TW201213359A - Block copolymer production method and copolymer precursor - Google Patents

Abstract

Provided is a production method for a novel copolymer that is useful as a pigment dispersant, etc. The disclosed production method uses a copolymer precursor that contains a block chain (A), which includes at least one type of repeat unit selected from a group comprised of repeat units that contain tertiary amino groups and repeat units that contain quaternary ammonium bases, and a block chain (B), which includes repeat units represented by formula (II) and repeat units that contain protected acid groups represented by formula (I). This product is then heated to produce a block copolymer that contains the block chain (A) and a block chain (B1), which includes repeat units represented by formula (II) and repeat units that contain an acid group represented by formula (III).

Description

201213359 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel (tetra) polymer such as a dispersant of a seed pigment, a manufacturing method, and a copolymer precursor. The present application claims priority to Japanese Patent Application No. 2010-148868, the entire disclosure of which is hereby incorporated by reference. [Prior Art] It is known that at least a repeating unit, a repeating unit containing an acidic group, and a source derived from a group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a tertiary ammonium salt group A random copolymer of units of alkyl (meth) acrylate. . Polymers such as Hai have various properties based on their unique structures, and thus have been developed and researched in various fields. Patent Document 1 describes a pigment composition containing a pigment, an organic functional group-containing organic dye, an alkali-soluble resin, and an organic solvent, which is a base having an amine group and/or a 4-grade ammonium-based alkali-soluble resin thereof. The equivalent weight is 3000 20000 g/eq, and the acid value is 3〇~2〇〇. Specifically, as the alkali-soluble resin, a random copolymer such as n-butyl methacrylate, fluorenyl 'methyl acrylate, methacrylic acid, and decylaminoethyl decyl acrylate is described. In Patent Documents 2 and 3, attention is paid to the property of a positively or negatively charged amphoteric polymer by treating the random copolymer with an acid or a base, and the random copolymer is used as an electrophoretic combination. Things. Further, in Patent Document 4, the random copolymer is used as a binder of decyl isocyanate, focusing on the carboxyl group of the random copolymer and the reactivity of 157144.doc 201213359 amine group. Further, in Patent Document 5, a carboxyl group of the random copolymer is crosslinked with an epoxy group, and an amine group of the random copolymer is used as a catalyst for the crosslinking reaction to form a powder. Used as a body coating composition. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open No. Hei 4-62880 (Patent Document 5) Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei 61-6866 [Invention] [Problems to be Solved by the Invention] In recent years, copolymers The use of the company is diversified, and the industry is seeking copolymers with various characteristics. For example, in the field of color liquid crystal display devices, since the requirements for high transmittance and south contrast of visible light are strong, the pigment particles are micronized to at least the wavelength of visible light. With regard to such fine particles, since the specific surface area of the pigment particles becomes larger than usual, the copolymer for the pigment dispersant which has been used up to now is insufficient in the initial pigment dispersibility and the dispersion stability over time. Moreover, higher performance has recently been demanded in addition to dispersion properties. The prior copolymers failed to achieve sufficient performance. Accordingly, an object of the present invention is to provide a method for producing a copolymer and a copolymer precursor which have excellent dispersion properties over time and which have good dispersion stability over time and which have higher performance in addition to dispersion properties. [Means for Solving the Problem] The present inventors have diligently studied to solve the above problems, and as a result, found that copolymerization of a repeating unit represented by the formula (II) and the block chain (B1) and the block chain (B1) The above problem can be solved by a block copolymer having a ratio of 90% by mass or more in the block chain (B1), which comprises a repeating unit selected from the group consisting of a tertiary amino group and a 4-grade ammonium salt. The copolymer of at least one repeating unit of the group consisting of repeating units, wherein the block chain (B1) comprises a repeating unit containing an acidic group represented by formula (III) and a formula (11) a copolymer of a repeating unit; further, it is found that the above block copolymer can be copolymerized by repeating a unit represented by the formula (I) which is protected by heating an acidic group having an acidic group-containing repeating unit represented by the formula (III) The precursor is manufactured to complete the present invention. That is, the present invention relates to the following: (1) A method for producing a block copolymer comprising a block chain (A) and a block chain (B1), wherein the block chain (A) is The block chain (B1) 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 tertiary ammonium salt group contains the formula (III) The copolymerization ratio of the repeating unit having an acidic group and the repeating unit represented by the formula (π) and the repeating unit represented by the formula (II) is 90% by mass or more in the block chain (B i), 157144.doc 201213359

In the gas atom or C1-C3 alkyl group, 'R6, R7, and R8 are independently shown to represent an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

Wherein R, R and R each independently represent a hydrogen atom or a ci~c3 alkyl group; X represents a single bond or is selected from C1 to C10 alkyl, _c(= 〇) 〇Rla·, -C(=〇) a group in the group consisting of NHR', _OC(=0)Ru_, and _R2a_〇c(=〇)Rla (Rla, 11 are independently represented by cl~cl〇 alkyl or C1~C10 alkylene, respectively) a method of: heating a copolymer precursor comprising a block chain (A) and a block chain (B), wherein the block chain (B) contains a formula The copolymerization ratio of the repeating unit having a protected acidic group and the repeating unit represented by the formula (II) shown in (I) and the repeating unit represented by the formula (II) is 90 in the block chain (B1) More than % by mass, [Chemical 1]

(wherein, R1, R2, R3, X represent the same meanings as in the formula (III), and R4 represents 157144.doc 201213359 hydrogen atom, Cl~C6 alkyl group, C6~CIO aryl group C~C6 alkyl group or C6~CIO An aryl group, R5 represents a C1-C6 alkyl group, a C6-CIO aryl ci~C6 alkyl group or a C6-CIO aryl group; (2) A method for producing a block copolymer according to the above (1), which contains a grade 3 The repeating unit of the amine group is a repeating unit represented by the formula (IV), [Chemical 4]

(wherein R10, Ru, and Ri2 each independently represent a hydrogen atom or a C1 to C3 alkyl group, and Y represents a group selected from C1 to C10, _c(=〇)〇Rlb_, _c(=〇)NHRlb-, - a group of OC(=〇)Rlb_ and -R2b_〇C(=〇)_Rib_ (Rb, R2b independently represent C1~C10 alkyl or C^cioalkyl-O-Cl~ And C. The repeating unit of the 4- to ammonium salt group is a repeating unit represented by the formula (V), [Chemical 5]

