TWI425012B - Preparation of Block Copolymer and Copolymer Precursor - Google Patents

Description

Method for producing block copolymer and copolymer precursor

This invention relates to a process for the manufacture of novel block copolymers useful as pigment dispersants, and novel copolymer precursors. The present application claims priority to Japanese Patent Application No. 2010-092952, filed on Apr. 14, 2010, the content of which is incorporated herein.

It is known to have at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group, a repeating unit having a polyoxyalkylene chain, and having an acidity a random copolymer of repeating units.

These polymers have been researched and developed in various fields because of their various properties based on this specific structure.

In Patent Document 1, the random copolymer is applied to the field of photolithography. Patent Document 1 specifically describes an ester compound of methacrylic acid, dimethylaminoethyl methacrylate, ethyl acrylate, and polyethylene glycol monomethyl ether having a molecular weight of 350 and methacrylic acid. And the obtained copolymer and the like. These are obtained by radically polymerizing a mixed solution of each monomer in a methyl ethyl ketone solvent by using azobisisobutyronitrile (AIBN) as a radical initiator. .

Further, in Patent Document 2, the random copolymer is used as a pigment dispersant in various fields such as paints, inks, and building materials. Patent Document 2 specifically describes 10 parts of styrene, 15 parts of methyl methacrylate, 15 parts of ethyl methacrylate, 20 parts of methacrylic acid, and tridecyl methacrylate. 10 parts, 20 parts of polyethylene glycol monomethyl ether methacrylate (number average molecular weight of 400), 10 parts of random copolymer of dimethylaminoethyl methacrylate, and the like. These are obtained by using 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical initiator in a mixed alcohol solvent of ethanol/methanol=95/5. The mixed solution was subjected to radical polymerization to obtain a random copolymer.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 6-128336

Patent Document 2: Japanese Patent Special Open 2009-24165

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, since the requirements for high transmittance and high contrast of visible light are enhanced, the pigment particles are micronized to at least the wavelength of visible light. In such fine particles, the specific surface area of the pigment particles becomes larger than usual, and thus the copolymer for the pigment dispersant which has been used up to now, the initial pigment dispersibility and the dispersion stability over time are insufficient. Moreover, high performance has recently been demanded in addition to dispersion properties, but previous copolymers have not been able to obtain sufficient performance.

In order to obtain a copolymer satisfying the above properties, the inventors of the present invention need to produce a block copolymer comprising the following block chains (A) and (B1) comprising containing a repeating unit selected from the group consisting of a tertiary amino group and having four stages. a block chain (A) of a polymer of at least one repeating unit of a group consisting of repeating units of an ammonium salt group, A block chain (B1) comprising a copolymer having a repeating unit having a polyoxyalkylene chain and a repeating unit having an acidic group represented by the formula (II).

However, a method of producing a block copolymer containing such a structure is not known.

The present inventors have found that a copolymer precursor containing the following block chains (A) and (B) can be a useful intermediate product of a block copolymer comprising containing a repeating unit selected from the group consisting of a tertiary amine group and a block chain (A) of a polymer having at least one repeating unit of a group consisting of repeating units of a quaternary ammonium salt group, comprising a repeating unit having a polyoxyalkylene chain and a formula (I) The block chain (B) of the copolymer of the repeating unit.

It is found that by heating the copolymer precursor, the repeating unit represented by the formula (I) is converted into a repeating unit having an acidic group represented by the formula (II), whereby the target block copolymer can be produced, thereby completing the present invention. invention.

That is, the present invention relates to (1) a method for producing a block copolymer comprising a block chain (A) and comprising a repeating unit having a polyoxyalkylene chain and a formula ( II) The block chain (B1) of the copolymer of the repeating unit having an acidic group represented by the method, characterized in that the following copolymer precursor containing the block chain (A) and the block chain (B) is heated a block chain (A) comprising a polymer comprising at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group, comprising a polyoxyl extension a repeating unit of an alkyl chain and a block chain (B) of a copolymer of a repeating unit having a protected acidic group represented by the formula (I), Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; X represents a single bond or is selected from a C1 to C10 alkyl group, -C(=O)OR ^1a -, -C (=O) NHR ^1a -, -OC(=O)R ^1a - and -R ^2a -OC(=O)R ^1a - the group in the group (R ^1a , R ^2a independently represent C1~C10 extension Alkyl or *C1~C10 alkylene-O-C1~C10 alkylene group *), R ⁴ represents a hydrogen atom, C1~C6 alkyl group, C6~C10 aryl C1~C6 alkyl group*, or 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; * represents a bonding position)

(wherein R ¹ , R ² , R ³ and X represent the same meanings as in the formula (I)); (2) a method for producing a block copolymer according to (1), wherein the block chain (B) and (B1) further contains a repeating unit represented by formula (III), (wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1 to C3 alkyl group, R ⁹ represents a C1 to C10 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*; * represents a bonding position (3) The method for producing a block copolymer according to (1) or (2), wherein the repeating unit having a tertiary amino group is a repeating unit represented by the following formula (IV), (wherein R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y represents an alkyl group selected from C1 to C10, -C(=O)OR ^1b -, -C(=O) NHR ^1b -, -OC(=O)R ^1b - and -R ^2b -OC(=O)R ^1b - a group of groups (R ^1b , R ^2b independently represent a C1 to C10 alkyl group or *C1~C10 alkylene-O-C1~C10 alkylene group *), R ¹³ and R ¹⁴ each independently represent C1~C6 alkyl group or C6~C10 aryl C1~C6 alkyl group*; * indicates bonding position (4) The method for producing a block copolymer according to (1) or (2), wherein the repeating unit having a quaternary ammonium salt group is a repeating unit represented by the following formula (V), Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y ¹ represents an alkyl group selected from C1 to C10, -C(=O)OR ^1c -, -C(= O) NHR ^1c - , -OC(=O)R ^1c - and -R ^2c -OC(=O)R ^1c - the group in the group (R ^1c , R ^2c independently represent C1~C10 alkyl) Or *C1~C10 alkyl-O-C1~C10 alkyl]*, R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a C1~C6 alkyl group or a C6~C10 aryl C1~C6 alkyl group*; Z ^- represents a counter ion; * represents a bonding position); (5) (1) through (4) a method for producing a block copolymer of any one of, wherein said polyoxyalkylene-based repeating unit having alkylene chains Expressed by the following formula (VI), Wherein R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; and Z ¹ represents a group selected from -C(=O)O-, -C(=O)NH-, -OC( =O)- and -R ^1d -OC(=O)- groups in the group (R ^1d represents C1~C10 alkyl or *C1~C10 alkyl-O-C1~C10 alkyl) ; * represents a bonding position), R ²⁴ represents a C2 ~ C4 alkylene, R ²⁵ represents a hydrogen atom or a C1 ~ C6 alkyl group, m represents any integer of 2 to 150, R ²⁴ O may be identical to each other, may (6) The method for producing a block copolymer according to any one of (1) to (5), which is a mixed solvent of a glycol ether ester solvent and an alcohol solvent, or a glycol ether ester It is carried out in a mixed solvent of a solvent and water.

