JPWO2012001946A1 - Method for producing block copolymer and copolymer precursor - Google Patents

Abstract

An object of the present invention is to provide a method for producing a novel copolymer useful as a pigment dispersant or the like. The production method of the present invention comprises a block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; And a copolymer precursor containing a repeating unit containing a protected acidic group represented by formula (II) and a block chain (B) containing the repeating unit represented by formula (II), and heating the copolymer precursor. Thus, the block co-polymer containing the block chain (A), the repeating unit containing the acidic group represented by the formula (III), and the block chain (B1) containing the repeating unit represented by the formula (II) This is a method for producing a coalescence.

Description

  The present invention relates to a method for producing a novel block copolymer useful as a pigment dispersant and a copolymer precursor. This application claims priority with respect to the Japan patent application 2010-148868 for which it applied on June 30, 2010, and uses the content here.

At least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base, a repeating unit containing an acidic group, and a unit derived from an alkyl (meth) acrylate Random copolymers containing are known.
Since these polymers have various properties based on their unique structures, development is being studied in various fields.

  Patent Document 1 discloses a pigment composition containing a pigment, an acidic functional group-containing organic dye derivative, an alkali-soluble resin, and an organic solvent, and having an amino group and / or its quaternary ammonium group. Has a basic equivalent weight of 3000 to 20000 g / eq, and an acid value of 30 to 200 mg KOH / g. Specifically, random copolymers of n-butyl methacrylate, methyl methacrylate, methacrylic acid and dimethylaminoethyl methacrylate are described as alkali-soluble resins.

  In Patent Documents 2 and 3, focusing on the fact that the random copolymer has the property of an amphoteric polymer that is positively or negatively charged by treatment with an acid or a base, the random copolymer is electrophoresed. It is used as a sex composition.

  Moreover, in patent document 4, paying attention to the reactivity of the carboxyl group and amino group in the said random copolymer, the said random copolymer is utilized as a binder of silyl isocyanate.

  Further, in Patent Document 5, a powder coating composition is obtained by causing a crosslinking reaction between a carboxyl group and an epoxy group of the random copolymer, and further using an amino group of the random copolymer as a catalyst for the crosslinking reaction. It is used as.

JP 2007-84659 A JP-A-6-289609 JP-A-5-295305 JP-A-4-62880 Japanese Patent Application Laid-Open No. 61-6866

In recent years, the use of copolymers has been diversified, and copolymers having various properties have been demanded.
For example, in the field of color liquid crystal display devices, pigment particles are finely divided to at least the wavelength of visible light or less due to the increasing demand for high visible light transmittance and high contrast. In such fine particles, the specific surface area of the pigment particles is larger than usual, so that the conventionally used copolymers for pigment dispersants have insufficient initial pigment dispersibility and dispersion stability over time. It was. In recent years, higher performance is required in addition to dispersion performance, and conventional copolymers have not been able to obtain sufficient performance.
Therefore, the present invention has an object to provide a method for producing a copolymer and a copolymer precursor, which have good initial pigment dispersibility and dispersion stability with time, and also have higher performance than dispersion performance. And

  As a result of earnest research to solve the above problems, the present inventors have obtained at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base. A block chain consisting of a polymer containing a block chain (A), a repeating unit containing an acidic group represented by formula (III), and a block chain comprising a copolymer containing a repeating unit represented by formula (II) A block copolymer containing (B1) and having a copolymerization ratio of the repeating unit represented by the formula (II) of 90% by mass or more in the block chain (B1) can solve the above problems, and The copolymer precursor has a repeating unit represented by the formula (I) in which the acidic group of the repeating unit containing the acidic group represented by the formula (III) is protected. Found that can be produced by heating a, thereby completing the present invention.

That is, the present invention
(1) a block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and the formula (I)

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1-C3 alkyl group. X represents a single bond or a C1-C10 alkylene group, —C (═O) OR ^1a. A group selected from the group consisting of —, —C (═O) NHR ^1a —, —OC (═O) R ^1a —, and —R ^2a —OC (═O) —R ^1a — (R ^1a and R ^2a are Each independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ⁴ represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group. Or a C6-C10 aryl group, R ⁵ represents a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group. Contains group Repeating units and formula that (II)

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1-C3 alkyl group, and R ⁹ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.) A copolymer precursor containing a block chain (B) containing a repeating unit represented by formula (II), wherein the copolymerization ratio of the repeating unit represented by formula (II) is 90% by mass or more in the block chain (B) The block chain (A) and the formula (III)

(Wherein R ¹ , R ² , R ³ and X represent the same meaning as in formula (I)), the repeating unit containing an acidic group represented by formula (II) and the repeating unit represented by formula (II) A block copolymer (B1) containing a block copolymer (B1), wherein the copolymerization ratio of the repeating unit represented by the formula (II) is 90% by mass or more in the block chain (B1),
(2) The repeating unit containing a tertiary amino group has the formula (IV)