Wherein RR and R each independently represent a hydrogen atom or a c 1 to C 3 alkyl group; Y 1 represents an alkyl group selected from C1 to C10, -C(=0)NHRlc-, -〇C(=〇)Ric_ and · r2c 〇丞, -C( = 〇) 〇 Rlc_, -〇C(=〇)_R' consists of 157144.doc 201213359 group (Rle, R2e independently represent cl~cl〇 alkyl or C1~C10 alkylene_〇_C1~C1〇alkyl), Rl8, r9, r20 each independently represent a Cl~C6 alkyl group or a C6~CIO aryl C1~C6 alkyl group, and the z- represents a counterbalance (4) The method for producing a block copolymer according to any one of the above 1 to 3, which is carried out in a mixed solvent of an organic solvent and water. Further, the present invention relates to the following: (5) a block copolymer comprising a block chain (A) and a block chain (B), wherein the block chain (A) contains a component selected from the group consisting of At least one repeating unit of the group consisting of a repeating unit of an amine group and a repeating unit containing a 4-hydroxyl group, the block bond (B) containing a protected acidic group represented by the formula (I) The copolymerization ratio of the repeating unit and the repeating unit represented by the formula (II) and the repeating unit represented by the formula (H) is 90% by mass or more in the block chain (B), [Chem. 6]

(wherein R1, R2, and R3 each independently represent a hydrogen atom or a C1 to C3 alkyl group; X represents a single bond or is selected from a C1-C10 alkyl group, -C(=0)0Rla-, -C(=0) a group of NHRla-, -0C(=0)Rla-, and -R2a-OC(=0)-Rla- (Rla, ana 2& independently represent Cl~CIO alkyl or C1- C10 alkyl-hydrazine-Cl~C10 alkylene) 'R4 represents a hydrogen atom, a C1 to C6 alkyl group, a C6-C10 aryl C1 to C6 alkyl group or a C6-C10 aryl group, and R5 represents a C1 to C6 alkyl group. , C6-C10 aryl C1~C6 alkyl or C6~C10 aryl) 157144.doc 201213359 [Chem. 7]

(wherein R6, R7, and R8 each independently represent a hydrogen atom or a Cl~C3 alkyl group, and R9 represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group); (6) A copolymer precursor of the above (5), which contains 3 The repeating unit of the amine group is a repeating unit represented by the formula (IV), [Chemical 8]

(wherein R10, R", R12 each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y represents an alkyl group selected from C1 to C10, -C(=0)0R b-, -C(=0) a group of NHRlb-, -〇C(=〇)Rlb· and _R2b-〇c(=〇)_Rlb- (Rlb, R2b independently represent Cl~CIO alkyl or C1~C10 alkyl-Ο-Cl~C10 alkylene group), R13 and R14 each independently represent a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group; and (7) a copolymerization as described in the above (5) The precursor of the precursor, wherein the repeating unit containing a 4- to ammonium salt group is a repeating unit represented by the formula (V), [Chem. 9]

(wherein ' Rl5 ' Rl6, Rl7 independently represent a hydrogen atom or a C1 to C3 alkane 157l44.doc 201213359 group; Y1 represents a group selected from a C1-C10 alkyl group, -C(= 〇)〇R"_, -C (=0) The base of the group consisting of NHRlc-, -OC(=0)Rlc-, and -R2c-〇C(=0)-Rlc- (Rle, R2e independently represent Cl~CIO C1 to C10 alkylene-O-Cl~C10 alkylene), R18, R19 and R2Q each independently represent a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group, and Z. represents a counter ion). [Embodiment] (I) Copolymer precursor The copolymer precursor used in the present invention contains at least one or less of the block chain (A) and the block chain (B), respectively. Block chain (A): contains a block chain block bond (B) of at least one repeating unit of a group consisting of a repeating unit having a 3-stage amine group and a repeating unit containing a 4-stage ammonium group: containing a repeat containing a protected acidic group a unit and a block chain of a repeating unit represented by the formula (II). Further, the copolymer precursor used in the present invention may contain other blocks in addition to the block chain (A) and the block chain (B). Chain 1) block chain (A) embedded In the segment bond (A), the repeating unit having a 3-stage amine group and the repeating unit having a 4-stage salt group are not particularly limited as long as they have the above cationic functional group in the side chain of the repeating unit. The block chain (A) includes a block chain comprising only a repeating unit containing a 3-stage amine group or a repeating unit containing a 4-stage ammonium salt group, a repeating unit containing a 3-stage amine group, or a 4-stage 157144.doc -10. 201213359 in a repeating unit of a salt group, at least one of two or more kinds of block chains, at least one type of repeating unit containing a third-order amine group, and a repeating unit containing a 4-stage ammonium salt group a block chain, and the block chain of the repeating unit derived from other copolymerizable monomers. The bonding of each repeating unit in the block chain (A) may be random, alternating, block, etc. Any of the above-mentioned (repeating unit containing a 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 for example, a repeat represented by the following formula (IV) can be exemplified. Unit. [10]

In the formula (IV), R10, R", and Ri2 are each independently a hydrogen atom or an alkyl group. Y is a group selected from C1 to C10 stretching groups, -C(=〇)〇Rlb_, _c(=〇)NHRlb_, -0C(=0)Rib_, and -R2b_〇c(=〇)_Rlb The base of R (R and R are independently C1~C10 alkyl or alkyl (~7) alkyl

C1~C10 alkylene). R is independently a C1 to C6 alkyl group or a C6-C10 aryl group C1 to C6. Here, as the C1 to C3 alkyl group and the C1 to C6 yard group, a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a second group can be exemplified. Base, n-pentyl, n-hexyl and the like.

