阅读说明：本技术 嵌段共聚物组合物及其制造方法 (Block copolymer composition and method for producing same ) 是由 新纳洋 茶谷俊介 许书尧 后藤淳 肖龙强 臧俊杰 于 2018-11-22 设计创作，主要内容包括：提供一种包含具有规定分子结构的嵌段共聚物,分子量分布为适度的范围的嵌段共聚物组合物。获得一种包含嵌段共聚物的嵌段共聚物组合物,所述嵌段共聚物对聚合性组合物进行聚合,全部嵌段的结构单元来源于乙烯基单体,至少一个嵌段具有支化结构；其中,聚合性组合物包含：在聚(甲基)丙烯酸酯链段的一个末端上具备具有自由基反应性不饱和双键的基团的大分子单体(A)、乙烯基单体(B)和有机碘化合物(C),或聚合性组合物包含：大分子单体(A)、乙烯基单体(B)、偶氮系自由基聚合引发剂(E)和碘。(Disclosed is a block copolymer composition which contains a block copolymer having a predetermined molecular structure and has a molecular weight distribution within an appropriate range. Obtaining a block copolymer composition comprising a block copolymer which polymerizes a polymerizable composition, structural units of all blocks being derived from a vinyl monomer, at least one block having a branched structure; wherein the polymerizable composition comprises: a macromonomer (a) having a group having a radically reactive unsaturated double bond at one end of a poly (meth) acrylate segment, a vinyl monomer (B), and an organoiodine compound (C), or a polymerizable composition comprising: a macromonomer (A), a vinyl monomer (B), an azo-based radical polymerization initiator (E), and iodine.)

1. A block copolymer composition comprising a block copolymer,

all the blocks of the block copolymer have structural units derived from vinyl monomers, at least one block has a branched structure, and the main chain and the branched chain are composed of the same structural unit.

2. A block copolymer composition comprising a block copolymer,

all blocks of the block copolymer have structural units derived from a vinyl monomer, at least one block has a branched structure,

the molecular weight distribution Mw/Mn of the block copolymer composition is 1.5-3.4.

3. The block copolymer composition of claim 2, the backbone and branches of the branched structure being comprised of the same structural units.

4. The block copolymer composition according to any one of claims 1 to 3, wherein the structural unit of at least one block is derived from a methacrylate-based monomer or an acrylate-based monomer.

5. The block copolymer composition according to any one of claims 1 to 4, wherein the block copolymer has an iodine atom at a terminal of a main chain thereof.

6. The block copolymer composition according to any one of claims 1 to 5, having a number average molecular weight Mn of 3,000 or more.

7. A block copolymer composition comprising a block copolymer,

the block copolymer composition is obtained by polymerizing a polymerizable composition comprising a macromonomer (A) represented by the following formula (I), a vinyl monomer (B) and an organoiodine compound (C),

[ CHEM 1]

In the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; z is a hydrogen atom or a group derived from a radical polymerization initiator; x¹～XⁿEach independently is a hydrogen atom or a methyl group; n is an integer of 2-10,000.

8. The block copolymer composition according to claim 7, which contains a block copolymer,

the block derived from the vinyl monomer (B) of the block copolymer has a branched structure, and the main chain and the branches are composed of the same structural unit.

9. The block copolymer composition according to claim 7 or 8, which contains a block copolymer,

the block derived from the vinyl monomer (B) of the block copolymer has a branched structure,

the molecular weight distribution of the block copolymer composition is 1.5-3.4.

10. The block copolymer composition according to any one of claims 7 to 9, wherein the block copolymer has an iodine atom at a terminal of a main chain.

11. The block copolymer composition according to any one of claims 7 to 10, wherein the vinyl monomer (B) is at least one selected from the group consisting of styrene monomers, methacrylate monomers and acrylate monomers.

12. A process for producing a block copolymer composition by polymerizing a polymerizable composition comprising a macromonomer (A) represented by the following formula (I), a vinyl monomer (B) and an organoiodine compound (C),

[ CHEM 2]

In the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; z is a hydrogen atom or a group derived from a radical polymerization initiator; x¹～XⁿEach independently is a hydrogen atom or a methyl group; n is an integer of 2-10,000.

13. The method for producing a block copolymer composition according to claim 12, wherein the polymerizable composition further contains either one or both of a catalyst (D) and an azo-based radical polymerization initiator (E).

14. A process for producing a block copolymer composition by polymerizing a polymerizable composition comprising a macromonomer (A) represented by the following formula (I), a vinyl monomer (B), an azo radical polymerization initiator (E) and iodine,

[ CHEM 3]

In the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; z is a hydrogen atom or a group derived from a radical polymerization initiator; x¹～XⁿEach independently is a hydrogen atom or a methyl group; n is an integer of 2-10,000.

15. The method for producing a block copolymer composition according to claim 14, wherein the polymerizable composition further contains a catalyst (D).

16. The method for producing a block copolymer composition according to claim 14, which satisfies at least one of the following formulas (i) or (ii),

(i)0＜[Q]/[P]＜0.60

wherein [ P ] represents the number of molar equivalents of the azo-based radical polymerization initiator (E), and [ Q ] represents the number of molar equivalents of iodine;

(ii)0＜Tp-T₁₀＜40

wherein Tp represents a polymerization temperature, T, at which the polymerizable composition is polymerized₁₀Represents a 10-hour half-life temperature ℃ of the azo radical polymerization initiator (E).

17. The method for producing a block copolymer composition according to claim 13 or 15, wherein the catalyst (D) is at least one selected from the group consisting of the following catalysts (D1) to (D6),

catalyst (D1): a non-metallic compound containing a halide ion and a non-metallic atom in a cationic state forming an ionic bond with the halide ion;

catalyst (D2): a compound comprising a carbon atom and at least one halogen atom directly bonded to the carbon atom, or a hydrocarbon compound as a precursor of the compound;

catalyst (D3): an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom and having redox properties;

catalyst (D4): a compound selected from the group consisting of ethylene, acetylene oligomers, polyacetylene, fullerene, carbon nanotubes, and derivatives thereof;

catalyst (D5): halogenated alkali metal compounds or halogenated alkaline earth metal compounds;

catalyst (D6): a compound selected from the group consisting of phosphorus compounds, nitrogen-containing compounds and oxygen-containing compounds other than the catalysts (D1) to (D5).

18. The method for producing a block copolymer composition according to any one of claims 12 to 17, wherein the vinyl monomer (B) is at least one selected from the group consisting of styrene monomers, methacrylate monomers and acrylate monomers.

Technical Field

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

The present application claims priority based on japanese application No. 2017-226326, 2018-092436, 2018-153588, 11-17, 2017-24, and is incorporated herein by reference.

Background

Polymers obtained by polymerizing vinyl monomers are used in various applications, and in particular, copolymers obtained by copolymerizing 2 or more vinyl monomers are widely used in order to meet various physical property requirements. However, when 2 or more vinyl monomers are mixed and copolymerized, the properties of each monomer unit are averaged, and it tends to be difficult to obtain desired physical properties. Even when 2 or more polymers are mixed, since these polymers are not uniformly mixed with each other, the properties of the monomer units of the respective polymers are often not sufficiently obtained.

As a copolymer which easily exhibits the characteristics of each monomer unit, a block copolymer is known. Since a block copolymer cannot be obtained by ordinary radical polymerization, living anion polymerization, living radical polymerization, or the like is used. According to living anion polymerization, living radical polymerization, or the like, a block copolymer can be produced while controlling the molecular weight and the molecular weight distribution, and a block copolymer having a narrow molecular weight distribution can be obtained. However, since a special compound or metal catalyst is used in the polymerization, a step of removing the compound or catalyst is required, which is industrially complicated.

As a method for producing a block copolymer, a method using a macromonomer that is a high molecular weight monomer having a radical reactive functional group is also known (for example, patent document 1). However, in the method using the macromonomer, it is difficult to control the molecular structure and the molecular weight distribution.

[ Prior art documents ]

[ patent document ]

[ patent document 1] International publication No. 2015/056668

Disclosure of Invention

[ problem to be solved by the invention ]

The purpose of the present invention is to provide a block copolymer composition containing a block copolymer having a predetermined molecular structure.

Further, an object of the present invention is to provide a block copolymer composition containing a block copolymer having a predetermined molecular structure and having a molecular weight distribution within an appropriate range.

Further, an object of the present invention is to provide a method for producing a block copolymer composition, which can sufficiently control a molecular structure and a molecular weight distribution.

[ MEANS FOR SOLVING PROBLEMS ] to solve the problems

The present invention has the following configuration.

[1] A block copolymer composition comprising a block copolymer,

the structural units of all blocks of the block copolymer are derived from vinyl monomers,

at least one of the blocks has a branched structure, and the main chain and the branches are composed of the same structural unit.