^{(Wherein, R 10, R 11, R} 12 are each independently, .Y represents a hydrogen atom or a C1~C3 alkyl group, C1 -C10 alkylene ^{group, -C (= O) OR 1b} -, - Groups selected from the group consisting of C (═O) NHR ^1b —, —OC (═O) R ^1b —, and —R ^2b —OC (═O) —R ^1b — (R ^1b and R ^2b are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹³ and R ¹⁴ are each independently a C1-C6 alkyl group or a C6-C10 aryl group. A method for producing a block copolymer according to (1), which is a repeating unit represented by (C1-C6 alkyl group).
(3) The repeating unit containing a quaternary ammonium base has the formula (V)

(Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a C1-C3 alkyl group. Y ¹ represents a C1-C10 alkylene group, —C (═O) OR ^1c —, Groups selected from the group consisting of —C (═O) NHR ^1c —, —OC (═O) R ^1c — and —R ^2c —OC (═O) —R ^1c — (R ^1c and R ^2c are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a C1-C6 alkyl group, or .Z representing the C6~C10 aryl C1~C6 alkyl group ^-. the process for producing a block copolymer described in (1) to a repeating unit represented by the representative) a counter ion and, ,
(4) The present invention relates to the method for producing a block copolymer according to any one of (1) to (3), which is performed in a mixed solvent of an organic solvent and water.

The present invention also provides:
(5) a block chain (A) containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and the formula (I)

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1-C3 alkyl group. X represents a single bond or a C1-C10 alkylene group, —C (═O) OR ^1a. A group selected from the group consisting of —, —C (═O) NHR ^1a —, —OC (═O) R ^1a —, and —R ^2a —OC (═O) —R ^1a — (R ^1a and R ^2a are Each independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ⁴ represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group. Or a C6-C10 aryl group, R ⁵ represents a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group. Contains group Repeating units and formula that (II)

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1-C3 alkyl group, and R ⁹ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.) A copolymer precursor containing a block chain (B) containing a repeating unit represented by formula (II), wherein the copolymerization ratio of the repeating unit represented by formula (II) is 90% by mass or more in the block chain (B) ,
(6) The repeating unit containing a tertiary amino group has the formula (IV)

^{(Wherein, R 10, R 11, R} 12 are each independently, .Y represents a hydrogen atom or a C1~C3 alkyl group, C1 -C10 alkylene ^{group, -C (= O) OR 1b} -, - Groups selected from the group consisting of C (═O) NHR ^1b —, —OC (═O) R ^1b —, and —R ^2b —OC (═O) —R ^1b — (R ^1b and R ^2b are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹³ and R ¹⁴ are each independently a C1-C6 alkyl group or a C6-C10 aryl group. A copolymer precursor according to (5), wherein the copolymer precursor is a repeating unit represented by (C1-C6 alkyl group), and
(7) The repeating unit containing a quaternary ammonium base has the formula (V)

(Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a C1-C3 alkyl group. Y ¹ represents a C1-C10 alkylene group, —C (═O) OR ^1c —, Groups selected from the group consisting of —C (═O) NHR ^1c —, —OC (═O) R ^1c — and —R ^2c —OC (═O) —R ^1c — (R ^1c and R ^2c are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a C1-C6 alkyl group, or .Z representing the C6~C10 aryl C1~C6 alkyl group ^- relates precursor copolymers described in (5) to a repeating unit represented by the representative) a counter ion..

(1) Copolymer precursor The copolymer precursor used in the present invention contains at least one of the following block chain (A) and block chain (B).
Block chain (A): Block chain containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base Block (B): protected The block chain containing the repeating unit containing an acidic group and the repeating unit represented by the formula (II) The copolymer precursor used in the present invention includes the block chain (A) and the block chain (B). In addition, other block chains may be contained.

1) Block chain (A)
In the block chain (A), the repeating unit containing a tertiary amino group and the repeating unit containing a quaternary ammonium base are those having the cationic functional group in the side chain of the repeating unit, There is no particular limitation.
Specifically, the block chain (A) is a repeating unit containing a tertiary amino group, or a repeating unit containing a tertiary amino group, a block chain consisting of only one type of repeating unit containing a quaternary ammonium base. Or a block chain composed of two or more repeating units containing a quaternary ammonium base, a block chain composed of at least one repeating unit containing a tertiary amino group and at least one repeating unit containing a quaternary ammonium base. And block chains of these and repeating units derived from other copolymerizable monomers. The bond of each repeating unit in the block chain (A) may be in any form such as random, alternating, or block.

(Repeating unit containing tertiary amino group)
The repeating unit containing a tertiary amino group is not particularly limited as long as it contains a tertiary amino group, and examples thereof include a repeating unit represented by the following general formula (IV).