a propyl chain, a propyl chain, a methyl extended ethyl chain, a butyl chain, an I]·didecyl extended ethylene chain, a pentyl chain, a methyl butyl chain, a 1,2-diyl group As a C6~CIO aryl C1~C6 alkyl group, it can be exemplified as: benzyl phenethyl, benzyl propyl, 1-phenyl hexyl A group, a naphthalene-1-ylmethyl group, a naphthalene-2-ylethyl group, a 1-(naphthalen-2-yl)-n-propyl group, a fluorenyl-methyl group or the like. Examples of the monomer which is a raw material of the repeating unit represented by the formula (IV) include didecylaminoethyl (meth)acrylate, dinonylaminopropyl (mercapto)acrylate, and mercapto. Didecylaminobutyl acrylate, diethylaminoethyl (meth) acrylate, diethyl aminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, and the like. (Repeating unit containing a quaternary ammonium salt group) The repeating unit containing the quaternary ammonium salt group is not particularly limited as long as it contains a quaternary ammonium salt group. For example, a repeating unit represented by the following formula can be exemplified. [化11]

In the formula (V), R15, R16 and R17 each independently represent a hydrogen atom or a C1 to C3 alkyl group. Y1 is selected from the group consisting of C1 to C10 alkyl, -CBu C〇〇Ric_, -C(=0)NHRlc-, -0C(=0)Rlc-, and -R2c-OC(=〇)-Ri. The groups in the group (Rle, R2e each independently represent a Cl~CIO alkyl group or a C1~C10 alkyl group-O-Cl~C10 alkyl group). R18, R丨9, and R2〇 are each independently a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group. Indicates the tooth ion, the chemical ion, the sulphonate ion, the oxynitride ion, the 157144.doc -12- 8 201213359 sulfate ion, sulfonate ion, phosphate ion or alkyl phosphate ion Wait for counter ions. Here, 'C1 to C3 alkyl group, C1 to C6 alkyl group, C1 to C10 alkylene group, and C6 to C10 aryl C1 to C6 alkyl group can be exemplified by the above formula (IV) having a repeating unit containing a tertiary amino group. ) the same. The monomer which is a raw material of the repeating unit represented by the formula (V) is exemplified by fluorinated (meth) propylene oxiranyl ethyl trimethyl ammonium chlorinated (meth) propylene oxy oxyethyl three Methylammonium, brominated (fluorenyl) propylene oxiranyloxyethyl trimethylate, broken (mercapto) propylene oxiranyl ethyl decyl ammonium, fluorinated (methyl) propylene Trimethylammonium, gasified (meth) propylene methoxy propyl trimethyl ketone, brominated (fluorenyl) propylene methoxy propyl trimethyl ammonium, iodized (meth) propylene oxime Propyltrimethylammonium, fluorinated (meth)propenyloxybutyltrimethylammonium, chlorinated (decyl)propenyloxybutyltrimethylammonium bromide, brominated (meth)acrylonitrile Butyl trimethyl ammonium, iodinated (fluorenyl) propylene methoxy butyl dimethyl ammonium, fluorinated (fluorenyl) propylene methoxyethyl benzyl dimethyl ammonium, gasification (fluorenyl) Propylene methoxyethyl benzyl decyl ammonium, brominated (fluorenyl) propylene oxyethyl benzyl dimethyl ammonium, iodide (decyl) propylene oxiranyl ethyl dimethyl dimethyl Ammonium, fluorinated (meth) propylene Oxypropyl propyl dimethyl ammonium, gasified (methyl) propyl methoxy propyl benzyl dimethyl, brominated (meth) propylene methoxy propyl benzyl dimethyl ammonium, Iodinated (meth) propylene methoxy propyl V dimethyl dimethyl, fluorinated (methyl) propylene oxy butyl benzyl dimethyl, gasified (methyl) propylene oxide Butyl benzyl dihydrazino, brominated (meth) propyl oxy butyl benzyl dimethyl ammonium, moth (meth) propylene methoxy butyl benzyl dimethyl ammonium, and the like. 157144.doc 13 201213359 (Other repeatable units may be contained) Examples of other repeating units which may be contained in the block chain (A) include: (fluorenyl) acrylic monomers, aromatic vinyl monomers, A repeating unit such as a lighter two-party monomer. The (meth)acrylic acid monomer, the aromatic vinyl monomer, and the conjugated diene monomer which are the raw materials of the above-mentioned repeating unit can be exemplified as follows. Examples of the (fluorenyl) acrylic monomer include (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; (meth)acrylic acid n-propyl vinegar; (methyl) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, (methyl) ) hexyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, i-ethylcyclohexyl (meth)acrylate, (meth)acrylic acid (A) Acrylic vinegar compound; (meth)acrylic acid 2-methoxyethyl ester, decyloxy polyethylene glycol (ethylene glycol unit number 2~1 〇〇) (meth) acrylate, B The oxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, etc. may be used alone or in combination of two or more. Examples of the aromatic ethylenic monomer include styrene, o-nonylstyrene, p-methylstyrene, p-tert-butylstyrene, α-mercaptostyrene, and p-tert-butoxybenzene. Ethylene, m-butoxystyrene, p-(1-ethoxyethoxy)styrene, 2,4-dimercaptostyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinyl Bismuth, 2-vinyl. a heteroaryl compound such as a pyridine, a 4-vinylpyridine, a 2-vinylquinoline, a 4-vinylquinoline, a 2-vinylthiophene or a 4-vinylthiophene, etc., which may be used alone, or 157144.doc •14· 201213359 Mixed use of 2 or more types. As a total of two rare-r si m, jin 'early body, can be cited. 1,3 - butadiene, isoprene, 2-ethyl-1,3-butanedifluoride - Γ «. Tablet 2 - second butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 'mercapto-1,3-butadiene, 1,3-pentadiene, 2_曱基-1,3 - pentane, az! 3, __ knee JT^-l, 3-pentyl, iota, hexadiene, 2-alumina '3 octene, 4,5-diethyl-1,3-octadiene , 3-butyl-indole, 3-octadiene, 1,3_cyclopentadiene, cyclohexane, w cyclopentate, ruthenium tricycle, laurel, chloroprene: These may be used alone or in combination of two or more. 2) Block chain (B) - The block bond (B) contains at least one repeating unit containing a protected acidic group and at least one repeating unit represented by the formula (11). In the insert key (B), the copolymerization ratio of at least the repeating unit represented by the formula (π) is 9 〇 by mass or more, preferably 3% by mass and % by mass. (Repeating unit containing a protected acidic group) Further, the heavy unit containing the protected acidic group in the chain (B) is a repeating unit represented by the formula (1). [化 12]