[2] A block copolymer composition comprising a block copolymer in which structural units of all blocks are derived from a vinyl monomer, at least one block has a branched structure,

the block copolymer composition has a molecular weight distribution (Mw/Mn) of 1.5 to 3.4.

[3] The block copolymer composition according to [2], wherein the main chain and the branch chain of the branched structure are composed of the same structural unit.

[4] The block copolymer composition according to any one of [1] to [3], wherein the structural unit of at least one block is derived from a methacrylate-based monomer or an acrylate-based monomer.

[5] The block copolymer composition according to any one of [1] to [4], wherein the block copolymer has an iodine atom at a terminal of a main chain thereof.

[6] The block copolymer composition according to any one of [1] to [5], which has a number average molecular weight Mn of 3,000 or more.

[7] A block copolymer composition comprising a block copolymer obtained by polymerizing a polymerizable composition comprising a macromonomer (A) represented by the following formula (I), a vinyl monomer (B), and an organoiodine compound (C).

[ CHEM 1]

(in the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Z is a hydrogen atom or a group derived from a radical polymerization initiator. X¹～XⁿEach independently is a hydrogen atom or a methyl group. N is 2 &An integer of 10,000. )

[8] The block copolymer composition according to [7], which comprises a block copolymer whose block derived from the vinyl monomer (B) has a branched structure, and whose main chain and branch chain are composed of the same structural unit.

[9] The block copolymer composition according to [7] or [8], which comprises a block copolymer having a branched structure in a block derived from the vinyl monomer (B), and has a molecular weight distribution of 1.5 to 3.4.

[10] The block copolymer composition according to any one of [7] to [9], wherein the block copolymer has an iodine atom at a terminal of a main chain.

[11] The block copolymer composition according to any one of [7] to [10], wherein the vinyl monomer (B) is at least one selected from the group consisting of styrene monomers, methacrylate monomers and acrylate monomers.

[12] A method for producing a block copolymer composition by polymerizing a polymerizable composition comprising a macromonomer (A) represented by the following formula (I), a vinyl monomer (B), and an organoiodine compound (C).

[ CHEM 2]

(in the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Z is a hydrogen atom or a group derived from a radical polymerization initiator. X¹～XⁿEach independently is a hydrogen atom or a methyl group. N is an integer of 2-10,000. ),

[13] the method for producing a block copolymer composition according to [12], wherein the polymerizable composition further comprises either or both of a catalyst (D) and an azo radical polymerization initiator (E).

[14] A method for producing a block copolymer composition by polymerizing a polymerizable composition comprising a macromonomer (A) represented by the following formula (I), a vinyl monomer (B), an azo radical polymerization initiator (E), and iodine.

[ CHEM 3]

(in the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Z is a hydrogen atom or a group derived from a radical polymerization initiator. X¹～XⁿEach independently is a hydrogen atom or a methyl group. N is an integer of 2-10,000. )

[15] The method for producing a block copolymer composition according to [14], wherein the polymerizable composition further contains a catalyst (D).

[16] The method for producing a block copolymer composition according to [14], which satisfies at least one of the following formulae (i) and (ii).

(i)0＜[Q]/[P]＜0.60

(wherein [ P ] represents the number of molar equivalents of the azo-based radical polymerization initiator (E) and [ Q ] represents the number of molar equivalents of iodine.)

(ii)0＜Tp-T₁₀＜40

(wherein Tp represents a polymerization temperature (. degree. C.) for polymerizing the polymerizable composition, and T represents₁₀Represents a 10-hour half-life temperature (. degree. C.) of the azo radical polymerization initiator (E). )

[17] The method for producing a block copolymer composition according to [13] or [15], wherein the catalyst (D) is at least one selected from the group consisting of the following catalysts (D1) to (D6).

Catalyst (D1): a non-metallic compound containing a halide ion and a non-metallic atom in a cationic state forming an ionic bond with the halide ion.

Catalyst (D2): a compound comprising a carbon atom, at least one halogen atom directly bonded to said carbon atom, or a hydrocarbon compound as a precursor of said compound.

Catalyst (D3): an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom and having redox properties.

Catalyst (D4): a compound selected from the group consisting of ethylene, acetylene oligomers, polyacetylene, fullerenes, carbon nanotubes, and derivatives thereof.

Catalyst (D5): halogenated alkali metal compounds or halogenated alkaline earth metal compounds.

Catalyst (D6): a compound selected from the group consisting of phosphorus compounds, nitrogen-containing compounds and oxygen-containing compounds other than the catalysts (D1) to (D5).

[18] The method for producing a block copolymer composition according to any one of [12] to [17], wherein the vinyl monomer (B) is at least one selected from the group consisting of styrene monomers, methacrylate monomers and acrylate monomers.

[ Effect of the invention ]

According to the present invention, a block copolymer composition having an appropriate viscosity and good workability and suitable for a dispersant, a resin additive, and the like can be obtained.

Further, according to the present invention, a block copolymer composition comprising a block copolymer having a molecular structure and a molecular weight distribution sufficiently controlled to have a specific molecular structure with a molecular weight distribution in an appropriate range can be obtained.

Detailed Description

(term description)

"Block copolymer" means a copolymer having a plurality of blocks in a polymer, and the blocks adjacent to each other have different constitutions (chemical structures). For example, adjacent blocks are made up of structural units derived from different monomers.

"macromonomer" means a monomer having a functional group (radical-polymerizable functional group or addition-reactive functional group) having radical reactivity, generally having a repeating structure, and a relatively large molecular weight. Preferably, the terminal has a functional group.

"vinyl monomer" means a compound containing at least one vinyl group (carbon-carbon unsaturated double bond).

"(meth) acrylate" means "acrylate" or "methacrylate".

"organoiodine compound" means a compound having a carbon-iodine bond in 1 molecule.

[ Block copolymer composition ]

The block copolymer composition according to the first aspect of the present invention is a block copolymer composition containing a block copolymer in which all the structural units of the blocks are derived from a vinyl monomer, at least one of the blocks has a branched structure, and the main chain and the branches are composed of the same structural unit. The block copolymer composition of the first embodiment of the present invention is preferably a block copolymer composition containing such a block copolymer as a main component, and more preferably a block copolymer composition substantially composed of such a block copolymer.

The block copolymer composition according to the second aspect of the present invention is a block copolymer composition comprising a block copolymer having a molecular weight distribution (Mw/Mn) of 1.5 to 3.4, wherein all the blocks of the block copolymer have structural units derived from a vinyl monomer, and at least one block has a branched structure. The block copolymer composition of the second embodiment of the present invention is preferably a block copolymer composition containing such a block copolymer as a main component, and more preferably a block copolymer composition substantially composed of such a block copolymer.

The block copolymer contained in the block copolymer composition of the present invention has a branched structure. The number of branched structures, i.e., the number of branches, of the block copolymer is preferably 1 to 8, more preferably 2 to 7, on average per 1 molecule. When the number of branches is not less than the lower limit, the viscosity is lowered and the workability is improved. When the number of branches is not more than the upper limit, the phase separation structure of the block copolymer becomes more clear, and the function of dispersion or the like by the block copolymer composition is easily expressed, which is preferable.

In the present invention, it is preferable that the main chain and the branch chain of the block having a branched structure of the block copolymer are composed of the same structural unit. Further, "the main chain and the branch chain are composed of the same structural unit" means that the structural unit of the branch chain is the same as the structural unit of the main chain in which the branch portion occurs.

The block copolymer has a branched structure, so that the viscosity is reduced, and the main chain and the branch chain of the block are composed of the same structural unit, so that the properties of each structural unit are sufficiently expressed as a block. Therefore, the block copolymer composition of the present invention is excellent in handling properties and exhibits high functions as various additives such as a resin additive, a dispersant, a coating composition, and a polymer for lithography.

The branched structure of the block copolymer contained in the block copolymer composition can be confirmed, for example, by the following method.

The degree of branching can be estimated by the Mark-Houwink-Sakurad (Mark-Houwink-Sakurad) formula as follows.

η＝K×M^a

(eta: intrinsic viscosity, M: absolute molecular weight, K and a being constants)

The K for a given polymer in the same solvent at the same temperature and concentration is constant, the index term a alone reflects the degree of branching of the polymer, and a decrease in the value of a indicates an increase in branching. The index "a" as an index of branching can be calculated, for example, from the slope of a logarithmic graph (Mark-Houwink-Sagita plot) of intrinsic viscosity and absolute molecular weight measured by GPC-TDA. Since at least one block of the block copolymer contained in the block copolymer composition of the present invention has a branched structure, the value of a is generally smaller than that of a typical linear polymer having a flexible chain (a > 0.7).