Further, the present invention relates to the following: (7) A copolymer precursor comprising: a group comprising a repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a quaternary ammonium salt group; a block chain (A) of a polymer of at least one repeating unit, a copolymer comprising a copolymer comprising a repeating unit having a polyoxyalkylene chain and a repeating unit having a protected acidic group represented by the formula (I) Segment chain (B), Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; X represents a single bond or is selected from a C1 to C10 alkyl group, -C(=O)OR ^1a -, -C (=O) NHR ^1a -, -OC(=O)R ^1a - and -R ^2a -OC(=O)R ^1a - the group in the group (R ^1a , R ^2a independently represent C1~C10 extension Alkyl or *C1~C10 alkylene-O-C1~C10 alkylene group *), R ⁴ represents a hydrogen atom, C1~C6 alkyl group, C6~C10 aryl C1~C6 alkyl group*, or C6~C10 An aryl group, R ⁵ represents a C1 to C6 alkyl group, a C6-C10 aryl C1 to C6 alkyl group*, or a C6-C10 aryl group; * represents a bonding position); (8) a copolymer precursor such as (7) Wherein the above block chain (B) further contains a repeating unit represented by the following formula (III), (wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1 to C3 alkyl group, R ⁹ represents a C1 to C10 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*; * represents a bonding position (9) The copolymer precursor according to (7) or (8), wherein the above repeating unit having a tertiary amino group is a repeating unit represented by the following formula (IV), (wherein R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y represents an alkyl group selected from C1 to C10, -C(=O)OR ^1b -, -C(=O) NHR ^1b -, -OC(=O)R ^1b - and -R ^2b -OC(=O)R ^1b - a group of groups (R ^1b , R ^2b independently represent a C1 to C10 alkyl group or *C1~C10 alkylene-O-C1~C10 alkylene group*), R ¹³ and R ¹⁴ each independently represent C1~C6 alkyl group or C6~C10 aryl C1~C6 alkyl group*; * indicates bonding (10) The copolymer precursor of (7) or (8), wherein the above repeating unit having a quaternary ammonium salt group is a repeating unit represented by the following formula (V), Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y ¹ represents an alkyl group selected from C1 to C10, -C(=O)OR ^1c -, -C(= O) NHR ^1c -, -OC(=O)R ^1c - and -R ^2c -OC(=O)R ^1c - groups in the group (R ^1c , R ^2c independently represent C1 to C10 alkylene groups) Or *C1~C10 alkyl-O-C1~C10 alkyl]*, R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a C1~C6 alkyl group or a C6~C10 aryl C1~C6 alkyl group* ; Z ^- represents a counter ion; * represents a bonding position); (11) (7) to (10) according to any one of the precursor copolymer, wherein said repeating units having a polyoxyethylene-based alkyl chain extending of the following Formula (VI), Wherein R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; and Z ¹ represents a group selected from -C(=O)O-, -C(=O)NH-, -OC( =O)- and -R ^1d -OC(=O)- groups in the group (R ^1d represents C1~C10 alkyl or *C1~C10 alkyl-O-C1~C10 alkyl) ; * represents a bonding position), R ²⁴ represents a C2 ~ C4 alkylene, R ²⁵ represents a hydrogen atom or a C1 ~ C6 alkyl group, m represents any integer of 2 to 150, R ²⁴ O may be identical to each other, may different).

(1) Copolymer precursor

The copolymer precursors of the present invention each contain at least one of the following block chain (A) and block chain (B).

Block chain (A): a polymer containing at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group

Block chain (B): a copolymer containing a repeating unit having a polyoxyalkylene chain and a repeating unit having a protected acidic group

Further, the copolymer precursor of the present invention may contain other block chains in addition to the block chain (A) and the block chain (B).

1) Block chain (A)

In the block chain (A), the repeating unit having a tertiary amino group and the repeating unit having a quaternary ammonium salt group are not particularly limited as long as they have the above cationic functional group in the side chain of the repeating unit. .

Specifically, the polymer of the block chain (A) comprises: a homopolymer comprising only one repeating unit having a tertiary amino group or a repeating unit having a quaternary ammonium salt group, and containing two or more kinds of tertiary amino groups. a repeating unit or a copolymer having a repeating unit of a quaternary ammonium salt group, a copolymer comprising at least one repeating unit having a tertiary amino group, and at least one repeating unit having a quaternary ammonium salt group, and the Copolymers of repeating units of other copolymerizable monomers. Copolymers include copolymers of random, alternating, block, and the like.

(repeating unit having a tertiary amino group)

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

In the formula (IV), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a C1 to C3 alkyl group. Y represents a group selected from C1 to C10 alkyl, -C(=O)OR ^1b -, -C(=O)NHR ^1b - , -OC(=O)R ^1b - and -R ^2b -OC(=O) R ^1b - a group in the group consisting of R ^1b and R ^2b independently represent a C1~C10 alkyl group or a *C1~C10 alkyl group-O-C1~C10 alkyl group*). R ¹³ and R ¹⁴ are each independently a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*; * represents a bonding position.

Here, as the C1 to C3 alkyl group and the C1 to C6 alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, and t-butyl groups are exemplified. , n-pentyl, n-hexyl and so on.

As the C1 to C10 alkylene group, a methylene chain, an ethylidene chain, a propyl group, a methyl group, an ethyl group, a butyl group, a 1,2-dimethyl group, and a methyl group can be exemplified. Base chain, 1-methyl butyl butyl chain, 2-methyl butyl butyl chain or hexyl chain.

As the C6-C10 aryl C1~C6 alkyl group*, benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, naphthalene-2- can be exemplified. Ethyl ethyl, 1-naphthalen-2-yl-n-propyl, dec-1-ylmethyl and the like.

