WO2011129077A1 - Procédé de production pour copolymère séquencé et précurseur de copolymère - Google Patents

Procédé de production pour copolymère séquencé et précurseur de copolymère Download PDF

Info

Publication number
WO2011129077A1
WO2011129077A1 PCT/JP2011/002083 JP2011002083W WO2011129077A1 WO 2011129077 A1 WO2011129077 A1 WO 2011129077A1 JP 2011002083 W JP2011002083 W JP 2011002083W WO 2011129077 A1 WO2011129077 A1 WO 2011129077A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
repeating unit
alkyl group
alkylene
copolymer
Prior art date
Application number
PCT/JP2011/002083
Other languages
English (en)
Japanese (ja)
Inventor
新谷　武士
祐一 立石
俊明 岡戸
Original Assignee
日本曹達株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本曹達株式会社 filed Critical 日本曹達株式会社
Priority to KR1020127025835A priority Critical patent/KR101454096B1/ko
Priority to JP2012510554A priority patent/JP5615351B2/ja
Priority to CN201180017897.3A priority patent/CN102858826B/zh
Publication of WO2011129077A1 publication Critical patent/WO2011129077A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a method for producing a novel block copolymer useful as a pigment dispersant, and a novel copolymer precursor.
  • Random copolymers containing units are known. Since these polymers have various properties based on their unique structures, development is being studied in various fields. In Patent Document 1, the random copolymer is applied to the field of photolithography.
  • Patent Document 1 specifically describes a copolymer obtained from an ester compound of methacrylic acid, dimethylaminoethyl methacrylate, ethyl acrylate, polyethylene glycol monomethyl ether having a molecular weight of 350 and methacryl, and the like. Yes. They are obtained as random copolymers by radical polymerization of a mixed solution of each monomer in a methyl ethyl ketone solvent using azobisisobutyronitrile (AIBN) as a radical initiator. In Patent Document 2, the random copolymer is applied as a pigment dispersant in various fields such as paints, inks, and building materials.
  • AIBN azobisisobutyronitrile
  • the inventors have at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base.
  • a block chain (A) composed of a polymer containing, a repeating unit containing a polyoxyalkylene chain, and a block chain consisting of a copolymer containing a repeating unit containing an acidic group represented by formula (II) ( It was necessary to produce a block copolymer containing B1).
  • a method for producing a block copolymer containing such a structure has not been known.
  • the present inventors have a block chain (A) comprising a polymer containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base.
  • a block copolymer is a copolymer precursor containing a block unit (B) comprising a repeating unit containing a polyoxyalkylene chain and a copolymer containing a repeating unit represented by formula (I) It was found that it can be an intermediate. By heating the copolymer precursor, the repeating unit represented by the formula (I) is converted into a repeating unit containing an acidic group represented by the formula (II).
  • the present inventors have found that a polymer can be produced and have completed the present invention.
  • the present invention (1) a block chain (A) comprising a polymer containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and polyoxy Repeating units containing an alkylene chain and the formula (I)
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • X represents a single bond or a C1-C10 alkylene group, —C ( ⁇ O) OR 1a A group selected from the group consisting of —, —C ( ⁇ O) NHR 1a —, —OC ( ⁇ O) R 1a — and —R 2a —OC ( ⁇ O) R 1a — (R 1a and R 2a are each Independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group.), R 4 represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group.
  • a process for producing a block copolymer according to (1) which comprises a repeating unit represented by: (3)
  • the repeating unit containing a tertiary amino group has the formula (IV)
  • R 10 , R 11 and R 12 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • Y represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1b —, — A group selected from the group consisting of C ( ⁇ O) NHR 1b —, —OC ( ⁇ O) R 1b — and —R 2b —OC ( ⁇ O) R 1b —
  • R 1b and R 2b are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group
  • R 13 and R 14 each independently represents a C1-C6 alkyl group or a C6-C10 aryl C1.
  • the repeating unit containing a quaternary ammonium base has the formula (V)
  • R 15 , R 16 and R 17 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • Y 1 represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1c —, A group selected from the group consisting of —C ( ⁇ O) NHR 1c —, —OC ( ⁇ O) R 1c —, and —R 2c —OC ( ⁇ O) R 1c —
  • R 1c and R 2c are each independently Represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group, and each of R 18 , R 19 and R 20 independently represents a C1 to C6 alkyl group, or It represents a C6 ⁇ C10 aryl C1 ⁇ C6 alkyl group .Z - the production of the block copolymer described in (1) or (2) to a repeating unit represented by) represents a counter ion.
