TWI844696B - Block copolymer, resin composition, and method for producing block copolymer - Google Patents

Abstract

The present invention provides a block copolymer that significantly reduces odor when exposed to high temperatures. Furthermore, the present invention provides a resin composition that can produce a molded product with high toughness. In addition, the present invention provides a resin composition that can produce a molded product that is also excellent in weather resistance. A block copolymer comprising at least two or more polymer blocks, wherein at least one terminal structure of the block copolymer is a structure represented by the following general formula (1) or a thiol group, and when the sulfur concentration (mass %) in the block copolymer is x and the number average molecular weight of the block copolymer is y, the product of (x/100) and y is 60 or less. (R is an alkyl group, an aryl group or an aralkyl group having 1 to 30 carbon atoms) A resin composition comprises the block copolymer.

Description

Block copolymer and resin composition, and method for producing block copolymer

The present invention relates to a block copolymer and a resin composition, and a method for producing the block copolymer.

As living radical polymerization methods, various polymerization methods are known, including reversible addition fragmentation chain transfer polymerization (RAFT method), nitroxide-mediated polymerization (NMP method), atom transfer radical polymerization (ATRP method), polymerization using organic tellurium compounds (TERP method), polymerization using organic antimony compounds (SBRP method), polymerization using organic bismuth compounds (BIRP method), and iodine transfer polymerization. Among these, the RAFT method, the NMP method, and the ATRP method are industrially utilized from the viewpoint of the controllability of self-polymerization and the ease of implementation. The RAFT method is particularly attracting attention because it is applicable to the widest range of vinyl monomers and is metal-free.

For industrial applications such as coatings, adhesives, sealants, and elastomers, resin compositions comprising vinyl block copolymers obtained by living radical polymerization based on the RAFT method have also been developed.

As a vinyl block copolymer obtained by the RAFT method used in such a resin composition, Patent Document 1 discloses a block copolymer having a polymer block (A) and an acrylic polymer block (B), wherein the polymer block (A) is a polymer having a glass transition temperature (Tg) of 150° C. or higher and containing structural units derived from styrene and maleimide compounds, and the acrylic polymer block (B) is a polymer having a solubility parameter of 9.9 or higher and a Tg of 20° C. or higher.

In addition, Patent Document 2 discloses a block copolymer having an acrylic polymer block (A) and an acrylic polymer block (B) as a vinyl block copolymer obtained by the RAFT method, wherein the acrylic polymer block (A) contains a specific structural unit and is a polymer having a Tg of 0°C or less, and each block contains an average of 1.0 or more crosslinking functional groups, and the acrylic polymer block (B) contains a specific structural unit and is a polymer having a Tg of 20°C or less. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2017/073287 [Patent Document 2] International Publication No. 2018/181251

[Problems to be solved by the invention] However, the block copolymers described in Patent Documents 1 and 2 have severe odor when exposed to high temperatures, and therefore there are problems such as limitations on the use of the block copolymers for applications requiring heat resistance. The patent documents do not disclose any suggestions regarding the odor of the block copolymers obtained by the RAFT method when exposed to high temperatures, and no solution to the odor has been disclosed. Furthermore, in applications such as sealants, elastomers, and adhesives for exterior tiles, a resin composition with high toughness of the molded product is required, and in particular, in applications such as sealants and adhesives for exterior tiles, weather resistance is also required.

The present invention was made in view of the above situation, and its purpose is to provide a block copolymer that significantly reduces the odor when exposed to high temperature. Furthermore, the purpose is to provide a resin composition that can obtain a molded product with high toughness, and further, the purpose is to provide a resin composition that also has excellent weather resistance of the molded product. [Means for solving the problem]

The inventors of the present invention have conducted intensive studies to solve the above problems and have found that by making the block copolymer have a specific terminal structure containing sulfur atoms and making the product of the sulfur concentration and the number average molecular weight in the block copolymer be below a specific value, the odor is greatly reduced and the toughness of a molded product of a resin composition containing the block copolymer is high, thereby completing the present invention. In particular, it has been found that a molded product of a resin composition containing the block copolymer and a polyoxyalkylene polymer having a crosslinking functional group is excellent in weather resistance.

The present invention is as follows. [1] A block copolymer comprising at least two polymer blocks, wherein at least one terminal structure of the block copolymer is a structure represented by the following general formula (1) or a thiol group, and when the sulfur concentration (mass %) in the block copolymer is x and the number average molecular weight of the block copolymer is y, the product of (x/100) and y is 60 or less; [Chemical 1] (R is an alkyl group, an aryl group or an aralkyl group having 1 to 30 carbon atoms). [2] A block copolymer as described in [1], wherein the block copolymer has a structural unit comprising polymer block (A)/polymer block (B)/polymer block (A). [3] A block copolymer as described in [1], wherein the block copolymer has a structural unit comprising polymer block (A)/polymer block (B)/polymer block (C). [4] A block copolymer as described in any one of [1] to [3], wherein at least one polymer block of the block copolymer has a (meth)acrylate compound as a main constituent monomer. [5] A block copolymer as described in any one of [2] to [4], wherein the polymer block (A) has a crosslinking functional group. [6] A block copolymer as described in [5], wherein the polymer block (A) contains an average of 0.7 or more of the crosslinking functional groups per molecule. [7] A resin composition comprising the block copolymer as described in any one of [1] to [6]. [8] The resin composition as described in [7], further comprising a polyoxyalkylene polymer having a crosslinking functional group. [9] The resin composition as described in [7] or [8], suitable for use in any of the following applications: a sealant, a bonding agent, an adhesive, a coating, or an elastomer. [10] A method for producing a block copolymer, the block copolymer comprising at least two polymer blocks, the method comprising: a step of producing a block copolymer (P1) comprising at least three polymer blocks and having a trithiocarbonate group represented by the following general formula (2) on a central polymer block of the block copolymer by a reversible addition-fragmentation chain transfer type living free radical polymerization method; and a step of reacting a nucleophile with the trithiocarbonate group of the block copolymer (P1) to produce a block copolymer (P2) comprising at least two polymer blocks; [Chemistry 2] 〔11〕A method for producing a block copolymer as described in〔10〕, wherein at least one polymer block of the block copolymer (P2) has a (meth)acrylate compound as a main constituent monomer, at least one terminal structure of the block copolymer (P2) is a structure represented by the following general formula (1) or a thiol group, and when the sulfur concentration (mass %) in the block copolymer (P2) is x and the number average molecular weight of the block copolymer (P2) is y, the product of (x/100) and y is 60 or less; [Chemistry 3] (R is an alkyl group, aryl group or aralkyl group having 1 to 30 carbon atoms). [Effects of the Invention]

According to the block copolymer of the present invention, the odor when exposed to high temperature is greatly reduced, and the toughness of the molded product of the resin composition containing the block copolymer can be improved. Furthermore, the weather resistance of the molded product can be excellent.

The present invention relates to a block copolymer comprising at least two polymer blocks and having a specific terminal structure.

According to the block copolymer of the present invention, the odor when exposed to high temperature is greatly reduced, and a resin composition containing the block copolymer and capable of obtaining a molded product with high toughness can be provided.

The following describes in detail various embodiments of the technology disclosed in this specification. In addition, in this specification, "(meth)acrylic acid" refers to acrylic acid and methacrylic acid, and "(meth)acrylate" refers to acrylate and methacrylate. In addition, "(meth)acryloyl" refers to acryl and methacryloyl. The following describes a block copolymer, a resin composition containing a block copolymer, and a method for producing a block copolymer.

1. Block copolymer The block copolymer of the present invention (hereinafter referred to as "the present block copolymer") is a block copolymer comprising at least two polymer blocks, and has the effect of significantly reducing odor when exposed to high temperature by making at least one terminal structure of the present block copolymer a structure represented by the general formula (1) or a thiol group, and making the product of (x/100) and y when the sulfur concentration (mass %) in the present block copolymer is x and the number average molecular weight of the block copolymer is y be 60 or less. The product of (x/100) and y is preferably 57.5 or less, more preferably 55.0 or less, further preferably 52.5 or less, and further preferably 50.0 or less. In addition, x and y can be measured by the method described in the embodiment.

Examples of the polymer block include the polymer block (A) and the polymer block (B) shown below.

1-1. Polymer block (A) As the monomer constituting the polymer block (A), there can be mentioned alkyl (meth)acrylate compounds, compounds represented by the following general formula (3), styrenes, maleimide compounds, and vinyl compounds containing amide groups, and one or more of these can be used. CH ₂ =CR ¹ -C(=O)O(R ² O) _n -R ³ (3) (wherein, R ¹ represents hydrogen or a methyl group, R ² represents a linear or branched alkylene group having 2 to 6 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; n represents an integer from 1 to 100)

Among the monomers, the (meth)acrylic acid alkyl ester compounds and the compounds represented by the general formula (3) are preferred in terms of the ease of obtaining a block copolymer having a low Tg and excellent fluidity. ＜(meth)acrylic acid alkyl ester compound＞ Specific examples of the (meth)acrylic acid alkyl ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, n-nonyl (meth)acrylate, 2-ethylhex ... linear or branched (meth)acrylic acid alkyl ester compounds such as isononyl (meth)acrylate, decyl (meth)acrylate and dodecyl (meth)acrylate; aliphatic cyclic ester compounds of acrylic acid such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentyl (meth)acrylate.

Among these, from the viewpoint of easily obtaining a block copolymer having a low Tg and excellent fluidity, an alkyl (meth)acrylate compound having an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl (meth)acrylate compound having an alkyl group having 2 to 12 carbon atoms is more preferred, and an alkyl (meth)acrylate compound having an alkyl group having 4 to 8 carbon atoms is further preferred.

The constituent units derived from the (meth) alkyl ester compound may be set to 50% by mass or more and 100% by mass or less relative to all constituent units of the polymer block (A). The reason is that if it is 50% by mass or more, it is also advantageous in terms of weather resistance. The constituent units are, for example, 60% by mass or more, for example, 70% by mass or more, for example, 80% by mass or more. For example, it is 98% by mass or less, for example, 95% by mass or less, for example, 90% by mass or less, for example, 85% by mass or less.

<Compounds represented by general formula (3)> When n is 1, the compound represented by general formula (3) has an oxyalkyl structure such as an oxyethyl chain, an oxypropyl chain, and an oxybutyl chain. Specific examples include methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, n-propoxypropyl (meth)acrylate, n-butoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, n-propoxybutyl (meth)acrylate, n-butoxybutyl (meth)acrylate, etc. As the alkoxyalkyl (meth)acrylate compound, an alkoxyalkyl (meth)acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms is preferred, and an alkoxyalkyl (meth)acrylate having an alkoxyalkyl group having 2 to 6 carbon atoms is more preferred, since a block copolymer having a low Tg and excellent fluidity can be easily obtained.

In addition, when n is 2 or more in the formula, there is a polyoxyalkylene structure such as a polyoxyethylene chain, a polyoxypropylene chain, and a polyoxybutylene chain. When n is 2 or more, ^R2 may be the same or different. Therefore, different types of polyoxyalkylene structures may be present in one molecule, such as a polyoxyethylene/polyoxypropylene block structure. As specific compounds, polyoxyethylene ethyl (meth)acrylate, polyoxypropylene (meth)acrylate, polyoxybutyl (meth)acrylate, and polyoxyethylene-polyoxypropylene (meth)acrylate may be listed. In addition, examples of the group having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms at the end include methoxypolyethylene glycol (meth)acrylate, lauryloxypolyethylene glycol (meth)acrylate, stearyloxypolyethylene glycol (meth)acrylate, octyloxypolyethylene glycol polypropylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, phenoxypolyethylene glycol polypropylene glycol (meth)acrylate, and the like.

On the other hand, among the monomers, styrenes are preferred in terms of easily obtaining block copolymers with high Tg and excellent heat resistance, and maleimide compounds and amide group-containing vinyl compounds are preferred in terms of easily obtaining block copolymers with high Tg and excellent oil resistance. <Styrenes> The styrenes include styrene and its derivatives. Specific examples of the compound include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-n-butylstyrene, p-isobutylstyrene, p-tert-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, p-chloromethylstyrene, o-chlorostyrene, p-chlorostyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and divinylbenzene. One or more of these compounds may be used. By polymerizing monomers containing styrenes, structural units derived from styrenes may be introduced into the polymer block (A). Among these, styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene are preferred from the viewpoint of self-polymerization. α-methylstyrene, β-methylstyrene, and vinylnaphthalene are preferred in that the Tg of the polymer block (A) can be increased and a block polymer having excellent heat resistance can be obtained.

In the polymer block (A), the proportion of the structural unit derived from the styrene is preferably 1% by mass or more and 70% by mass or less relative to all the structural units of the polymer (P1). It is more preferably 5% by mass or more and 70% by mass or less, further preferably 10% by mass or more and 70% by mass or less, and further preferably 20% by mass or more and 60% by mass or less. In addition, for example, it can be 20% by mass or more and 40% by mass or less. If the structural unit derived from the styrene is 1% by mass or more, a block copolymer with excellent moldability can be obtained. On the other hand, if it is 70% by mass or less, the required amount of the structural unit derived from the maleimide compound described later can be ensured, so that a block copolymer with excellent heat resistance and oil resistance can be obtained.