Examples of the monomer which is a raw material of the repeating unit represented by the formula (IV) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and (methyl). Dimethylaminobutyl acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, and the like.

(repeating unit having a quaternary ammonium salt group)

The repeating unit having a quaternary ammonium salt group is not particularly limited as long as it has a quaternary ammonium salt group, and examples thereof include a repeating unit represented by the following formula (V).

[Chemistry 13]

In the formula (V), R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C1 to C3 alkyl group. Y ¹ is selected from C1 to C10 alkyl, -C(=O)OR ^1c -, -C(=O)NHR ^1c -, -OC(=O)R ^1c - and -R ^2c -OC(=O R ^1c - a group in the group (R ^1c and R ^2c are each independently a C1 to C10 alkyl group or a *C1 to C10 alkyl group - O-C1 to C10 alkyl group *). R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a C1 to C6 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*; * represents a bonding position. Z ^- represents a counter ion such as a halide ion, a halogenated alkane ion, an alkylcarboxylate ion, an oxynitride ion, an alkylsulfate ion, a sulfonate ion, a phosphate ion or an alkyl phosphate ion.

Here, the C1 to C3 alkyl group, the C1 to C6 alkyl group, the C1 to C10 alkylene group, and the C6 to C10 aryl C1 to C6 alkyl group * can be exemplified by the above-mentioned repeating unit having a tertiary amino group ( IV) the same.

The monomer which is a raw material of the repeating unit represented by the formula (V) is exemplified by (meth)acryloxyethyltrimethylammonium fluoride and (meth)acryloxyethyltrimethylmethyl group. Ammonium chloride, (meth) propylene oxiranyl ethyl trimethyl ammonium bromide, (meth) propylene oxiranyl ethyl trimethyl ammonium iodide, (meth) propylene methoxy propyl trimethyl Ammonium fluoride, (meth) propylene methoxy propyl trimethyl ammonium chloride, (meth) propylene methoxy propyl trimethyl ammonium bromide, (meth) propylene methoxy propyl three Ammonium methyl iodide, (meth) propylene oxy butyl trimethyl ammonium fluoride, (meth) propylene methoxy butyl trimethyl ammonium chloride, (methyl) Propylene methoxy butyl trimethyl ammonium bromide, (meth) propylene methoxy butyl trimethyl ammonium iodide, and the like.

(other repeatable units that can be included)

The repeating unit which may be contained in the block chain (A) is a repeating unit derived from a (meth)acrylic monomer, an aromatic vinyl monomer, a conjugated diene monomer, or the like.

The (meth)acrylic 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 (meth)acrylic monomer include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, Glycidyl methacrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylate compound; 2-methoxyethyl (meth) acrylate, methoxy polyethylene glycol (ethylene glycol unit number is 2 to 100) (meth) acrylate, ethoxylate 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 vinyl monomer include styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, α-methyl styrene, and p-t-butoxybenzene. Ethylene, m-butoxystyrene, p-(1-ethoxyethoxy)styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinyl Bismuth, 2-vinylpyridine, 4-B A heteroaryl compound such as an alkenylpyridine, a 2-vinylquinoline, a 4-vinylquinoline, a 2-vinylthiophene or a 4-vinylthiophene, which may be used alone or in combination of two or more.

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, and 2-tert-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-tricyclo The decadiene, the myrcene, the chloroprene, etc. may be used alone or in combination of two or more.

2) Block chain (B)

The block chain (B) is a copolymer containing at least one repeating unit having a polyoxyalkylene chain and at least one repeating unit having an acidic group.

Copolymers include copolymers of random, alternating, block, and the like.

(repeating unit containing a polyoxyalkylene chain)

The repeating unit having a polyoxyalkylene chain in the block chain (B) is not particularly limited as long as it has a polyoxyalkylene chain, and for example, a repeating unit represented by the formula (VI) can be exemplified.

In the formula (VI), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a C1 to C3 alkyl group. Z ¹ is a group selected from the group consisting of -C(=O)O-, -C(=O)NH-, -OC(=O)-, and -R ^1d -OC(=O)- (R ^1d is C1 ~ C10 alkylene group or a C1 ~ C10 alkylene * -O-C1 ~ C10 alkylene group *; * represents a bonding position). R ²⁴ represents a C2 to C4 alkylene group, and R ²⁵ represents a hydrogen atom or a C1 to C6 alkyl group. m represents an integer of 2 to 150, and R ²⁴ O may be the same or different.

Here, as the C1 to C3 alkyl group and the C1 to C6 alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, and t-butyl groups are exemplified. , n-pentyl, n-hexyl and so on.

Examples of the C2~C4 alkylene group and the C1~C10 alkylene group include a methylene chain, an extended ethyl chain, a propyl chain, a methyl extended ethyl chain, a butyl chain, and a 1,2-dimethyl group. An ethyl chain, a pentyl chain, a 1-methyl butyl chain, a 2-methyl butyl chain, a hexyl chain, and the like are extended.

In the above formula (VI), m is preferably from 2 to 10.

Examples of the monomer which is a raw material of the repeating unit represented by the formula (VI) include polyethylene glycol (2 to 150: a value of m in the formula (VI), the same applies hereinafter) (meth) acrylate, Poly(ethylene glycol (1~75)-propylene glycol (1~75)) (meth) acrylate, polypropylene glycol (2~150) (meth) acrylate, etc., which can be used alone or in combination. the above.

(repeating unit with protected acidic group)

The repeating unit represented by the formula (I) having a protected acidic group in the block chain (B).

[化15]

In the formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1 to C3 alkyl group. X is a single bond or is selected from C1 to C10 alkyl, -C(=O)OR ^1a -, -C(=O)NHR ^1a -, -OC(=O)R ^1a - and -R ^2a -OC ( =O) R ^1a - the group in the group (R ^1a , R ^2a are independently C1~C10 alkyl or *C1~C10 alkyl-O-C1~C10 alkyl)*, R ⁴ Is a hydrogen atom, a C1~C6 alkyl group, a C6~C10 aryl C1~C6 alkyl group*, or a C6~C10 aryl group, R ⁵ is a C1~C6 alkyl group, a C6~C10 aryl C1~C6 alkyl group*, Or C6~C10 aryl; * indicates the bonding position.