In addition, if proceed¹³When the quaternary carbon adjacent methine group is detected at 38 to 41ppm by C-NMR measurement, the block copolymer is judged to have a branched structure. Further, based on the peak intensity, the average number of branches per 1 molecule of the block copolymer in the block copolymer composition can be determined.

Regarding the matter that the main chain and the branch chain are composed of the same structural unit, the measurement results can be obtained by¹H-NMR was confirmed by tracing the change of composition during the polymerization.

The block copolymer composition of the present invention has substantially all of the structural units of the blocks derived from a vinyl monomer. However, the polymer may have a structural unit derived from a monomer other than a vinyl monomer within a range not significantly affecting the effect of the present invention.

Examples of the vinyl monomer include those exemplified as the vinyl monomer (B) described later. Each block may consist of 1 vinyl monomer or more than 2. Preferably, the structural unit of at least one block of the block copolymer of the present invention is derived from a methacrylate-based monomer or an acrylate-based monomer.

Preferably, the block copolymer of the present invention has an iodine atom at the end of the main chain. The terminal of the main chain having an iodine atom can be introduced with a functional group by substituting the iodine atom at the terminal with a nucleophile. If the treatment is carried out at a high temperature as required, the terminal iodine atom may be removed.

The functional group can be introduced by substitution with a nucleophile, and examples thereof include an alkyl group, an amino group, an amide group, and a carboxyl group. For example, a block copolymer having a polar group such as an amino group or a carboxyl group at the end of the main chain exhibits particularly excellent performance as a dispersant due to interaction such as adsorption to a dispersion medium. In this case, the terminal amino group or carboxyl group may have an alkylene structure (- (CH) with the main chain of the polymer₂)_n-)。

The value of the molecular weight distribution (Mw/Mn) (hereinafter, also simply referred to as "Mw/Mn") of the block copolymer composition of the present invention is preferably 1.5 or more, more preferably 1.6 or more, and further preferably 1.7 or more. The value of Mw/Mn is preferably 3.4 or less, more preferably 3.2 or less, still more preferably 3.0 or less, and particularly preferably 2.8 or less. The Mw/Mn of the block copolymer composition of the present invention is preferably 1.5 to 3.4. When the Mw/Mn is not more than the upper limit of the above range, it is easy to control the phase structure of the block copolymer composition at a high level. When the Mw/Mn is not less than the lower limit of the above range, the melt viscosity and the solution viscosity of the block copolymer composition decrease, and the workability improves.

The block copolymer composition of the present invention has a number average molecular weight (hereinafter also referred to as "Mn") of preferably 3,000 or more at the lower limit, more preferably 5,000 or more, and still more preferably 10,000 or more at the upper limit, and preferably 1,000,000 or less, more preferably 500,000 or less, and still more preferably 200,000 or less at the upper limit. The Mn of the block copolymer composition of the present invention is preferably 3,000 to 1,000,000. When the Mn of the block copolymer composition is not less than the lower limit of the above range, the mechanical strength of a molded article or a coating film comprising the block copolymer composition tends to be good. When the Mn of the block copolymer composition is not more than the upper limit of the above range, the solubility, melt viscosity, and solution viscosity suitable for obtaining a molded article or a coating film can be obtained.

The Mn and Mw/Mn are values calculated based on a calibration curve of polymethyl methacrylate (PMMA) using Gel Permeation Chromatography (GPC).

The block copolymer composition of the present invention has a phase structure, has functions such as high dispersibility possessed by the block copolymer, exhibits good solubility and melt viscosity, and can be suitably used as a dispersant, a resin additive, and the like. The dispersant and the resin additive are usually treated in a solution state or a mixed state with other resin materials, and a low viscosity is preferable in view of workability. In the case of a polymer having an equivalent molecular weight, the narrower the molecular weight distribution, the higher the viscosity, and the broader the molecular weight distribution, the lower the viscosity, but the lower the molecular weight distribution, the more excellent the function as a dispersant or a resin additive tends to be. Further, even if the molecular weight is the same, the viscosity is lowered because the polymer has a branched structure.

In order to exhibit excellent functions as a dispersant and a resin additive and to improve workability such as viscosity, it is preferable that the block copolymer composition has a molecular weight distribution within the above range and contains a block copolymer having the above branched structure.

[ method for producing Block copolymer composition ]

The method for producing the block copolymer composition of the present invention is not particularly limited, but a preferred production method is described below.

The method for producing the block copolymer composition of the first embodiment of the present invention includes a method for obtaining a block copolymer composition by polymerizing a polymerizable composition containing a macromonomer (a), a vinyl monomer (B), and an organoiodine compound (C).

(macromonomer (A))

The macromonomer (A) is represented by the formula (I).

In the formula (I), "…" represents a state in which the monomer unit is polymerized. The macromonomer (a) has, at one end of a poly (meth) acrylate segment: groups with free-radically reactive unsaturated double bonds.

[ CHEM 4]

In the formula (I), R and R¹～RⁿEach independently is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Z is a hydrogen atom or a group derived from a radical polymerization initiator. X¹～XⁿEach independently is a hydrogen atom or a methyl group. n is an integer of 2-10,000.

R and R¹～RⁿThe alkyl group, cycloalkyl group, aryl group and heterocyclic group in (1) may have a substituent.

R and R¹～RⁿPreferably at least 1 selected from alkyl and cycloalkyl, more preferably alkyl.

As R and R¹～RⁿExamples of the alkyl group of (2) include a branched or straight-chain alkyl group having 1 to 20 carbon atoms. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group, and particularly preferably a methyl group, from the viewpoint of controlling the easiness of polymerization.

As R and R¹～RⁿExamples of the cycloalkyl group of (2) include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and adamantaneAnd (4) a base. The cycloalkyl group is preferably a cyclopropyl group, a cyclobutyl group or an adamantyl group in view of controlling easiness of polymerization.

As R and R¹～RⁿExamples of the aryl group of (2) include aryl groups having 6 to 18 carbon atoms. Specific examples of the aryl group having 6 to 18 carbon atoms include phenyl, benzyl and naphthyl.

As R and R¹～RⁿExamples of the heterocyclic group of (2) include heterocyclic groups having 5 to 18 carbon atoms. Examples of the hetero atom contained in the heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom. Specific examples of the heterocyclic group include a γ -lactone group, a caprolactone group and a morpholine group.

As R and R¹～RⁿExamples of the substituent in (1) include, independently, an alkyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group (-COOR '), a carbamoyl group (-CONR' R '), a cyano group, a hydroxyl group, an amino group, an amide group (-NR' R ')), a halogen atom, an allyl group, an epoxy group, an alkoxy group (-OR'), and a group showing hydrophilicity OR ionicity. R 'or R' are each independently the same group as R (wherein, excluding heterocyclic groups).

About as R and R¹～RⁿExamples of the alkoxycarbonyl group as the substituent of (3) include methoxycarbonyl group.

About as R and R¹～RⁿAs the carbamoyl group as the substituent(s) of (1), there may be mentioned N-methylcarbamoyl group and N, N-dimethylcarbamoyl group.

About as R and R¹～RⁿExamples of the halogen atom of the substituent(s) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

About as R and R¹～RⁿExamples of the alkoxy group as the substituent(s) include alkoxy groups having 1 to 12 carbon atoms, and specific examples thereof include methoxy groups.

About as R and R¹～RⁿExamples of the substituent(s) in (b) include a hydrophilic or ionic group such as an alkali metal salt of a carboxyl group or a sulfinyl group (sulfinyl), a poly (oxyalkylene) group such as a polyoxyethylene group or a polyoxypropylene group, and a cationic substituent such as a quaternary ammonium salt group.

X¹～XⁿEach independently is a hydrogen atom or a methyl group, preferably a methyl group.

In the macromonomer (A), X is preferred from the viewpoint of ease of synthesis¹～XⁿMore than half of them are methyl groups.

Z is a hydrogen atom or a group (fragment) derived from a radical polymerization initiator, and examples thereof include the same groups as the terminal groups of a polymer obtained by a known radical polymerization. In the case where a radical polymerization initiator is not used in the production, Z is a hydrogen atom.

n means the number of monomer units in the molecule of the macromonomer (A) 1. n is an integer of 2 to 10,000, preferably an integer of 10 to 1,000, and more preferably an integer of 30 to 500.

The Mn of the macromonomer (A) is preferably 1,000 to 1,000,000. When Mn of the macromonomer (a) is not less than the lower limit of the above range, the physical properties, particularly the mechanical properties of the block copolymer tend to be good. The Mn of the macromonomer (a) is more preferably 3,000 or more, and further preferably 5,000 or more. Further, Mn of the macromonomer (a) is more preferably 500,000 or less, further preferably 300,000 or less, and particularly preferably 100,000 or less.