(I) η 中 '^^ is independently a gas atom or a ~(tetra) group. = early bond or selected from the group consisting of C1~C10 stretching base, ·c(-_0)0Rla-, -__R, ton, Rla• and Rla 157144.doc •15- 201213359 group (Rla) R2a is independently a Cl~Cl0 alkyl group or a Cl~Cl0 stretching group-0-C1~CIO alkyl group) 'R4 is a hydrogen atom, a Cl~C6 alkyl group, a C6~Cl0 aryl C1~C6 alkyl group. Or a C6~CIO aryl group, R5 is a C1~C6 leucoyl group, a C6~C10 aryl C1~C6 alkyl group or a C6~cl〇 aryl group. Examples of the monomer which is a raw material of the repeating unit represented by the formula (1) include methoxymethyl acrylate, ethoxymethyl acrylate, hydrazine acrylate-ethoxyethyl ester, and 1-methoxyethyl acrylate.丨-ethoxypropyl acrylate, 1-propoxyethyl acrylate, hydrazine isopropyl isopropoxide, hydrazine acrylate-benzyloxyethyl hydrazine, 2-ethyl acrylate ethoxyethyl ester, 2_Methylpropionate, methoxymethoxy, 2-methyl-acrylic acid ethoxypropyl, 2-methylpropionic acid, propionic acid, S, 2, methacrylic acid, isopropyl Oxygen from the purpose, 2_methyl propylene

Two or more types are used in combination.

The repeating unit of the base. (Repeating unit represented by the formula (II)) The repeating monoblock chain (B) further contains at least one of the following formula (π). [Chem. 13]

157144.doc •16- 201213359 In the formula (π), R6, R7 and R8 represent a hydrogen atom or a C1 to C3 alkyl group, and represent an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. In the present invention, the ～(10) group can be exemplified as the same as the above formula (IV) containing the repeating unit of the ternary amine group. In the present invention, the aliphatic hydrocarbon group of R9 may be any of saturated or unsaturated, and includes a C1 to C2 fluorene group, an alkyl group of C2 to C2, and an alkynyl group of C2 to C2. Examples of the alkyl group of C1 to C20 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl-n-pentyl group, an isopentyl group, and a neopentyl group. , third mercapto, 2_mercaptobutyl, n-hexyl, isohexyl 3·methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl*, third Octyl, 2-ethylhexyl, 3-methylheptyl, n-decyl, isodecyl, i-methyloctyl, ethylheptyl, n-decyl, fluorenylmethyl decyl, n-undecane Base, M-dimethylindenyl, n-dodecyl, n-tetradecyl, n-heptadecyl, n-octadecyl and the like. Among these, an alkyl group of C1 to C6 is preferred. Examples of the alkenyl group of C2 to C20 include a vinyl group, a fluorene-propenyl group, a 2-propenyl group, a butenyl group, a 2-butenyl group, a 3-butenyl group, and a decyl-2-propenyl group. 2-methyl-2-propenyl, indolyl, 2-pentenyl, = alkenyl, 4-pentenyl, 1-methyl-2-nitinyl, 2-methyl-2-butene , "hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl' 5-hexenyl, heptenyl, octenyl, nonenyl, pentadecenyl, hexa Alkenyl, behenyl, etc.. Among these, a C2 to C6 group is preferred. Examples of the above C2 to C20 alkynyl group include an ethynyl group, a fluorenyl group, and a 157144.doc -17. · 201213359 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-2-propynyl, 1- Pentynyl, 2-pentynyl, 3-pentenyl, 4-pentopenyl, 1-indenyl-2-butanyl, 2-methyl-2-butanyl, 丨-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 丨-heptyl, 1-octynyl, 1,4-decyl, 1-pentadecanyl, 1 _ twenty fast radicals, 1-tetracosyl alkynyl, etc., preferably C2 to C6 alkynyl groups Further, in the present invention, the alicyclic hydrocarbon group is a saturated or unsaturated hydrocarbon group having a monocyclic or polycyclic cyclic structure in any part of the group, and includes: a C3 to C20 cycloalkyl group, a C4-C20 group. Alkyl-substituted ring-based, C4-C20 cycloalkylalkyl, C3-C2 fluorene cycloalkenyl, C4-C2 oxime-substituted cycloalkenyl, C4~C20 cycloalkenyl The cross-linked cyclic hydrocarbon group of C7 to C20, etc. Examples of the cycloalkyl group of C3 to C20 include a cyclopropyl group, a cyclobutyl group, a decylpentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Preferably, it is a C3 to C8 cycloalkyl group. As the above-mentioned C4 to C20 alkyl group-substituted cycloalkyl group, 丨-methylcyclopropyl group, 2-ethylcyclopropyl group, 3-methyl group are mentioned. Cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 2-methylcyclooctyl, etc. Preferably, an alkyl-substituted cycloalkyl group of C4 to C10 is used. The cycloalkyl group of C3 to C20 may, for example, be cyclopropylmethyl, cyclobutylmethyl, cyclopentyldecyl, cyclohexylmethyl, cycloheptylethyl or cyclooctylethyl. a cycloalkyl group of C4 to C10 Examples of the above-mentioned C3-C20 ring-dense group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctyl group, and a cyclopentyl group 157144.doc • 18· 201213359 The dienyl group is preferably a C3 to C8 cycloalkenyl group. The alkyl group-substituted cycloalkenyl group of the above C4 to C20 may, for example, be 3-ethylcyclopentenyl or hexenyl. 4-methylcyclohexenyl, 4-ethylcyclohexenyl, etc., preferably an alkyl-substituted cycloalkenyl group of CM to C10. Examples of the cycloalkylenealkyl group of the above C4 to C20 include a cyclopropenylmethyl group, a cyclobutenylmethyl group, a cyclopentenylethyl group, and a cyclohexenylethyl group. More preferably, it is a C4 to C10 cycloalkenylalkyl group. Examples of the crosslinked cyclic hydrocarbon group of the above C7 to C.20 include a tricyclo[5·2·1·〇2'6]decane-8-yl group, an adamantyl group, a dicyclopentenyl group, and an isoclinic group. Wait. (Other repeating units which may be contained) Examples of other repeating units which may be contained in the block chain include a repeating unit derived from an aromatic vinyl monomer or a conjugated diene monomer. Examples of the aromatic vinyl monomer include styrene, o-methylphenyrene, p-nonylstyrene, p-tert-butylstyrene, α-mercaptostyrene, and p-butoxybenzene. Ethylene, m-butoxystyrene, p-(1-ethoxyethoxy)styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinyl蒽, 2_vinyl β-pyridinium, 4_vinyl ratio bite, 2-ethylene sulfonium, 4-ethylene sulfonium, 2-ethylene thiophene, 4-ethylene thiophene, etc. An aryl compound or the like may be used alone or in combination of two or more. Examples of the total diene monomer include 1,3-butadiene, isoprene, 2-ethyl-1,3·butadiene, and 2·t-butyl-hydrazine, 3-butadiene. Alkene, 2-phenyl-1,3·butadiene, 2,3-dimercapto·ι,3-butadiene, 1,3-decadiene, 2- I57144.doc •19· 201213359 methyl -1,3-pentadiene, 3-methyl-1,3-pentadiene, iota, 3-hexadiene, 2-methyl-1,3-octane dilute, 4,5-diethyl -1,3-octane, 3-butyl-1,3-octanedipine, anthracene, 3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1 In the case of 3-tricyclodecadiene, myrcene, and gas butadiene, these may be used alone or in combination of two or more. 3) Other matters (block chains which may be contained in addition to the block chains (A) and (B) in the copolymer) The copolymer precursor used in the present invention may contain other inlays in addition to the block chain. Segment chain. Examples of such a block chain include an inlaid bond containing a repeating unit derived from a (meth)acrylic monomer, an aromatic vinyl monomer, or a conjugated diene monomer, and a bonding of each repeating unit. It may be any form such as homopolymerization or random copolymerization 'alternating copolymerization, block copolymerization, and the like. The (fluorenyl) acrylic monomer, the aromatic vinyl monomer, the conjugated diene monomer, and the like can be exemplified as described above. (The ratio of the block chain (A) to the block chain (B) in the copolymer and the physical properties such as the molecular weight) The ratio of the block chain (A) to the block chain (B) in the copolymer of the present invention is not particularly The limit is 1 〇 to 4 重量 in a weight-% ratio: 9 〇 to 6 〇, preferably 丨 5 to 35: 85 to 65 〇 again, measured by GPC (gel permeation chromatography) The weight average molecular weight is 2 000 to 5 Å, and the copolymer precursor is particularly preferably 4,000 to 15, 〇〇〇. The ratio of the weight average molecular weight to the number average molecular weight measured by Gpc is 157144.doc •20·201213359 (2) Method for producing copolymer precursor The method for producing the copolymer precursor used in the present invention is It is not particularly limited and can be produced by a known method. For example, a monomer can be polymerized by living polymerization to form a block copolymer. As the living polymerization, active from