Examples of the monomer which is a raw material of the repeating unit represented by the formula (I) include methoxymethyl acrylate, ethoxymethyl acrylate, 1-ethoxyethyl acrylate, and 1-methoxy acrylate. Ethyl ester, 1-ethoxypropyl acrylate, 1-propoxyethyl acrylate, 1-isopropoxyethyl acrylate, 1-benzyloxyethyl acrylate, 1-ethoxy methacrylate Ethyl ester, 2-methoxyethyl 2-methacrylate, 1-ethoxypropyl 2-methacrylate, 1-propoxyethyl 2-methacrylate, 1-iso- 2-methacrylate Propyloxyethyl ester, 2-benzyloxyethyl 2-methacrylate, and the like. Among these, 1-ethoxyethyl acrylate and 1-ethoxyethyl 2-methacrylate are preferred. These may be used singly or in combination of two or more.

The repeating unit having a protected acidic group is deprotected by the production method of the present invention, and can be converted into a repeating unit having an acidic group as described below.

(other repeatable units that can be included)

The repeating unit which may be contained in the block chain (B), a repeating unit derived from a (meth)acrylic monomer, an aromatic vinyl monomer, a conjugated diene monomer, etc. can be illustrated.

Among these, a repeating unit represented by the formula (III) is preferred.

In the formula (III), R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1 to C3 alkyl group. R ⁹ is a C1 to C10 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*.

Here, as the C1 to C3 alkyl group and the C1 to C6 alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, and t-butyl groups are exemplified. , n-pentyl, n-hexyl and so on.

As the C6-C10 aryl C1~C6 alkyl group*, benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, naphthalene-2- can be exemplified. Ethyl ethyl, 1-(naphthalen-2-yl)-n-propyl, indol-1-ylmethyl and the like.

The (meth)acrylic 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 (meth)acrylic monomer include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, Glycidyl methacrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) propylene a (meth) acrylate compound such as 1-ethylcyclohexyl acid or benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate or methoxy polyethylene glycol (ethylene glycol) The number of units is 2 to 100) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, etc., and these may be used alone. Or use two or more kinds in combination.

Examples of the aromatic vinyl monomer include styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, α-methyl styrene, and p-t-butoxybenzene. Ethylene, m-butoxystyrene, p-(1-ethoxyethoxy)styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinyl a heteroaryl compound such as hydrazine, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene or 4-vinylthiophene, etc. Use one type or a mixture of two or more types.

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, and 2-tert-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-tricyclo The decadiene, the myrcene, the chloroprene, etc. may be used alone or in combination of two or more.

(block chains other than the block chain (A) and (B) in the copolymer)

The copolymer of the present invention may have a block chain containing other polymers in addition to the block chains (A) and (B).

The polymer may, for example, be a homopolymer or a random copolymer containing a repeating unit derived from a (meth)acrylic monomer, an aromatic vinyl monomer, or a conjugated diene monomer. Copolymers, block copolymers, and the like.

The (meth)acrylic monomer, the aromatic vinyl monomer, the conjugated diene monomer, and the like can be exemplified as described above.

(The ratio of block chain (A) to block chain (B) in the copolymer and physical properties such as molecular weight)

The ratio of the block chain (A) to the block chain (B) in the copolymer of the present invention is not particularly limited, and is 10 to 40: 90 to 60, preferably 15 to 35: 85 by weight%. ~65.

Further, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) is preferably 2,000 to 50,000, more preferably 2,000 to 20,000. The copolymer precursor is preferably from 4,000 to 30,000, more preferably from 4,000 to 15,000. The ratio of the weight-to-weight molecular weight to the number average molecular weight measured by 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 of the present invention is not particularly limited, and it can be produced by a known method. For example, a monomer can be polymerized by living polymerization to form a block copolymer. The living polymerization may be carried out by living radical polymerization or living anionic polymerization, and more preferably, it is living anionic polymerization.

In order to form a block copolymer, after polymerizing the monomer of the block chain (A) or (B), the monomer of the other block may be continuously polymerized to block copolymerize, or the block chain may be A) After reacting each monomer of the block chain (B) to form a block, each block is bonded. Living anionic polymerization can be strictly controlled composition or The molecular weight is preferred.

In the case of production by living radical polymerization, the reaction may be carried out in the same manner as the living anionic polymerization, or after the monomer of a certain block is polymerized, the polymer may be temporarily purified before the polymerization of the next monomer. After the remaining monomers of the previous reaction, the next monomer was polymerized. In the case where it is preferred that 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 may 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 a block polymer of a desired arrangement, the monomers of the respective blocks are sequentially added dropwise in such a manner as to be in a desired arrangement, and are allowed to react.

In order to polymerize a monomer of a block, the monomer of the next block is polymerized, and after the polymerization of the previous block is completed, the monomer of the next block is started to be dropped. The progress of the polymerization can be confirmed by detecting the remaining amount of the monomer by gas chromatography or liquid chromatography. Further, after the completion of the dropwise addition of the monomer of the former block, the monomer of the next block may be added dropwise after stirring for 1 minute to 1 hour, depending on the type of the monomer or the solvent.

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, and 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 of the above alkali metal. An allyl compound, an aryl compound, and more preferably an alkyl lithium. Specifically, ethyl lithium, n-butyl lithium, second butyl lithium, tert-butyl lithium, ethyl sodium, biphenyl lithium, naphthyl lithium, triphenyl lithium, naphthyl sodium, naphthalene can be used. Potassium, α-methylstyrene sodium dianion, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, 1,4-dilithium-2-butene Alkene, 1,6-dilithium hexane, polystyryllithium, cumyl potassium, cumene hydrazine, and the like. These anionic polymerization initiators may be used alone or in combination of two or more.

The starting amount of the anionic polymerization is usually from 0.0001 to 0.2 equivalents, preferably from 0.0005 to 0.1 equivalents, based on the total of the anionic polymerizable monomers used. 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 as long as it is a side reaction such as no shift reaction or a reaction such as stopping the reaction, and the polymerization is carried out, and is preferably carried out in a temperature range of -100 ° C or higher and a solvent boiling point or lower. Further, the concentration of the monomer in the polymerization solvent is not particularly limited, but is usually 1 to 40% by weight, preferably 2 to 15% by weight.

The polymerization solvent to be used in the production method of the present invention is not particularly limited as long as it is a solvent which does not participate in the polymerization reaction and is compatible with the polymer, and specifically, diethyl ether, tetrahydrofuran (THF), and the like are exemplified. Alkane, three An ether compound such as an alkane; a polar solvent such as a tertiary amine such as tetramethylethylenediamine or hexamethylphosphonium triamine; or a nonpolar solvent such as an aliphatic, aromatic or alicyclic hydrocarbon compound such as hexane or toluene or Low polar solvent. These solvents may be used singly 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. More than or equal to 20% by volume, and 50% by volume or more may be used.