The Mw/Mn of the macromonomer (A) is preferably 1.0 to 5.0, more preferably 1.5 to 3.0.

Mn and Mw/Mn of the macromonomer (A) are values calculated based on a calibration curve of polymethyl methacrylate (PMMA) using Gel Permeation Chromatography (GPC).

The macromonomer (a) of the present invention contains a vinyl monomer unit as a structural unit, but the vinyl monomer used for obtaining the macromonomer (a) can be selected independently of the vinyl monomer (B) as a copolymer component described later.

As examples of the vinyl monomer used for obtaining the macromonomer (A), there can be exemplified methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, n-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, t-butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate.

Examples of commercially available products of these vinyl monomers include PLACCEL FM (trade name, caprolactone addition monomer of (meth) acrylate, product of xylonite chemical corporation), BLEMMER PME-100 (trade name, methoxypolyethylene glycol methacrylate (product of ethylene glycol chain 2), product of Nippon oil Co., Ltd.), BLEMMER PME-200 (trade name, methoxypolyethylene glycol methacrylate (product of ethylene glycol chain 4, product of Nippon oil Co., Ltd.), BLEMER PME-400 (trade name, methoxypolyethylene glycol methacrylate (product of ethylene glycol chain 9), product of Nippon oil Co., Ltd.), BLEMER 50POEP-800B (trade name, product of octyloxypolyethylene glycol-polypropylene glycol-methacrylate (product of ethylene glycol chain 8, propylene glycol chain 6), product of Nippon oil Co., Ltd.) and BLEMER 20ANEP-600 (trade name, nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate, manufactured by Nippon oil Co., Ltd.), BLEMER AME-100 (trade name, manufactured by Nippon oil Co., Ltd.), BLEMER AME-200 (trade name, manufactured by Nippon oil Co., Ltd.), and BLEMER 50AOEP-800B (trade name, manufactured by Nippon oil Co., Ltd.).

Among these examples, methacrylic acid esters are preferable from the viewpoint of controlling the ease of polymerization.

The methacrylate is preferably methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate or 4-hydroxybutyl methacrylate, more preferably methyl methacrylate, n-butyl methacrylate or 2-ethylhexyl methacrylate, and particularly preferably methyl methacrylate, from the viewpoint of transparency of the molded article or coating film.

Further, among these examples, it is preferable that an acrylic ester is contained in addition to a methacrylic ester from the viewpoint of obtaining a copolymer excellent in the residence deterioration resistance.

The acrylic acid ester is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, or tert-butyl acrylate, and from the viewpoint of easiness of obtaining, methyl acrylate is preferred.

The vinyl monomer used for obtaining the macromonomer (A) may contain other vinyl monomers than methacrylic acid esters and acrylic acid esters.

As the other vinyl monomer, unsaturated carboxylic acid is preferable. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

The vinyl monomers used for obtaining the macromonomer (A) may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the methacrylic acid ester in the total of the vinyl monomers used for obtaining the macromonomer (A) is preferably 80 to 99.5% by mass, more preferably 82 to 99% by mass, further preferably 84 to 99% by mass, and particularly preferably 85 to 99% by mass, based on the total mass of the vinyl monomers, from the viewpoint of the residence deterioration resistance of the copolymer.

The content of the acrylic ester in the total amount of the vinyl monomers used for obtaining the macromonomer (A) is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, based on the total mass of the vinyl monomers.

As the macromonomer (A), 1 kind may be used alone, or 2 or more kinds may be used in combination.

Examples of the method for producing the macromonomer (A) include a method of producing the macromonomer using a cobalt chain transfer agent (see, U.S. Pat. No. 4680352), a method of using an α -substituted unsaturated compound such as α -bromomethylstyrene as a chain transfer agent (see, International publication No. 88/04304), a method of chemically bonding polymerizable groups (see, Japanese patent laid-open Nos. Sho 60-133007 and 5147952), and a method of thermally decomposing the polymerizable groups (see, Japanese patent laid-open No. Hei 11-240854).

The method for producing the macromonomer (a) is preferably a method of producing the macromonomer using a cobalt chain transfer agent, from the viewpoint of using a catalyst having a high chain transfer constant with a small number of production steps. By using a cobalt chain transfer agent having a high chain transfer constant, a small amount of macromonomer (A) having a controlled molecular weight can be obtained.

Examples of the method for producing the macromonomer (a) using a cobalt chain transfer agent include aqueous dispersion polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these, from the viewpoint of simplifying the recovery process of the macromonomer (a), aqueous dispersion polymerization methods such as suspension polymerization method and emulsion polymerization method are preferable, and suspension polymerization is particularly preferable.

As the cobalt chain transfer agent, those described in the specification of U.S. Pat. No. 4680352 can be used. As the cobalt chain transfer agent, a complex of monovalent cobalt obtained by the reaction of cobalt (II) acetate with diphenylglyoxime, boron trifluoride diethyl etherate, may also be used.

The amount of the cobalt chain transfer agent used is preferably 0.1 to 50ppm, more preferably 1 to 25ppm, based on the total amount of the vinyl monomers used for producing the macromonomer (A).

Examples of the solvent used in obtaining the macromonomer (A) by the solution polymerization method include hydrocarbons such as toluene; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane and chloroform; ketones such as acetone; alcohols such as methanol; nitriles such as acetonitrile; vinyl esters such as ethyl acetate; carbonates such as ethylene carbonate; and supercritical carbon dioxide. As the solvent, can be used alone, can also be used in combination with 2 or more.

Specific examples of the method for producing the macromonomer (a) include the following methods.

A raw material composition comprising a dispersant, a water-soluble salt, a vinyl monomer, a cobalt chain transfer agent, and a polymerization initiator is prepared. And carrying out suspension polymerization on the raw material composition at 70-100 ℃ for 2-7 hours to prepare an aqueous suspension containing the macromonomer (A). From the resulting aqueous suspension, the macromonomer (A) is recovered by filtration.

As the macromonomer (a), a substance obtained by suspension polymerization of a vinyl monomer using a cobalt chain transfer agent is preferable. In the production of the copolymer, a powdery product obtained by recovering and purifying the macromonomer (A) produced by the above-mentioned method may be used, or an aqueous suspension containing the synthesized macromonomer (A) in suspension polymerization may be used as it is.

As the macromonomer (A), commercially available products can be used. As a commercially available product of the macromonomer (A), ELVACITE (ELVACITE; registered trademark) series (manufactured by Lucite International Co., Ltd.) can be exemplified.

(vinyl monomer (B))

As the vinyl monomer (B), the same monomers as those exemplified as the vinyl monomer used for obtaining the macromonomer (A) can be exemplified.

The vinyl monomer (B) may be used alone in 1 kind or in combination of 2 or more kinds.

The vinyl monomer (B) is preferably at least one selected from the group consisting of styrene monomers, methacrylate monomers, and acrylate monomers from the viewpoint of controlling polymerization.

As styrenic monomers, mention may be made of styrene, α -methylstyrene, o-, m-or p-methoxystyrene, o-, m-or p-tert-butoxystyrene, o-, m-or p-chloromethylstyrene, o-, m-or p-chlorostyrene, o-, m-or p-hydroxystyrene, o-, m-or p-styrenesulfonic acid and derivatives thereof, sodium o-, m-or p-styrenesulfonate, o-, m-or p-styreneboronic acid and derivatives thereof. Among them, styrene is preferable from the viewpoint of controlling the polymerization.

As the methacrylate-based monomer and the acrylate-based monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth), 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, n-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, t-butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate; more preferred are methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and methoxyethyl acrylate.

(organic iodine Compound (C))

In the method for producing a block copolymer composition according to the first aspect of the present invention, an organoiodine compound (C) having a carbon-iodine bond (dormant species) is added, and iodine imparted to a growing chain from the organoiodine compound (C) is used as a protecting group. The organic iodine compound (C) is not particularly limited as long as it has at least 1 carbon-iodine bond in the molecule and functions as a dormant species. As the organic iodine compound (C), a compound containing 1 or 2 iodine atoms in 1 molecule is preferable.

The organic iodine compound (C) may be added to the polymerizable composition as the organic iodine compound (C), or may be added to the polymerizable composition as another compound to react with the polymerizable composition to produce the organic iodine compound (C).