From the group polymerization, living anionic polymerization and the like, among them, the living anion is more preferably polymerized. A. In order to form a block copolymer, after the monomer of the block chain (A) or (B) is polymerized, the monomer of the other block may be continuously polymerized to block copolymerize, or the block chain may be obtained. (A) After reacting with each monomer of the block chain (B) to form a block, each block is bonded. The living anionic polymerization is preferred in terms of tightly controlling the composition or molecular weight. In the case of production by living radical polymerization, the reaction can be carried out in the same manner as the living anionic polymerization. Alternatively, after the monomer of a certain block is polymerized, the polymer is temporarily purified and removed before the next monomer is polymerized. The former one: After the residual monomer, the next monomer is polymerized. In the case where the monomers of the respective blocks are not mixed with each other, it is preferred to carry out purification of the polymer. In the case of producing a block copolymer by living anionic polymerization, for example, a desired monomer can be added dropwise to a solvent to which an additive and a polymerization initiator are added to carry out polymerization. At this time, in order to form the block polymer ' of the desired arrangement, each block is sequentially dropped and reacted in such a manner as to have a desired arrangement. In order to polymerize the monomer of a block, the monomer of the lower block is repolymerized, and after the polymerization of the pre-block is completed, the dropwise addition of the monomer of the next block is started. The polymerization can be carried out by using gas chromatography or liquid chromatography 157144.doc • 21· 201213359 to detect the remaining amount of the monomer and confirming that the monomer of the m block is added after the end. The type of the solvent may vary, but it is also possible to start the dropwise addition of the monomer of the next block after stirring for 1 minute to 1 hour. In the case where a plurality of monomers are contained in each block, these may be added dropwise or may be added dropwise at the same time. The anionic polymerization initiator used for the polymerization of the monomer is not particularly limited as long as it is a nucleophilic agent and has a function of starting polymerization of the anion polymerizable monomer. For example, an alkali metal or an organic alkali metal compound can be used. Wait. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and the like. The organic alkali metal compound may, for example, be an alkylate, an allyl compound or an aryl compound of the above alkali metal, and more preferably an alkyl lithium. Specifically, s can be used: ethyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, ethyl sodium, biphenyl lithium, naphthyl lithium, triphenyl lithium, naphthyl sodium , naphthyl potassium, sodium a-methylstyrene dianion, ul-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 14 dilithium 2 -butene, 16 - dilithium hexane, polystyryl lithium, cumyl potassium, cumene hydrazine, and the like. These anionic polymerization initiators may be used singly or in combination, and the amount of use of two or more kinds of anionic polymerization initiators is usually 0.0001 to 0 2 equivalents relative to all anionic polymerizable monomers used. Good for 〇〇〇〇 5 ~ 〇丄 equivalent. By using an anionic polymerization initiator of this range, the target polymer can be produced in a good yield. The polymerization temperature 'is not particularly limited to -locrc or more, as long as it does not cause a side reaction such as a shift reaction or a reaction such as a reaction, and the monomer is consumed and the polymerization is completed. It is carried out within the temperature range below the boiling point. Further, the concentration of the monomer relative to the polymerization solvent is not particularly limited and is usually from 1 to 40% by weight. /. Preferably, it is from 1 to 30% by weight. The polymerization solvent to be 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 specific examples thereof include diethyl ether, tetrahydrofuran (THF), and An ether compound such as alkane or dioxane; a polar solvent such as a third amine such as tetramethylethylenediamine or hexamethylphosphonium triamine; or an aliphatic, aromatic or alicyclic hydrocarbon such as hexane or methyl bromide. A non-polar solvent such as a compound or a low-polarity solvent may be used alone or in combination of two or more. In the production method of the present invention, even when a nonpolar solvent or a low polar solvent is used in combination with a polar solvent, the polymerization can be controlled with high precision, for example, a nonpolar solvent or a low polar solvent can be used with respect to all solvents. The volume% or more may be 20% by volume or more, and may be 5% by volume or more. In the present invention, an organic metal such as a dialkyl group such as diethyl zinc or a dialkyl magnesium or a triethyl aluminum such as dibutyl magnesium may be used as a polymerization stabilizer, a monomer or a solvent. Agent. In the present invention, a metal salt or a soil test metal additive may be added at the start of polymerization or during the polymerization as needed. Specific examples of such an additive include a mineral acid salt or a dentate such as a sulfate of sodium, potassium, barium or magnesium, a nitrate or a borate; more specifically, a vapor of lithium or cesium is exemplified. , bromide, iodide, or lithium borate, magnesium nitrate, sodium chloride 'chlorination and so on. Among these, it is preferably a tooth of a bell, such as gasification, lithium desertification, lithium iodide, lithium fluoride, and particularly preferably lithium vapor. 157144.doc •23- 201213359 It is generally difficult to polymerize monomers containing a quaternary ammonium salt group by living anionic polymerization. When a monomer having a repeating unit having a (quaternary ammonium salt group) is produced by living anionic polymerization, a monomer which can be polymerized into a raw material of a repeating unit containing a tertiary amino group can be produced by a known method. The tertiary amine group is 4-staged. As the 4-staged agent, there may be mentioned: gasification of octenant, or gas-fired, gas-fired, and desertified: methylated, dimethyl sulfate, sulfuric acid A general alkylating agent such as diethyl ester or di-n-propyl sulfate. (3) Block copolymer The block copolymer produced in the present invention contains at least one of the following block chains (A) and block chains, respectively. (B1) Talk about the segment chain (A): a block chain 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 4-stage salt group; (B1): a block chain comprising a repeating unit containing an acidic group and a repeating unit represented by the formula (π). Further, the copolymer of the present invention is in addition to the above-mentioned block chain (A) and block chain (B1). May contain other block chains. 1) Block chain (A) Block chain (A) in block copolymer and embedded in the above copolymer precursor The bond (A) is the same. 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). .doc -24- 8 201213359 The copolymerization ratio of at least one of the repeating units represented by the formula (II) in the stagnation button (B1) is 90% by mass or more, preferably 91% by mass to 99% by mass. .

