight of methyl methacrylate, 9.7 parts by weight of butyl acrylate, 6.6 parts by weight of stearyl methacrylate, 28.7 parts by weight of the polyfunctional macromonomer (a2-2) prepared in Synthesis Example 2, 6.3 parts by weight of 3-methacryloxypropyltrimethoxysilane, 8.6 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 9.3 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 7.4 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 (P-5) with a number average molecular weight of 1,920 (GPC molecular weight). The polyfunctional macromonomer equivalent of the solids in this solution was 0.014 mmol / g, the reactive silicon group equivalent was 0.69 mmol / g, and the sulfur atom concentration was 14,037 ppm.

[0155] (Synthesis Example 19) 44.4 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 of 40.8 parts by weight of methyl methacrylate, 54.2 parts by weight of butyl acrylate, 0.5 parts by weight of 2-ethylhexyl acrylate, 0.5 parts by weight of stearyl methacrylate, 0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, 3.5 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 15.6 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.1 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 4.7 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-6) with a number average molecular weight of 3,770 (GPC molecular weight). The reactive silicon group equivalent in the solid content of this solution was 0.20 mmol / g, and the sulfur atom concentration was 5,716 ppm.

[0156] (Examples 1-3, Comparative Examples 2-3) Isobutanol was removed by heating and defoliating the isobutanol from the isobutanol solutions of the (meth)acrylic acid ester copolymers (A-1) to (A-3) obtained in Synthesis Examples 5 to 7, and the isobutanol solutions of the (meth)acrylic acid ester copolymers (P-2) to (P-3) obtained in Synthesis Examples 15 to 16, and the viscosity of each resulting polymer was measured by the following method.

[0157] (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 polymer was measured at that time. A rheometer (ARES-G2) manufactured by TA Instruments was used. The results are shown in Table 1.

[0158] [Table 1]

[0159] (1) n-butyl acrylate (2) Stearyl methacrylate (3) 3-Methacryloxypropyltrimethoxysilane (4) 3-mercaptopropyltrimethoxysilane

[0160] As shown in Table 1, in Examples 1 to 3, reactive silicon group-containing (meth)acrylic acid ester copolymers (A-1) to (A-3) were synthesized by copolymerizing both a polyfunctional macromonomer (a2), which is a polyoxyalkylene polymer having one or more (meth)acryloyl groups in one molecule, and a chain transfer agent (a3) ​​having mercapto groups. These copolymers (A-1) to (A-3) include block copolymers formed by copolymerizing the polyfunctional macromonomer (a2) with butyl acrylate or the like.

[0161] On the other hand, when copolymerization was carried out without using a chain transfer agent having a mercapto group (a3) ​​(Comparative Example 1), gelation occurred during the polymerization process, and a copolymer could not be obtained.

[0162] Comparative Example 2, the (meth)acrylic acid ester copolymer (P-2), was synthesized without using the polyfunctional macromonomer (a2) and is a random copolymer. From Table 1, it can be seen that the (meth)acrylic acid ester copolymers (A-1) to (A-3) have lower viscosity relative to their weight-average molecular weight (Mw) compared to the (meth)acrylic acid ester copolymer (P-2). For example, (A-3) has a slightly larger weight-average molecular weight than (P-2), yet its viscosity is about one-quarter that of (P-2). Also, (A-2) has a weight-average molecular weight about three times larger than (P-2), yet its viscosity is about the same.

[0163] The (meth)acrylic acid ester copolymer (P-3) in Comparative Example 3 was synthesized using an allyl group-containing polyoxyalkylene polymer (p-1) instead of an acryloyl group-containing polyoxyalkylene polymer (a2-1). Judging from its weight-average molecular weight (Mw), it can be seen that copolymerization of (p-1) has hardly progressed. In other words, the (meth)acrylic acid ester copolymers (A-1) to (A-3) have low viscosity despite the copolymerization of the polyfunctional macromonomer (a2) progressing.

[0164] (Examples 4-7, Comparative Examples 4-6) The tensile properties of the cured products obtained by curing using isobutanol solutions of (meth)acrylic acid ester copolymers (A-4) to (A-7) obtained in Synthesis Examples 8 to 11, or isobutanol solutions of (meth)acrylic acid ester copolymers (P-4) to (P-6) obtained in Synthesis Examples 17 to 19, were measured by the following method.

[0165] (Tensile properties) To each polymer solution, 1 part by weight of Neostan U-20 (dibutyltin dibutylmalate, manufactured by Nitto Kasei Co., Ltd.) was mixed as a curing catalyst (amount per 100 parts by weight of solids in each polymer solution), and sheets with a thickness of 100 μm were prepared. The obtained sheets were cured for 2 weeks under conditions of 23°C and 50% RH. A 70 mm × 10 mm strip test piece was cut from the obtained sheet, the gripping distance was set to 40 mm, and the tensile properties were measured at 23°C. The stress at 30% elongation (M30), strength at break (TB), elongation at break (EB), and Young's modulus were measured. The tensile properties were measured using a Shimadzu Autograph (AGS-X) at a tensile speed of 20 mm / min. The obtained results are shown in Table 2.

[0166] [Table 2]

[0167] (1) Methyl methacrylate (2) n-butyl acrylate (3) 2-Ethylhexylacrylate (4) Stearyl methacrylate (5) 3-Methacryloxypropyltrimethoxysilane (6) 3-mercaptopropyltrimethoxysilane (7) n-dodecyl mercaptan

[0168] As shown in Table 2, the cured products obtained from the (meth)acrylic acid ester copolymers (A-4) to (A-7) of Examples 4 to 7 have higher values ​​of 30% modulus (M30), tensile strength (TB), and Young's modulus compared to the cured product obtained from the (meth)acrylic acid ester copolymer (P-4) of Comparative Example 4, which uses a lower ratio of polyfunctional macromonomer (a2) to the chain transfer agent (a3) ​​containing mercapto groups.