Wherein ^{(IV), R 10, R} 11, R 12 are each independently hydrogen atom or a C1~C3 alkyl group. Y represents a C1 to C10 alkylene group, —C (═O) OR ^1b —, —C (═O) NHR ^1b —, —OC (═O) R ^1b — and —R ^2b —OC (═O) —R. ^A group selected from the group consisting of ^1b- (R ^1b and R ^2b each independently represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group). R ¹³ and R ¹⁴ are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
Here, as a C1-C3 alkyl group and a C1-C6 alkyl group, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n -Hexyl etc. are illustrated.
Examples of the C1-C10 alkylene group include a methylene chain, an ethylene chain, a propylene chain, a methylethylene chain, a butylene chain, a 1,2-dimethylethylene chain, a pentylene chain, a 1-methylbutylene chain, a 2-methylbutylene chain, and a hexylene chain. Is exemplified.
C6-C10 aryl C1-C6 alkyl groups include benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, naphthalen-2-ylethyl, 1-naphthalene-2 -Yl-n-propyl, inden-1-ylmethyl and the like are exemplified.

  As monomers used as a raw material of the repeating unit represented by the formula (IV), dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylamino Examples include propyl (meth) acrylate and diethylaminobutyl (meth) acrylate.

(Repeating unit containing quaternary ammonium base)
The repeating unit containing a quaternary ammonium base is not particularly limited as long as it contains a quaternary ammonium base, and examples thereof include a repeating unit represented by the following general formula (V).

In formula (V), R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a C1-C3 alkyl group. Y ¹ represents a C1-C10 alkylene group, —C (═O) OR ^1c —, —C (═O) NHR ^1c —, —OC (═O) R ^1c — and —R ^2c —OC (═O) —. A group selected from the group consisting of R ^1c — (R ^1c and R ^2c each independently represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group). R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group. Z ⁻ represents a counter ion such as a halide ion, an alkyl halide ion, an alkyl carboxylate ion, a nitroxide ion, an alkyl sulfate ion, a sulfonate ion, a phosphate ion, or an alkyl phosphate ion.
Here, the C1-C3 alkyl group, the C1-C6 alkyl group, the C1-C10 alkylene group, and the C6-C10 aryl C1-C6 alkyl group are represented by the formula (IV) of the repeating unit containing the tertiary amino group. The thing similar to what is in can be illustrated.

  As a monomer used as a raw material of the repeating unit represented by the formula (V), (meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (Meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium iodide (Meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloylo Cibutyltrimethylammonium chloride, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium iodide, (meth) acryloyloxyethylbenzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (Meth) acryloyloxyethylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium iodide, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyl Oxypropylbenzyldimethylammonium bromide, (Meth) acryloyloxypropylbenzyldimethylammonium iodide, (meth) acryloyloxybutylbenzyldimethylammonium fluoride, (meth) acryloyloxybutylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxy Examples thereof include butylbenzyldimethylammonium iodide.

(Other repeating units that can be contained)
Examples of other repeating units that can be contained in the block chain (A) include repeating units derived from (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers, and the like.
Examples of the (meth) acrylic acid-based monomer, aromatic vinyl-based monomer, and conjugated diene-based monomer that are the raw materials for the repeating unit include
Examples of (meth) acrylic acid monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) (Meth) acrylic acid ester compounds such as 2-ethylhexyl acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, methoxypolyethylene glycol (ethylene glycol) The number of units is 2 to 100) (meth) acrylate, ethoxypolyethylene glycol Meth) acrylate can be exemplified by phenoxy polyethylene glycol (meth) acrylate and the like, these are mixed singly, or two or more can be used.
Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene, and the like. These can be used alone or in admixture of two or more.
Conjugated diene monomers include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene, and the like. These can be used alone or in combination of two or more.

2) Block chain (B)
The block chain (B) is a block chain containing at least one repeating unit containing a protected acidic group and at least one repeating unit represented by the formula (II).
In the block chain (B), the copolymerization ratio of at least one repeating unit represented by the formula (II) is 90% by mass or more, preferably 91% by mass to 99% by mass.

(Repeating units containing protected acidic groups)
The repeating unit containing a protected acidic group in the block chain (B) is a repeating unit represented by the formula (I).

In formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom or a C1-C3 alkyl group. X is a single bond or a C1-C10 alkylene group, —C (═O) OR ^1a —, —C (═O) NHR ^1a —, —OC (═O) R ^1a — and —R ^2a —OC (═O ) -R ^1a — is a group selected from the group consisting of —R ^1a — (R ^1a and R ^2a are each independently a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group), and R. ⁴ is a hydrogen atom, C1 -C6 alkyl groups, C6-C10 aryl C1 -C6 alkyl group or a C6-C10 aryl group, ^{R 5} is C1 -C6 alkyl, C6-C10 aryl C1 -C6 alkyl group Or a C6-C10 aryl group.