(Repeating unit containing an acidic group) The repeating unit containing an acidic group in the block chain (B1) is a repeating unit represented by the formula (111). [Chem. 14]

In the formula (III), 'R1, R2, R3 and X have the same meanings as the repeating unit having a protected acidic group represented by the formula (1). The repeating unit represented by the formula (III) can be obtained by deprotecting the protective group of the protected acid group represented by the formula (1) by the production method of the present invention. (Repeating unit represented by the 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 above copolymer precursor. (Other repeating units which may be contained) The other repeating unit which may be contained in the block chain (B1) is the same as the other repeating unit which may be contained in the block chain (B) of the above copolymer precursor. (Block bond which may be contained in the block copolymer other than the block chain (A) or (B1)) The copolymer used in the present invention may have, in addition to the block chain (A) and (B1), Other block chains comprising a polymer. 157144.doc •25· 201213359 In the copolymer precursor, such a block chain is the same as the block chain which may be contained other than the block chains (A) and (B). (The ratio of the block chain (A) to the block chain (B1) in the copolymer and the physical properties such as molecular weight) The block bond (A) and the block chain (B i) in the copolymer used in the present invention The ratio is not particularly limited, and is 1 〇 to 4 重量 in a weight-% ratio: 9 〇 to 6 〇, preferably 15 to 35: 85 to 65 ^ Further, the content ratio of the repeating unit having an acidic group in the copolymer It is 0.5 to 20% by weight 'preferably 15% by weight. Further, the weight average molecular weight measured by GPC is 2 Torr to 5 Torr, and the dispersing agent is preferably 2,000 to 2 Torr, more preferably 4 Torr to 15 Torr. The ratio of the weight average molecular weight to the number average molecular weight measured by GPC is 1.0 to 2.0 Å as a dispersing agent, particularly preferably 1. 〇~丨5. (4) Process for producing block copolymer The block copolymer of the present invention can be obtained by heating the above copolymer precursor. The protecting group protecting the acidic group in the copolymer precursor is deprotected by heating the copolymer precursor. The heating temperature varies depending on the structure of the protecting group for protecting the acidic group, but there is no particular limitation as long as the temperature at which the deprotection reaction can be rapidly carried out. It is usually preferably from 8 〇 t to 200. (Below, more preferably 1〇〇〇c~160〇C. The deprotection reaction can directly heat the copolymer precursor, or can be heated in a state where the ruthenium polymer precursor is dissolved in a solvent. Examples of the solvent include water; ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate. Base solubilizer, bismuth-based cellosolve, propylene glycol monomethyl scale, 157144.doc • 26· 201213359 propylene glycol monoethyl (tetra) and diethylene glycol dimethyl (10) and other diol mono or diterpenoid solvents; toluene, single An aromatic hydrocarbon solvent such as chlorobenzene; an alcohol solvent such as acetamidine, isopropanol, n-butanol or 1-methoxy-2-propanol (PGME); lactic acid ethyl acetate, butyl acetate and pyruvic acid The above-mentioned H-containing agent; and the above-mentioned two or more kinds of mixed solvents and the like are included. Among them, the diol test (4) (4), the diol brewing solvent and the alcohol solvent are mixed with the H(tetra) solvent and water. The solvent mixture is preferably a mixed solvent of a diol-based solvent and an alcohol-based solvent from the viewpoint of lowering the reaction temperature. The diol (4) is a mixed solvent of a solvent and water, and more preferably a mixed solvent of a glycol ether ester solvent and water. From the viewpoint of easily removing by-products formed by the deprotection reaction, it is preferably a diol vinegar. A solvent mixture of a solvent and water is particularly preferably a mixed solvent of PGMEA and water. In a mixed solvent of a glycol ether ester solvent and an alcohol solvent, the mixing ratio 'as long as the copolymer precursor is soluble' is not particularly The limitation is usually preferably 95/5 wt% to 1/99.9 wt%, more preferably 5〇/5〇~〇1/99 9 wt%. In a mixed solvent of a glycol ether ester solvent and water. The mixing ratio is not particularly limited as long as the copolymer precursor is soluble, and is usually preferably 95/5 to 50/50% by weight, more preferably 9〇/10 to 6〇/4〇% by weight, particularly The temperature is preferably 90/10 to 70/30% by weight. 