  • R 21 , R 22 and R 23 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • Z 1 represents —C ( ⁇ O) O—, —C ( ⁇ O) NH A group selected from the group consisting of —, —OC ( ⁇ O) — and —R 1d —OC ( ⁇ O) — (R 1d is a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group; R 24 represents a C2-C4 alkylene group, R 25 represents a hydrogen atom or a C1-C6 alkyl group, m represents an integer from 2 to 150, and R 24 O may be the same or different from each other.)
  • the method for producing a block copolymer according to any one of (1) to (4), and (6) The method according to any one of (1) to (5), wherein the reaction is carried out in a mixed solvent of a glycol ether ester solvent and an alcohol solvent
  • the present invention also provides: (7) a block chain (A) comprising a polymer containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base, and polyoxy Repeating units containing an alkylene chain and formula (I)
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • X represents a single bond or a C1-C10 alkylene group, —C ( ⁇ O) OR 1a A group selected from the group consisting of —, —C ( ⁇ O) NHR 1a —, —OC ( ⁇ O) R 1a — and —R 2a —OC ( ⁇ O) R 1a — (R 1a and R 2a are each Independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group.), R 4 represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group.
  • R 5 contains a protected acidic group represented by a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl) Repetitive Copolymer precursor which is characterized by containing a copolymer consisting of body block chain (B) containing and units, (8)
  • the block chain (B) is further represented by the formula (III)
  • R 6 , R 7 and R 8 each independently represents a hydrogen atom or a C1-C3 alkyl group, and R 9 represents a C1-C10 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
  • the repeating unit containing a tertiary amino group has the formula (IV)
  • R 10 , R 11 and R 12 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • Y represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1b —, — A group selected from the group consisting of C ( ⁇ O) NHR 1b —, —OC ( ⁇ O) R 1b — and —R 2b —OC ( ⁇ O) R 1b —
  • R 1b and R 2b are each independently Represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group
  • R 13 and R 14 each independently represents a C1-C6 alkyl group or a C6-C10 aryl C1.
  • the repeating unit containing a quaternary ammonium base has the formula (V)
  • R 15 , R 16 and R 17 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • Y 1 represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1c —, A group selected from the group consisting of —C ( ⁇ O) NHR 1c —, —OC ( ⁇ O) R 1c —, and —R 2c —OC ( ⁇ O) R 1c —
  • R 1c and R 2c are each independently Represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group, and each of R 18 , R 19 and R 20 independently represents a C1 to C6 alkyl group, or .Z representing a C6 ⁇ C10 aryl C1 ⁇ C6 alkyl group -. is that a counter ion), characterized in that a repeating unit represented by (7) or copolymer precursors described (8), (1
  • R 21 , R 22 and R 23 each independently represents a hydrogen atom or a C1-C3 alkyl group.
  • Z 1 represents —C ( ⁇ O) O—, —C ( ⁇ O) NH A group selected from the group consisting of —, —OC ( ⁇ O) — and —R 1d —OC ( ⁇ O) — (R 1d is a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group; R 24 represents a C2-C4 alkylene group, R 25 represents a hydrogen atom or a C1-C6 alkyl group, m represents an integer from 2 to 150, and R 24 O may be the same or different from each other.)
  • the copolymer precursor of the present invention contains at least one of the following block chains (A) and block chains (B).
  • the copolymer precursor of the present invention is not limited to the block chain (A) and the block chain (B). It may contain a block chain.
  • Block chain (A) In the block chain (A), the repeating unit containing a tertiary amino group and the repeating unit containing a quaternary ammonium base are those having the cationic functional group in the side chain of the repeating unit, There is no particular limitation. Specifically, the polymer of the block chain (A) is a homopolymer consisting of only one of a repeating unit containing a tertiary amino group or a repeating unit containing a quaternary ammonium base, and a tertiary amino group.
  • a copolymer comprising two or more repeating units containing or a repeating unit containing a quaternary ammonium base, at least one repeating unit containing a tertiary amino group, and at least one repeating unit containing a quaternary ammonium base
  • Copolymers of seeds and copolymers of these with repeating units derived from other copolymerizable monomers are included.
  • Copolymers include random, alternating, block, etc. copolymers.