In the present invention, an organic metal such as dialkylzinc such as diethyl zinc or dialkylmagnesium such as dibutylmagnesium or triethylaluminum may be used as a purification agent for a polymerization stabilizer, a monomer or a solvent.

In the present invention, an additive such as an alkali metal salt or an alkaline earth metal salt may be added at the start of polymerization or during polymerization as needed. Specific examples of such an additive include a mineral acid salt or a halide such as a sulfate, a nitrate or a borate of sodium, potassium, barium or magnesium, and more specifically, a chloride, a bromide or an iodide of lithium or barium. Or lithium borate, magnesium nitrate, sodium chloride, potassium chloride, and the like. Among these, lithium halides such as lithium chloride, lithium bromide, lithium iodide, lithium fluoride, and particularly preferably lithium chloride are also preferred.

It is generally difficult to polymerize a monomer having a quaternary ammonium salt group by living anionic polymerization. Therefore, when a polymer containing a repeating unit having a quaternary ammonium salt group is produced by living anionic polymerization, the monomer can be polymerized after being polymerized into a raw material of a repeating unit having a tertiary amino group. The amine group is quaternized by a known method. Examples of the quaternization agent include chlorotoluene, bromotoluene, iodine toluene, and the like, or a halogenated alkane such as methyl chloride, ethyl chloride, methyl bromide or methyl iodide, or dimethyl sulfate, diethyl sulfate or sulfuric acid. A general alkylating agent such as an alkyl sulfate such as propyl ester.

(3) block copolymer

The block copolymer of the present invention may contain at least one of the following block chain (A) and block chain (B1), respectively.

Block chain (A): a polymer containing at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group

Block chain (B1): a copolymer containing a repeating unit having a polyoxyalkylene chain and a repeating unit having an acidic group

Further, the copolymer precursor of the present invention may contain other block chains in addition to the block chain (A) and the block chain (B1).

1) Block chain (A)

The block chain (A) in the block copolymer is the same as the block chain (A) in the above copolymer precursor.

2) Block chain (B1)

The block chain (B1) is a copolymer containing at least one repeating unit having a polyoxyalkylene chain and at least one repeating unit having an acidic group.

Copolymers include copolymers of random, alternating, block, and the like.

(repeating unit having a polyoxyalkylene chain)

The repeating unit having a polyoxyalkylene chain in the block chain (B1) is the same as the repeating unit having a polyoxyalkylene chain in the above copolymer precursor.

(repeating unit with acidic group)

The repeating unit having an acidic group in the block chain (B1) is a repeating unit represented by the formula (II).

[化17]

In the formula (II), R ¹ , R ² , R ³ and X have the same meanings as the repeating unit having a protected acidic group represented by the formula (I).

The repeating unit represented by the formula (II) can be obtained by deprotecting the protective group of the protected acidic group represented by the formula (I) by the production method of the present invention.

(other repeatable units that can be included)

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) in the above copolymer precursor.

(blockchains other than the block chain (A) and (B1) in the block copolymer)

The copolymer of the present invention may have a block chain containing other polymers in addition to the block chains (A) and (B1).

Such a block chain is the same as the block chain which may be contained in the copolymer precursor other than the block chain (A) and (B).

(The ratio of block chain (A) to block chain (B1) in the copolymer and physical properties such as molecular weight)

The ratio of the block chain (A) to the block chain (B1) in the copolymer of the present invention is not particularly limited, and is 10 to 40: 90 to 60, preferably 15 to 35: 85 by weight%. ~65. Further, the ratio of the repeating unit having an acidic group in the copolymer is from 0.5 to 20% by weight, preferably from 1 to 15% by weight.

Further, the weight average molecular weight measured by GPC is preferably from 2,000 to 50,000, more preferably from 2,000 to 20,000. As the dispersing agent, it is preferably from 4,000 to 30,000, more preferably from 4,000 to 15,000. The ratio of the weight average molecular weight to the number average molecular weight measured by GPC is 1.0 to 2.0, especially the dispersant. Good is 1.0~1.5.

(4) Method for producing block copolymer

The block copolymer of the present invention can be obtained by heating the above copolymer precursor. The protective group protecting the acidic group in the copolymer precursor is deprotected by heating the copolymer precursor.

The deprotection reaction may directly heat the copolymer precursor or may be heated in a state where the copolymer precursor is dissolved in a solvent. Examples of such a solvent include water; glycol ethers such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate. Ester solvent; ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether and diethylene glycol dimethyl ether diol mono or diether solvent; toluene, monochlorobenzene and other aromatic a hydrocarbon solvent; an alcohol solvent such as ethanol, isopropanol, n-butanol or 1-methoxy-2-propanol (PGME); an ester solvent such as ethyl lactate, butyl acetate or ethyl pyruvate; Containing two or more kinds of mixed solvents; and the like. Among these, a glycol ether ester solvent, a mixed solvent of a glycol ether ester solvent and an alcohol solvent, and a mixed solvent of a glycol ether ester solvent and water are preferable. From the viewpoint of lowering the reaction temperature, a mixed solvent of a glycol ether ester solvent and an alcohol solvent, a mixed solvent of a glycol ether ester solvent and water, and a glycol ether ester solvent and water are preferred. a mixed solvent.

From the viewpoint of easily removing by-products generated by the deprotection reaction, a mixed solvent of a glycol ether ester-based solvent and water is preferred, and a mixed solvent of PGMEA and water is preferred.

In the mixed solvent of the glycol ether ester-based solvent and the alcohol-based solvent, the mixing ratio is not particularly limited as long as the copolymer precursor is soluble, and it is usually preferred. It is 95/5 wt% to 0.1/99.9% by weight, more preferably 50/50 to 0.1/99.9% by weight.

In the mixed solvent of the glycol ether ester-based solvent and water, the mixing ratio is not particularly limited as long as it can dissolve the copolymer precursor, and is usually preferably 95/5 to 50/50% by weight, more preferably 90/. 10~60/40% by weight, especially preferably 90/10~75/25% by weight.

The heating temperature varies depending on the structure of the protecting group protecting the acidic group and the reaction solvent, but it is not particularly limited as long as it is a temperature at which the deprotection reaction proceeds rapidly.