<Maleimide Compound> The maleimide compound includes maleimide and N-substituted maleimide compounds. Examples of the N-substituted maleimide compounds include N-alkyl-substituted maleimide compounds such as N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-laurylmaleimide, and N-stearylmaleimide; N-cyclopentylmaleimide; N-cycloalkyl-substituted maleimide compounds such as maleimide, N-cyclohexylmaleimide, etc.; N-phenylmaleimide, N-(4-hydroxyphenyl)maleimide, N-(4-acetylphenyl)maleimide, N-(4-methoxyphenyl)maleimide, N-(4-ethoxyphenyl)maleimide, N-(4-chlorophenyl)maleimide, N-(4-bromophenyl)maleimide, N-benzylmaleimide, etc., and one or more of them can be used. By polymerizing a monomer containing a maleimide compound, a structural unit derived from the maleimide compound can be introduced into the polymer (P1). Among the above, the compound represented by the following general formula (4) is preferred in terms of the fact that the obtained block copolymer has better oil resistance. (4) [wherein ^R1 represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or ^PhR2 ; wherein Ph represents a phenyl group, and ^R2 represents hydrogen, a hydroxyl group, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, or a halogen]

In the polymer block (A), the proportion of the structural units derived from the maleimide compound relative to all the structural units of the polymer block (A) is 30% by mass or more and 99% by mass or less. Preferably, it is 30% by mass or more and 95% by mass or less, more preferably, it is 30% by mass or more and 90% by mass or less, and further preferably, it is 40% by mass or more and 80% by mass or less. For example, it can be 50% by mass or more, and further, for example, it can be 60% by mass or more. For example, it can be 75% by mass or less, and further, for example, it can be 70% by mass or less. For example, it can be 50% by mass or more and 75% by mass or less, and further, it can be 60% by mass or more and 70% by mass or less. When the structural units derived from the maleimide compound are 30% by mass or more, the obtained block copolymer has excellent heat resistance and oil resistance. On the other hand, when the content is 99 mass % or less, the structural unit other than the structural unit derived from the maleimide compound is present, resulting in excellent fluidity and moldability.

From the perspective of achieving more excellent oil resistance, the block copolymer may further include a structural unit derived from an amide group-containing vinyl compound.

<Vinyl compounds containing amide groups> Specific examples of vinyl compounds containing amide groups include (meth)acrylamide, and (meth)acrylamide derivatives such as tert-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and (meth)acrylmorpholine; and N-vinylamide monomers such as N-vinylacetamide, N-vinylformamide, and N-vinylisobutylamide. These compounds may be used alone or in combination of two or more.

By polymerizing a monomer containing an amide group-containing vinyl compound, a structural unit derived from an amide group-containing vinyl compound can be introduced into the polymer block (A).

As other monomers other than the above, there can be listed amino group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; aliphatic cyclic ester compounds of (meth)acrylate such as isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentyl (meth)acrylate; aromatic vinyl compounds of (meth)acrylate such as styrene, α-methylstyrene, benzyl (meth)acrylate, phenyl (meth)acrylate and naphthyl (meth)acrylate; vinyl acetate, (meth)acrylonitrile, maleic acid monoester compounds, etc.

<Crosslinking functional group> In terms of improving the breaking strength of the molded product, the polymer block (A) preferably contains an average of 0.7 or more crosslinking functional groups in each block, more preferably 1.0 or more, further preferably 1.5 or more, and further preferably 2.0 or more. In terms of excellent elongation at break, it is preferably 10 or less, more preferably 7 or less, and further preferably 5 or less.

There is no particular limitation on the method for introducing the crosslinking functional group, and for example, the crosslinking functional group can be introduced by copolymerizing a vinyl monomer having a crosslinking functional group. In this case, the polymer block (A) has a constituent unit derived from a vinyl monomer having a crosslinking functional group (hereinafter, also referred to as a "crosslinking constituent unit"). Examples of the crosslinking functional group include a hydrolyzable silyl group, a carboxyl group, a hydroxyl group, an epoxy group, a primary amine group or a secondary amine group, and examples of the vinyl monomer having a crosslinking functional group include a hydrolyzable silyl group-containing vinyl compound, an unsaturated carboxylic acid, an unsaturated acid anhydride, a hydroxyl group-containing vinyl compound, an epoxy group-containing vinyl compound, a primary amine group or a secondary amine group-containing vinyl compound, an oxazoline group-containing vinyl compound, and an isocyanate group-containing vinyl compound. The vinyl monomer having a crosslinkable functional group may be used alone or in combination of two or more.

Examples of the vinyl compound containing a hydrolyzable silyl group include vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl methyl dimethoxysilane, and vinyl dimethyl methoxysilane; (meth)acrylates containing an alkoxysilyl group such as trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, methyl dimethoxysilylpropyl (meth)acrylate, and dimethyl methoxysilylpropyl (meth)acrylate; vinyl ethers containing an alkoxysilyl group such as trimethoxysilylpropyl vinyl ether; and vinyl esters containing an alkoxysilyl group such as trimethoxysilyl undecanoate. These compounds may be used alone or in combination of two or more. In the vinyl compound, the hydrolyzable silyl groups may be dehydrated and condensed with each other. Therefore, it is suitable in terms of being able to efficiently carry out the polymerization reaction for producing the block copolymer and the subsequent crosslinking reaction. Furthermore, since the hydrolyzable silyl group as a whole is considered to be one reaction point, in the present invention, the hydrolyzable silyl group as a whole is regarded as one crosslinking functional group. That is, vinyltrimethoxysilane having three methoxysilyl groups in the molecule and vinylmethyldimethoxysilane having two methoxysilyl groups in the molecule both introduce one crosslinking functional group by copolymerization.

Examples of the unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, liconic acid, cinnamic acid, and monoalkyl esters of unsaturated dicarboxylic acids (monoalkyl esters of maleic acid, fumaric acid, itaconic acid, liconic acid, maleic anhydride, itaconic anhydride, liconic anhydride, etc.). These compounds may be used alone or in combination of two or more.

Examples of the unsaturated anhydride include maleic anhydride, itaconic anhydride, citric anhydride, etc. These compounds may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing vinyl compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and mono(meth)acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. These compounds may be used alone or in combination of two or more.

Examples of the epoxy group-containing vinyl compound include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. These compounds may be used alone or in combination of two or more.

Examples of the vinyl compound containing a primary or secondary amino group include (meth)acrylates containing an amino group such as aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, and N-ethylaminoethyl (meth)acrylate; and (meth)acrylamides containing an amino group such as aminoethyl (meth)acrylamide, aminopropyl (meth)acrylamide, N-methylaminoethyl (meth)acrylamide, and N-ethylaminoethyl (meth)acrylamide.

Among the vinyl monomers having a crosslinkable functional group, compounds containing a hydrolyzable silyl group are preferred in terms of excellent elongation at break and breaking strength of the resulting molded product.

As other methods for introducing hydrolyzable silyl groups as crosslinking functional groups, 1) the addition reaction of the carboxyl group of an unsaturated carboxylic acid as a monomer constituting the polymer block (A) with an epoxy compound containing a hydrolyzable silyl group can be listed. As the unsaturated carboxylic acid, it is preferably at least one selected from the group consisting of (meth)acrylic acid, maleic anhydride and itaconic acid. In addition, 2) the addition reaction of the epoxy group of an epoxy-containing vinyl compound as a monomer constituting the polymer block (A) with an amine compound containing a hydrolyzable silyl group can also be listed. As the monomer containing the epoxy group, it is preferably a (meth)acrylate containing a glycidyl group.

Furthermore, by copolymerizing a multifunctional polymerizable monomer having two or more polymerizable unsaturated groups in the molecule, a polymerizable unsaturated group can be introduced into the polymer block (A) as a crosslinking functional group. The multifunctional polymerizable monomer is a compound having two or more polymerizable functional groups such as (meth)acryl groups and alkenyl groups in the molecule, and examples thereof include multifunctional (meth)acrylate compounds, multifunctional alkenyl compounds, and compounds having both (meth)acryl groups and alkenyl groups. For example, in addition to alkanediol diacrylates such as hexanediol diacrylate, examples thereof include allyl (meth)acrylate, isoacrylate (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, which have both (meth)acryl groups and alkenyl groups in the molecule. These compounds may be used alone or in combination of two or more.

A polymerizable unsaturated group can also be introduced by preparing a polymer having a functional group in the molecule and then reacting the polymer with a compound having a functional group capable of reacting with the functional group and a polymerizable unsaturated group. For example, a polymer having a hydroxyl group can be prepared and then reacted with a compound having both an isocyanate group and a polymerizable unsaturated group to introduce a polymerizable unsaturated group into the polymer. Alternatively, for example, a compound having both an epoxy group and a polymerizable unsaturated group can be reacted with a polymer having a carboxyl group.

In addition to the above, the crosslinking functional group can also be introduced by preparing the polymer block (A) in the presence of a polymerization control agent such as a RAFT agent having a crosslinking functional group.

The crosslinking constituent unit in the polymer block (A) is not particularly limited, and can be set to, for example, 0.01 mol% or more, for example, 0.1 mol% or more, for example, 0.5 mol% or more, relative to all the constituent units of the polymer block (A). If the amount of the crosslinking constituent unit introduced is 0.01 mol% or more, it is easy to obtain a block copolymer with high mechanical strength. On the other hand, from the perspective of softness, the upper limit of the crosslinking constituent unit is, for example, 95 mol% or less, for example, 90 mol% or less, for example, 80 mol% or less, for example, 60 mol% or less. The upper limit is, for example, 50 mol% or less, for example, 40 mol% or less, for example, 30 mol% or less, for example, 20 mol% or less, for example, 10 mol% or less.

In the polymer block (A), the proportion of the constituent units derived from the other monomers is preferably in the range of 0 mass % to 50 mass % with respect to all the constituent units of the polymer block (A), for example, 40 mass % or less, for example, 30 mass % or less, for example, 20 mass % or less, for example, 10 mass % or less.

(Number average molecular weight) The number average molecular weight of the polymer block (A) is not particularly limited, but is preferably 1,000 to 80,000. Furthermore, when the block copolymer has a plurality of polymer blocks (A), the number average molecular weight of the polymer block (A) refers to the sum of the number average molecular weights of all polymer blocks (A). For the block copolymer, if the number average molecular weight of the polymer block (A) is 1,000 or more, sufficient strength or durability can be exerted in the molded product. In addition, if it is 80,000 or less, good fluidity and coating properties can be ensured. From the viewpoint of the strength and fluidity of the molded product, the number average molecular weight of the polymer block (A) is more preferably in the range of 2,000 to 60,000, further preferably in the range of 3,000 to 40,000, further preferably in the range of 4,000 to 20,000, further preferably in the range of 5,000 to 10,000.

1-2. Polymer block (B) Monomers constituting the polymer block (B) are similar to those of the polymer block (A) (however, different from the polymer block (A)), and include the above-mentioned alkyl (meth)acrylate compounds, compounds represented by the above-mentioned general formula (3), styrenes, maleimide compounds, and amide group-containing vinyl compounds, and one or more of these can be used.

In the polymer block (B), from the viewpoint of obtaining a block copolymer with excellent flexibility, it is preferred that the monomers contain alkyl acrylate as the main constituent unit. Furthermore, among these, alkyl acrylate compounds having an alkyl group with 4 to 12 carbon atoms are preferred. In addition, from the viewpoint of the fluidity of the block copolymer, the acrylic acid-based compound is more preferably an alkyl acrylate compound containing an alkyl group with 4 to 8 carbon atoms.

In the polymer block (B), the constituent unit derived from the (meth)acrylic acid alkyl ester compound may be set to 50 mass % or more and 100 mass % or less. It is more preferably 60 mass % or more and 100 mass % or less, further preferably 70 mass % or more and 100 mass % or less, and further preferably 80 mass % or more and 100 mass % or less. When the constituent unit is within the above range, there is a tendency to obtain a block copolymer with good mechanical properties.

The polymer block (B) may further include a crosslinking constituent unit derived from the vinyl monomer having a crosslinking functional group.

The crosslinking constituent units in the polymer block (B) are preferably provided in addition to the crosslinking constituent units of the polymer block (A) as needed. Although not particularly limited, the crosslinking constituent units can be set to, for example, 0.01 mol% or more, for example, 0.1 mol% or more, and for example, 0.5 mol% or more relative to all the constituent units of the polymer block (B). If the amount of the crosslinking constituent units introduced is 0.01 mol% or more, it is easy to obtain a block copolymer with high mechanical strength. On the other hand, from the perspective of softness, the upper limit of the crosslinking constituent units is, for example, 20 mol% or less, for example, 10 mol% or less, and for example, 5 mol% or less. Furthermore, from the viewpoint of forming a uniform cross-linked structure, it is preferred that the cross-linking points are concentrated in the polymer block (A), and the ratio of the cross-linking constituent units to the total constituent units of the polymer block (B) is preferably not more than the ratio of the cross-linking constituent units to the total constituent units of the polymer block (A).

(Number average molecular weight) The number average molecular weight (Mn) of the polymer block (B) is not particularly limited, but is preferably 9,000 to 250,000. Furthermore, when the block copolymer has a plurality of polymer blocks (B), the number average molecular weight of the polymer block (B) refers to the sum of the number average molecular weights of all polymer blocks (B). For the block copolymer, if the number average molecular weight of the polymer block (B) is 9,000 or more, sufficient strength or durability can be exerted in the molded product. In addition, if it is 250,000 or less, good fluidity and coating properties can be ensured. The block copolymer can form a uniform cross-linked structure, so the molecular weight of the block copolymer corresponding to the distance between the cross-linking points can be ensured. From the viewpoint of strength and fluidity of the molded product, the molecular weight of the polymer block (B) is more preferably in the range of 14,000 to 150,000, further preferably in the range of 19,000 to 100,000, further preferably in the range of 23,000 to 80,000, further preferably in the range of 25,000 to 55,000.