As a monomer used as a raw material of the repeating unit represented by the formula (I), acrylic acid methoxymethyl ester, acrylic acid ethoxymethyl ester, acrylic acid 1-ethoxy-ethyl ester, acrylic acid 1-methoxy-ethyl ester, acrylic acid 1-ethoxy-propyl ester, acrylic acid 1-propoxy-ethyl ester, acrylic acid 1-isopropoxy-ethyl ester, acrylic acid 1-benzyloxy-ethyl ester, 2-methyl-acrylic acid 1-ethoxy-ethyl ester, 2 -Methyl-acrylic acid 1-methoxy-ethyl ester, 2-methyl-acrylic acid 1-ethoxy-propyl ester, 2-methyl-acrylic acid 1-propoxy-ethyl ester, 2-methyl-acrylic acid 1-isopropoxyethyl ester 2-methyl-a Acrylic acid 1-benzyloxy - ethyl ester. Of these, acrylic acid 1-ethoxy-ethyl ester and 2-methyl-acrylic acid 1-ethoxy-ethyl ester are preferred. These can be used alone or in admixture of two or more.
The repeating unit containing a protected acidic group can be converted to a repeating unit containing an acidic group described below by deprotecting the protective group by the production method of the present invention.

(Repeating unit represented by formula (II))
The block chain (B) further contains at least one repeating unit represented by the following formula (II).

Wherein ^{(II), R 6, R} 7, R 8 represents a hydrogen atom or a C1~C3 alkyl group, ^{R 9} represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

In the present invention, examples of the C1-C3 alkyl group for R ⁶ , R ⁷ , and R ⁸ include those similar to those in formula (IV) of the repeating unit having the tertiary amino group.
In the present invention, the aliphatic hydrocarbon group for R ⁹ may be either saturated or unsaturated, and includes a C1 to C20 alkyl group, a C2 to C20 alkenyl group, and a C2 to C20 alkynyl group.
Examples of the C1-C20 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, and n- Hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, Examples include 1-methyloctyl, ethylheptyl, n-decyl, 1-methylnonyl, n-undecyl, 1,1-dimethylnonyl, n-dodecyl, n-tetradecyl, n-heptadecyl, and n-octadecyl group. Of these, a C1-C6 alkyl group is preferred.
Examples of the C2-C20 alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- Examples include hexenyl, heptenyl, octenyl, decenyl group, pentadecenyl, eicocenyl group, tricocenyl and the like. Of these, a C2-C6 alkenyl group is preferable.
Examples of the C2-C20 alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-2-propynyl, 1- Pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-2-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, Examples include 1-heptynyl, 1-octynyl, 1-decynyl, 1-pentadecynyl, 1-eicosinyl, 1-tricosinyl and the like. Preferably, it is a C2-C6 alkynyl group.

In the present invention, the alicyclic hydrocarbon group means a saturated or unsaturated hydrocarbon group having a monocyclic or polycyclic ring structure in any part of the group, and is a C3-C20 cyclohexane. Alkyl group, C4-C20 alkyl-substituted cycloalkyl group, C4-C20 cycloalkylalkyl group, C3-C20 cycloalkenyl group, C4-C20 alkyl-substituted cycloalkenyl group, C4-C20 cycloalkenylalkyl group, C7 -C20 bridged ring hydrocarbon group and the like are included.
Examples of the C3 to C20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Preferably, it is a C3-C8 cycloalkyl group.
Examples of the C4-C20 alkyl-substituted cycloalkyl group include 1-methylcyclopropyl, 2-ethylcyclopropyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 2-ethylcyclohexyl, And methylcyclooctyl. Preferably, it is a C4-C10 alkyl-substituted cycloalkyl group.
Examples of the C3-C20 cycloalkylalkyl group include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylethyl, cyclooctylethyl and the like. Preferably, it is a C4-C10 cycloalkylalkyl group.
Examples of the C3-C20 cycloalkenyl group include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, and the like. Preferably, it is a C3-C8 cycloalkenyl group.
Examples of the C4-C20 alkyl-substituted cycloalkenyl group include 3-ethylcyclopentenyl, hexenyl 4-methylcyclohexenyl, 4-ethylcyclohexenyl, and the like. Preferably, it is a C4-C10 alkyl-substituted cycloalkenyl group.
Examples of the C4-C20 cycloalkenylalkyl group include cyclopropenylmethyl, cyclobutenylmethyl, cyclopentenylethyl, cyclohexenylethyl and the like. Preferably, it is a C4 to C10 cycloalkenylalkyl group.
Examples of the C7 to C20 bridged ring hydrocarbon group include tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, adamantyl group, dicyclopentenyl group, and isobornyl group.

(Other repeating units that can be contained)
Examples of other repeating units that can be contained in the block chain (B) include repeating units derived from aromatic vinyl monomers, conjugated diene monomers, and the like.
Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene, and the like. These can be used alone or in admixture of two or more.

  Conjugated diene monomers include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene and the like, and these can be used alone or in combination of two or more.

3) Other matters (block chains other than block chains (A) and (B) in the copolymer)
The copolymer precursor used in the present invention may have other block chains in addition to the block chains (A) and (B).
Examples of such a block chain include a block chain containing a repeating unit derived from a (meth) acrylic acid monomer, an aromatic vinyl monomer, a conjugated diene monomer, and the like. Any form such as random copolymerization, alternating copolymerization, and block copolymerization may be used.
Examples of the (meth) acrylic acid monomer, aromatic vinyl monomer, conjugated diene monomer, and the like are exemplified.