  • the repeating unit containing a tertiary amino group is not particularly limited as long as it contains a tertiary amino group, and examples thereof include a repeating unit represented by the following general formula (IV).
  • R 10 , R 11 and R 12 are each independently a hydrogen atom or a C1-C3 alkyl group.
  • Y represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1b —, —C ( ⁇ O) NHR 1b —, —OC ( ⁇ O) R 1b — and —R 2b —OC ( ⁇ O) R 1b
  • R 13 and R 14 are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
  • the C1-C3 alkyl group and the C1-C6 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n -Hexyl and the like are exemplified.
  • Examples of the C1-C10 alkylene group include a methylene chain, an ethylene chain, a propylene chain, a methylethylene chain, a butylene chain, a 1,2-dimethylethylene chain, a pentylene chain, a 1-methylbutylene chain, a 2-methylbutylene chain, and a hexylene chain. Is exemplified.
  • C6-C10 aryl C1-C6 alkyl groups include benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, naphthalen-2-ylethyl, 1-naphthalene-2 Examples include -yl-n-propyl, inden-1-ylmethyl and the like.
  • dimethylaminoethyl (meth) acrylate dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylamino
  • examples thereof include propyl (meth) acrylate and diethylaminobutyl (meth) acrylate.
  • the repeating unit containing a quaternary ammonium base is not particularly limited as long as it contains a quaternary ammonium base, and examples thereof include a repeating unit represented by the following general formula (V).
  • R 15 , R 16 and R 17 are each independently a hydrogen atom or a C1-C3 alkyl group.
  • Y 1 represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1c —, —C ( ⁇ O) NHR 1c —, —OC ( ⁇ O) R 1c — and —R 2c —OC ( ⁇ O) R.
  • a group selected from the group consisting of 1c — R 1c and R 2c are each independently a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group).
  • R 18 , R 19 and R 20 are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
  • Z ⁇ represents a counter ion such as a halide ion, an alkyl halide ion, an alkyl carboxylate ion, a nitroxide ion, an alkyl sulfate ion, a sulfonate ion, a phosphate ion or an alkyl phosphate ion.
  • the C1-C3 alkyl group, the C1-C6 alkyl group, the C1-C10 alkylene group, and the C6-C10 aryl C1-C6 alkyl group are represented by the formula (IV) of the repeating unit containing the tertiary amino group. The thing similar to what is in can be illustrated.
  • repeating units that can be contained examples include repeating units derived from (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers, and the like. Examples of the (meth) acrylic acid-based monomer, aromatic vinyl-based monomer, and conjugated diene-based monomer that are the raw materials for the repeating unit include the following.
  • (Meth) acrylic acid monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, glycidyl (meth) acrylate, (meth (Meth) acrylate compounds such as cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate , Methoxy polyethylene glycol (ethylene glycol has 2 to 100
  • Aromatic vinyl monomers include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, ⁇ -methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene.
  • Conjugated diene monomers include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene, and the like. These can be used alone or in combination
  • Block chain (B) is a copolymer containing at least one repeating unit containing a polyoxyalkylene chain and at least one repeating unit containing a protected acidic group. Copolymers include random, alternating, block, etc. copolymers.
  • the repeating unit containing a polyoxyalkylene chain in the block chain (B) is not particularly limited as long as it contains a polyoxyalkylene chain, and examples thereof include a repeating unit represented by the formula (VI).
  • R 21 , R 22 and R 23 are each independently a hydrogen atom or a C1-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 a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group.
  • R 24 represents a C2-C4 alkylene group
  • R 25 represents a hydrogen atom or a C1-C6 alkyl group.
  • n-C3 alkyl group and the C1-C6 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n -Hexyl and the like are exemplified.
  • C2-C4 alkylene group and C1-C10 alkylene group include methylene chain, ethylene chain, propylene chain, methylethylene chain, butylene chain, 1,2-dimethylethylene chain, pentylene chain, 1-methylbutylene chain, 2-methyl Examples include butylene chain or hexylene chain.
  • m is preferably 2 to 10.
  • polyethylene glycol (2 to 150: the value of m in the formula (VI) is shown.
  • These may be used alone or in admixture of two or more. it can.
  • the repeating unit containing a protected acidic group in the block chain (B) is a repeating unit represented by the formula (I).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom or a C1-C3 alkyl group.