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 it is a temperature at which the deprotection reaction can be rapidly carried out. When a glycol ether ester solvent is used, it is usually preferably 157144.doc •27·201213359 80t~2〇n: The next step is more preferably carried out in the mouth of the Nagasaki q 7G. When using a mixed solvent of a diol (tetra) solvent and an alcohol solvent, it is preferably um^uot. Further, it is preferably carried out under U (rc~i4 (r. under rc. When diol is used as a mixed solvent of a solvent and water, it is preferably carried out at 7 ° C to 12 G ° C, more Preferably, it is carried out at 9 G ° C to 12 G ° C. From the viewpoint of lowering the color of the polymer solution formed by the deprotection reaction, it is preferred that the heating temperature is lowered. [Examples] The present invention is described in detail, but the technical scope of the present invention is not limited by the examples. [Example 1] (Polymerization step) To a reaction vessel, 55 7 parts of tetrahydrofuran (hereinafter sometimes abbreviated as THF), lithium chloride (concentration of 4.54% by weight of 1's solution), 4.65 parts, and 0.45 parts of stilbene were added. , cooled to -60 ° C. Thereafter, 22 parts of n-butyllithium ruthenium (15-36 wt% of a hexane solution) was added and aged for 1 Torr. Next, 1 to 66 parts of methacrylic acid methacrylate (hereinafter sometimes abbreviated as EEMA) and n-butyl methacrylate (hereinafter sometimes abbreviated as η ΒΜΑ) 9·9 parts were added dropwise in 120 minutes. A mixture of methyl acrylate (hereinafter sometimes abbreviated as MMA) of 4.14 parts was allowed to continue to react for 15 minutes after the dropwise addition. Then, the measurement was carried out by gas chromatography (hereinafter abbreviated as GC) to confirm the disappearance of the monomer. Next, 3.96 parts of 2-(dimethylamino)acetic acid (hereinafter sometimes referred to as DMMA) of mercaptopropionate was added dropwise, and the reaction was continued for 30 minutes after the dropwise addition. Then, after confirming the disappearance of the monomer by 157144.doc • 28 - 201213359 GC measurement, 0.41 parts of sterol was added to stop the reaction. Analyzed by gel permeation chromatography (hereinafter referred to as GPC) (mobile phase DMF (dimethylformamide), polymethyl methacrylate (hereinafter sometimes referred to as PMMA) as a standard) The copolymer obtained was confirmed to have a molecular weight (Mw) of 12,220, a molecular weight distribution (Mw/Mn) of 1.46, and a composition ratio of DMMA-[nBMA/MMA/EEMA]=21-[48/22/9]% by weight. Copolymer. (Deprotection step) 16.64 parts of water was added to 65.64 parts of a solution of propylene glycol monodecyl ether acetate (hereinafter sometimes abbreviated as PGMEA) having a concentration of 25% by weight of the precursor polymer obtained, and heated to 1 Torr. The reaction was allowed to proceed for 8 hours at °C. The water was distilled off to prepare a solution of 40% by weight of 2PGMEA. The obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA) to confirm that 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-[5 0/23/5]% by weight of the copolymer (ΜΑ represents methacrylic acid). The polymer solution obtained was slightly yellowish transparent. [Example 2] (Polymerization step) 600.30 parts of THF, 10.80 parts of lithium chloride (3.63 wt% of a solution of butyl hydride), 3.84 parts of stilbene were added to a reaction vessel, and it was cooled to -60. Thereafter, 9.60 parts of n-butyllithium (15.36% by weight of a hexane solution) was added and aged for 10 minutes. Next, a mixture of nBMA 103·84 parts and EEMA 13.45 parts of 157144.doc 29-201213359 was added dropwise over 30 minutes, and the reaction was continued for 15 minutes after the dropwise addition. Then, by GC, it was confirmed that the monomer disappeared. A portion of the reaction liquid was sampled and analyzed by GPC (mobile phase DMF, using PMMA as a standard). The resulting 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 dropwise addition. Then, after measuring by GC, it was confirmed that the monomer disappeared, and 3.42 parts of methanol was added to stop the reaction. The copolymer obtained was analyzed by GPC (mobile phase DMF, PMMA), and the molecular weight (Mw) was 4,010 and the molecular weight distribution (Mw/Mn) was 1.07. (Deprotection step) 220 parts of the PGMEA solution having a concentration of the obtained copolymer of 50% by weight was heated to 160 ° C and aged for 3 hours. The obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA as a standard, and the column was replaced), and it was confirmed that the molecular weight (Mw) was 12,040, the molecular weight distribution (Mw/Mn) was 1.24, and the composition ratio was DMMA-[ nBMA/MA]=22-[73/5]% by weight of the copolymer. The polymer solution obtained was brown. [Industrial Applicability] According to the present invention, a block copolymer containing a copolymerization ratio of a block chain (A) and a block chain (B1) and a repeating unit represented by the formula (II) can be produced. It is 90% by mass or more in the block chain (B1), and the block chain (A) contains at least one selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a 4-stage ammonium salt group. In the case of one repeating unit, the block chain (B1) contains a repeating unit containing an acidic group and a repeating unit represented by the formula (II) represented by the formula 157144.doc • 30·201213359 (III). These block copolymers are especially useful as dispersants for pigments and the like. 157144.doc -31 -

Claims (1)