1-3. Block copolymer The block copolymer is a block copolymer comprising at least two polymer blocks, preferably having at least one polymer block (A) and one polymer block (B). The block copolymer may have a structural unit (ABA) comprising polymer block (A)/polymer block (B)/polymer block (A), or may have a structural unit (ABC) comprising polymer block (A)/polymer block (B)/polymer block (C). The monomer constituting the polymer block (C) is the same as that of the polymer block (A) and the polymer block (B) (however, different from the polymer block (A) and the polymer block (B)), and may include the above-mentioned (meth) acrylate alkyl ester compound, the compound represented by the above-mentioned general formula (3), styrene, maleimide compound, and amide group-containing vinyl compound, and one or more of these may be used.

Here, when the block copolymer has a structure of A-(BA) _n (where n represents an integer greater than or equal to 1), it is preferred that the polymer block (A) contains a crosslinking constituent unit from the viewpoint of the strength of the molded product. With this structure, the polymer block (A) containing the crosslinking constituent unit functions as a crosslinking chain segment, and thus a uniform crosslinking structure can be obtained while ensuring the molecular weight between the crosslinking points, thereby achieving excellent performance in mechanical properties such as elongation at break and strength at break of the molded product.

The content ratio of the polymer block (A) relative to 100 parts by mass of the total amount of the polymer block (A) and the polymer block (B) in the block copolymer is not particularly limited, but is preferably 60 parts by mass or less, more preferably 2 parts by mass or more and 60 parts by mass or less, further preferably 4 parts by mass or more and 50 parts by mass or less, further preferably 6 parts by mass or more and 40 parts by mass or less, further preferably 8 parts by mass or more and 30 parts by mass or less, further preferably 10 parts by mass or more and 20 parts by mass or less. In the case where the block copolymer contains a crosslinking constituent unit, if it is within such a range, it is easy to obtain a molded product having good mechanical properties from the polymer block (A) constituting a crosslinking chain segment as a crosslinking point and the polymer block (B) which can be a non-crosslinking chain segment.

The number average molecular weight (Mn) of the block copolymer is not particularly limited, but is preferably 10,000 to 300,000. For the block copolymer, if the number average molecular weight is 10,000 or more, sufficient strength or durability can be exerted in the molded product. In addition, if it is 300,000 or less, good fluidity and coating properties can be ensured. From the viewpoint of the strength and fluidity of the molded product, the number average molecular weight of the block copolymer is more preferably in the range of 15,000 or more and 200,000 or less, and further preferably in the range of 20,000 or more and 150,000 or less, and further preferably in the range of 25,000 or more and 90,000 or less, and further preferably in the range of 30,000 or more and 60,000 or less.

In addition, from the viewpoint of mechanical properties (elongation at break and breaking strength, etc.), the molecular weight distribution (Mw/Mn) obtained by dividing the weight average molecular weight (Mw) of the block copolymer by the value of the number average molecular weight (Mn) is preferably 4.00 or less. In the case where the block copolymer includes a crosslinking constituent unit, from the viewpoint of forming a uniform crosslinking structure and ensuring the mechanical properties (elongation at break and breaking strength, etc.), it is more preferably 3.00 or less, further preferably 2.00 or less, further preferably 1.80 or less, further preferably 1.50 or less, and further more preferably 1.40 or less. In addition, the molecular weight distribution (Mw/Mn) is preferably 1.05 or more, can be 1.10 or more, and can also be 1.30 or more.

2. Resin composition Even if the block copolymer is used alone, it can be used as a sealant, adhesive, coating, or elastomer, but it can also be used as a resin composition that is blended with known additives as needed.

In addition, when the block copolymer has a crosslinking functional group, a necessary crosslinking agent, other polymers having a crosslinking functional group, and a crosslinking accelerator can be formulated according to the type to prepare a curable resin composition, and further, a molded product corresponding to the application can be obtained by applying a heat treatment or the like as needed.

Examples of the crosslinking agent (curing agent) include glycidyl compounds having two or more glycidyl groups, isocyanate compounds having two or more isocyanate groups, aziridine compounds having two or more aziridine groups, oxazoline compounds having oxazoline groups, metal chelate compounds, butylated melamine compounds, etc. Among these, aziridine compounds, glycidyl compounds, and isocyanate compounds are preferred, and isocyanate compounds are preferred in terms of excellent physical properties of molded products under high temperature conditions.

Examples of the aziridine compound include 1,6-bis(1-aziridinylcarbonylamino)hexane, 1,1'-(methylene-bis-p-phenylene)bis-3,3-aziridinylurea, 1,1'-(hexamethylene)bis-3,3-aziridinylurea, ethylbis-(2-aziridinylpropionate), tris(1-aziridinyl)phosphine oxide, 2,4,6-triaziridinyl-1,3,5-triazine, and trihydroxymethylpropane-tris-(2-aziridinylpropionate).

Examples of the glycidyl compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidyl xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trihydroxymethylpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like.

As the isocyanate compound, for example, a compound having two or more isocyanate groups can be used. As the isocyanate compound, various isocyanate compounds of aromatic, aliphatic, and alicyclic series, and modified products of these isocyanate compounds (modified isocyanates) can be used.

As aromatic isocyanates, diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate (NDI), terephthalene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), toluidine diisocyanate (TODI), etc. can be listed. As aliphatic isocyanates, hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), lysine triisocyanate (LTI), etc. can be listed. Examples of alicyclic isocyanates include isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (CHDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), etc. In addition, examples of modified isocyanates include urethane modified products, dimers, trimers, carbodiimide modified products, allophanate modified products, biuret modified products, urea modified products, isocyanurate modified products, oxazolidinone modified products, isocyanate group-terminated prepolymers, etc. of the above-mentioned isocyanate compounds.

When the resin composition disclosed in this specification contains a crosslinking agent (hardening agent), its content may be set to 0.01 to 10 parts by mass, or 0.03 to 5 parts by mass, or 0.05 to 2 parts by mass, relative to 100 parts by mass of the block copolymer.

Examples of other polymers having a crosslinking functional group include polyoxyalkylene polymers having a crosslinking functional group, (meth)acrylic polymers having a crosslinking functional group (however, different from the present block copolymer), polyester polymers having a crosslinking functional group, polyurethane polymers having a crosslinking functional group, polybutadiene polymers having a crosslinking functional group, hydrogenated polybutadiene polymers having a crosslinking functional group, and polyisobutylene polymers having a crosslinking functional group, hydrocarbon polymers, polyamide polymers, bisphenol polymers, and the like. Among these, when the block copolymer uses a (meth)acrylate compound as the main constituent monomer, a polyoxyalkylene polymer having a crosslinking functional group is preferred from the viewpoint of excellent self-compatibility, excellent mechanical properties of the molded product, and excellent weather resistance. Here, as the crosslinking functional group, the above functional groups can be listed.

The polyoxyalkylene polymer having a crosslinkable functional group is not particularly limited as long as it contains a repeating unit represented by the following general formula (5). -OR ¹ - (5) (wherein R ¹ is a divalent alkyl group) Examples of R ¹ in the general formula (5) include the following. ·(CH ₂ ) _n (n is an integer of 1 to 10) ·CH(CH ₃ )CH ₂ ·CH(C ₂ H ₅ )CH ₂ ·C(CH ₃ ) ₂ CH ₂ The polyoxyalkylene polymer may contain one or a combination of two or more of the repeating units. Among these, CH(CH ₃ )CH ₂ is preferred in terms of excellent workability.

As the crosslinking functional group contained in the polyoxyalkylene polymer, from the viewpoint of excellent compatibility, excellent mechanical properties of the molded product, and excellent weather resistance, a crosslinking silyl group is particularly preferred. As the crosslinking silyl group, there is no particular limitation, and alkoxysilyl groups, halogenated silyl groups, silanol groups, etc. can be listed. From the aspect of easy control of reactivity, alkoxysilyl groups are preferred. As specific examples of alkoxysilyl groups, trimethoxysilyl groups, methyldimethoxysilyl groups, dimethylmethoxysilyl groups, triethoxysilyl groups, methyldiethoxysilyl groups, dimethylethoxysilyl groups, etc. can be listed.

There is no particular limitation on the method for producing the polyoxyalkylene polymer. For example, there can be cited a polymerization method using a corresponding epoxy compound or diol as a raw material and using an alkaline catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst, a polymerization method using a composite metal cyanide complex catalyst, a polymerization method using phosphazene, etc. In addition, the polyoxyalkylene polymer can be any one of a linear polymer and a branched polymer. In addition, these can also be used in combination.

From the viewpoint of mechanical properties and adhesion of the self-curing material, the average value of the number of cross-linked silyl groups contained in one molecule of the polyoxyalkylene polymer is preferably in the range of 1 to 4, and more preferably in the range of 1.5 to 3. The position of the cross-linked silyl groups contained in the polyoxyalkylene polymer is not particularly limited, and can be set to the side chain and/or the end of the polymer. In addition, the polyoxyalkylene polymer can be any of a linear polymer and a branched polymer. In addition, these combinations can also be used.

From the viewpoint of mechanical properties, the number average molecular weight (Mn) of the polyoxyalkylene polymer is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more. Mn may be 18,000 or more, 22,000 or more, or 25,000 or more. From the viewpoint of workability (viscosity) during application of the self-hardening resin composition, the upper limit of Mn is preferably 60,000 or less, more preferably 50,000 or less, and further preferably 40,000 or less. The range of Mn can be set by combining the upper limit value and the lower limit value, for example, from 5,000 to 60,000, from 15,000 to 60,000, from 18,000 to 50,000, or from 22,000 to 50,000.

As the polyoxyalkylene polymer, a commercially available product may be used. Specific examples include "MS polymer S203", "MS polymer S303", "MS polymer S810", "SILYL SAT200", "SILYL SAT350", "SILYL EST280", and "SILYL SAT30" manufactured by Kaneka Co., Ltd., and "EXCESTAR ES-S2410", "EXCESTAR ES-S2420", and "EXCESTAR ES-S3430" manufactured by AGC Co., Ltd. (all trade names).

In addition, examples of the additives include plasticizers, fillers, adhesion-imparting agents, dehydrating agents, hardening accelerators, anti-aging agents, ultraviolet absorbers, and oils.

As plasticizers, there can be listed liquid polyurethane resins, polyester plasticizers obtained from dicarboxylic acids and diols; etherified or esterified products of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyether plasticizers such as sugar polyethers obtained by adding polymerized ethylene oxides such as propylene oxide to sugar polyols such as sucrose and then etherifying or esterifying; polystyrene plasticizers such as poly-α-methylstyrene; poly(meth)acrylates without crosslinking functional groups, etc. Among these, poly(meth)acrylates without crosslinking functional groups are preferred in terms of durability such as weather resistance of the cured product. Among these, those with Mw in the range of 1,000 to 7,000 and a glass transition temperature of -30°C or below are more preferred. The amount of the plasticizer used is preferably in the range of 0 to 100 parts by mass, and may be in the range of 0 to 80 parts by mass, or in the range of 0 to 50 parts by mass, relative to 100 parts by mass of the total amount of the polyoxyalkylene polymer and the present block copolymer. As fillers, there can be exemplified light calcium carbonate having an average particle size of about 0.02 μm to 2.0 μm, heavy calcium carbonate having an average particle size of about 1.0 μm to 5.0 μm, titanium oxide, carbon black, synthetic silica, talc, zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide, barium sulfate, glass balloons, silica balls, and polymethyl methacrylate balls. By using these fillers, the mechanical properties of the hardened material are improved, and the tensile strength or tensile elongation can be increased. Among these, light calcium carbonate, heavy calcium carbonate and titanium oxide, which have a high effect of improving physical properties, are preferred, and a mixture of light calcium carbonate and heavy calcium carbonate is more preferred. The amount of filler added is preferably 20 to 300 parts by mass, and more preferably 50 to 200 parts by mass, relative to 100 parts by mass of the total amount of the polyoxyalkylene polymer and the present block copolymer. When a mixture of light calcium carbonate and heavy calcium carbonate is prepared as described above, the mass ratio of light calcium carbonate/heavy calcium carbonate is preferably in the range of 90/10 to 50/50.

Examples of the adhesion-imparting agent include aminosilanes such as "KBM602", "KBM603", "KBE602", "KBE603", "KBM902", and "KBM903" manufactured by Shin-Etsu Silicones Co., Ltd.

Examples of the dehydrating agent include methyl orthoformate, methyl orthoacetate, and vinylsilane.

As a hardening accelerator, known compounds such as tin-based catalysts, titanium-based catalysts, and tertiary amines can be used. Examples of tin-based catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetonate, and dioctyltin dilaurate. Specifically, examples include trade names such as "Neostann U-28", "Neostann U-100", "Neostann U-200", "Neostann U-220H", "Neostann U-303", and "SCAT-24" manufactured by Nitto Kasei Co., Ltd. Examples of titanium catalysts include tetraisopropyl titanium ester, tetra-n-butyl titanium ester, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetylacetonate, dibutyloxytitanium diacetylacetonate, diisopropoxytitanium diacetylacetonate, titanium octylene glycolate, and titanium lactate. Examples of tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), diazabicyclononene (DBN), N-methylmorpholine, and N-ethylmorpholine. The amount of the curing accelerator used is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the total amount of the polyoxyalkylene polymer and the present block copolymer.

As the anti-aging agent, ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds and oxalic acid anilide compounds, light stabilizers such as hindered amine compounds, antioxidants such as hindered phenol compounds, heat stabilizers, or a mixture of these can be used.

Examples of the ultraviolet absorber include "TINUVIN 571", "TINUVIN 1130", and "TINUVIN 327" manufactured by BASF. Examples of the light stabilizer include "TINUVIN 292", "TINUVIN 144", and "TINUVIN 123" manufactured by BASF, and "Sanol 770" manufactured by Sankyo Co., Ltd. Examples of the thermal stabilizer include "Irganox 1135", "Irganox 1520", and "Irganox 1330" manufactured by BASF. "TINUVIN B75" manufactured by BASF, which is a mixture of an ultraviolet absorber/light stabilizer/thermal stabilizer, can also be used.