(Physical properties such as ratio and molecular weight of block chain (A) and block chain (B) in copolymer)
The ratio of the block chain (A) to the block chain (B) in the copolymer of the present invention is not particularly limited, but is 10 to 40 to 90 to 60, preferably 15 to 35 to 85 in weight percent ratio. ~ 65.
Moreover, the weight average molecular weight measured using GPC is 2,000-50,000, and 4,000-15,000 are especially preferable as a copolymer precursor. The ratio of the weight average molecular weight to the number average molecular weight, measured using GPC, is 1.0 to 2.0, preferably 1.0 to 1.5.

(2) Method for Producing Copolymer Precursor The method for producing the copolymer precursor used in the present invention is not particularly limited and can be produced by a known method. It can be polymerized to form a block copolymer. Examples of the living polymerization include living radical polymerization and living anion polymerization, among which living anion polymerization is more preferable.
In order to obtain a block copolymer, after the monomer of the block chain (A) or (B) is polymerized, another block monomer may be continuously polymerized to form a block copolymer, Each block of A) and the block chain (B) may be reacted separately to produce a block, and then each block may be combined. Living anionic polymerization is preferable because the composition and molecular weight can be strictly controlled.
In the case of producing by living radical polymerization, the reaction can be carried out in the same manner as living anion polymerization, or after polymerizing a certain block of monomer and before polymerizing the next monomer, the polymer is once purified, It is also possible to polymerize the next monomer after removing the remainder of the monomer in the reaction. When it is preferable that the monomers of each block do not mix with each other, it is preferable to purify the polymer.
In the case of producing a block copolymer by living anionic polymerization, for example, a desired monomer can be dropped and polymerized in a solvent to which an additive and a polymerization initiator are added. At this time, in order to obtain a block polymer having a desired sequence, the monomers of each block are sequentially added dropwise so as to have a desired sequence and reacted.
In order to polymerize the monomer of a certain block and polymerize the monomer of the next block, the dropping of the monomer of the next block is started after completion of the polymerization reaction of the previous block. The progress of the polymerization reaction can be confirmed by detecting the remaining amount of the monomer by gas chromatography or liquid chromatography. Further, after completion of the monomer dropping of the previous block, although depending on the kind of the monomer and the solvent, the dropping of the monomer of the next block can be started after stirring for 1 minute to 1 hour.
When a plurality of types of monomers are included in each block, they may be dropped separately or simultaneously.

The anionic polymerization initiator used for the polymerization of the monomer is not particularly limited as long as it is a nucleophile and has a function of initiating the polymerization of the anionic polymerizable monomer. For example, alkali metal, organic Alkali metal compounds and the like can be used.
Examples of the alkali metal include lithium, sodium, potassium, cesium and the like.
Examples of the organic alkali metal compound include alkylated products, allylated products, and arylated products of the above alkali metals, and alkyllithium is particularly preferable. Specifically, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, potassium naphthalene, α-methylstyrene sodium dianion, 1 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryl lithium, cumyl potassium, cumyl cesium and the like can be used. These anionic polymerization initiators can be used alone or in combination of two or more.

The usage-amount of an anionic polymerization initiator is 0.0001-0.2 equivalent normally with respect to the whole anionic polymerizable monomer to be used, Preferably it is 0.0005-0.1 equivalent. By using an anionic polymerization initiator in this range, the target polymer can be produced with high yield.
The polymerization temperature is not particularly limited as long as the side reaction such as transfer reaction or termination reaction does not occur and the monomer is consumed and the polymerization is completed, but the polymerization temperature is not lower than −100 ° C. but not higher than the solvent boiling point. preferable. Further, the concentration of the monomer with respect to the polymerization solvent is not particularly limited, but is usually 1 to 40% by weight, and preferably 10 to 30% by weight.
The polymerization solvent used in the production method of the present invention is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer, and specifically includes diethyl ether, tetrahydrofuran (THF), dioxane. , Polar compounds such as ether compounds such as trioxane, tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide, and non-aliphatic, aromatic or alicyclic hydrocarbon compounds such as hexane and toluene A polar solvent or a low polarity solvent can be illustrated. These solvents can be used alone or as a mixed solvent of two or more. In the production method of the present invention, polymerization can be accurately controlled even when a nonpolar solvent or a low polarity solvent is used in combination with a polar solvent. For example, the nonpolar solvent or the low polarity solvent is based on the whole solvent. 5 vol% or more can be used, 20 vol% or more may be used, and 50 vol% or more may be used.

In the present invention, a dialkyl zinc such as diethyl zinc, a dialkyl magnesium such as dibutyl magnesium, or an organic metal such as triethylaluminum can be used as a polymerization stabilizer, a monomer or a solvent purifier, if necessary.
In the present invention, an additive such as an alkali metal salt or an alkaline earth metal salt can be added at the start of polymerization or during polymerization as required. Specific examples of such additives include mineral salts and halides such as sodium, potassium, barium and magnesium sulfates, nitrates and borates. More specifically, lithium And barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride and the like. Among these, lithium halides such as lithium chloride, lithium bromide, lithium iodide, and lithium fluoride are preferable, and lithium chloride is particularly preferable.
It is generally difficult to polymerize a monomer containing a quaternary ammonium base by living anionic polymerization. Therefore, in the case of producing a polymer containing a repeating unit containing a quaternary ammonium base by living anionic polymerization, after polymerizing a monomer as a raw material of a repeating unit containing a tertiary amino group, It can be quaternized by a known method. Quaternizing agents include benzyl chloride, benzyl bromide, benzyl iodide, and the like, alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, di-n-sulfate. Common alkylating agents such as propyl can be mentioned.