  • X is a single bond or a C1-C10 alkylene group, —C ( ⁇ O) OR 1a —, —C ( ⁇ O) NHR 1a —, —OC ( ⁇ O) R 1a — and —R 2a —OC ( ⁇ O And R 4a is a group selected from the group consisting of R 1a — (R 1a and R 2a are each independently a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group), and R 4.
  • R 5 is a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, Or a C6-C10 aryl group.
  • Examples of monomers used as a raw material for the repeating unit represented by the formula (I) include acrylic acid methoxymethyl ester, acrylic acid ethoxymethyl ester, acrylic acid 1-ethoxy-ethyl ester, acrylic acid 1-methoxy-ethyl ester, and acrylic acid.
  • acrylic acid 1-ethoxy-ethyl ester and 2-methyl-acrylic acid 1-ethoxy-ethyl ester are preferred. These can be used alone or in admixture of two or more.
  • the repeating unit containing a protected acidic group can be converted to a repeating unit containing an acidic group described below by deprotecting the protective group by the production method of the present invention.
  • repeating units that can be contained examples include repeating units derived from (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers, and the like. Among these, Preferably, it is a repeating unit represented by Formula (III).
  • R 6 , R 7 and R 8 are each independently a hydrogen atom or a C1-C3 alkyl group.
  • R 9 is a C1-C10 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
  • the C1-C3 alkyl group and the C1-C6 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n -Hexyl and the like are exemplified.
  • C6-C10 aryl C1-C6 alkyl groups include benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, naphthalen-2-ylethyl, 1-naphthalene-2 Examples include -yl-n-propyl, inden-1-ylmethyl and the like.
  • Examples of the (meth) acrylic acid-based monomer, aromatic vinyl-based monomer, and conjugated diene-based monomer that are the raw materials for the repeating unit include the following.
  • (Meth) acrylic acid monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, glycidyl (meth) acrylate, (meth (Meth) acrylate compounds such as cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate , Methoxy polyethylene glycol (ethylene glycol has 2 to 100
  • Aromatic vinyl monomers include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, ⁇ -methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene.
  • Conjugated diene monomers include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene, and the like. These can be used alone or in combination
  • the copolymer of the present invention may have a block chain made of another polymer in addition to the block chains (A) and (B).
  • Such polymers include homopolymers, random copolymers, alternating copolymers, blocks containing repeating units derived from (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers, etc. Examples thereof include copolymers. Examples of the (meth) acrylic acid monomer, aromatic vinyl monomer, conjugated diene monomer, and the like are exemplified.
  • the ratio of the block chain (A) to the block chain (B) in the copolymer of the present invention is not particularly limited, but is 10 to 40:90 to 60, preferably 15 to 35 to 85 in terms of% by weight. ⁇ 65. Further, the weight average molecular weight measured using GPC is preferably 2,000 to 50,000, more preferably 2,000 to 20,000.
  • the copolymer precursor is particularly preferably 4,000 to 30,000, and more preferably 4,000 to 15,000.
  • the ratio of the weight average molecular weight to the number average molecular weight, measured using GPC is 1.0 to 2.0, preferably 1.0 to 1.5.
  • the method for producing the copolymer precursor of the present invention is not particularly limited and can be produced by a known method.
  • a monomer is polymerized by living polymerization, It can be a block copolymer.
  • living polymerization include living radical polymerization and living anion polymerization, and among these, living anion polymerization is more preferable.
  • another block monomer may be continuously polymerized to form a block copolymer, Each block of A) and the block chain (B) may be reacted separately to produce a block, and then each block may be combined.
  • Living anionic polymerization is preferable because the composition and molecular weight can be strictly controlled.
  • the reaction can be carried out in the same manner as living anion polymerization, or after polymerizing a certain block of monomer and before polymerizing the next monomer, the polymer is once purified, It is also possible to polymerize the next monomer after removing the remainder of the monomer in the reaction.
  • the monomers of each block do not mix with each other, it is preferable to purify the polymer.
  • a desired monomer can be dropped and polymerized in a solvent to which an additive and a polymerization initiator are added.
  • the monomers of each block are sequentially added dropwise so as to have a desired sequence and reacted.
  • the dropping of the monomer of the next block is started after completion of the polymerization reaction of the previous block.
  • the progress of the polymerization reaction can be confirmed by detecting the remaining amount of the monomer by gas chromatography or liquid chromatography.
  • the dropping of the monomer of the next block can be started after stirring for 1 minute to 1 hour.