In the case of a glycol ether ester-based solvent, it is usually preferably carried out at 80 ° C to 200 ° C, more preferably at 100 ° C to 160 ° C. In the case of a mixed solvent of a glycol ether ester-based solvent and an alcohol-based solvent, it is preferably carried out at 100 ° C to 140 ° C, more preferably at 110 ° C to 140 ° C. In the case of a mixed solvent of a glycol ether ester solvent and water, it is preferably carried out at 70 ° C to 100 ° C, more preferably at 90 ° C to 100 ° C. From the viewpoint of lowering the color of the polymer solution formed by the deprotection reaction, the heating temperature is preferably lower.

[Examples]

Hereinafter, the present invention will be described in detail using examples, but the technical scope of the present invention is not limited to the examples.

[Example 1-1] (aggregation step)

4,000.35 g of tetrahydrofuran (hereinafter sometimes abbreviated as THF) and lithium chloride (3.63 wt% concentration of THF solution) were added to a 1000 mL flask. g, cooled to -60 °C. Thereafter, 7.89 g (15.36% by weight of a hexane solution) of n-butyllithium was added, and the mixture was aged for 10 minutes.

Next, 4.04 g of 1-ethoxyethyl methacrylate (hereinafter sometimes abbreviated as EEMA) and 61.33 g of n-butyl methacrylate (hereinafter sometimes abbreviated as nBMA) were added dropwise over 30 minutes, and methoxypolyethyl b. A mixed liquid of diol monomethacrylate (PME-200, manufactured by Nippon Oil Co., Ltd.) (hereinafter sometimes abbreviated as PEGMA) of 26.19 g was added, and the reaction was continued for 30 minutes after the dropwise addition. Then, by gas chromatography (hereinafter abbreviated as GC), gel permeation chromatography (hereinafter abbreviated as GPC) (mobile phase THF, DMF (dimethylformamide, dimethylformamide)), the confirmation sheet is confirmed. The body disappears.

Next, 39.71 g of 2-(dimethylamino)ethyl methacrylate (hereinafter sometimes abbreviated as DMMA) was added dropwise, and the reaction was continued for 30 minutes after the dropwise addition. Then, after measuring by GC and GPC (mobile phase DMF), it was confirmed that the monomer disappeared, and 3.21 g of methanol was added to stop the reaction.

The copolymer obtained by GPC (mobile phase DMF) analysis was confirmed to have a molecular weight (Mw) of 5,260, a molecular weight distribution of 1.09, and a composition ratio of DMMA-[nBMA/PEGMA/EEMA]=30-[47/20/3. ] % by weight of copolymer.

(deprotection step)

200 g of a 50% by weight concentration of propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) solution of the obtained precursor polymer was heated to 160 ° C for 3 hours.

The copolymer obtained by GPC (mobile phase DMF) analysis confirmed that the molecular weight (Mw) was 5,140, the molecular weight distribution was 1.08, and the composition ratio was DMMA-[nBMA/PEGMA/MA]=31-[47/20/2 ]% by weight of copolymer (MA) Methacrylate).

The polymer solution obtained was pale brown.

[Example 1-2] (deprotection step)

10.0 g of a PGMEA/n-butanol solution (30/70 wt%) having a concentration of 25% by weight of the precursor polymer obtained in the polymerization step of Example 1-1 was heated to 115 ° C for 8 hours. The n-butanol was distilled off to prepare a PGFEA solution having a concentration of 40% by weight.

The polymer solution obtained was colorless and transparent.

[Example 1-3] (deprotection step)

A PPGEA/water solution (62.5/37.5 wt%) having a concentration of 20% by weight of the precursor polymer obtained in the polymerization step of Example 1-1 obtained in the polymerization step of Example 1-1, and a PGMEA/water solution having a concentration of 20 wt% (65%) were respectively prepared. /35 wt%), 20 wt% concentration of PGMEA/water solution (75/25 wt%), 20 wt% concentration of PGMEA/water solution (87.5/12.5 wt%), 20 wt% concentration of PGMEA/water solution (93.75/6.25) weight%). The prepared solution was separately heated to 100 ° C and reacted for 8 hours. Water was distilled off to prepare a 40 wt% concentration of PGMEA solution. In the PGMEA/water (93.75/6.25 wt%) solution, the precursor polymer partially remained, while in other solutions, the deprotection reaction ended. Among them, in the PGMEA/water (93.75/6.25 wt%) solution, the deprotection reaction was completed by setting the reaction time to 24 hours.

The respective polymer solutions obtained were colorless and transparent.

From the results of Examples 1-1 to 1-3, it is known that the precursor is aggregated. The PGMEA solution of the compound is placed under heating to deprotect the protecting group. Further, it has been found that by making a mixed solution of PGMEA and an alcohol, the reaction temperature can be further lowered, and by further preparing a mixed solution of PGMEA and water, the reaction temperature can be further lowered.

[Embodiment 2] (aggregation step)

695.92 g of THF and 13.83 g of lithium chloride (3.63 wt% concentration of THF solution) were added to a 1000 mL flask, and the mixture was cooled to -60 °C. Thereafter, 9.29 g of n-butyllithium (15.36 wt% concentration of a hexane solution) was added, and the mixture was aged for 10 minutes.

Next, a mixed liquid of EEMA 8.47 g, nBMA 71.15 g, and PEGMA 31.16 g was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the dropwise addition. Then, the measurement was confirmed by GC or GPC (mobile phase THF, DMF) to confirm the disappearance of the monomer.

Next, 45.39 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after the dropwise addition. Then, after measuring by GC and GPC (mobile phase DMF), it was confirmed that the monomer disappeared, and 3.21 g of methanol was added to stop the reaction.

The copolymer obtained by GPC (mobile phase DMF) analysis was confirmed to have a molecular weight (Mw) of 5610, a molecular weight distribution of 1.10, and a composition ratio of DMMA-[nBMA/PEGMA/EEMA]=29-[46/20/5 ] % by weight of copolymer.

(deprotection step)

213 g of a PPGEA solution having a concentration of 50% by weight of the obtained copolymer was heated to 160 ° C and aged for 3.5 hours.

The copolymer obtained by GPC (mobile phase DMF) analysis confirmed that the molecular weight (Mw) was 4,800, the molecular weight distribution was 1.12, and the composition ratio was DMMA- [nBMA/PEGMA/MA]=30-[47/20/3]% by weight of the copolymer.