Examples of the organic iodine compound (C) include iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, iodomethane, triiodoethane, iodoethane, diiodopropane, isopropyliodide, t-butyliodide, iododichloroethane, chlorodiiodoethane, diiodopropane, chloroiodopropane, iododibromoethane, bromoiodopropane, 2-iodo-2-polyvinylglycosylpropane, 2-iodo-2-amidinopropane, 2-iodo-2-cyanobutane, 2-iodo-2-cyano-4-methylpentane, 2-iodo-2-cyano-4-methyl-4-methoxypentane, 4-iodo-4-cyanopentane, methyl-2-iodoisobutyrate, 2-iodo-2-methylpropionamide, 2-iodo-2, 4-dimethylpentane, 2-iodo-2-cyanobutanol, 2-iodo-2-methyl-N- (2-hydroxyethyl) propionamido-4-methylpentane, 2-iodo-2-methyl-N- (1, 1-bis (hydroxymethyl) -2-hydroxyethyl) propionamido-4-methylpentane, 2-iodo-2- (2-imidazolin-2-yl) propane, 2-iodo-2- (2- (5-methyl-2-imidazolin-2-yl) propane, iodobenzonitrile (PhCN-I), ethyl 2-iodophenylacetate (PhE-I), Diethyl 2-iodo-2-methylmalonate (EEMA-I), 2-iodo-2-cyanopropane (CP-I), 1-iodo-1-cyanoethane (CE-I), 1-iodo-1-phenylethane (PE-I), ethyl 2-iodo-isobutyrate (EMA-I), ethyl 2-iodo-valerate (EPA-I), ethyl 2-iodo-propionate (EA-I), ethyl 2-iodo-acetate (E-I), 2-iodo-isobutyric acid (MAA-I), hydroxyethyl 2-iodo-isobutyrate (HEMA-I), 2-iodo-propionamide (AAm-I), ethylene glycol bis (2-iodo-isobutyrate) (EMA-II), diethyl 2, 5-diiodoadipate (EA-II), Glycerol-tris (2-iodoisobutyrate) (EMA-III), 6- (2-iodo-2-Isobutoxy) Hexyltriethoxysilane (IHE).

The organic iodine compound (C) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among the organic iodine compounds (C), at least one selected from the group consisting of PhCN-I, PhE-I, EEMA-I, CP-I, CE-I, PE-I, EMA-I, EPA-I, EA-I, E-I, MAA-I, HEMA-I, AAm-I, EMA-II, EA-II, EMA-III and IHE is preferable from the viewpoint of controlling polymerization.

In the present production method, it is preferable that the polymerizable composition described later further contain a catalyst (D) or an azo radical polymerization initiator (E), because the polymerization rate and the monomer conversion rate can be easily increased.

A preferred production method is a method of obtaining a block copolymer composition by polymerizing a polymerizable composition containing the macromonomer (a), the vinyl monomer (B), the organoiodine compound (C), and the catalyst (D).

As the macromonomer (a), the vinyl monomer (B) and the organoiodine compound (C), the same substances as those described above can be used.

(catalyst (D))

The catalyst (D) is used for the purpose of extracting an iodine atom having a carbon atom-iodine atom bond. By adding the catalyst (D), the uniform dissociation reaction of iodine atoms from carbon atom-iodine atom bonds can be promoted, and the polymerization rate can be increased. The catalyst (D) may contain, in addition to the catalyst itself, a precursor which generates a catalyst when added to the polymerizable composition during the polymerization reaction.

The catalyst (D) is preferably at least one selected from the group consisting of the following catalysts (D1) to (D6).

Catalyst (D1): a non-metallic compound containing a halide ion and a non-metallic atom in a cationic state forming an ionic bond with the halide ion.

Catalyst (D2): a compound containing a carbon atom, at least one halogen atom directly bonded to the carbon atom (hereinafter also referred to as "compound (D21)"), or a hydrocarbon compound constituting a precursor of the compound (D21).

Catalyst (D3): an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom and having redox properties.

Catalyst (D4): a compound selected from the group consisting of ethylene, acetylene oligomers, polyacetylene, fullerene, carbon nanotubes, and derivatives thereof.

Catalyst (D5): halogenated alkali metal compounds or halogenated alkaline earth metal compounds.

Catalyst (D6): a compound selected from the group consisting of phosphorus compounds, nitrogen-containing compounds and oxygen-containing compounds other than the catalysts (D1) to (D5).

Examples of the catalyst (D1) include the following compounds.

As the non-metal compound having a nitrogen atom as a non-metal atom, an imidazole salt compound, a pyridinium salt compound, a quaternary amine salt compound, and derivatives thereof can be exemplified.

Examples of the imidazole salt compound include 1-methyl-3-methyl-imidazolium iodide (EMIZI) and 1-ethyl-3-methyl-imidazolium bromide (EMIZBr).

As the pyridinium compound, 2-chloro-1-methylpyridinium iodide (CMPI) can be exemplified.

As quaternary ammonium salt compounds, tetra-n-butylammonium iodide (BNI), tetra-n-butylammonium triiodide (BNI) are exemplified₃) Tetra-n-butyl ammonium bromide diiodide (BNBrI)₂)。

As the non-metallic compound having a phosphorus atom as a non-metallic atom, there can be exemplified phosphonium salt compounds such as methyltributylphosphonium iodide (BMPI), tetraphenylphosphonium iodide (PPI) and derivatives thereof.

As the non-metallic compound having a sulfur atom as a non-metallic atom, tributyl sulfonium iodide (BSI) and derivatives thereof can be exemplified.

As the non-metal compound having an iodine atom as a non-metal atom, diphenyliodonium iodide (PII) can be exemplified.

As the non-metal compound having 2 non-metal atoms, bis (triphenylphosphoranylidene) ammonium chloride (PPNCl) and a derivative thereof can be exemplified.

Examples of the catalyst (D2) include the following compounds.

Examples of the compound (D21) include halocarbons (CI)₄Etc.), halogenated alkanes ((CH)₃)₃CI、(CH₃)₂CI₂、CH₃CI₃Etc.), halogenated aromatic hydrocarbons (e.g., methylene iodide diphenyl), halogenated heteroaromatics.

Examples of the hydrocarbon compound which is a precursor of the compound (D21) include compounds in which a halogen atom bonded to a carbon atom in the compound (D21) is replaced with a hydrogen atom.

For example, a compound having 1 or 2 hydrogen atoms and 2 or 3 substituents for radical stabilization bonded to a carbon atom is preferable. The radical stabilizing substituent is preferably a substituent that forms a resonance structure together with a carbon atom of the central element. The carbon atom of the central element may be bonded with 1 other substituent other than the hydrogen atom and the radical stabilizing substituent, but it is preferable that the carbon atom of the central element is not bonded with other substituents.

Examples of the catalyst (D3) include organic compounds having a nitrogen atom, a phosphorus atom, a sulfur atom, and an oxygen atom and having redox properties.

Examples of the organic compound having a nitrogen atom include trialkylamine (triethylamine, tributylamine, etc.), tetrakis (dimethylamino) ethylene (TDAE), 1,4,8, 11-tetramethyl-1, 4,8, 11-Tetraazacyclotetradecanetributylphosphine (TDME). Organic compounds having hole transport ability may also be used. Furthermore, phthalimides, pyridines, bipyridines, N', N ", N ″ -Pentamethyldiethylenetriamine (PMDETA), ethylenediamine, dimethylethylenediamine, tetramethylethylenediamine, tetramethyldiaminomethane, tris (2-aminoethyl) amine, tris (2- (methylamino) ethyl) amine, hematoporphyrin, and derivatives thereof may also be used.

Examples of the organic compound having a phosphorus atom include trialkylphosphine (e.g., triethylphosphine), triarylphosphine (e.g., triphenylphosphine), phosphonic acid, 1, 2-bis (diphenylphosphino) methane, and derivatives thereof.

Examples of the organic compound having a sulfur atom include thiophene, a thiophene oligomer, polythiophene, tetrathiafulvalene (TTF), bis (ethylenedithiol) tetrathiafulvalene (BTTF), 3, 4-Ethylenedioxythiophene (EDOT), poly (3, 4-ethylenedioxythiophene) (PEDOT), and derivatives thereof.

As the organic compound having an oxygen atom, furan oligomer, polyfuran, and derivatives thereof can be exemplified.

The catalyst (D4) is a compound having a carbon atom as a central element such as ethylene, acetylene oligomer, polyacetylene, fullerene, carbon nanotube, and derivatives thereof.

Examples of the alkali metal atom of the alkali halide compound in the catalyst (D5) include lithium, sodium, potassium, rubidium, cesium, and francium. Examples of the alkaline earth metal atom of the halogenated alkaline earth metal compound include beryllium, magnesium, calcium, strontium, barium and radium. Among these, sodium, potassium, cesium, magnesium, and calcium are preferable, and sodium and potassium are particularly preferable.

Examples of the halogen atom contained in the alkali metal halide compound and the alkaline earth metal halide compound include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, from the viewpoint of easiness of narrowing the molecular weight distribution, a bromine atom or an iodine atom is preferable, and an iodine atom is particularly preferable.

Examples of the alkali metal halide compound include sodium iodide, potassium iodide, and cesium iodide.