  • the anionic polymerization initiator used for the polymerization of the monomer is not particularly limited as long as it is a nucleophile and has a function of initiating the polymerization of the anionic polymerizable monomer.
  • alkali metal organic Alkali metal compounds and the like can be used.
  • the alkali metal include lithium, sodium, potassium, cesium and the like.
  • the organic alkali metal compound include alkylated products, allylated products, and arylated products of the above alkali metals, and alkyllithium is particularly preferable.
  • anionic polymerization initiators can be used alone or in combination of two or more.
  • the amount of the anionic polymerization initiator used is usually from 0.0001 to 0.2 equivalent, preferably from 0.0005 to 0.1 equivalent, based on the whole anionic polymerizable monomer to be used. By using an anionic polymerization initiator in this range, the target polymer can be produced with high yield.
  • the polymerization temperature is not particularly limited as long as the side reaction such as transfer reaction or termination reaction does not occur and the monomer is consumed and the polymerization is completed, but the polymerization temperature is not lower than ⁇ 100 ° C. but not higher than the solvent boiling point. preferable.
  • the concentration of the monomer with respect to the polymerization solvent is not particularly limited, but is usually 1 to 40% by weight, and preferably 2 to 15% by weight.
  • the polymerization solvent used in the production method of the present invention is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer, and specifically includes diethyl ether, tetrahydrofuran (THF), dioxane.
  • Polar compounds such as ether compounds such as trioxane, tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide, and non-aliphatic, aromatic or alicyclic hydrocarbon compounds such as hexane and toluene
  • a polar solvent or a low polarity solvent can be illustrated. These solvents can be used alone or as a mixed solvent of two or more.
  • polymerization can be accurately controlled even when a nonpolar solvent or a low polarity solvent is used in combination with a polar solvent.
  • the nonpolar solvent or the low polarity solvent is based on the whole solvent. 5 vol% or more can be used, 20 vol% or more may be used, and 50 vol% or more may be used.
  • a dialkyl zinc such as diethyl zinc, a dialkyl magnesium such as dibutyl magnesium, or an organic metal such as triethylaluminum can be used as a polymerization stabilizer, a monomer or a solvent purifier, if necessary.
  • an additive such as an alkali metal salt or an alkaline earth metal salt can be added at the start of polymerization or during polymerization as required. Specific examples of such additives include mineral salts and halides such as sodium, potassium, barium and magnesium sulfates, nitrates and borates.
  • lithium And barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride and the like lithium halides such as lithium chloride, lithium bromide, lithium iodide, and lithium fluoride are preferable, and lithium chloride is particularly preferable. It is generally difficult to polymerize a monomer containing a quaternary ammonium base by living anionic polymerization.
  • Quaternizing agents include benzyl chloride, benzyl bromide, benzyl iodide, etc., alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, di-n sulfate.
  • -Common alkylating agents such as alkyl sulfates such as propyl.
  • Block copolymer contains at least one of the following block chains (A) and block chains (B1).
  • Block chain (A) a polymer comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base
  • Block block (B1) polyoxyalkylene
  • the copolymer precursor of the present invention is a block chain other than the block chain (A) and the block chain (B1). May be contained.
  • Block chain (A) The block chain (A) in the block copolymer is the same as the block chain (A) in the copolymer precursor.
  • Block chain (B1) The block chain (B1) is a copolymer containing at least one repeating unit containing a polyoxyalkylene chain and at least one repeating unit containing an acidic group. Copolymers include random, alternating, block, etc. copolymers.
  • the repeating unit containing a polyoxyalkylene chain in the block chain (B1) is the same as the repeating unit containing a polyoxyalkylene chain in the copolymer precursor.
  • the repeating unit containing an acidic group in the block chain (B1) is a repeating unit represented by the formula (II).
  • R 1 , R 2 , R 3 and X have the same meaning as in the repeating unit containing a protected acidic group represented by formula (I).
  • the repeating unit represented by the formula (II) can be obtained by deprotecting the protecting group of the protected acidic group represented by the formula (I) by the production method of the present invention.
  • the other repeating unit that can be contained in the block chain (B1) is the same as the other repeating unit that can be contained in the block chain (B) in the copolymer precursor.
  • the copolymer of the present invention may have a block chain made of another polymer in addition to the block chains (A) and (B1). Such a block chain is the same as the block chain other than the block chains (A) and (B) in the copolymer precursor.
  • the ratio of the block chain (A) to the block chain (B1) in the copolymer of the present invention is not particularly limited, but is 10 to 40:90 to 60, preferably 15 to 35 to 85 in terms of% by weight. ⁇ 65.