In order to adjust the performance, coating properties, processability, etc. of the resin composition containing the block copolymer, other thermoplastic resins may be added. Specific examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene, vinyl resins such as polyvinyl chloride, polyester resins, polyamide resins, etc. In addition, known elastomers may be added and mixed.

The curable resin composition of the present invention can be prepared as a single component type, that is, all the prepared components are prepared in advance and sealed, and hardened by absorbing moisture in the air after coating. In addition, it can also be prepared as a two-component type, that is, a single curing catalyst, filler, plasticizer, water and other components as a curing agent are prepared, and the prepared materials are mixed with the polymer composition before use. A single component type is more preferred because it is easy to operate and has fewer mixing errors during coating.

The resin composition containing the block copolymer exhibits good fluidity when heated to about room temperature (25°C) to 150°C. Therefore, it can be applied to various molding processes based on various methods such as extrusion molding, injection molding, and casting molding in addition to various coatings.

3. Method for producing block copolymers The method for producing a block copolymer comprising at least two polymer blocks of the present invention comprises: a step of producing a block copolymer (P1) comprising at least three polymer blocks and having a trithiocarbonate group represented by the general formula (2) on the central polymer block of the block copolymer by reversible addition-fragmentation chain transfer living free radical polymerization (RAFT); and a step of reacting a nucleophile with the trithiocarbonate group of the block copolymer (P1) to produce a block copolymer (P2) comprising at least two polymer blocks.

3-1. Production steps of block copolymer (P1) The living radical polymerization can be carried out by any process such as batch process, semi-batch process, tubular continuous polymerization process, continuous stirred tank reactor (CSTR) process, etc. In addition, the polymerization form can be applied to various forms such as bulk polymerization without using solvent, solution polymerization of solvent system, emulsion polymerization of water system, microemulsion polymerization or suspension polymerization.

In the RAFT method, a polymerization controlled by a reversible chain transfer reaction is carried out in the presence of a specific polymerization control agent (RAFT agent) and a general free radical polymerization initiator. As the RAFT agent, a compound having a trithiocarbonate group represented by the general formula (2) can be used. As the compound having a trithiocarbonate group represented by the general formula (2), S,S-dibenzyl trithiocarbonate, bis[4-(2,3-dihydroxypropoxycarbonyl)benzyl]trithiocarbonate, bis[4-(2-hydroxyethoxycarbonyl)benzyl]trithiocarbonate, etc. can be listed. Here, when the compound having the trithiocarbonate group represented by the general formula (2) does not have the structure represented by the general formula (1) or the thiol group as a substituent, the structure of one end of the block copolymer (P2) becomes the structure represented by the general formula (1) or the thiol group. On the other hand, when the compound having the trithiocarbonate group represented by the general formula (2) has the structure represented by the general formula (1) or the thiol group as a substituent, the structure of both ends of the block copolymer (P2) becomes the structure represented by the general formula (1) or the thiol group. In addition, the amount of the RAFT agent used is appropriately adjusted according to the type of monomer and RAFT agent used.

As the polymerization initiator used in the RAFT polymerization, known radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used, but azo compounds are preferred from the viewpoints of safety, ease of handling and low occurrence of side reactions during radical polymerization. Specific examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), etc. The radical polymerization initiator may be used alone or in combination of two or more.

The ratio of the radical polymerization initiator is not particularly limited, but from the perspective of obtaining a polymer with a smaller molecular weight distribution, the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is preferably set to 0.5 mol or less, and more preferably set to 0.3 mol or less. In addition, from the perspective of stably performing the polymerization reaction, the lower limit of the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is 0.001 mol. Therefore, the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is preferably in the range of 0.001 mol or more and 0.5 mol or less, and more preferably in the range of 0.005 mol or more and 0.3 mol or less.

The reaction temperature when performing the polymerization reaction by the RAFT method is preferably 30° C. or higher and 120° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and further preferably 50° C. or higher and 100° C. or lower. If the reaction temperature is 30° C. or higher, the polymerization reaction can proceed smoothly. On the other hand, if the reaction temperature is 120° C. or lower, side reactions can be suppressed and restrictions on usable initiators or solvents can be relaxed.

By using a compound having a trithiocarbonate group represented by the general formula (2) as a RAFT agent, an A-(BA)n type structure comprising polymer block (A)-polymer block (B)-polymer block (A) can be obtained by a living radical polymerization method. In this case, first, as a first polymerization step, a polymer block (A) is obtained using a constituent monomer of the polymer block (A). Then, as a second polymerization step, a polymer block (B) is obtained using a constituent monomer of the polymer block (B), thereby obtaining a BAB triblock copolymer. Furthermore, as a third polymerization step, a polymer block (A) is obtained using a constituent monomer of the polymer block (A), thereby obtaining a higher order block copolymer such as an ABABA pentablock copolymer.

In the present disclosure, the polymerization of the block copolymer can be carried out in the presence of a chain transfer agent as needed, regardless of the polymerization method. The chain transfer agent can be a known one, and specifically, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, 1-hexanethiol, 2-hexanethiol, 2-methylheptane-2-thiol, 2-butylbutane-1-thiol, 1,1-dimethyl-1-pentanethiol, 1-octanethiol, 2-octanethiol, 1-decanethiol, 3-decanethiol, 1-undecanethiol, 1- Alkyl mercaptan compounds having an alkyl group having 2 to 20 carbon atoms, such as dodecanethiol, 2-dodecanethiol, 1-tridecanethiol, 1-tetradecanethiol, 3-methyl-3-undecanethiol, 5-ethyl-5-decanethiol, tri-tetradecanethiol, 1-hexadecanethiol, 1-heptadecanethiol and 1-octadecanethiol, and butylacetic acid, butylpropionic acid, 2-butylethanol, etc., can be used alone or in combination.

In the present disclosure, a known polymerization solvent in living radical polymerization can be used. Specifically, orthoester compounds such as trimethyl orthoacetate and triethyl orthoacetate; aromatic compounds such as benzene, toluene, xylene and anisole; ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; ketone compounds such as acetone and methyl ethyl ketone; dimethylformamide, acetonitrile, dimethyl sulfoxide, alcohol, water, etc. In addition, it is also possible to perform the polymerization in a bulk polymerization manner without using a polymerization solvent.

3-2. Step of producing block copolymer (P2) The method of producing a polymer of the present invention comprises the step of reacting a nucleophile with a trithiocarbonate group in the block copolymer (P1) to obtain a block copolymer (P2). For example, when the block copolymer (P1) is a triblock copolymer, the block copolymer (P2) can be obtained as a diblock copolymer, and when the block copolymer (P1) is a pentablock copolymer, the block copolymer (P2) can be obtained as a triblock copolymer.

As the nucleophilic agent, there can be listed amines, primary amine and/or secondary amine compounds, alkali metal alkoxides, hydroxides and thiols, and these can be known compounds. It is speculated that by reacting the nucleophilic agent with the thiocarbonylthio group, the thiocarbonylthio group is converted into a thiol group, and the thiol group and the residual acrylate compound undergo Michael addition reaction, and as a result, the odor of the obtained block copolymer is reduced. Among these, primary amine and/or secondary amine compounds are preferred in terms of self-reactivity.

The molar equivalent of the nucleophile relative to the thiocarbonylthio group is 2 to 90 molar equivalents. From the aspect of self-reaction efficiency, it is preferably 3 molar equivalents or more, and the lower limit can be 4 molar equivalents or more, 5 molar equivalents or more, 10 molar equivalents or more, and 15 molar equivalents or more. In addition, from the aspect that the influence of the unreacted nucleophile on the odor is small, it is preferably 75 molar equivalents or less, more preferably 60 molar equivalents or less, and particularly preferably 50 molar equivalents or less.

The molecular weight of the nucleophile is preferably 150 or less, more preferably 110 or less, and particularly preferably 60 or less, from the viewpoint of easy removal of unreacted nucleophile.

As the reactor, a known reactor such as a batch reactor and a tubular reactor can be used, but a batch reactor is preferred because there is no possibility of clogging which is a problem in a tubular reactor.

The reaction temperature is preferably 10° C. or higher, more preferably 15° C. or higher, and particularly preferably 25° C. or higher from the viewpoint of reaction efficiency. In addition, from the viewpoint of less proneness to side reactions such as nucleophilic reactions with the polymer main chain, it is preferably 80° C. or lower, more preferably 60° C. or lower, and particularly preferably 50° C. or lower.

As the reaction time, from the aspect of reaction efficiency, it is preferably more than 1 hour, further preferably more than 2 hours, and particularly preferably more than 3 hours. In addition, from the aspect of side reactions such as nucleophilic reaction to the polymer main chain that are not easy to occur, it is preferably less than 48 hours, further preferably less than 36 hours, and particularly preferably less than 24 hours.

The reaction pressure is usually normal pressure, but may be increased or decreased as required.

Here, at least one polymer block of the block copolymer (P2) has a (meth)acrylate compound as the main constituent monomer, at least one terminal structure of the block copolymer (P2) is a structure represented by the general formula (1) or a thiol group, and when the sulfur concentration (mass %) in the block copolymer (P2) is x and the number average molecular weight of the block copolymer (P2) is y, the product of (x/100) and y is 60 or less, thereby achieving a significant effect of reducing odor when exposed to high temperatures. The product of (x/100) and y is preferably 57.5 or less, more preferably 55.0 or less, further preferably 52.5 or less, and further preferably 50.0 or less. In this regard, it is preferred that the block copolymer (P2) is obtained by reacting the nucleophilic agent with the trithiocarbonate group in the block copolymer (P1) without re-precipitating the block copolymer (P1) for purification. [Example]

Hereinafter, the present disclosure will be specifically described based on the examples. Furthermore, the present disclosure is not limited to these examples. Furthermore, in the following, "parts" and "%" refer to parts by mass and mass % unless otherwise specified. The analysis method of the block copolymers obtained in the preparation examples, comparative preparation examples, examples and comparative examples is described below.

<Molecular weight measurement> The obtained block copolymer was subjected to gel permeation chromatography (GPC) measurement under the conditions described below to obtain the number average molecular weight (Mn) and weight average molecular weight (Mw) converted to polystyrene. In addition, the molecular weight distribution (Mw/Mn) was calculated from the obtained values. ○Measurement conditions Column: TSKgel SuperMultiporeHZ-M × 4 manufactured by Tosoh Solvent: Tetrahydrofuran Temperature: 40°C Detector: Refractometer (RI) Flow rate: 600 μL/min

>Monomer Reaction Rate Determination> The obtained polymer was subjected to gas chromatography (GC) measurement under the following conditions, and the monomer reaction rate (%) was calculated from the obtained monomer concentration (wt%). ○ Measurement conditions Chromatographic column: Capillary chromatographic column Agilent CP-Wax52CB (60 m×0.32 mm inner diameter, df = 0.5μm) and Agilent DB-1 (30 m×0.32 mm inner diameter, df = 1.0μm) Solvent: Tetrahydrofuran Column temperature: 50°C (5 minutes), 7°C/min, 230°C (5 minutes)

<Viscosity measurement> Using a TVE-20H viscometer (cone/plate type, manufactured by Toki Sangyo Co., Ltd.), the E-type viscosity was measured under the following conditions. ○Measurement conditions Cone shape: angle 1°34', radius 24 mm (less than 10000 mPa·s) Angle 3°, radius 7.7 mm (more than 10000 mPa·s) Temperature: 25℃±0.5℃

<Sulfur concentration (mass %): x> For block copolymers d1 to d31 listed in Tables 8 and 9 and x in e-2, e-4 and e-6 listed in Comparative Preparation Examples 1 to 3, the following method was used for determination. In addition, in this determination, it was accurately weighed to the fourth decimal place. 2 g of the block copolymer was collected in four 20 ml-perfluoroalkoxy fluorine resin (PerFluoroAlkoxy, PFA) bottles. 1 g, 2 g, and 3 g of the following 20 ppm-S standard solution were added to three PFA bottles. In addition, the following 20 ppm-S standard solution was not added to one of the PFA bottles. In addition, each was diluted with 2-propanol (IPA) to a total of 10 g to prepare a test solution. The test solution was measured using an inductively coupled plasma (ICP) luminescence spectrometer to observe the luminescence intensity of sulfur. The sulfur concentration in the test solution was obtained from the first regression line of the standard addition concentration and the luminescence intensity. The dilution rate of the test solution was converted to obtain x in the block copolymers d1 to d31, e-2, e-4 and e-6. The results are shown in Tables 8 and 9 and Comparative Preparation Examples 1 to 3. · Pretreatment environment: clean room (class 1000) and clean draft room (clean draft) (class 100) · ICP spectrophotometer: Spectro ARCOS SOP (organic solvent introduction conditions) · 2-propanol (IPA): Primepure (M) manufactured by Kanto Chemical · Dimethyl sulfoxide (DMSO): manufactured by Fuji Film Wako Pure Chemical Industries (reagent special grade) · 1000 ppm-S standard solution: dilute 1.22 g of DMSO with IPA to a total of 50 g, and dilute 5 g of it with IPA to a total of 50 g. · 20 ppm-S standard solution: dilute 1 g of the above 1000 ppm-S standard solution with IPA to a total of 50 g.

<Product of (x/100) and y> The number average molecular weight (Mn) of block copolymers d1 to d31 listed in Tables 8 and 9 and e-2, e-4 and e-6 listed in Comparative Preparation Examples 1 to 3 was set as y, and the product of (x/100) and y was calculated. These results are shown in Tables 8 and 9 and Comparative Preparation Examples 1 to 3.