Examples of the halogenated alkaline earth metal compound include magnesium iodide and calcium iodide.

Examples of the catalyst (D6) include the following compounds.

Examples of the phosphorus compound include phosphites and hypophosphorous acid ester compounds.

Examples of the phosphite ester include dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphite, dibenzyl phosphite, bis (2-ethylhexyl) phosphite, bis (2,2, 2-trifluoroethyl) phosphite, diallyl phosphite, and vinyl phosphite.

Examples of the hypophosphite series compound include diperfluoroethyl hypophosphite, ethoxyphenyl hypophosphite, phenylphenoxy hypophosphite, ethoxymethyl hypophosphite, and phenoxymethyl hypophosphite.

The phosphorus compound is preferably dimethyl phosphite, diethyl phosphite, dibutyl phosphite, or diphenyl phosphite in view of availability and solubility. These phosphorus compounds, can be used alone, also can be used in combination with 2 or more.

As the nitrogen-containing compound, an imide-based compound can be exemplified.

Examples of the imide-based compound include succinimide, 2-dimethylsuccinimide, α -dimethyl- β -methylsuccinimide, 3-ethyl-3-methyl-2, 5-pyrrolidinedione, cis-1, 2,3, 6-tetrahydrophthalimide, α -methyl- α -propylsuccinimide, 5-methylhexahydroisoindole-1, 3-dione, 2-phenylsuccinimide, α -methyl- α -phenylsuccinimide, 2, 3-diacetoxysuccinimide, maleimide, phthalimide, 4-methylphthalimide, N-chlorophthalimide, N-bromophthalimide, N-hydroxysuccinimide, and their salts, 4-nitrophthalimide, 2, 3-naphthoylimide, pyromellitimide, 5-bromoisoindole-1, 3-dione, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide (NIS).

The nitrogen-containing compound is preferably succinimide, phthalimide, N-chlorosuccinimide, N-bromosuccinimide, or NIS from the viewpoints of availability and solubility. These nitrogen-containing compounds may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of the oxygen-containing compound include phenolic compounds having a phenolic hydroxyl group, iodoxyphenyl compounds which are iodides of phenolic hydroxyl groups, and vitamins.

Examples of the phenol compound include fine particles of a phenol-based polymer, hydroquinone, methoxyhydroquinone, t-butylphenol, t-butylmethylphenol, catechol, resorcinol, di-t-butylhydroxytoluene, dimethylphenol, and trimethylphenol di-t-butyl-based polymer. They can also be used as polymerization inhibitors for preservation.

As the iodoxyphenyl compound, thymol iodide may be exemplified.

Examples of the vitamins include vitamin C and vitamin E.

The oxygen-containing compound is preferably phenol, catechol, vitamin C, or vitamin E from the viewpoint of availability and solubility. These oxygen-containing compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

In the present production method, the polymerizable reaction product may further contain an azo-based radical polymerization initiator (E) described later.

Another preferable production method is a method of obtaining a block copolymer composition by polymerizing a polymerizable composition containing the macromonomer (a), the vinyl monomer (B), the organoiodine compound (C), and the azo-based radical polymerization initiator (E).

As the macromonomer (a), the vinyl monomer (B) and the organoiodine compound (C), the same substances as those described above can be used.

(azo radical polymerization initiator (E))

The azo-based radical polymerization initiator (E) is used for the purpose of increasing the radical concentration in the polymerizable composition and increasing the polymerization rate when polymerizing the polymerizable composition containing the macromonomer (a), the vinyl monomer (B), and the organoiodine compound (C).

Examples of the azo radical polymerization initiator (E) include 2,2 ' -azobis (isobutyronitrile), 2 ' -azobis (2-methylbutyronitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 1 ' -azobis (cyclohexane-1-carbonitrile), and 2,2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile).

The azo-based radical polymerization initiator (E) may be used alone in 1 kind or in combination of 2 or more kinds.

Among azo radical polymerization initiators (E), 2 '-azobis (isobutyronitrile) (10-hour half-life temperature 65 ℃ C.), 2' -azobis (2-methylbutyronitrile) (10-hour half-life temperature 67 ℃ C.), 2 '-azobis (2, 4-dimethylvaleronitrile) (10-hour half-life temperature 51 ℃ C.), and 1, 1' -azobis (cyclohexane-1-carbonitrile) (10-hour half-life temperature 88 ℃ C.) are preferred. This is because these azo radical polymerization initiators have a 10-hour half-life temperature in an appropriate range, and are easy to control the polymerization.

The method for producing the block copolymer composition according to the second embodiment of the present invention includes a method of polymerizing a composition containing a macromonomer (A), a vinyl monomer (B), an azo radical polymerization initiator (E), and iodine (I)₂) The block copolymer composition of (1), and a method for obtaining the block copolymer composition.

In the present production method, at least a part of each of the azo radical polymerization initiator (E) and iodine reacts during the polymerization of the polymerizable composition to form the organic iodine compound (C) in the polymerizable composition, and the organic iodine compound functions as a dormant species.

As the macromonomer (A), the vinyl monomer (B) and the azo-based radical polymerization initiator (E), the same ones as described above can be used.

In the present production method, since the polymerization rate and the monomer conversion rate are easily increased, it is preferable that the polymerizable composition further contains the catalyst (D). As the catalyst (D), the same ones as those described above can be used.

(composition of polymerizable composition)

The composition of the polymerizable composition used in the above-described method for producing a block copolymer composition will be described. Hereinafter, "amount used" means an amount charged into the polymerizable composition.

< case where the polymerizable composition comprises the macromonomer (A), the vinyl monomer (B) and the organoiodine compound (C) >

The amount of the macromonomer (a) used is arbitrary, but is preferably more than 15% by mass, more preferably more than 30% by mass in terms of charge ratio (mass ratio) relative to the total amount of the macromonomer (a) and the vinyl monomer (B). Further, it is preferably less than 85% by mass, more preferably less than 70% by mass. When the amount of the macromonomer (a) used is in the above range, various physical properties can be expected to be imparted to the block copolymer by using the macromonomer (a), and the properties can be more easily reflected in the copolymer.

The amount of the vinyl monomer (B) used is arbitrary, but is preferably more than 15% by mass, more preferably more than 30% by mass in terms of the charge ratio (mass ratio) relative to the total amount of the macromonomer (a) and the vinyl monomer (B). Further, it is preferably less than 85% by mass, more preferably less than 70% by mass. When the amount of the vinyl monomer (B) used is in the above range, various physical properties can be expected to be imparted to the block copolymer by using the vinyl monomer (B), and the vinyl monomer (B) can be more easily reflected in the copolymer.

The amount of the organoiodine compound (C) used is arbitrary, but the vinyl monomer (B) is preferably 0.001 to 0.5 mol, more preferably 0.002 to 0.1 mol, per 1 mol. If the amount of the organoiodine compound (C) used is within the above range, sufficient iodine can be supplied as a protecting group to the growing chain without extremely decreasing the polymerization rate.

< case where the polymerizable composition comprises the macromonomer (A), the vinyl monomer (B), the organoiodine compound (C) and the azo radical polymerization initiator (E) >

The amount of the azo-based radical polymerization initiator (E) to be used is preferably more than 0.001 equivalent, and more preferably more than 0.002 equivalent, in terms of molar equivalents relative to the organoiodine compound (C). Further, the amount of the azo-based radical polymerization initiator (E) used is preferably not more than 10 equivalents, more preferably not more than 5 equivalents, in terms of molar equivalents relative to the organoiodine compound (C). When the amount of the azo-based radical polymerization initiator (E) used is not less than the lower limit of the above range, an appropriate polymerization rate can be obtained. When the amount of the azo radical polymerization initiator (E) used is not more than the upper limit of the above range, the amount of the homopolymer of the vinyl monomer (B) produced as a by-product in the block copolymer composition can be suppressed.

< case where the polymerizable composition comprises the macromonomer (A), the vinyl monomer (B), the azo type radical polymerization initiator (E) and iodine >

The amount of the azo-based radical polymerization initiator (E) used is arbitrary, but the vinyl monomer (B) is preferably 0.001 to 0.05 mol, more preferably 0.002 to 0.02 mol, per 1 mol of the monomer. When the amount of the azo-based radical polymerization initiator (E) used is in the above range, an appropriate polymerization rate can be obtained.

The amount of iodine used preferably satisfies the following condition (i).

(i)0＜[Q]/[P]＜0.60

Wherein [ Q ] is the number of molar equivalents of iodine in the polymerizable composition, and [ P ] is the number of molar equivalents of the azo-based radical initiator (E).