  • the content of the repeating unit having an acidic group in the copolymer is 0.5 to 20% by weight, preferably 1 to 15% by weight.
  • the weight average molecular weight measured using GPC is preferably 2,000 to 50,000, more preferably 2,000 to 20,000.
  • the dispersant is particularly preferably 4,000 to 30,000, and more preferably 4,000 to 15,000.
  • the ratio of the weight average molecular weight to the number average molecular weight, measured using GPC is 1.0 to 2.0, and the dispersant is particularly preferably 1.0 to 1.5.
  • the block copolymer of this invention can be obtained by heating the said copolymer precursor.
  • the protecting group protecting the acidic group in the copolymer precursor is deprotected.
  • the copolymer precursor may be heated as it is, or may be heated in a state where the copolymer precursor is dissolved in a solvent.
  • glycol ether ester solvents such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate
  • PGMEA propylene glycol monomethyl ether acetate
  • ethyl cellosolve methyl cellosolve
  • propylene glycol monomethyl ether propylene glycol monomethyl ether
  • Glycol mono- or diether solvents such as propylene glycol monoethyl ether and diethylene glycol dimethyl ether
  • aromatic hydrocarbon solvents such as toluene and monochlorobenzene
  • ethanol isopropanol, n-butanol, 1-methoxy-2-propanol (PGME), etc.
  • Alcohol solvents such as ethyl lactate, butyl acetate and ethyl pyruvate; and these A mixed solvent consisting of seeds or more; and the like.
  • glycol ether ester solvents mixed solvents of glycol ether ester solvents and alcohol solvents, and mixed solvents of glycol ether ester solvents and water are preferred.
  • a mixed solvent of a glycol ether ester solvent and an alcohol solvent a mixed solvent of a glycol ether ester solvent and water is preferable, and a mixture of a glycol ether ester solvent and water is preferable.
  • a mixed solvent is particularly preferred.
  • a mixed solvent of glycol ether ester solvent and water is preferable, and a mixed solvent of PGMEA and water is particularly preferable.
  • the mixing ratio is not particularly limited as long as the copolymer precursor can be dissolved, but usually 95/5 wt% to 0.1 / 99.9. % By weight is preferable, and 50/50 to 0.1 / 99.9% by weight is more preferable.
  • the mixing ratio is not particularly limited as long as the copolymer precursor can be dissolved, but it is usually preferably 95/5 to 50/50% by weight, It is more preferably 90/10 to 60/40% by weight, particularly preferably 90/10 to 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 is not particularly limited as long as the deprotection reaction proceeds rapidly.
  • a glycol ether ester solvent it is usually preferably carried out at 80 ° C. to 200 ° C., more preferably 100 ° C. to 160 ° C.
  • a mixed solvent of a glycol ether ester solvent and an alcohol solvent it is preferably carried out at 100 to 140 ° C., more preferably 110 to 140 ° C.
  • a mixed solvent of a glycol ether ester solvent and water it is preferably carried out at 70 to 100 ° C, more preferably 90 to 100 ° C. From the viewpoint of reducing the coloration of the polymer solution produced by the deprotection reaction, it is preferable to lower the heating temperature.
  • Example 1-1 Polymerization process
  • THF tetrahydrofuran
  • lithium chloride 3.63% by weight concentration THF solution
  • EEMA 1-ethoxyethyl methacrylate
  • nBMA n-butyl methacrylate
  • PME- methoxypolyethylene glycol monomethacrylate
  • PEGMA Manufactured by NOF Corporation 200
  • GC gas chromatography
  • GPC gel permeation chromatography
  • DMMA 2- (dimethylamino) ethyl methacrylate
  • the copolymer was confirmed to be a copolymer by weight%.
  • Example 1-2 (Deprotection process) 10.0 g of a 25 wt% PGMEA / n-butanol solution (30/70 wt%) of the precursor polymer obtained in the polymerization step of Example 1-1 was heated to 115 ° C. and reacted for 8 hours. . n-Butanol was distilled off to prepare a 40 wt% PGMEA solution. The polymer solution obtained was colorless and transparent.