<Odor intensity> For block copolymers d1 to d31 listed in Tables 8 and 9 and e-2, e-4 and e-6 listed in Comparative Production Examples 1 to 3, the odor intensity was measured by the following method. After 1 g of the block copolymer was placed in a test tube, an odor bag (manufactured by ASONE Co., Ltd.) was attached to the test tube, and the odor intensity in the odor bag was sensory evaluated after heating at 60°C for 30 minutes. The sensory evaluation group consisted of 5 people, each of whom prepared an odorless bag separately and compared it with the sample for evaluation. According to the following standard, the score was assigned in 6 stages between 0 and 5, and the average of the scores was used as the odor intensity of the sample. In addition, after each evaluation of each sample, a rest period of more than 3 minutes was taken. The results are shown in Tables 10 and 11. 0 points: No odor 1 point: Finally detectable odor 2 points: Faint odor that can be identified 3 points: Easily detectable odor 4 points: Strong odor 5 points: Strong odor

<Composition Ratio of Block Copolymer> The composition ratio of the obtained ^block copolymer was identified and calculated by ¹ H-nuclear magnetic resonance ( ¹ H-NMR) measurement.

<Preparation and evaluation method of resin composition in the embodiment and comparative example> The components were blended according to the blending ratios shown in Table 1 (Blend A, Blend B, Blend C, and Blend D) below, and the resin composition was prepared according to a conventional method.

In addition, the abbreviations in Table 1 refer to the following. · Polyoxyalkylene polymer X: silylated product of polypropylene glycol described in Synthesis Example 1 below · Polyoxyalkylene polymer Y: Branched modified silicone EXCESTAR ES-S3430 (manufactured by AGC Corporation) · UP-1110: Acrylic plasticizer, ARUFON (registered trademark) UP-1110 (manufactured by Toagosei Co., Ltd.) · jER828: Epoxy resin jER828 (manufactured by Mitsubishi Chemical Corporation) · jER Cure H30: Epoxy hardener jER Cure H30 (manufactured by Mitsubishi Chemical Corporation) · Light calcium carbonate: Baiyanhua CCR (Shiraishi Calcium Calcium) Heavy calcium carbonate: Super SS (Maruo Calcium) R820: Titanium oxide R-820 (Ishihara Sangyo) #45: Carbon black #45 (Ishihara Sangyo) Irganox 1010: Phenolic antioxidant, Irganox 1010 (BASF) B75: Anti-aging agent, Tinuvin B75 (Ciba Specialty Chemicals) SH6020: 3-(2-aminoethylamino)propyltrimethoxysilane, SH6020 (Toray Dow Corning) Corning) S340: N-(1,3-dimethylbutylene)-3-(triethoxysilyl)propylamine, Sila-Ace 340 (JNC) SZ6300: Vinyl trimethoxysilane, SZ6300 (Toray Dow Corning) U-220H: Tin catalyst (dibutyltin diethylpyruvate), Neostann U-220H (Nitto Chemical)

[Table 1] Table 1 Type of blend Preparation A (mass) Preparation B (mass basis) Preparation C (mass) Mix D (mass serving) Base resin Block copolymers 100 60 100 55 Polyoxyalkylene polymers X 40 Polyoxyalkylene polymer Y 55 Plasticizer UP-1110 50 50 40 Epoxy jER828 3 Epoxy Hardener jER cured H30 1.5 filler Light calcium carbonate 100 100 75 Heavy calcium carbonate 60 60 75 Pigments R820 2.5 2.5 4 #45 2 Antioxidants Irganox 1010 0.03 Anti-aging agents B75 2 2 2 Follow-up administration SH6020 3 3 S340 3 Dehydrating agent SZ6300 2 2 2 Hardening Catalyst U-220H 1 1 0.5

<Tensile test> Each resin composition (Preparation A, Preparation B, and Preparation D) was applied to a Teflon (registered trademark) sheet at room temperature (25°C) with a thickness of 2 mm, cured at 23°C and 50% RH for 6 days, and then cured at 50°C and a saturated water vapor environment for 1 day to produce a sheet with a thickness of 2 mm. In addition, each resin composition (Preparation C) was dissolved in tetrahydrofuran (THF) to prepare a solution with a base resin concentration of 10%, poured into a mold, and the THF was dried by distillation to produce a casting with a thickness of 2 mm. From the sheet obtained above, the elongation at break [EL (%)] and the breaking strength [Ts (MPa)] were measured using a No. 3 dumbbell punch test piece and a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation). The measurement was carried out at a temperature of 23°C and a humidity of 50% at a tensile speed of 200 mm/min. In addition, the tensile product was calculated as follows. Tensile product = elongation at break [EL (%)] × breaking strength [Ts (MPa)]/2

<Weathering test> Each resin composition (Preparation D) was applied to a Teflon (registered trademark) sheet at room temperature (25°C) with a thickness of 2 mm, and cured for 1 week at 23°C and 50% RH to prepare a hardened sheet. The hardened sheet was placed in a metal weathering meter ("DAIPLA METAL WEATHER KU-R5NCI-A" manufactured by Daipla Wintes) to perform an accelerated weathering test. The conditions were set to 63°C, 70% RH, and an illuminance of 80 mW/ ^cm2 , and a spray test was performed for 1500 hours with a 2-minute spray every 2 hours. After 1500 hours, the color difference (△E) was calculated by visual inspection of the surface condition (whether cracks were generated) and a colorimeter (spectrocolorimeter SE-2000 manufactured by Nippon Denshoku Co., Ltd.), and the weather resistance was evaluated based on the degree of fading. The color difference (△E) was calculated by substituting the values of brightness (L*), chromaticity in the red-green direction (a*), and chromaticity in the yellow-blue direction (b*) measured by the spectrocolorimeter into the following formula (1). [Figure 1] (1) L * ₁₅₀₀ : L * after 1500 hours L * ₀ : Initial L * a * ₁₅₀₀ : a * after 1500 hours a * ₀ : Initial a * b * ₁₅₀₀ : b * after 1500 hours b * ₀ : Initial b *

<Adhesion strength test> The test was conducted using mortar board and exterior inlay tile according to the adhesion strength test method of organic adhesive for exterior tile affixing in Japanese Industrial Standards (JIS) A5557 (2006). Each adhesive composition (formulation D) was applied to a mortar board (TP Giken, 10 mm × 50 mm × 50 mm) with a thickness of about 5 mm, and after being outlined with a comb applicator, a commercial exterior inlay tile (45 mm × 45 mm) that complies with the regulations of JIS A5209 was attached. After curing for 4 weeks at 23°C and 50% RH, special clamps were installed on the tile side and the mortar side, and a tensile test was performed using a tensile testing machine (Autograph AGS-J, manufactured by Shimadzu Corporation) at 23°C at a tensile speed of 3 mm/min to measure the bonding strength.

≪Synthesis of polyoxyalkylene polymers with crosslinking functional groups≫ In a 1000 mL pressurized stirring tank reactor equipped with an oil jacket, zinc hexacyanocobaltate glyme complex (0.05 g), polypropylene glycol (Mn: 2000, 50 g), and propylene glycol (510 g) were placed, heated to 120°C, and reacted until the pressure change disappeared. Then, the mixture was heated at 120°C for 1 hour in vacuum, and the volatile components were distilled off. Thereafter, a 28% methanol solution of sodium methoxide (12.6 g) was added, and the pressure was reduced at 100°C for 1 hour to distill off the methanol. Then, allyl chloride (5.2 g) was added and heated at 100°C for 2 hours. The reaction solution was then washed twice with water (300 ml) to remove salt. After dehydration was performed by vacuum heating at 100°C for 2 hours, chloroplatinic acid hexahydrate (0.02 g) and methyldimethoxysilane (8.3 g) were added and reacted for 4 hours to obtain a polypropylene glycol silylated product at both ends (also referred to as "polyoxyalkylene polymer X"). The molecular weight of polyoxyalkylene polymer X was Mn 22,900 and Mw 25,200 as measured by GPC (gel permeation chromatography) (polystyrene conversion).

≪Production of polymer block (A)≫ (Synthesis Example 1: Production of polymer a-1) In a 500 mL flask equipped with a stirrer and a thermometer, S,S-dibenzyl trithiocarbonate (hereinafter also referred to as "DBTTC") (7.4 g), 2,2'-azobis(2-methylbutyronitrile) (hereinafter also referred to as "ABN-E") (0.49 g), n-butyl acrylate (hereinafter also referred to as "nBA") (75 g), trimethoxysilylpropyl methacrylate (25 g) and trimethyl orthoacetate (hereinafter also referred to as "MOA") (5.1 g) were placed as RAFT agents, and the mixture was fully degassed by nitrogen bubbling, and polymerization was started in a thermostatic bath at 60°C. After 7 hours, the reaction was stopped by cooling to room temperature. The molecular weight of the obtained polymer a-1 was Mn 3,300, Mw 5,200, and Mw/Mn 1.59 as measured by GPC (gel permeation chromatography) (polystyrene conversion). The reaction rates of nBA and trimethoxysilylpropyl methacrylate were 75% and 98%, respectively, as measured by GC (gas chromatography).

(Synthesis Example 2 to Synthesis Example 18: Preparation of polymer a-2 to polymer a-18) The same operation as Synthesis Example 1 was performed except that the raw materials charged were used as shown in Table 2 and the reaction temperature and reaction time were appropriately adjusted to obtain polymer a-2 to polymer a-18. The molecular weight of each polymer and the reaction rate of the monomer were measured and recorded in Table 2 and Table 3.

In addition, the abbreviations other than those described in Synthesis Example 1 in Tables 2 and 3 refer to the following compounds. ·EA: ethyl acrylate ·TDA: tetradecyl acrylate ·PhMI: N-phenylmaleimide ·St: styrene

[Table 2] Table 2 Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Polymer No. a-1 a-2 a-3 a-4 a-5 a-6 a-7 a-8 a-9 Loading raw materials polymerization Single nB 75 76 86 93 52 41 90 88 71 TDA 18 Trimethoxysilylpropyl methacrylate 25 Methyldimethoxysilylpropyl methacrylate twenty four 14 7 48 59 10 12 12 Control agent DBTTC 7.4 7.5 4.3 2.1 14.9 23.2 5.8 7.5 7.3 Initiator ABN-E 0.49 0.49 0.48 0.47 0.49 0.54 0.48 0.50 0.48 Solvent MOA 5.1 5.2 5.0 4.9 5.6 5.9 5.1 5.2 5.2 Reaction temperature (℃) 60 60 60 60 60 60 60 70 60 Reaction time (h) 7 7 7 7 7 7 7 4 7 Response rate (%) nB 75 80 90 86 88 90 87 96 91 TDA 92 Trimethoxysilylpropyl methacrylate 98 Methyldimethoxysilylpropyl methacrylate 99 100 100 97 97 99 100 99 Molecular weight Mn 3,300 3,400 6,500 12,800 2,200 1,400 4,800 3,900 4,200 M 5,200 5,400 8,500 15,600 4,300 3,200 6,400 5,300 5,900 Mw/Mn 1.59 1.58 1.31 1.22 1.97 2.31 1.34 1.35 1.41

[Table 3] Table 3 Synthesis Example 10 Synthesis Example 11 Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 Polymer No. a-10 a-11 a-12 a-13 a-14 a-15 a-16 a-17 a-18 Loading raw materials polymerization Single nB 90 93 95 64 52 51 66 67 EA 7 Ph.M.I. 22.7 St 13.7 Methyldimethoxysilylpropyl methacrylate 10 7 5 36 48 49 34 25 Control agent DBTTC 10.2 9.2 9.4 7.5 7.5 3.3 15.0 7.8 0.38 Initiator ABN-E 0.68 0.61 0.62 0.50 0.50 0.37 0.50 0.52 0.05 Solvent MOA 5.1 5.1 5.1 5.2 5.2 4.1 5.5 5.2 Acetonitrile 71.4 Reaction temperature (℃) 60 60 60 70 70 60 60 70 70 Reaction time (h) 7 7 7 4 4 7 7 4 4 nB 92 90 90 95 96 72 88 89 EA 91 Ph.M.I. 99 St 99 Methyldimethoxysilylpropyl methacrylate 99 100 100 99 99 90 98 99 Molecular weight Mn 2,900 3,200 3,100 3,900 4,000 7,200 2,100 3,800 27,700 M 4,300 4,600 4,400 6,600 8,000 11,100 3,200 6,400 31,300 Mw/Mn 1.48 1.45 1.42 1.68 1.97 1.54 1.53 1.68 1.13

≪Production of triblock copolymer≫ (Synthesis Example 19: Production of triblock copolymer b-1) In a 500 mL flask equipped with a stirrer and a thermometer, polymer a-1 (5.3 g), nBA (95 g), ABN-E (0.10 g) and MOA (42 g) obtained in Synthesis Example 1 were placed, and the mixture was fully degassed by nitrogen bubbling. Polymerization was started in a 60°C thermostat. In Synthesis Example 1, unreacted residual nBA and trimethoxysilylpropyl methacrylate copolymerized with the newly added nBA, but since the amount of unreacted residual trimethoxysilylpropyl methacrylate was very small, almost only nBA was polymerized alone. After 6 hours, the reaction was stopped by cooling to room temperature. The molecular weight of the obtained triblock copolymer b-1 was Mn 66,000, Mw 74,600, and Mw/Mn 1.13 according to GPC (gel permeation chromatography) measurement (polystyrene conversion). In addition, according to GC (gas chromatography) measurement, the total reaction rate of the unreacted residual nBA in Synthesis Example 1 and the newly added nBA was 84%.

(Synthesis Examples 20 to 42: Preparation of triblock copolymers b-2 to b-24) The same operation as in Synthesis Example 19 was performed except that the raw materials charged were used as described in Tables 4 and 5 and the reaction time was appropriately adjusted to obtain triblock copolymers b-2 to b-24. The molecular weight of each triblock copolymer and the reaction rate of the monomer were measured and recorded in Tables 4 and 5.