(3) Block copolymer The block copolymer produced in the present invention contains at least one of the following block chains (A) and block chains (B1).
Block chain (A): Block chain containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base Block chain (B1): an acidic group The repeating unit to be contained and the block chain containing the repeating unit represented by the formula (II) The copolymer of the present invention contains other block chains in addition to the block chain (A) and the block chain (B1). You may do it.

1) Block chain (A)
The block chain (A) in the block copolymer is the same as the block chain (A) in the copolymer precursor.
2) Block chain (B1)
The block chain (B1) is a copolymer containing at least one repeating unit containing an acidic group and at least one repeating unit represented by the formula (II).
In the block chain (B1), the copolymerization ratio of at least one of the repeating units represented by the formula (II) is 90% by mass or more, preferably 91% by mass to 99% by mass.
Copolymers include random, alternating, block, etc. copolymers.

(Repeating unit containing acidic group)
The repeating unit containing an acidic group in the block chain (B1) is a repeating unit represented by the formula (III).

In formula (III), R ¹ , R ² , R ³ and X have the same meaning as in the repeating unit containing a protected acidic group represented by formula (I).
The repeating unit represented by the formula (III) can be obtained by deprotecting the protecting group of the protected acidic group represented by the formula (I) by the production method of the present invention.

(Repeating unit represented by formula (II))
The repeating unit represented by the formula (II) in the block chain (B1) is the same as the repeating unit represented by the formula (II) in the copolymer precursor.

(Other repeating units that can be contained)
The other repeating unit that can be contained in the block chain (B1) is the same as the other repeating unit that can be contained in the block chain (B) in the copolymer precursor.

(Block chains other than block chains (A) and (B1) in the block copolymer)
The copolymer used in the present invention may have a block chain made of another polymer in addition to the block chains (A) and (B1).
Such a block chain is the same as the block chain other than the block chains (A) and (B) in the copolymer precursor.

(Physical properties such as ratio and molecular weight of block chain (A) and block chain (B1) in copolymer)
The ratio of the block chain (A) and the block chain (B1) in the copolymer used in the present invention is not particularly limited, but is 10 to 40:90 to 60, preferably 15 to 15% by weight. 35 to 85-65. Moreover, the content rate of the repeating unit which has an acidic group in a copolymer is 0.5 to 20 weight%, Preferably, it is 1 to 15 weight%.
Moreover, the weight average molecular weight measured using GPC is 2,000-50,000, As a dispersing agent, 2,000-20,000 are preferable, More preferably, it is 4,000-15,000. . The ratio of the weight average molecular weight to the number average molecular weight, measured using GPC, is 1.0 to 2.0, and the dispersant is particularly preferably 1.0 to 1.5.

(4) Manufacturing method of block copolymer The block copolymer of this invention can be obtained by heating the said copolymer precursor. By heating the copolymer precursor, the protecting group protecting the acidic group in the copolymer precursor is deprotected.
The heating temperature varies depending on the structure of the protecting group protecting the acidic group, but is not particularly limited as long as the deprotection reaction proceeds rapidly. Usually, it is preferable to carry out at 80 to 200 degreeC, and it is more preferable that it is 100 to 160 degreeC.
In the deprotection reaction, the copolymer precursor may be heated as it is, or may be heated in a state where the copolymer precursor is dissolved in a solvent. Examples of such solvents include water; glycol ether ester solvents such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, Glycol mono or diether solvents such as propylene glycol monoethyl ether and diethylene glycol dimethyl ether; aromatic hydrocarbon solvents such as toluene and monochlorobenzene; ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol (PGME), etc. Alcohol solvents; ester solvents such as ethyl lactate, butyl acetate and ethyl pyruvate; and these A mixed solvent consisting of seeds or more; and the like. Of these, glycol ether ester solvents, mixed solvents of glycol ether ester solvents and alcohol solvents, and mixed solvents of glycol ether ester solvents and water are preferred. From the viewpoint that the reaction temperature can be lowered, a mixed solvent of a glycol ether ester solvent and an alcohol solvent, a mixed solvent of a glycol ether ester solvent and water is preferable, and a mixture of a glycol ether ester solvent and water is preferable. A mixed solvent is particularly preferred. From the viewpoint of easy removal of by-products generated by the deprotection reaction, a mixed solvent of glycol ether ester solvent and water is preferable, and a mixed solvent of PGMEA and water is particularly preferable.
In the mixed solvent of the glycol ether ester solvent and the alcohol solvent, the mixing ratio is not particularly limited as long as the copolymer precursor can be dissolved, but is usually 95/5 wt% to 0.1 / 99.9. % By weight is preferable, and 50/50 to 0.1 / 99.9% by weight is more preferable.
In the mixed solvent of glycol ether ester solvent and water, the mixing ratio is not particularly limited as long as the copolymer precursor can be dissolved, but it is usually preferably 95/5 to 50/50% by weight, 90/10 to 60/40% by weight is more preferable, and 90/10 to 70/30% by weight is particularly preferable.
The heating temperature varies depending on the structure of the protecting group protecting the acidic group and the reaction solvent, but is not particularly limited as long as the deprotection reaction proceeds rapidly.
In the case of a glycol ether ester solvent, it is usually preferably performed at 80 ° C to 200 ° C, more preferably 100 ° C to 170 ° C. In the case of a mixed solvent of a glycol ether ester solvent and an alcohol solvent, it is preferably performed at 100 ° C to 140 ° C, more preferably 110 ° C to 140 ° C. In the case of a mixed solvent of a glycol ether ester solvent and water, it is preferably performed at 70 ° C to 120 ° C, more preferably 90 ° C to 120 ° C. From the viewpoint of reducing the coloration of the polymer solution produced by the deprotection reaction, it is preferable to lower the heating temperature.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the technical scope of this invention is not limited to these illustrations.