[ Q ]/[ P ] is preferably 0.01 or more, more preferably 0.1 or more. If [ Q ]/[ P ] is not less than the lower limit of the above range, the molecular weight and the molecular weight distribution can be sufficiently controlled. If [ Q ]/[ P ] is less than 0.60, inhibition of polymerization by side reactions is easily suppressed. The initiator efficiency of the azo-based radical polymerization initiator (E) is usually about 0.6 to 0.7. Therefore, the amount of iodine used is most preferably 0.1 ≦ Q/[ P ] < 0.60.

When the polymerizable composition described later contains the catalyst (D), it is preferable to set [ Q ]/[ P ] in the above range, and when the polymerizable composition does not contain the catalyst (D), it is necessary to further control the polymerization, and in particular, it is preferable to set [ Q ]/[ P ] in the above range.

< case where the polymerizable composition contains at least the macromonomer (A), the vinyl monomer (B) and the catalyst (D) >

The polymerizable composition may further contain 1 or more kinds selected from the group consisting of an organic iodine compound (C), an azo radical polymerization initiator (E) and iodine.

The amount of the catalyst (D) used is preferably 0.1 to 1000 mmol, and more preferably 0.5 to 500 mmol, based on 1 liter of the reaction solution. When the amount of the catalyst (D) used is within the above range, the polymerization rate can be sufficiently accelerated and the molecular weight distribution can be narrowed.

(solvent)

An appropriate solvent may be added to the polymerizable composition. Examples of the solvent include the same solvents as those used in the polymerization for obtaining the macromonomer (a).

When a solvent is used, the amount of the solvent used is preferably 30 parts by mass or more and 700 parts by mass or less with respect to 100 parts by mass of the vinyl monomer (B).

Other additives may be added to the polymerizable composition as needed. Examples of the other additive include chain transfer agents such as mercaptans.

[ polymerization conditions ]

The polymerization method in the method for producing the block copolymer composition of the present invention is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.

The polymerization reaction may be carried out in the presence of air, but in view of the efficiency of radical polymerization, it is preferable to carry out the polymerization reaction under a condition in which air is replaced with an inert gas such as nitrogen or argon.

The polymerization temperature is preferably 0 to 150 ℃ from the viewpoint of polymerization speed or the like, and more preferably 20 to 120 ℃ from the viewpoint of controlling polymerization.

From the viewpoint of facilitating the polymerization to the extent that the monomer conversion is high, the polymerization temperature is preferably maintained constant until the conversion of the vinyl monomer (B) reaches 60%. The temperature condition after the monomer conversion is more than 60% is not limited fixedly, and for example, it may be further increased in temperature.

Further, from the viewpoint of controlling the polymerization, the polymerization temperature preferably satisfies the following condition (ii).

(ii)0＜Tp-T₁₀＜40

Wherein, T_pIn terms of polymerization temperature (. degree. C.), T₁₀The 10-hour half-life temperature (. degree. C.) of the azo radical polymerization initiator (E) was determined. The 10-hour half-life temperature is an inherent value in the composition of the radical polymerization initiator.

By making Tp-T₁₀Within the above range, the polymerization rate can be maintained and the monomer conversion can be increased, and the polymerization control can be easily performed. When the polymerizable composition does not contain the catalyst (D), it is necessary to control the polymerization, and in particular, it is preferable to use Tp-T₁₀The above range.

The polymerization time is not particularly limited, and may be, for example, 0.5 to 24 hours.

(mechanism of polymerization)

The macromonomer (A) used in the present invention can also function as an addition-fragmentation chain transfer agent. Therefore, since a macromonomer having a structural unit derived from the vinyl monomer (B) can also be produced during the polymerization, the block derived from the vinyl monomer (B) of the block copolymer contained in the block copolymer composition of the present invention has a branched structure.

The specific polymerization mechanism will be described by taking as an example a case where a macromonomer having a structural unit derived from Methyl Methacrylate (MMA) is used as the macromonomer (a), n-Butyl Acrylate (BA) is used as the vinyl monomer (B), 2-iodo-2-cyanopropane (CP-I) is used as the organoiodine compound (C), and tetra-n-butylammonium iodide (BNI) is used as the catalyst (D). It is considered that the polymerization in this example was carried out in the following manners (1) to (4).

(1) As shown in the following formula (1), first, a carbon radical is generated from CP-I which is the organoiodine compound (C) by the behavior of BNI which is the catalyst (D). The generated carbon radical reacts with BA as the vinyl monomer (B) to become a growing radical having a structural unit derived from BA.

(2) As shown in the following formula (2), the growth radical undergoes addition fragmentation chain transfer when it reacts with the macromonomer (A), and is formed in the system: a macromonomer (B ') having a structural unit derived from BA, a growth radical (A') derived from the macromonomer (A).

(3) As shown in the following formula (3), the growth radical (A') is bonded to iodine to generate a dormant species.

(4) As shown in the following formula (4), the dormant species regenerate the growth radical by the behavior of the catalyst (D). By carrying out the reaction of the growing radical with BA, a block copolymer grows.

[ CHEM 5]

By the above-described mechanism, the macromonomer (a) is consumed at the initial stage of polymerization, and a block copolymer in which a block derived from the macromonomer (a) and a block derived from BA as the vinyl monomer (B) are bonded is produced. In addition, a macromonomer (B') having a structural unit derived from BA is produced. Further, the polymerization is carried out in a state controlled by the presence of terminal iodine.

The growing radical may also react with the macromonomer (B') having a structural unit derived from BA. As a result, the block derived from BA is introduced as a branched chain, and the macromonomer (B') having a structural unit derived from BA formed in the system is consumed.

The above is the mechanism of the polymerization reaction of the polymerizable composition comprising the macromonomer (a), the vinyl monomer (B), the organoiodine compound (C) and the catalyst (D), but it is considered that the polymerization reaction can be carried out by a similar reaction mechanism with respect to the other plural preferable production methods described above.

The result of the polymerization reaction is finally obtainable: all the blocks have structural units derived from a vinyl monomer, at least one block has a branched structure, and the main chain and the branches are block copolymers composed of the same structural units.

The block copolymer produced by the above-described production method has an iodine atom at the end of the main chain. The terminal iodine atom can be removed by treatment at high temperature, substitution with a nucleophile, or the like, or a functional group derived from a nucleophile can be introduced, if necessary.

The Mw/Mn of the resulting polymer in a typical controlled polymerization is generally less than 1.5. The polymerization mechanism of the polymerization reaction of the present invention is also conducted in a controlled polymerization mode, but the Mw/Mn is usually further increased in the range of 1.5 to 3.4 by the formation of a branched structure.

The use of the block copolymer composition of the present invention is not particularly limited, but examples thereof include a dispersant, a resin additive, a coating composition, and a polymer for lithography.

Hereinafter, the present invention will be described specifically by examples, but the present invention is not limited to the following descriptions. In addition, "eq" represents "number of molar equivalents". The amount of the solvent is represented by the amount of the solvent (mass%) when the total amount of the solvent is 100 mass%.

[ number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) ]

The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the macromonomer and block copolymer composition were calculated from a calibration curve of PMMA by GPC ("HLC-8220" manufactured by Tosoh corporation) to obtain Mn and Mw/Mn. The measurement conditions were as follows.

A chromatographic column: TSK GUARD COLUMN SUPER HZ-L (4.6 mm. times.35 mm) and TSK-GELSUPER HZM-N (6.0 mm. times.150 mm) in series,

Eluent: tetrahydrofuran, tetrahydrofuran,

Measuring temperature: at 40 deg.C,

Flow rate: 0.6 mL/min.

[ monomer conversion ]

The monomer conversion (%) of each example was calculated as the ratio of the amount of the polymer formed to the total of the amount of the residual monomer and the amount of the polymer formed, which was determined by NMR measurement (product of Bruker, "BBF 0400", 400 MHz).

[ evaluation of branched Structure ]

The branched structure of the block copolymer contained in the block copolymer composition was confirmed as follows.

The intrinsic viscosity η and the absolute molecular weight M of the copolymer were measured by GPC-TDA (manufactured by Viscotek), and the slope of a logarithmic graph (mark-houwing-cherry plot) thereof was obtained as an index term a indicating branching. The presence or absence of a branched structure was judged by comparing this value with a typical linear polymer having a flexible chain (a > 0.7).

Then, proceed with¹³When quaternary carbon-adjacent methine groups (38 to 41ppm) were detected by C-NMR measurement, it was judged that the copolymer had a branched structure, and the average number of branches per 1 molecule of the block copolymer was determined based on the peak intensity.

In the polymerization process of the present invention, in addition to the block copolymer produced by polymerization of the block derived from the macromonomer (a) and the vinyl monomer (B), the vinyl monomer (B) is polymerized and the macromonomer (B') composed of the structural unit derived from the monomer is present. By utilizing its reaction mechanism by¹H-NMR confirmed that the main chain and the branch chain derived from the block of the vinyl monomer (B) consisted of the same structural unit by tracing the generation and consumption of "the macromonomer (B') having the vinyl monomer (B) as a structural unit".