[Table 4] Table 4 Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 Synthesis Example 22 Synthesis Example 23 Synthesis Example 24 Synthesis Example 25 Synthesis Example 26 Synthesis Example 27 Synthesis Example 28 Synthesis Example 29 Synthesis Example 30 Triblock copolymer No. b-1 b-2 b-3 b-4 b-5 b-6 b-7 b-8 b-9 b-10 b-11 b-12 Loading raw materials polymerization Monomer of polymer block (B) nB 95 95 92 84 97 98 93 94 75 95 95 96 TDA 19 Polymer block (A) Polymer a-1 5.3 Polymer a-2 5.3 Polymer a-3 8.2 Polymer a-4 16.5 Polymer a-5 3.1 Polymer a-6 2.2 Polymer a-7 7.2 Polymer a-8 5.8 Polymer a-9 6.0 Polymer a-10 5.0 Polymer a-11 4.8 Polymer a-12 4.8 Initiator ABN-E 0.10 0.10 0.10 0.05 0.11 0.12 0.10 0.10 0.10 0.11 0.10 0.10 Solvent MOA 42 42 42 5 5 5 5 25 5 5 5 5 Ethyl acetate 19 20 20 20 20 20 20 20 Reaction temperature (℃) 60 60 60 60 60 60 60 60 60 60 60 60 Reaction time (h) 6 7 5 3 7 8 5 5 5 5 5 5 Response rate (%) nB 84 89 77 71 94 98 88 89 89 90 89 90 TDA 90 Molecular weight Mn 66,000 66,300 61,300 75,700 71,500 63,400 64,800 63,500 66,400 57,100 64,200 67,100 M 74,600 74,900 68,700 86,300 82,900 75,400 73,200 70,400 80,300 64,500 72,500 75,800 Mw/Mn 1.13 1.13 1.12 1.14 1.16 1.19 1.13 1.11 1.21 1.13 1.13 1.13

[Table 5] Table 5 Synthesis Example 31 Synthesis Example 32 Synthesis Example 33 Synthesis Example 34 Synthesis Example 35 Synthesis Example 36 Synthesis Example 37 Synthesis Example 38 Synthesis Example 39 Synthesis Example 40 Synthesis Example 41 Synthesis Example 42 Triblock copolymer No. b-13 b-14 b-15 b-16 b-17 b-18 b-19 b-20 B-21 B-22 b-23 b-24 Loading raw materials polymerization Monomer of polymer block (B) nB 94 94 91 95 92 96 97 97 93 85 90 198 EA 9 Polymer block (A) Polymer a-2 4.1 3.0 Polymer a-3 4.2 10.1 Polymer a-4 7.2 Polymer a-13 5.8 Polymer a-14 5.8 Polymer a-15 9.5 Polymer a-16 4.8 7.9 Polymer a-17 5.7 Polymer a-18 108 Initiator ABN-E 0.10 0.10 0.08 0.11 0.10 0.11 0.09 0.10 0.09 0.13 0.09 Solvent MOA 25 25 5 5 5 9 9 9 11 26 5 Ethyl acetate 20 20 20 34 34 34 34 20 Acetonitrile 155 Reaction temperature (℃) 60 60 60 60 60 60 60 60 60 60 60 60 Reaction time (h) 5 5 5 5 5 5 7 7 7 5 7 6 Response rate (%) nB 90 90 87 87 85 91 91 90 87 91 86 92 EA 92 Molecular weight Mn 64,800 65,100 72,500 41,500 26,100 87,000 121,400 161,000 181,100 66,900 71,200 164,000 M 73,700 75,000 83,400 47,300 29,800 107,000 168,700 227,000 255,400 81,400 83,300 203,000 Mw/Mn 1.14 1.15 1.15 1.14 1.14 1.26 1.39 1.41 1.41 1.22 1.17 1.24

≪Preparation of Pentablock Copolymer≫ (Synthesis Example 43: Preparation of Pentablock Copolymer c-1) In a 500 mL flask equipped with a stirrer and a thermometer, the triblock copolymer b-1 (141 g), trimethoxysilylpropyl methacrylate (1.17 g), ABN-E (0.043 g) and MOA (0.44 g) obtained in Synthesis Example 19 were placed, and the mixture was fully degassed by nitrogen bubbling, and polymerization was started in a thermostatic bath at 60°C. The unreacted residual nBA in Synthesis Example 19 was copolymerized with the newly added trimethoxysilylpropyl methacrylate, and after 7 hours, the mixture was cooled to room temperature to stop the reaction, thereby obtaining a solution containing the pentablock copolymer c-1. The molecular weight of the obtained pentablock copolymer c-1 was Mn 68,200, Mw 79,800, and Mw/Mn 1.17 as measured by GPC (gel permeation chromatography) (polystyrene conversion). The pentablock copolymer c-1 is a pentablock copolymer having a polymer block (A) containing nBA and trimethoxysilylpropyl methacrylate and a polymer block (B) containing nBA, and having a structural unit of (A)-(B)-(A)-(B)-(A). Based on the polymerization rate, the composition ratio of the polymer block (A) to the acrylic polymer block (B) is (A)/(B)/(A)/(B)/(A) = 2/41/14/41/2 wt%, and the total is (A)/(B) = 18/82 wt%.

(Synthesis Examples 44 to 66: Preparation of Pentablock Copolymers C-2 to C-24) Except that the raw materials charged were used as described in Tables 6 and 7, the same operation as in Synthesis Example 43 was performed to obtain Pentablock Copolymers C-2 to C-24. The molecular weight of each block copolymer and the (A)/(B) ratio or (A)/(B)/(C) ratio of the polymer blocks are described in Tables 6 and 7.

In addition, the abbreviations other than those mentioned above in Table 7 refer to the following compounds. ·ACMO: acrylamide morpholine

[Table 6] Table 6 Synthesis Example 43 Synthesis Example 44 Synthesis Example 45 Synthesis Example 46 Synthesis Example 47 Synthesis Example 48 Synthesis Example 49 Synthesis Example 50 Synthesis Example 51 Synthesis Example 52 Synthesis Example 53 Synthesis Example 54 Pentablock copolymer No. c-1 c-2 c-3 c-4 c-5 c-6 c-7 c-8 c-9 c-10 c-11 c-12 Monomers of polymer block (A) Trimethoxysilylpropyl methacrylate 1.17 Methyldimethoxysilylpropyl methacrylate 1.37 1.00 1.05 1.19 0.97 0.66 0.49 0.62 0.42 0.28 0.18 Triblock copolymer Triblock copolymer b-1 141 Triblock copolymer b-2 141 Triblock copolymer b-3 141 Triblock copolymer b-4 124 Triblock copolymer b-5 124 Triblock copolymer b-6 124 Triblock copolymer b-7 124 Triblock copolymer b-8 124 Triblock copolymer b-9 124 Triblock copolymer b-10 124 Triblock copolymer b-11 125 Triblock copolymer b-12 125 Initiator ABN-E 0.043 0.029 0.031 0.032 0.037 0.038 0.037 0.038 0.038 0.043 0.038 0.038 Solvent MOA 0.44 0.56 0.40 0.22 0.25 0.20 0.13 0.07 0.12 0.05 0.03 0.02 Reaction temperature (℃) 60 60 60 60 60 60 60 60 60 60 60 60 Reaction time (h) 7 7 7 7 7 7 7 7 7 7 7 7 Molecular weight Mn 68,200 69,500 69,800 81,500 72,100 65,600 65,900 64,700 67,200 58,600 65,000 69,500 M 79,800 80,500 81,000 96,200 85,800 82,000 77,100 74,300 85,300 67,400 75,400 79,900 Mw/Mn 1.17 1.16 1.16 1.18 1.19 1.25 1.17 1.15 1.27 1.15 1.16 1.15 Composition ratio Polymer block (A) 18 13 twenty four 30 7 4 14 13 12 11 13 12 Polymer block (B) 82 87 76 70 93 96 86 87 88 89 87 88

[Table 7] Table 7 Synthesis Example 55 Synthesis Example 56 Synthesis Example 57 Synthesis Example 58 Synthesis Example 59 Synthesis Example 60 Synthesis Example 61 Synthesis Example 62 Synthesis Example 63 Synthesis Example 64 Synthesis Example 65 Synthesis Example 66 Pentablock copolymer No. c-13 c-14 c-15 c-16 c-17 c-18 c-19 c-20 c-21 c-22 c-23 c-24 Monomers of polymer block (A) Methyldimethoxysilylpropyl methacrylate 1.80 2.40 3.21 1.10 2.14 0.83 0.63 0.50 0.45 1.23 Ph.M.I. 27 St 18 Monomer of polymer block (C) ACMO 50 Triblock copolymer Triblock copolymer b-13 123 Triblock copolymer b-14 122 Triblock copolymer b-15 121 Triblock copolymer b-16 124 Triblock copolymer b-17 122 Triblock copolymer b-18 142 Triblock copolymer b-19 142 Triblock copolymer b-20 142 Triblock copolymer b-21 142 Triblock copolymer b-22 123 Triblock copolymer b-24 461 461 Initiator ABN-E 0.037 0.037 0.033 0.040 0.040 0.057 0.063 0.068 0.066 0.047 Solvent MOA 0.41 0.55 0.77 0.23 0.50 0.14 0.11 0.14 0.14 0.20 Acetonitrile 193 193 Reaction temperature (℃) 60 60 60 60 60 60 60 60 60 60 70 70 Reaction time (h) 7 7 7 7 7 7 7 7 7 7 8 8 Molecular weight Mn 65,800 66,200 74,900 42,700 27,800 88,100 124,500 170,500 189,300 71,200 196,000 189,000 M 78,500 80,500 92,100 49,100 32,000 111,000 178,000 254,000 284,000 88,600 280,000 275,000 Mw/Mn 1.19 1.22 1.23 1.15 1.15 1.30 1.43 1.49 1.50 1.24 1.43 1.46 Composition ratio Polymer block (A) 13 13 17 15 18 12 11 13 16 12 30 14 Polymer block (B) 87 87 83 85 82 88 89 87 84 88 70 70 Polymer block (C) 16

≪Post-treatment step of pentablock copolymer c-1 to pentablock copolymer c-24 and triblock copolymer b-23≫ (Preparation Example 1: Preparation of triblock copolymer d-1) The solution containing pentablock copolymer c-1 obtained in Synthesis Example 43 was fully degassed by nitrogen bubbling, and then n-propylamine (2.78 g, 40 molar equivalents relative to the thiocarbonylthio group of pentablock copolymer c-1) was added, and the decomposition reaction of the thiocarbonyl group was started in a constant temperature bath at 40°C. After 4 hours, the solution was cooled to room temperature to stop the reaction, and a solution containing triblock copolymer d-1 was obtained. The solution was depressurized to 20 kPa, and volatile components such as unreacted monomers and solvents were continuously distilled off using a thin film evaporator maintained at 120°C, and triblock copolymer d-1 was recovered as a non-volatile component. The obtained triblock copolymer d-1 is a triblock copolymer having a polymer block (A) containing nBA and trimethoxysilylpropyl methacrylate and a polymer block (B) containing nBA, and having a structural unit of (A)-(B)-(A), and is a Michael adduct of a thiol obtained by decomposing the thiocarbonylthio group of the block copolymer c-1 by n-propylamine and a residual acrylate compound contained in the block copolymer c-1. According to ¹ H-NMR measurement, it was confirmed that the peak (4.8 ppm) of hydrogen bonded to the carbon adjacent to the thiocarbonylthio group observed in the pentablock copolymer c-1 disappeared in the triblock copolymer d-1, and peaks (3.3 ppm, 2.9 ppm) derived from the Michael adduct with the residual acrylate compound (terminal molecular structure represented by (general formula (1)) appeared. On the other hand, the molecular weight of the triblock copolymer d-1 was Mn 41,400, Mw 51,800, and Mw/Mn 1.25. In addition, the number of crosslinking functional groups per molecule contained in block (A) was calculated based on the average amount of trimethoxysilylpropyl methacrylate introduced per RAFT agent, and the result was an average of 3.9. Furthermore, x is 0.129, the product of (x/100) and y is 53.4, and the E-type viscosity is 500,500 mPa·s.

(Preparation Example 2: Preparation of triblock copolymer d-2) The solution containing block copolymer c-1 obtained in Synthesis Example 43 was reprecipitated and purified from a mixed solvent of methanol/water = 80/20 by mass ratio, and vacuum dried to obtain block copolymer c-1. Pentablock copolymer c-1 (100 g), ethyl acetate (40 g) and MOA (10 g) were placed in a 500 mL flask equipped with a stirrer and a thermometer. After sufficient degassing by nitrogen bubbling, n-propylamine (2.78 g, 40 molar equivalents relative to the thiocarbonylthio group of pentablock copolymer c-1) was added, and the decomposition reaction of the thiocarbonyl group was started in a constant temperature bath at 40°C. After 4 hours, the mixture was cooled to room temperature to stop the reaction, and a solution containing triblock copolymer d-2 was obtained. The solution was depressurized to 20 kPa, and volatile components such as unreacted monomers and solvents were continuously distilled off using a thin film evaporator maintained at 120°C, and triblock copolymer d-2 was recovered as a non-volatile component. The obtained triblock copolymer d-2 was a triblock copolymer having a polymer block (A) containing nBA and trimethoxysilylpropyl methacrylate and a polymer block (B) containing nBA, and having a structural unit of (A)-(B)-(A), and the thiocarbonylthio group of the block copolymer c-1 was decomposed by n-propylamine, and the ω-terminus became a thiol group. According to ¹ H-NMR measurement, it was confirmed that the peak (4.8 ppm) of hydrogen bonded to the carbon adjacent to the thiocarbonylthio group observed in the pentablock copolymer c-1 disappeared in the triblock copolymer d-2 and was completely decomposed into thiols. On the other hand, the molecular weight of the triblock copolymer d-2 was Mn 41,800, Mw 52,300, and Mw/Mn 1.25. In addition, the number of crosslinking functional groups per molecule contained in block (A) was calculated based on the amount of trimethoxysilylpropyl methacrylate introduced per RAFT agent, and the result was an average of 3.9. Furthermore, x was 0.129, the product of (x/100) and y was 53.9, and the E-type viscosity was 501,000 mPa·s.