[Example 3] (aggregation step)

To a 1000 mL flask, 57.66 g of THF and 11.20 g of lithium chloride (3.63 wt% concentration of THF solution) were added, and the mixture was cooled to -60 °C. Thereafter, 7.34 g of n-butyllithium (15.36 wt% concentration of a hexane solution) was added, and the mixture was aged for 10 minutes.

Then, 4.30 g of methyl methacrylate (hereinafter sometimes abbreviated as MMA) was added, and the reaction was continued for 5 minutes. Then, after confirming the disappearance of the monomer by GC measurement, a part of the sample was sampled and subjected to GPC measurement to obtain a polymer having a molecular weight of 293 (2.92 polymer).

Next, 4.53 g of EEMA, 19.80 g of methacrylic acid methacrylate (hereinafter sometimes abbreviated as EHMA), 19.50 g of nBMA, 36.48 g of MMA, and benzyl methacrylate were added dropwise over 30 minutes (hereinafter sometimes referred to simply as A mixture of 15.03 g of BzMA) and 11.99 g of PEGMA was added and the reaction was continued for 30 minutes after the dropwise addition. Then, the measurement was confirmed by GC or GPC (mobile phase THF, DMF) to confirm the disappearance of the monomer.

Next, 36.98 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after the dropwise addition. Then, after measuring by GC and GPC (mobile phase DMF), it was confirmed that the monomer disappeared, and 3.21 g of methanol was added to stop the reaction.

The copolymer obtained by GPC (mobile phase DMF) analysis was confirmed to have a molecular weight (Mw) of 6780, a molecular weight distribution of 1.08, and a composition ratio of DMMA-[MMA/nBMA/EHMA/PEGMA/BzMA/EEMA]=25- [28/13/13/8/10/3] wt% copolymer.

(deprotection step)

200 g of a PPGEA solution having a concentration of 50% by weight of the obtained copolymer was heated to 160 ° C and reacted for 3 hours.

The copolymer obtained by GPC (mobile phase DMF) analysis confirmed that the molecular weight (Mw) was 6,120, the molecular weight distribution was 1.10, and the composition ratio was DMMA-[MMA/nBMA/EHMA/PEGMA/BzMA/MA]=25- [28/13/14/8/10/2] wt% copolymer.

[Example 4-1] (aggregation step)

To a 1000 mL flask, 683.03 g of THF and 11.92 g of lithium chloride (3.63 wt% concentration of THF solution) were added, and the mixture was cooled to -60 °C. Thereafter, 8.32 g of n-butyllithium (15.36 wt% concentration of a hexane solution) was added, and the mixture was aged for 10 minutes.

Then, MMA 5.06g was added and the reaction was continued for 5 minutes. Then, after confirming the disappearance of the monomer by GC measurement, the sample was partially sampled and subjected to GPC measurement to obtain a polymer having a molecular weight of 311 (3.10 polymer).

Then, a mixed liquid of EEMA 9.68 g, EHMA 22.0 g, nBMA 22.09 g, MMA 41.60 g, BzMA 16.83 g, and PEGMA 13.75 g was added dropwise over 30 minutes, and the reaction was continued for 30 minutes after the dropwise addition. Then, the measurement was confirmed by GC or GPC (mobile phase THF, DMF) to confirm the disappearance of the monomer.

Next, 42.06 g of DMMA was added dropwise, and the reaction was continued for 30 minutes after the dropwise addition. Then, after measuring by GC and GPC (mobile phase DMF), it was confirmed that the monomer disappeared, and 4.48 g of methanol was added to stop the reaction.

The copolymer obtained by GPC (mobile phase DMF) analysis was confirmed as a fraction The sub-quantity (Mw) is 6980, the molecular weight distribution is 1.10, and the composition ratio is DMMA-[MMA/nBMA/EHMA/PEGMA/BzMA/EEMA]=24-[27/13/13/8/10/5]% by weight. Copolymer.

(deprotection step)

212.32 g of a PPGEA solution having a concentration of 50% by weight of the obtained precursor polymer was heated to 160 ° C for 4 hours.

The copolymer obtained by GPC (mobile phase DMF) analysis was confirmed to have a molecular weight (Mw) of 5,300, a molecular weight distribution of 1.13, and a composition ratio of DMMA-[MMA/nBMA/EHMA/PEGMA/BzMA/MA]=25- [28/13/13/8/10/3] wt% copolymer.

The polymer solution obtained was pale brown.

[Example 4-2] (deprotection step)

212.32 g of a 50 wt% PGMEA solution of the precursor polymer obtained in the polymerization step of Example 4 was heated to 130 ° C for 17 hours. The polymer solution obtained was yellow and transparent.

[Example 4-3] (deprotection step)

The solution of 50% by weight of PGMEA/1-methoxy-2-propanol (20/80% by weight) of 4.64 g of the precursor polymer obtained in the polymerization step of Example 4-1 was heated to 130 ° C, and the reaction was carried out. hour. The PGME was distilled off to prepare a 40% by weight solution of PGMEA. The polymer solution obtained was colorless and transparent.

From the results of Examples 4-1 to 4-3, it was found that the protective group could be deprotected by placing the PPGEA solution of the precursor polymer under heating. Protection. Further, it was found that the reaction temperature can be further lowered by preparing a mixed solution of PGMEA and an alcohol. By lowering the reaction temperature, the coloration of the obtained polymer solution can be lowered.

[Industrial availability]

According to the present invention, a block copolymer comprising the following block chains (A), (B1) comprising: a repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a quaternary ammonium salt group can be produced. a block chain (A) of a polymer of at least one repeating unit in the group, and a block chain comprising a repeating unit having a polyoxyalkylene chain and a repeating unit having an acidic group represented by the formula (II) B1). These block copolymers are especially useful as pigment dispersants for color liquid crystals.