201213359 VII. Patent Application Range: 1. A method for producing a block copolymer comprising a block chain (A) and a block chain (B1), wherein the block chain (A) is selected from the group consisting of The at least one repeating unit of the group consisting of a repeating unit having a third-order amine group and a repeating unit containing a fourth-order ammonium salt group, wherein the block chain (B1) contains an acidic group represented by the formula (III) The copolymerization ratio of the repeating unit and the repeating unit represented by the formula (II) and the repeating unit represented by the formula (II) is 90% by mass or more in the block chain (B1), [Chemical 2] (wherein R6, R7 and R8 each independently represent a hydrogen atom or a C1 to C3 alkyl group; R9 represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group) [Chemical 3] Wherein R 1 , R 2 and R 3 each independently represent a hydrogen atom or a C 1 C to C 3 alkyl group; X represents a single bond or is selected from a C 1 -C 10 alkyl group, -C(=0)0 Rla-, -C (=〇 a group of NHRla_,_0C(=0)Rla- and _R2a-〇C(=〇)-Rla_ (Rla, 1123 independently represent C1~Cl〇 alkyl or C1~C10 alkylene a method of heating a copolymer precursor comprising a block chain (A) and a block chain (B), wherein the block bond (B) contains a copolymerization ratio of a repeating unit having a protected acidic group and a repeating unit represented by the formula (II) represented by the formula (1) and having a repeating unit of 157144.doc 201213359 represented by the formula (Π) in the block chain (B) Medium is 90 quality. /〇以[化1] (wherein R 1 , R 2 , R 3 and X represent the same meanings as in the formula (III), and r 4 represents a hydrogen atom, a C 1 -C 6 alkyl group, a C 6 -C 10 aryl C 1 -C 6 alkyl group or a C 6 -C 10 aryl group, r 5 Represents ci~C6 alkyl, C6~C10 aryl C1~C6 or C6~C10 aryl). 2. The method for producing a block copolymer according to claim 1, wherein the repeating unit having a tertiary amino group is a repeating unit represented by the formula (IV), [Chemical 4] (wherein, Ri, Rn, and R 2 each independently represent a hydrogen atom or an alkyl group, and Y represents a radical selected from C1 to C10, -c(= 〇)〇Rlb_C(~0)NHR a group in the group consisting of b-, -〇C(=〇)Rlb- and -R2b_〇c(=〇)-Rib_ (R b, R2b independently represent c 1~c 1 〇 stretching base, respectively) Or C 卜 CIO alkyl _ 〇 _C1 ~ C1 烷基 alkyl), R13, Rl4 independently represent C1 ~ C6 alkyl or C6 ~ C10 aryl C1 ~ C6 yard base) 长 with long term 1 embedded The method for producing a copolymer, wherein the repeating unit having a 4-stage salt base is a repeating unit represented by the formula (V), 157J44.doc 8 -2 201213359 [Chemical 5] (wherein R15, R16, and R!7 each independently represent a hydrogen atom or a silane group, and Y1 represents a group selected from C1 to C10, _C(= 〇) 〇Rlc-, The group in the group (Rlc, R2c independently represent Ci~ci〇 extension base or C1~C10 extension base-Ο-Cl~C10 extension base), and R18, r19, r2〇 respectively represent cn~ C6 alkyl or C6 to C10 aryl C1 to C6 alkyl, ζ· represents a counter ion). 4. 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. 5. A copolymer precursor comprising a block chain ( A) and block bond (B), the 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 4-hydroxyl group The enemy group bond (B) is a combination of a repeating unit having a protected acidic group represented by the formula (I) and a repeating unit represented by the formula (II) and a repeating unit represented by the formula (II). The polymerization ratio is 90% by mass or more in the block chain (B), [Chemical 6] 157144.doc 201213359 (wherein R 1 , R 2 , and r 3 each independently represent an argon atom or a ChC 3 alkyl group; X represents a single bond or is selected from a C 1 alkyl group, -C(=0)0 Rla-' -C ( =〇)NHRla- > -OC(=〇)R, a-^-R2a-0C(=0)-Rla-m ^ The group in the group (Rla, R2a independently represent Cl~CIO) a group or a Cl~CIO alkyl group _〇_C1~C1 〇 alkyl group), R4 represents a hydrogen atom, a C1~C6 alkyl group, a C6~ci〇 aryl ci~C6 alkyl group or a C6~C10 aryl group, R5 Represents C1~C6 alkyl, C6~C10 aryl C1-C6 alkyl or C6~C10 aryl)' [Chemical 7] (wherein R6, R7 and R8 each independently represent a hydrogen atom or a C1 to C3 alkyl group 'R9 represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group). 6. The copolymer precursor of claim 5, wherein the repeating unit having a tertiary amino group is a repeating unit represented by the formula (IV), [Chem. 8] (wherein R10, R", base; Y represents a selected from, _C(=〇)NHRlb-R12 independently represents a hydrogen atom or a Ci~C3 alkane from a C1 to C10 alkyl group, _c(= 〇)〇Rlb · -0C (=0) Rlb- and -R2b_OC(=〇)_Rib are groups in the group (Rlb, R2b independently represent C1~cl〇 alkyl or C1~C10 alkyl-〇_C卜C10 alkylene), Rn, ri4 are independently, 57, 44doc -4- 8 201213359 represents Cl~C6 fluorenyl or C6~C10 aryl C1~C6 alkyl). 7. A copolymer precursor according to the kiss 5, wherein the repeating unit having a 4- to 4-ammonium group is a repeating unit represented by the formula (V), [Chemical 9] Wherein R15, R16 and R17 each independently represent a hydrogen atom or a Cl~C3 alkyl group; Υ1 represents an alkyl group selected from C1 to C10, -C(=0)0Rlc-, -C(=〇)NHRlc- , -0C (=0) Rlc- and -R2c-0C (=0)-Rle- group in the group (Rle, R2e independently represent Cl~CIO alkyl or ~C10 alkyl)-〇 -C1~C10 alkylene group), R18, R19 and R2Q each independently represent a C1~C6 alkyl group or a C6~C10 aryl C1~C6 alkyl group, and Z· represents a counter ion). 157144.doc 201213359 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 157144.doc 8