(Production Example 3 to Production Example 31: Production of triblock copolymers d-3 to d-23, triblock copolymers d-25 to d-31, and diblock copolymer d-24) The same operation as in Production Example 1 was performed except that the charged raw materials were used as described in Tables 8 and 9 and the desolvation temperature was appropriately adjusted to obtain triblock copolymers d-3 to d-23, triblock copolymers d-25 to d-31, and diblock copolymer d-24. The molecular weight of each block copolymer was measured and recorded in Tables 8 and 9. The number of crosslinking functional groups per molecule contained in block (A) was calculated from the average amount of methyldimethoxysilylpropyl methacrylate introduced per RAFT agent and recorded in Tables 8 and 9. Furthermore, the product of x, (x/100) and y, and the E-type viscosity are shown in Tables 8 and 9.

In addition, the abbreviations of the amine compounds in Tables 8 and 9 refer to the following compounds. ·PAm: n-propylamine ·BAm: n-butylamine ·HAm: n-hexylamine

[Table 8] Table 8 Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Manufacturing Example 9 Manufacturing Example 10 Manufacturing Example 11 Manufacturing Example 12 Manufacturing Example 13 Manufacturing Example 14 Manufacturing Example 15 Manufacturing Example 16 Post-processing steps Nucleophile treatment Block copolymers No. c-1 c-1 c-2 c-3 c-4 c-5 c-6 c-7 c-8 c-9 c-10 c-11 c-12 c-13 c-14 c-15 Number of blocks five five five five five five five five five five five five five five five five Nucleophile Types of amines PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM PAM Molar equivalent (relative to trithiocarbonate group) 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Desolventization Decompression (kPa) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Temperature(℃) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Flow rate (kg/h) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The block copolymer obtained by the post-treatment step Block copolymers No. d-1 d-2 d-3 d-4 d-5 d-6 d-7 d-8 d-9 d-10 d-11 d-12 d-13 d-14 d-15 d-16 Number of blocks three three three three three three three three three three three three three three three three Terminal structure General formula (1) Thiol General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) Mn:y 41,400 41,800 42,900 39,600 46,300 40,100 39,100 40,500 39,000 38,600 33,700 39,800 38,100 39,800 40,300 45,100 M 51,800 52,300 53,400 49,100 57,900 50,500 49,700 50,600 48,000 52,100 42,100 50,100 47,200 50,100 51,600 57,700 Mw/Mn 1.25 1.25 1.24 1.24 1.25 1.26 1.27 1.25 1.23 1.35 1.25 1.26 1.24 1.26 1.28 1.28 Number of cross-linking functional groups contained in block (A) per molecule (average number) 3.9 3.9 4.3 3.9 4.1 4.0 3.2 2.2 1.7 2.0 1.2 0.9 0.6 5.9 7.9 12.0 E-type viscosity (mPa・s) 500,500 501,000 501,300 454,100 601,000 518,300 448,600 517,700 377,600 130,500 312,000 495,200 386,000 521,300 579,100 628,700 Sulfur concentration in block copolymer: x (mass %) 0.129 0.129 0.119 0.129 0.108 0.126 0.131 0.125 0.130 0.135 0.147 0.129 0.131 0.128 0.127 0.113 (x/100)×y 53.4 53.9 51.1 51.1 50.0 50.5 51.2 50.6 50.7 52.1 49.5 51.3 49.9 50.9 51.2 51.0

[Table 9] Table 9 Manufacturing Example 17 Manufacturing Example 18 Manufacturing Example 19 Manufacturing Example 20 Manufacturing Example 21 Manufacturing Example 22 Manufacturing Example 23 Manufacturing Example 24 Manufacturing Example 25 Manufacturing Example 26 Manufacturing Example 27 Manufacturing Example 28 Manufacturing Example 29 Manufacturing Example 30 Manufacturing Example 31 Post-processing steps Nucleophile treatment Block copolymers No. c-16 c-17 c-18 c-19 c-20 c-21 c-22 b-23 c-2 c-2 c-2 c-2 c-2 c-23 c-24 Number of blocks five five five five five five five three five five five five five five five Nucleophile Types of amines PAM PAM PAM PAM PAM PAM PAM PAM PAM BAm HAm PAM PAM PAM PAM Molar equivalent (relative to trithiocarbonate group) 40 40 40 40 40 40 40 40 40 40 40 80 80 20 20 Desolventization Decompression (kPa) 20 20 20 20 20 20 20 20 20 20 20 20 20 0.6 0.6 Temperature(℃) 120 120 120 120 120 120 120 120 120 120 120 120 150 90 90 Flow rate (kg/h) 1 1 1 1 1 1 1 1 1 1 1 1 1 - - The block copolymer obtained by the post-treatment step Block copolymers No. d-17 d-18 d-19 d-20 d-21 d-22 d-23 d-24 d-25 d-26 d-27 d-28 d-29 d-30 d-31 Number of blocks three three three three three three three two three three three three three three three Terminal structure General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) Mn:y 25,000 15,600 55,300 74,100 92,100 106,300 42,400 38,200 42,800 42,900 43,000 45,100 48,700 99,000 98,000 M 31,500 19,800 70,200 95,600 117,888 136,100 52,600 47,800 52,644 53,400 53,500 64,000 79,900 146,000 147,000 Mw/Mn 1.26 1.27 1.27 1.29 1.28 1.28 1.24 1.25 1.23 1.24 1.24 1.42 1.64 1.47 Number of cross-linking functional groups contained in block (A) per molecule (average number) 2.5 2.8 3.9 3.9 3.9 4.0 3.9 2.0 4.3 4.3 4.3 4.3 4.3 - - E-type viscosity (mPa・s) 150,100 60,500 956,000 1,955,000 2,821,000 3,970,000 500,700 475,400 516,000 522,800 523,400 957,600 1,127,000 - - Sulfur concentration in block copolymer: x (mass %) 0.202 0.324 0.092 0.068 0.055 0.048 0.120 0.130 0.119 0.119 0.119 0.119 0.119 0.049 0.048 (x/100)×y 50.5 50.5 50.9 50.4 50.7 51.0 50.9 49.7 50.9 51.1 51.2 53.7 58.0 48.5 47.0

≪Synthesis of RAFT agent≫ (Synthesis of 1,4-bis(n- dodecyl sulfanylthiocarbonyl sulfanylmethyl) benzene) 1-Dodecanethiol (42.2 g), 20% KOH aqueous solution (63.8 g), and trioctylmethylammonium chloride (1.5 g) were placed in an eggplant-shaped flask, cooled in an ice bath, and carbon disulfide (15.9 g) and tetrahydrofuran (hereinafter also referred to as "THF") (38 ml) were added, and stirred for 20 minutes. A THF solution (170 ml) of α,α'-dichloro-p-xylene (16.6 g) was added dropwise over 30 minutes. After reacting at room temperature for 1 hour, the mixture was extracted with chloroform, washed with pure water, dried with anhydrous sodium sulfate, and concentrated with a rotary evaporator. The crude product was purified by column chromatography and recrystallized from ethyl acetate to obtain 1,4-bis(n-dodecylthiothiocarbonylthiomethyl)benzene (hereinafter also referred to as "DLBTTC") represented by the following formula (6) with a yield of 80%. The peaks of the target compound were confirmed at 7.2 ppm, 4.6 ppm, and 3.4 ppm by ¹ H-NMR measurement. [Chemistry 5] (6)

(Comparative Production Example 1) In a 1 L flask equipped with a stirrer and a thermometer, DLBTTC (9.9 g), ABN-E (0.246 g), nBA (400 g) and acetonitrile (100 g) as RAFT agents were placed, and nitrogen bubbling was used to fully deaerate, and polymerization was started in a constant temperature bath at 60°C. After 4 hours, the reaction was stopped by cooling to room temperature. The polymerization solution was reprecipitated and purified from a mixed solvent with a mass ratio of methanol/water = 70/30, and vacuum dried to obtain polymer e-1. According to GPC measurement (polystyrene conversion), the molecular weight of the obtained polymer e-1 was Mn 25,300, Mw 30,400, and Mw/Mn 1.20. In a 0.5 L flask equipped with a stirrer and a thermometer, polymer e-1 (100.0 g), ABN-E (0.065 g), nBA (37.5 g), triethoxysilylpropyl methacrylate (2.5 g) and MOA (50 g) were placed, and the mixture was fully degassed by bubbling with nitrogen, and polymerization was started in a thermostatic bath at 70°C. After 4 hours, the mixture was cooled to room temperature, the reaction was stopped, and a solution containing the triblock copolymer e-2 was obtained. The solution was depressurized to 20 kPa, and volatile components such as unreacted monomers or solvents were continuously distilled off using a thin film evaporator maintained at 120°C, and the triblock copolymer e-2 as a non-volatile component was recovered. The molecular weight of the obtained triblock copolymer e-2 is Mn 35,000, Mw 45,200, and Mw/Mn is 1.29. The triblock copolymer e-2 has a polymer block (A) containing nBA and triethoxysilylpropyl methacrylate and a polymer block (B) containing nBA, and has a structural unit of (A)-(B)-(A). According to the polymerization rate, the composition ratio of the polymer block (A) to the acrylic polymer block (B) is (A)/(B)=28/72 wt%. In addition, the number of crosslinking functional groups per molecule contained in the block (A) was calculated based on the amount of triethoxysilylpropyl methacrylate introduced per RAFT agent, and the result was calculated to be an average of 2.1. Furthermore, x is 0.557, and the product of (x/100) and y is 195.

(Comparative Production Example 2) In a 1 L flask equipped with a stirrer and a thermometer, 2-{[(2-carboxyethyl)thiothiocarbonyl]thio}propionic acid (37 g), ABN-E (2.8 g), nBA (371 g), methyldimethoxysilylpropyl methacrylate (67 g) and MOA (22 g) as RAFT agents were placed, and the mixture was fully degassed by nitrogen bubbling, and polymerization was started in a 60°C thermostat. After 7 hours, the mixture was cooled to room temperature to stop the reaction. The molecular weight of the obtained polymer e-3 was Mn 2,800, Mw 4,100, and Mw/Mn 1.50 as measured by GPC (gel permeation chromatography) (polystyrene conversion). In a 1 L flask equipped with a stirrer and a thermometer, polymer e-3 (41 g), nBA (361 g), ABN-E (0.39 g) and MOA (98 g) were added, and nitrogen bubbling was used to fully deaerate, and polymerization was started in a 60°C thermostat. After 5 hours, the mixture was cooled to room temperature to stop the reaction, and then methyl dimethoxysilylpropyl methacrylate (5.5 g) and ABN-E (0.79 g) were added, and nitrogen bubbling was used to fully deaerate, and polymerization was started in a 60°C thermostat. After 7 hours, the mixture was cooled to room temperature, the reaction was stopped, and a solution containing the triblock copolymer e-4 was obtained. The solution was depressurized to 20 kPa, and volatile components such as unreacted monomers or solvents were continuously distilled off using a thin film evaporator maintained at 120°C, and the triblock copolymer e-4 was recovered as a non-volatile component. According to GPC (gel permeation chromatography) measurement (polystyrene conversion), the molecular weight of the obtained triblock copolymer e-4 was Mn 37,400, Mw 42,200, and Mw/Mn 1.13. The triblock copolymer e-4 has a polymer block (A) containing nBA and methyldimethoxysilylpropyl methacrylate and a polymer block (B) containing nBA, and has a structural unit of (A)-(B)-(A). Based on the polymerization rate, the composition ratio of the polymer block (A) to the acrylic polymer block (B) is (A)/(B) = 14/86 wt%. In addition, the number of crosslinking functional groups per molecule contained in the block (A) was calculated based on the amount of methyldimethoxysilylpropyl methacrylate introduced per RAFT agent, and the result was an average of 3.9. Furthermore, x is 0.278, and the product of (x/100) and y is 104.

(Comparative Production Example 3) In a 1 L flask equipped with a stirrer and a thermometer, DBTTC (33 g), ABN-E (2.2 g), nBA (389 g), methyldimethoxysilylpropyl methacrylate (53 g) and MOA (23 g) as RAFT agents were placed, and the mixture was fully degassed by nitrogen bubbling, and polymerization was started in a 70°C thermostat. After 4 hours, the mixture was cooled to room temperature to stop the reaction. According to GPC (gel permeation chromatography) measurement (polystyrene conversion), the molecular weight of the obtained polymer e-5 was Mn 3,900, Mw 5,300, and Mw/Mn 1.35. In a 1 L flask equipped with a stirrer and a thermometer, polymer e-5 (49 g), n-butyl acrylate (354 g), ABN-E (0.43 g), ethyl acetate (78 g) and MOA (19 g) were placed, and the mixture was fully degassed by bubbling with nitrogen, and polymerization was started in a thermostat at 60°C. After 5 hours, the mixture was cooled to room temperature, the reaction was stopped, and a solution containing the triblock copolymer e-6 was obtained. The solution was depressurized to 20 kPa, and volatile components such as unreacted monomers or solvents were continuously distilled off using a thin film evaporator maintained at 120°C, and the triblock copolymer e-6 as a non-volatile component was recovered. The molecular weight of the obtained triblock copolymer e-6 was Mn 33,300, Mw 37,200, and Mw/Mn 1.12 according to GPC (gel permeation chromatography) measurement (polystyrene conversion). The triblock copolymer e-6 has a polymer block (A) containing nBA and methyldimethoxysilylpropyl methacrylate and a polymer block (B) containing nBA, and has a structural unit of (A)-(B)-(A). According to the polymerization rate, the composition ratio of the polymer block (A) to the acrylic polymer block (B) is (A)/(B)=11/89 wt%. In addition, the number of crosslinking functional groups per molecule contained in the block (A) was calculated based on the average amount of methyldimethoxysilylpropyl methacrylate introduced per RAFT agent, and the result was calculated to be 2.0 on average. Furthermore, x is 0.267, and the product of (x/100) and y is 88.8.