Claims (11)

A method for producing a block copolymer comprising a block chain (A), and a repeating unit comprising a repeating unit having a polyoxyalkylene chain and an acidic group represented by formula (II) The block chain (B1) of the copolymer, characterized in that the copolymer precursor comprising the block chain (A) and the block chain (B) is heated; wherein the block chain (A) comprises a polymer selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group, the block chain (B) comprising a polyoxyalkylene chain a repeating unit and a copolymer of a repeating unit having a protected acidic group represented by the formula (I), Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; X represents a single bond or is selected from a C1 to C10 alkyl group, -C(=O)OR ^1a -, -C (=O) NHR ^1a -, -OC(=O)R ^1a - and -R ^2a -OC(=O)R ^1a - the group in the group (R ^1a , R ^2a independently represent C1~C10 extension Alkyl or *C1~C10 alkylene-O-C1~C10 alkylene group *), R ⁴ represents a hydrogen atom, C1~C6 alkyl group, C6~C10 aryl C1~C6 alkyl group*, or 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; * represents a bonding position) [Chemical 2] (wherein R ¹ , R ² , R ³ and X represent the same meanings as in the formula (I)). The method for producing a block copolymer according to claim 1, wherein the block chain (B) and (B1) further comprise a repeating unit represented by the following formula (III). (wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1 to C3 alkyl group, R ⁹ represents a C1 to C10 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*; * represents a bonding position ). The method for producing a block copolymer according to claim 1 or 2, wherein the repeating unit having a tertiary amino group is a repeating unit represented by the following formula (IV), (wherein R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y represents an alkyl group selected from C1 to C10, -C(=O)OR ^1b -, -C(=O) NHR ^1b -, -OC(=O)R ^1b - and -R ^2b -OC(=O)R ^1b - a group of groups (R ^1b , R ^2b independently represent a C1 to C10 alkyl group or *C1~C10 alkylene-O-C1~C10 alkylene group*), R ¹³ and R ¹⁴ each independently represent C1~C6 alkyl group or C6~C10 aryl C1~C6 alkyl group*; * indicates bonding position). The method for producing a block copolymer according to claim 1 or 2, wherein the repeating unit having a quaternary ammonium salt group is a repeating unit represented by the following formula (V), Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y ¹ represents an alkyl group selected from C1 to C10, -C(=O)OR ^1c -, -C(= O) NHR ^1c -, -OC(=O)R ^1c - and -R ^2c -OC(=O)R ^1c - groups in the group (R ^1c , R ^2c independently represent C1 to C10 alkylene groups) Or *C1~C10 alkyl-O-C1~C10 alkyl]*, R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a C1~C6 alkyl group or a C6~C10 aryl C1~C6 alkyl group* ;Z ^- indicates a counter ion; * indicates a bonding position). The method for producing a block copolymer according to claim 1 or 2, wherein the above repeating unit having a polyoxyalkylene chain is represented by the following formula (VI): Wherein R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; and Z ¹ represents a group selected from -C(=O)O-, -C(=O)NH-, -OC( =O)- and -R ^1d -OC(=O)- groups in the group (R ^1d represents C1~C10 alkyl or *C1~C10 alkyl-O-C1~C10 alkyl) ; * represents a bonding position), R ²⁴ represents a C2 ~ C4 alkylene, R ²⁵ represents a hydrogen atom or a C1 ~ C6 alkyl group, m represents any integer of 2 to 150, R ²⁴ O may be identical to each other, may different). The method for producing a block copolymer according to claim 1 or 2, which is carried out by using a mixed solvent of a glycol ether ester-based solvent and an alcohol-based solvent or a mixed solvent of a glycol ether ester-based solvent and water. A copolymer precursor characterized by comprising: a block chain comprising a polymer comprising at least one repeating unit selected from the group consisting of a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group; (A), a block chain (B) comprising a copolymer comprising a repeating unit having a polyoxyalkylene chain and a repeating unit having a protected acidic group represented by the formula (I), Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; X represents a single bond or is selected from a C1 to C10 alkyl group, -C(=O)OR ^1a -, -C (=O) NHR ^1a -, -OC(=O)R ^1a - and -R ^2a -OC(=O)R ^1a - the group in the group (R ^1a , R ^2a independently represent C1~C10 extension Alkyl or *C1~C10 alkylene-O-C1~C10 alkylene group *), R ⁴ represents a hydrogen atom, C1~C6 alkyl group, C6~C10 aryl C1~C6 alkyl group*, or C6~C10 An aryl group, R ⁵ represents a C1 to C6 alkyl group, a C6-C10 aryl C1 to C6 alkyl group*, or a C6-C10 aryl group; * represents a bonding position). The copolymer precursor of claim 7, wherein the block chain (B) further comprises a repeating unit represented by the following formula (III), (wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C1 to C3 alkyl group, R ⁹ represents a C1 to C10 alkyl group or a C6 to C10 aryl C1 to C6 alkyl group*; * represents a bonding position ). The copolymer precursor of claim 7 or 8, wherein the above repeating unit having a tertiary amino group is a repeating unit represented by the following formula (IV), (wherein R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y represents an alkyl group selected from C1 to C10, -C(=O)OR ^1b -, -C(=O) NHR ^1b -, -OC(=O)R ^1b - and -R ^2b -OC(=O)R ^1b - a group of groups (R ^1b , R ^2b independently represent a C1 to C10 alkyl group or *C1~C10 alkylene-O-C1~C10 alkylene group *), R ¹³ and R ¹⁴ each independently represent C1~C6 alkyl group or C6~C10 aryl C1~C6 alkyl group*; * indicates bonding position ). The copolymer precursor of claim 7 or 8, wherein the above repeating unit having a quaternary ammonium salt group is a repeating unit represented by the following formula (V), Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C1 to C3 alkyl group; Y ¹ represents an alkyl group selected from C1 to C10, -C(=O)OR ^1c -, -C(= O) NHR ^1c -, -OC(=O)R ^1c - and -R ^2c -OC(=O)R ^1c - groups in the group (R ^1c , R ^2c independently represent C1 to C10 alkylene groups) Or *C1~C10 alkyl-O-C1~C10 alkyl]*, R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a C1~C6 alkyl group or a C6~C10 aryl C1~C6 alkyl group* ;Z ^- indicates a counter ion; * indicates a bonding position). The copolymer precursor of claim 7 or 8, wherein the above repeating unit having a polyoxyalkylene chain is represented by formula (VI), Wherein R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a C1 to C3 alkyl group; and Z ¹ represents a group selected from -C(=O)O-, -C(=O)NH-, -OC( =O)- and -R ^1d -OC(=O)- groups in the group (R ^1d represents C1~C10 alkyl or *C1~C10 alkyl-O-C1~C10 alkyl) ; * represents a bonding position), R ²⁴ represents a C2 ~ C4 alkylene, R ²⁵ represents a hydrogen atom or a C1 ~ C6 alkyl group, m represents any integer of 2 to 150, R ²⁴ O may be identical to each other, may different).