That is, when the macromonomer (B') is consumed and introduced into the block copolymer, it is introduced as a branch chain into the main chain of the block having the vinyl monomer (B) as a constituent unit. Therefore, if this is detected, it is confirmed that the vinyl monomer (B) as the main chain of the block copolymer has the same structural unit as the vinyl monomer (B) derived from the macromonomer (B') as the branch chain, and the main chain and the branch chain are composed of the same structural unit.

[ abbreviation ]

The abbreviation in this example is as follows.

< macromonomer (A) >)

ELVACITE: PMMA macromonomer (ELVACITE 1010, manufactured by Lucite International Co., Ltd., Mn 3,900)

< vinyl monomer (B) >

BA: n-butyl acrylate (manufactured by Tokyo chemical industry Co., Ltd.)

St: styrene (manufactured by Tokyo chemical industry Co., Ltd.)

< organic iodine Compound (C) >)

And (3) CP-I: 2-iodo-2-cyanopropane (manufactured by Tokyo chemical industry Co., Ltd.)

< azo radical polymerization initiator (E) >)

AIBN: 2, 2' -azobis (isobutyronitrile) (Tokyo chemical industry Co., Ltd.)

V-40: 1, 1' -azobis (cyclohexane-1-carbonitrile) (Fuji film and Wako pure chemical industries, Ltd.)

V-65: 2, 2' -azobis (2, 4-dimethylvaleronitrile) (Fuji film and Wako pure chemical industries, Ltd.)

< iodine >

I₂: iodine (manufactured by Tokyo chemical industry Co., Ltd.)

< catalyst (D) >

BNI: tetra-n-butylammonium iodide (manufactured by Tokyo chemical industry Co., Ltd.)

ONI: tetra n-octyl ammonium iodide (manufactured by Tokyo chemical industry Co., Ltd.)

DPM: diphenylmethane (Tokyo chemical industry Co., Ltd.)

DEPh: diethyl phosphite (manufactured by Tokyo chemical industry Co., Ltd.)

< other (non-azo radical polymerization initiator) >)

BPO: benzoyl peroxide (Tokyo chemical industry Co., Ltd.)

[10 hours half-life temperature T₁₀]

The 10-hour half-life temperatures of the azo-based radical polymerization initiators (E) (AIBN, V-40, V-65) are shown in Table 1.

[ TABLE 1]

[ example 1]

A polymerizable composition was prepared from macromonomer (a), vinyl monomer (B), azo radical polymerization initiator (E), iodine, and catalyst (D) in the composition shown in table 2. The polymerizable composition was transferred to a glass reaction vessel, the gas phase was replaced with argon gas, and then the polymerizable composition was reacted at a polymerization temperature of 110 ℃ for 24 hours under stirring to obtain a block copolymer composition.

In addition, it is considered that the azo-based radical polymerization initiator (E) reacts with iodine in the reaction system to produce the organoiodine compound (C). The same is true in the following examples.

[ examples 2 to 9]

A block copolymer composition was obtained in the same manner as in example 1, except that the composition of the polymerizable composition was changed to the composition shown in table 2.

[ example 10]

A block copolymer composition was obtained in the same manner as in example 1, except that the composition of the polymerizable composition was changed to the composition shown in Table 2, the polymerization temperature was changed to 80 ℃ and the polymerization time was changed to 6 hours.

Comparative examples 1 and 2

A block copolymer composition was obtained in the same manner as in example 1, except that the composition of the polymerizable composition was changed to the composition shown in table 2.

Comparative example 3

A block copolymer composition was obtained in the same manner as in example 1, except that the composition of the polymerizable composition was changed to the composition shown in Table 2, the polymerization temperature was changed to 80 ℃ and the polymerization time was changed to 4 hours.

The results of measuring the number average molecular weight Mn, the molecular weight distribution Mw/Mn and the monomer conversion of the block copolymer compositions of the respective examples are shown in Table 2. The monomer conversion column in Table 2, "> 99" means greater than 99%.

[ TABLE 2]

[ example 11]

A polymerizable composition was prepared from macromonomer (a), vinyl monomer (B), azo radical polymerization initiator (E) and iodine with the composition shown in table 3. The polymerizable composition was transferred to a glass reaction vessel, the gas phase was replaced with argon gas, and then a polymerization reaction was carried out at a polymerization temperature and a polymerization time shown in table 3 while stirring, to obtain a block copolymer composition.

In addition, it is considered that the azo-based radical polymerization initiator (E) reacts with iodine in the reaction system to produce the organoiodine compound (C). The same is true in the following examples.

[ examples 12 to 29]

A block copolymer composition was obtained in the same manner as in example 12, except that the composition of the polymerizable composition, the polymerization temperature and the polymerization time were changed as shown in tables 3 and 4.

[ comparative examples 4 to 6]

A block copolymer composition was obtained in the same manner as in example 12, except that the composition of the polymerizable composition, the polymerization temperature and the polymerization time were changed as shown in table 4.

The results of measuring the number average molecular weight Mn, the molecular weight distribution Mw/Mn and the monomer conversion of the block copolymer compositions of the respective examples are shown in tables 3 and 4. The monomer conversion column "> 99" in Table 4 means greater than 99%.

[ TABLE 3]

[ TABLE 4]

Next, the block copolymers contained in the block copolymer compositions obtained in examples 4 and 9 and comparative example 1 were used. The index term a obtained based on the slope of the Mark-Houwink-Fangtian diagram is shown in Table 5.

Further, the results of time-tracing of the amounts of "macromonomer (A)" and "macromonomer (B') having vinyl monomer (B) as a structural unit" in the polymerization reactions of examples 4 and 9 are shown in Table 6.

[ TABLE 5]

[ TABLE 6]

Based on table 5, the block copolymer compositions of examples 4 and 9 and comparative example 1 had an index term a of 0.7 or less, and the value of a was smaller than that of a typical linear polymer having a flexible chain (a > 0.7), indicating that the block copolymer contained in the block copolymer composition had a branched structure. That is, these block copolymer compositions contain, as a main component, a block copolymer in which at least one block has a branched structure. Comparative example 1, a, was smaller than examples 4 and 9, suggesting more branching. In other examples produced in the same manner as in examples 4 and 9, similarly, it is considered that the block copolymer contained in the block copolymer composition has a branched structure.

In addition, the block copolymer compositions of examples 4 and 9 were subjected to¹³When the quaternary carbon-adjacent methine group (38 to 41ppm) was detected by C-NMR measurement, it was confirmed that at least one block of the block copolymer contained in these compositions had a branched structure. Further, in any of examples 4 and 9, it was confirmed that: based on the peak intensity of the quaternary carbon adjacent methine groups, there are on average 4 branches per 1 molecule of block copolymer. In other examples produced in the same manner as in examples 4 and 9, it is similarly considered that at least one block of the block copolymer contained in the block copolymer composition has a branched structure and has about 2 to 7 branches.

Further, as shown in table 6, it was confirmed that the macromonomer (B') having a structural unit derived from the vinyl monomer (B) was produced and consumed during the polymerization. That is, it was found that the block copolymers contained in the block copolymer compositions of examples 4 and 9 had a branched structure in the block having the structural unit derived from the vinyl monomer (B), and both the main chain and the branch chain thereof were composed of the structural unit derived from the vinyl monomer (B), and therefore the main chain and the branch chain were the same structural unit. In other examples produced in the same manner as in examples 4 and 9, similarly, it is considered that a block having a structural unit derived from the vinyl monomer (B) has a branched structure, and the main chain and the branch of the block are the same structural unit.

As is clear from tables 2 to 4, the molecular weight distribution Mw/Mn of any of the block copolymer compositions of the examples was within a proper range (1.5 to 3.4). Further, when the number average molecular weight Mn is high to some extent, the monomer conversion is also high.

The block copolymer composition obtained in this example can control the phase structure at a high level, exhibits good solubility and melt viscosity, and can be used for resin additives, dispersants, coating compositions, lithographic polymers, and the like. That is, the effects of the block copolymer composition of the present invention are supported by the examples.

On the other hand, the molecular weight distribution Mw/Mn of the block copolymer compositions obtained in comparative examples 1,3 to 6 was large and could not be controlled sufficiently. The copolymer composition shown in comparative example 1 is suggested to have a branched structure formed based on Table 5, but is not preferable for applications such as a dispersant and a resin additive because it is difficult to control the phase structure because a is smaller, branched and Mw/Mn is larger than those of examples.

Comparative example 2 polymerization did not proceed, and a block copolymer composition could not be obtained.