≪Preparation and evaluation of resin composition≫ (Example 1) Using the triblock copolymer d-1 obtained in Preparation Example 1 as the base resin, resin compositions (formulation A and formulation B) were prepared according to the above formulation table (Table 1), and sheets (molded products) were prepared according to the above method. The results of the mechanical properties of the sheets are shown in Table 10.

(Example 2 to Example 23, Example 25 to Example 29, Comparative Example 1 to Comparative Example 3) Using the triblock copolymers d-2 to triblock copolymers d-23 and triblock copolymers d-25 to triblock copolymers d-29 obtained in Preparation Examples 2 to 23 and Preparation Examples 25 to 29 and the triblock copolymers e-2, e-4 and e-6 obtained in Comparative Preparation Examples 1 to 3, resin compositions (blending A and blending B) were prepared according to the above blending table (Table 1), and sheets (molded products) were prepared according to the above method. The results of the mechanical properties of the sheets are shown in Tables 10 and 11.

(Example 24) The diblock copolymer d-24 obtained in Example 24 was used to prepare a resin composition (formulation B) according to the above formulation table (Table 1), and a sheet (molded product) was prepared according to the above method. The results of the mechanical properties of the sheet are shown in Table 11.

(Example 30 and Example 31) The triblock copolymer d-30 and triblock copolymer d-31 obtained in Preparation Example 30 and Example 31 were used to prepare a resin composition (formulation C) according to the above formulation table (Table 1), and sheets (molded products) were prepared according to the above method. The results of the mechanical properties of the sheets are shown in Table 11.

[Table 10] Table 10 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Block copolymers No. d-1 d-2 d-3 d-4 d-5 d-6 d-7 d-8 d-9 d-10 d-11 d-12 d-13 d-14 d-15 d-16 d-17 Number of blocks three three three three three three three three three three three three three three three three three Mn Block copolymers 41,400 41,800 42,900 39,600 46,300 40,100 39,100 40,500 39,000 38,600 33,700 39,800 38,100 39,800 40,300 45,100 25,000 Polymer block (A) 7,500 7,500 5,600 9,500 13,900 2,800 1,600 5,700 5,100 4,600 3,700 5,200 4,600 5,200 5,200 7,700 3,800 Polymer block (B) 33,900 34,300 37,300 30,100 32,400 37,300 37,500 34,800 33,900 34,000 30,000 34,600 33,500 34,600 35,100 37,400 21,300 Composition ratio Polymer block (A) 18 18 13 twenty four 30 7 4 14 13 12 11 13 12 13 13 17 15 Polymer block (B) 82 82 87 76 70 93 96 86 87 88 89 87 88 87 87 83 85 Number of cross-linking functional groups contained in block (A) per molecule (average number) 3.9 3.9 4.3 3.9 4.1 4.0 3.2 2.2 1.7 2.0 1.2 0.9 0.6 5.9 7.9 12 2.5 Terminal structure (general formula (1) or thiol group) General formula (1) Thiol General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) (x/100)×y 53.4 53.9 51.1 51.1 50.0 50.5 51.2 50.6 50.7 52.1 49.5 51.3 49.9 50.9 51.2 51.0 50.5 Odor intensity (min) 2.0 2.1 1.9 1.7 1.6 1.8 1.8 1.9 1.3 2.1 2.2 1.7 1.8 2.1 2.4 1.6 2.8 Tensile properties Table 1 shows the types of blends A A A A A A A A A A A A A A A A A Ts(MPa) 0.85 0.87 0.86 0.90 0.93 0.55 0.42 0.51 0.23 0.20 0.21 0.15 0.12 0.82 0.85 0.91 0.72 EL(%) 180 100 210 190 150 180 120 270 320 210 330 280 210 220 200 170 240 Tensile strength (Ts*EL/2) 77 44 90 86 70 50 25 69 37 twenty one 35 twenty one 13 90 85 77 86 Table 1 shows the types of blends B B B B B B B B B B B B B B B B B Ts(MPa) 0.99 1.12 0.95 1.02 1.05 0.67 0.54 0.71 0.46 0.86 0.42 0.35 0.28 0.96 0.97 1.01 0.86 EL(%) 320 150 340 310 290 260 220 390 420 540 450 460 300 250 190 180 370 Tensile strength (Ts*EL/2) 158 84 162 158 152 87 59 138 97 232 95 81 42 120 92 91 159

[Table 11] Table 11 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 Comparison Example 1 Comparison Example 2 Comparison Example 3 Block copolymers No. d-18 d-19 d-20 d-21 d-22 d-23 d-24 d-25 d-26 d-27 d-28 d-29 d-30 d-31 e-2 e-4 e-6 Number of blocks three three three three three three two three three three three three three three three three three Mn Block copolymers 15,600 55,300 74,100 92,100 106,300 42,400 38,200 42,800 42,900 43,000 45,100 48,700 99,000 98,000 35,000 37,400 33,300 Polymer block (A) 2,800 6,600 8,200 12,000 17,000 5,100 3,400 5,600 5,600 5,600 5,900 6,300 30,200 13,600 9,700 5,200 3,700 Polymer block (B) 12,800 48,700 65,900 80,100 89,300 37,300 34,800 37,200 37,300 37,400 39,200 42,400 68,800 68,100 25,300 32,200 29,600 Polymer block (C) 16,300 Composition ratio Polymer block (A) 18 12 11 13 16 12 9 13 13 13 13 13 30 14 28 14 11 Polymer block (B) 82 88 89 87 84 88 91 87 87 87 87 87 70 70 72 86 89 Polymer block (C) 17 Number of cross-linking functional groups contained in block (A) per molecule (average number) 2.8 3.9 3.9 3.9 4.0 3.9 2.0 4.3 4.3 4.3 4.3 4.3 - - 2.1 2.0 2.0 Terminal structure (general formula (1) or thiol group) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) General formula (1) None None None (x/100)×y 50.5 50.9 50.4 50.7 51.0 50.9 49.7 50.9 51.1 51.2 53.7 58.0 48.5 47.0 195 104 88.8 Odor intensity (min) 3.5 1.5 1.4 1.2 1.1 1.8 2.0 1.8 1.7 1.7 1.8 2.5 1.2 1.1 4.5 3.4 3.6 Tensile properties Table 1 shows the types of blends A A A A A A - A A A A A - - A A A Ts(MPa) 0.75 0.81 0.78 0.60 0.55 0.84 - 0.82 0.81 0.80 0.80 0.79 - - 0.40 0.36 0.31 EL(%) 220 200 190 210 200 230 - 200 210 220 210 200 - - 300 280 130 Tensile strength (Ts*EL/2) 83 81 74 63 55 97 - 82 85 88 84 79 - - 60 50 20 Table 1 shows the types of blends B B B B B B B B B B B B C C B B B Ts(MPa) 0.74 0.97 0.95 0.75 0.68 0.98 0.43 0.96 0.95 0.96 0.94 0.95 12.0 9.0 0.56 0.55 0.52 EL(%) 350 330 310 300 320 290 600 330 330 320 320 300 550 700 340 330 150 Tensile strength (Ts*EL/2) 130 160 147 113 109 142 129 158 157 154 150 143 3,300 3,150 95 91 39

(Example 32 and Example 33, Comparative Example 4) The triblock copolymers d-2 and d-8 obtained in Preparation Example 2 and Preparation Example 8 and the triblock copolymer e-6 obtained in Comparative Preparation Example 3 were used to prepare a resin composition (Preparation D) according to the above-mentioned formulation table (Table 1), and mixed for 1 hour at a temperature of 60°C and 10 Torr using a planetary mixer to obtain an adhesive composition. Each adhesive composition was tested according to the above-mentioned method, and the test results of the mechanical properties, weather resistance and adhesive strength of the sheet are shown in Table 12.

[Table 12] Table 12 Embodiment 32 Embodiment 33 Comparison Example 4 Block copolymers No. d-2 d-8 e-6 Number of blocks three three three Mn Block copolymers 41,800 40,500 33,300 Polymer block (A) 7,500 5,700 3,700 Polymer block (B) 34,300 34,800 29,600 Composition ratio Polymer block (A) 18 14 11 Polymer block (B) 82 86 89 Number of cross-linking functional groups contained in block (A) per molecule (average number) 3.9 2.2 2.0 Terminal structure (general formula (1) or thiol group) Thiol General formula (1) None (x/100)×y 53.9 50.6 88.8 Odor intensity (min) 2.1 1.9 3.6 Table 1 shows the types of blends D D D Tensile properties Ts(MPa) 1.23 0.83 0.44 EL(%) 70 160 90 Tensile strength (Ts*EL/2) 86 133 40 Weather resistance Surface condition No change No change Cracks Color difference ⊿E 5 3 14 Then the strength Strength (MPa) 1.8 1.5 1.1 Destruction Cohesion Cohesion Cohesion

<Odor intensity and mechanical properties> The results of Examples 1 to 33 clearly show that the block copolymer of the present invention significantly reduces the odor when exposed to high temperatures, and the sheets obtained from the resin compositions (blending A, B, C, and D) containing the block copolymers show good mechanical properties (elongation at break and strength at break) and excellent toughness. Among them, Examples 1 to 29 (blending A and B) are particularly suitable for use as sealing materials, and Examples 30 and 31 (blending C) are particularly suitable for use as elastomers. In contrast, the block copolymers (Comparative Examples 1 to 4) in which the product of (x/100) and y exceeds 60 have severe odor when exposed to high temperatures and are difficult to use in practice.

<Weather resistance and bonding strength> The results of Examples 32 and 33 clearly show that the sheet obtained from the resin composition containing the block copolymer of the present invention (formulation D) has excellent weather resistance, and when the resin composition is used as an adhesive for exterior tiles, it has excellent bonding strength. Therefore, it can be said that the resin composition of the present invention is particularly suitable for use as a sealing material and an adhesive for exterior tiles. In contrast, the sheet obtained from the resin composition containing a block copolymer in which the product of (x/100) and y exceeds 60 (Comparison Example 4) has poor weather resistance and bonding strength. [Industrial Applicability]

The block copolymer significantly reduces the odor when exposed to high temperature, thereby improving the toughness of the molded product of the resin composition containing the block copolymer. Therefore, it can be used as a sealant, adhesive, adhesive, coating, elastomer, etc., and is particularly suitable for use as a sealant and exterior tile adhesive because of its excellent weather resistance. The adhesive composition containing the resin composition of the present invention is also excellent in adhesion, so it can be suitably used as an adhesive for exterior tiles.

without

without

Claims (10)

A block copolymer comprising at least two polymer blocks, wherein at least one terminal structure of the block copolymer is a structure represented by the following general formula (1) or a thiol group, wherein the block copolymer has at least one polymer block (A) and at least one polymer block (B), wherein the polymer block (A) contains an average of at least 0.7 cross-linking functional groups per molecule, and when the sulfur concentration (mass %) in the block copolymer is x and the number average molecular weight of the block copolymer is y, the product of (x/100) and y is 60 or less;

(R refers to an alkyl group, an aryl group or an aralkyl group having 1 to 30 carbon atoms). The block copolymer as described in claim 1, wherein the block copolymer has a structural unit comprising polymer block (A)/polymer block (B)/polymer block (A). The block copolymer as described in claim 1, wherein the block copolymer has a structural unit comprising polymer block (A)/polymer block (B)/polymer block (C). A block copolymer as described in any one of claim 1 to claim 3, wherein at least one polymer block of the block copolymer has a (meth)acrylate compound as the main constituent monomer. A resin composition comprising a block copolymer as described in any one of claims 1 to 4. The resin composition as described in claim 5 further comprises a polyoxyalkylene polymer having a cross-linking functional group. The resin composition as described in claim 5 or claim 6 is suitable for use as any of sealants, adhesives, adhesives, coatings or elastomers. A method for producing a block copolymer, wherein the block copolymer comprises at least two polymer blocks, and the method comprises: a step of producing a block copolymer (P1) comprising at least three polymer blocks and having a trithiocarbonate group represented by the following general formula (2) on the central polymer block of the block copolymer by a reversible addition-fragmentation chain transfer type living free radical polymerization method; and a step of reacting the trithiocarbonate group of the block copolymer (P1) with a nucleophile to produce a block copolymer (P2) having at least one polymer block (A) and one polymer block (B); wherein the polymer block (A) has a crosslinking functional group,

A method for producing a block copolymer as described in claim 8, wherein at least one polymer block of the block copolymer (P2) has a (meth)acrylate compound as a main constituent monomer, at least one terminal structure of the block copolymer (P2) is a structure represented by the following general formula (1) or a thiol group, and when the sulfur concentration (mass %) in the block copolymer (P2) is x and the number average molecular weight of the block copolymer (P2) is y, the product of (x/100) and y is 60 or less;

(R refers to an alkyl group, an aryl group or an aralkyl group having 1 to 30 carbon atoms). A method for producing a block copolymer as described in claim 8 or claim 9, wherein the polymer block (A) contains an average of 0.7 or more of the cross-linking functional groups per molecule.