[Example 1]
(Polymerization process)
Add 55.7 parts of tetrahydrofuran (hereinafter sometimes abbreviated as THF), 4.65 parts of lithium chloride (4.54 wt% concentration THF solution), and 0.45 parts of diphenylethylene to the reaction vessel, and cool to −60 ° C. did. Thereafter, 1.22 parts of n-butyllithium (15.36 wt% hexane solution) was added and aged for 10 minutes.
Next, 1.66 parts of 1-ethoxyethyl methacrylate (hereinafter abbreviated as EEMA), 9.9 parts of n-butyl methacrylate (hereinafter abbreviated as nBMA), methyl methacrylate (hereinafter, (It may be abbreviated as MMA) 4.14 parts of the mixed solution was added dropwise over 120 minutes, and the reaction was continued for 15 minutes after the addition. And it measured by gas chromatography (henceforth GC), and the loss | disappearance of the monomer was confirmed.
Next, 3.96 parts of 2- (dimethylamino) ethyl methacrylate (hereinafter sometimes abbreviated as DMMA) was added dropwise, and the reaction was continued for 30 minutes after the addition. And after measuring GC and confirming the loss | disappearance of a monomer, 0.41 part of methanol was added and reaction was stopped.
The obtained copolymer was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC) (mobile phase DMF, polymethyl methacrylate (hereinafter abbreviated as PMMA) standard), and molecular weight (Mw) Is a copolymer having a molecular weight distribution (Mw / Mn) of 1.46 and a composition ratio of DMMA- [nBMA / MMA / EEMA] = 21- [48/22/9]% by weight. did.
(Deprotection process)
16.44 parts of water was added to 65.64 parts of a 25 wt% concentration propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) solution of the obtained precursor polymer, and the mixture was heated to 100 ° C. and heated for 8 hours. Reacted. Water was distilled off to prepare a 40 wt% PGMEA solution.
The obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard), the molecular weight (Mw) was 12,720, the molecular weight distribution (Mw / Mn) was 1.46, and the composition ratio was DMMA- [nBMA / MMA. / MA] = 22- [50/23/5]% by weight of copolymer (MA represents methacrylic acid).
The obtained polymer solution was slightly yellow and transparent.

[Example 2]
(Polymerization process)
To the reaction vessel were added 600.30 parts of THF, 10.80 parts of lithium chloride (3.63% by weight concentration THF solution), and 3.84 parts of diphenylethylene, and the mixture was cooled to -60 ° C. Thereafter, 9.60 parts of n-butyllithium (15.36 wt% hexane solution) was added and aged for 10 minutes.
Next, a mixed solution of 103.84 parts of nBMA and 13.45 parts of EEMA was added dropwise over 30 minutes, and the reaction was continued for 15 minutes after the addition. And it measured by GC and confirmed the disappearance of the monomer. A part of the reaction solution was sampled and analyzed by GPC (mobile phase DMF, PMMA standard). As a result, the molecular weight (Mw) was 2,910 and the molecular weight distribution (Mw / Mn) was 1.03.
Next, 32.25 parts of DMMA was added dropwise, and the reaction was continued for 30 minutes after the addition. And after measuring by GC and confirming the loss | disappearance of a monomer, 3.42 parts of methanol was added and reaction was stopped.
When the obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard), the molecular weight (Mw) was 4,010 and the molecular weight distribution (Mw / Mn) was 1.07.
(Deprotection process)
220 parts of a PGMEA solution having a concentration of 50% by weight of the obtained copolymer was heated to 160 ° C. and aged for 3 hours.
The obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard, column changed), the molecular weight (Mw) was 12,040, the molecular weight distribution (Mw / Mn) was 1.24, and the composition ratio was DMMA- It was confirmed that the copolymer was [nBMA / MA] = 22- [73/5]% by weight.
The resulting polymer solution was brown.