[0169] Furthermore, the (meth)acrylic acid ester copolymer (P-5) of Comparative Example 5 was modified by increasing the amount of monomer (a4) having reactive silicon groups and polymerizable unsaturated groups compared to (P-4) of Comparative Example 4, thereby increasing the reactive silicon group equivalent. Compared to Comparative Example 4, Comparative Example 5 showed slightly higher tensile strength and Young's modulus values, but significantly lower elongation. Examples 4 to 6 showed higher tensile strength and Young's modulus values, as well as greater elongation, compared to Comparative Example 5. The (meth)acrylic acid ester copolymer (P-6) of Comparative Example 6, which was synthesized without using the polyfunctional macromonomer (a2), produced a cured product that was too soft, making it impossible to prepare test specimens.

[0170] (Examples 8-9) The tensile properties of the cured products obtained by curing the (meth)acrylic acid ester copolymers (A-8) to (A-9) obtained in Synthesis Examples 12 to 13 using a mixed solution of aromatic hydrocarbon solvent and aliphatic hydrocarbon solvent were measured by the method described above.

[0171] [Table 3]

[0172] (1) Methyl methacrylate (2) n-butyl acrylate (4) Stearyl methacrylate (5) 3-Methacryloxypropyltrimethoxysilane (6) 3-mercaptopropyltrimethoxysilane

[0173] As shown in Table 3, the cured products obtained from the (meth)acrylic acid ester copolymers (A-8) to (A-9) of Examples 8 to 9 exhibit a high Young's modulus.

Claims

1. A (meth)acrylic acid ester copolymer (A) having a reactive silicon group as shown in the following formula (1), The monomer components constituting the copolymer are (meth)acrylic acid ester (a1), A polyoxyalkylene polymer (a2) having one or more (meth)acryloyl groups in the molecule and having a number-average molecular weight of 500 or more, and It contains a chain transfer agent (a3) ​​having a mercapto group, The molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent having a mercapto group (a3) ​​is 0.06 or higher, and (Meth)acrylic acid ester copolymer (A), 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 (meth)acrylic acid ester copolymer (A) according to claim 1, wherein the value calculated by the formula: (weight-average molecular weight of copolymer (A)) / (weight-average molecular weight of polyoxyalkylene polymer (a2)) is 0.65 or greater.

3. The (meth)acrylic acid ester copolymer (A) 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. (Meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 3, wherein a chain transfer agent (a3) ​​having a mercapto group accounts for 0.4 mol% to 15 mol% of the monomer component.

5. The (meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 4, wherein the number average molecular weight of the polyoxyalkylene polymer (a2) is 50,000 or less.

6. The (meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 5, wherein the number average molecular weight of the polyoxyalkylene polymer (a2) is 1,000 or more.

7. The (meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 6, wherein the content of the polyoxyalkylene polymer (a2) is 5% by weight or more in the monomer component.

8. The (meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 7, wherein the content of the polyoxyalkylene polymer (a2) is 60% by weight or less in the monomer component.

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

10. (Meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 9, wherein c in formula (1) is 0.

11. The (meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 10, wherein (meth)acrylic acid ester (a1) contains at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate.

12. The (meth)acrylic acid ester copolymer (A) according to claim 11, wherein, of the total amount of monomer components excluding the polyoxyalkylene polymer (a2), at least one monomer selected from the group consisting of methacrylic acid ester, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentanyl acrylate, which is the (meth)acrylic acid ester (a1) component, accounts for 60% by weight or more.

13. The (meth)acrylic acid ester copolymer (A) according to any one of claims 1 to 12, wherein the sulfur atom concentration in the (meth)acrylic acid ester copolymer (A) is 700 ppm or more and 20,000 ppm or less.

14. A (meth)acrylic acid ester copolymer (A) having reactive silicon as shown in the following formula (1), The copolymer has a structure in which two first molecular chains are linked via one second molecular chain, with both ends of the second molecular chain each bonded to the non-terminal portion of the first molecular chain. The first molecular chain is composed of molecular chains of (meth)acrylic acid ester polymers. The second molecular chain is composed of molecular chains of polyoxyalkylene polymers. The reactive silicon group is bonded to the first molecular chain, The first molecular chain has -S-R at one of its ends. ３ (In the formula, S represents a sulfur atom, R ３ (where represents a hydrocarbon group which may have the reactive silicon group) and has a structure represented by The aforementioned -SR-R ３ The molar ratio of the polyoxyalkylene polymer to is 0.06 or higher. (Meth)acrylic acid ester copolymer (A), wherein the molecular chain of the polyoxyalkylene polymer is formed from a polyoxyalkylene polymer (a2) having one or more (meth)acryloyl groups in the molecule and a number average molecular weight of 500 or more. -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.)

15. A curable composition comprising the (meth)acrylic acid ester copolymer (A) described in any one of claims 1 to 14.

16. A cured product of the curable composition according to claim 15.

17. A method for producing a (meth)acrylic acid ester copolymer (A) having a reactive silicon group as shown in the following formula (1), The process includes copolymerizing monomer components, The monomer component is (meth)acrylic acid ester (a1), A polyoxyalkylene polymer (a2) having one or more (meth)acryloyl groups in the molecule and having a number-average molecular weight of 500 or more, and It contains a chain transfer agent (a3) ​​having a mercapto group, The molar ratio of the polyoxyalkylene polymer (a2) to the chain transfer agent having a mercapto group (a3) ​​is 0.06 or higher, and A method for producing a (meth)acrylic acid ester copolymer (A), 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.)

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