  According to the present invention, a block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base, and the formula (III) Containing a repeating unit containing an acidic group represented by formula (II) and a block chain (B1) containing a repeating unit represented by formula (II), wherein the copolymerization ratio of the repeating unit represented by formula (II) is blocked A block copolymer that is 90% by mass or more in the chain (B1) can be produced. Those block copolymers are particularly useful as pigment dispersants for color liquid crystals.

Claims (7)

A block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and the formula (I)

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1-C3 alkyl group. X represents a single bond or a C1-C10 alkylene group, —C (═O) OR ^1a. A group selected from the group consisting of —, —C (═O) NHR ^1a —, —OC (═O) R ^1a —, and —R ^2a —OC (═O) —R ^1a — (R ^1a and R ^2a are Each independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ⁴ represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group. Or a C6-C10 aryl group, and R ⁵ represents a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group.) Contains The repeating unit and the formula (II)

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1-C3 alkyl group, and R ⁹ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.) A copolymer precursor containing a block chain (B) containing a repeating unit represented by formula (II), wherein the copolymerization ratio of the repeating unit represented by formula (II) is 90% by mass or more in the block chain (B) The block chain (A) and the formula (III)

(Wherein R ¹ , R ² , R ³ and X represent the same meaning as in formula (I)), the repeating unit containing an acidic group represented by formula (II) and the repeating unit represented by formula (II) The block copolymer (B1) containing, The manufacturing method of the block copolymer whose copolymerization ratio of the repeating unit represented by Formula (II) is 90 mass% or more in a block chain (B1). The repeating unit containing a tertiary amino group has the formula (IV)

^{(Wherein, R 10, R 11, R} 12 are each independently, .Y represents a hydrogen atom or a C1~C3 alkyl group, C1 -C10 alkylene ^{group, -C (= O) OR 1b} -, - Groups selected from the group consisting of C (═O) NHR ^1b —, —OC (═O) R ^1b —, and —R ^2b —OC (═O) —R ^1b — (R ^1b and R ^2b are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹³ and R ¹⁴ are each independently a C1-C6 alkyl group or a C6-C10 aryl group. The method for producing a block copolymer according to claim 1, wherein the repeating unit is a C1-C6 alkyl group. The repeating unit containing a quaternary ammonium base has the formula (V)

(Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a C1-C3 alkyl group. Y ¹ represents a C1-C10 alkylene group, —C (═O) OR ^1c —, Groups selected from the group consisting of —C (═O) NHR ^1c —, —OC (═O) R ^1c — and —R ^2c —OC (═O) —R ^1c — (R ^1c and R ^2c are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a C1-C6 alkyl group, or .Z representing the C6~C10 aryl C1~C6 alkyl group ^- the method for producing a block copolymer according to claim 1, characterized in that the repeating unit represented by the representative) a counter ion.. The method for producing a block copolymer according to any one of claims 1 to 3, which is carried out in a mixed solvent of an organic solvent and water. A block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and the formula (I)

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1-C3 alkyl group. X represents a single bond or a C1-C10 alkylene group, —C (═O) OR ^1a. A group selected from the group consisting of —, —C (═O) NHR ^1a —, —OC (═O) R ^1a —, and —R ^2a —OC (═O) —R ^1a — (R ^1a and R ^2a are Each independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ⁴ represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group. Or a C6-C10 aryl group, and R ⁵ represents a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group.) Contains The repeating unit and the formula (II)

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1-C3 alkyl group, and R ⁹ represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.) A copolymer precursor containing a block chain (B) containing a repeating unit represented by formula (II), wherein the copolymerization ratio of the repeating unit represented by formula (II) is 90% by mass or more in the block chain (B) . The repeating unit containing a tertiary amino group has the formula (IV)

^{(Wherein, R 10, R 11, R} 12 are each independently, .Y represents a hydrogen atom or a C1~C3 alkyl group, C1 -C10 alkylene ^{group, -C (= O) OR 1b} -, - Groups selected from the group consisting of C (═O) NHR ^1b —, —OC (═O) R ^1b —, and —R ^2b —OC (═O) —R ^1b — (R ^1b and R ^2b are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹³ and R ¹⁴ are each independently a C1-C6 alkyl group or a C6-C10 aryl group. The copolymer precursor according to claim 5, wherein the copolymer precursor is a repeating unit represented by a C1-C6 alkyl group. The repeating unit containing a quaternary ammonium base has the formula (V)

(Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a C1-C3 alkyl group. Y ¹ represents a C1-C10 alkylene group, —C (═O) OR ^1c —, Groups selected from the group consisting of —C (═O) NHR ^1c —, —OC (═O) R ^1c — and —R ^2c —OC (═O) —R ^1c — (R ^1c and R ^2c are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O-C1-C10 alkylene group.), R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a C1-C6 alkyl group, or an C6~C10 aryl C1~C6 alkyl group .Z ^- pairs copolymer precursor of claim 5, characterized in that the repeating unit represented by the representative) ions..