  • Example 1-3 (Deprotection process) 20% by weight PGMEA / water solution (62.5 / 37.5% by weight), 20% by weight PGMEA / water solution (65/35% by weight) of the precursor polymer obtained in the polymerization step of Example 1-1 ), 20 wt% PGMEA / water solution (75/25 wt%), 20 wt% PGMEA / water solution (87.5 / 12.5 wt%), 20 wt% PGMEA / water solution (93.75). /6.25% by weight) was prepared in an amount of 12.80 g. Each of the prepared solutions was heated to 100 ° C. and reacted for 8 hours.
  • the protecting group can be deprotected by subjecting the precursor polymer PGMEA solution to heating conditions. Moreover, it turns out that reaction temperature can be made lower by setting it as the mixed solution of PGMEA and alcohol, and also reaction temperature can be made still lower by setting it as the mixed solution of PGMEA and water.
  • Example 3 (Polymerization process) To a 1000 mL flask were added 578.66 g of THF and 11.20 g of lithium chloride (3.63 wt% THF solution), and the mixture was cooled to ⁇ 60 ° C. Thereafter, 7.34 g of n-butyllithium (15.36 wt% hexane solution) was added and aged for 10 minutes. Subsequently, 4.30 g of methyl methacrylate (hereinafter sometimes abbreviated as MMA) was added, and the reaction was continued for 5 minutes.
  • MMA methyl methacrylate
  • EEMA Ethylhexyl methacrylate
  • BzMA benzyl methacrylate
  • Example 4-1 (Polymerization process) To a 1000 mL flask were added 683.03 g of THF and 11.92 g of lithium chloride (3.63% by weight concentration THF solution), and the mixture was cooled to ⁇ 60 ° C. Thereafter, 8.32 g of n-butyllithium (15.36 wt% hexane solution) was added and aged for 10 minutes. Subsequently, 5.06 g of MMA was added, and the reaction was continued for 5 minutes. Then, after confirming disappearance of the monomer by GC measurement, a part thereof was sampled and GPC measurement was performed. As a result, a polymer having a molecular weight of 311 (3.10 mer) was produced.
  • Example 4-2 (Deprotection process) 212.32 g of a 50 wt% PGMEA solution of the precursor polymer obtained in the polymerization step of Example 4-1 was heated to 130 ° C. and reacted for 17 hours. The resulting polymer solution was yellow and transparent.
  • Example 4-3 (Deprotection process) 4.64 g of a 50 wt% PGMEA / 1-methoxy-2-propanol solution (20/80 wt%) of the precursor polymer obtained in the polymerization step of Example 4-1 was heated to 130 ° C. and reacted for 9 hours. I let you. PGME was distilled off to prepare a 40% strength by weight PGMEA solution. The polymer solution obtained was colorless and transparent.
  • Example 4-3 From the results of Example 4-1 to Example 4-3, it can be seen that the protecting group can be deprotected by subjecting the PGMEA solution of the precursor polymer to heating conditions. Furthermore, reaction temperature can be made lower by using a mixed solution of PGMEA and alcohol. It turns out that coloring of the polymer solution obtained can be reduced by making reaction temperature low.
  • a block chain (A) comprising a polymer containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base;
  • a block copolymer containing a block chain (B1) comprising a copolymer containing a repeating unit containing a polyoxyalkylene chain and a repeating unit containing an acidic group represented by formula (II) is produced.
  • block copolymers are particularly useful as pigment dispersants for color liquid crystals.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Graft Or Block Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un procédé de production pour un nouveau copolymère qui est utile en tant qu'agent de dispersion de pigment ou similaire. Le procédé décrit est comme suit : un précurseur de polymère est chauffé, ledit précurseur contenant : une chaîne séquencée (A) formée de polymères contenant au moins un type de motif de répétition choisi dans le groupe constitué d'un motif de répétition ayant un groupe amino tertiaire, et un motif de répétition ayant un groupe de sel d'ammonium quaternaire ; et une chaîne séquencée (B) formée de copolymères contenant des motifs de répétition ayant une chaîne polyoxyalkylène, et des motifs de répétition ayant un groupe acide protégé représenté par la formule (I). Un copolymère séquencé est ainsi produit et contient la chaîne séquencée (A), et une chaîne séquencée (B1) formée de copolymères contenant des motifs de répétition ayant une chaîne polyoxyalkylène, et des motifs de répétition ayant un groupe acide représenté par la formule (II).
PCT/JP2011/002083 2010-04-14 2011-04-08 Procédé de production pour copolymère séquencé et précurseur de copolymère WO2011129077A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020127025835A KR101454096B1 (ko) 2010-04-14 2011-04-08 블록 공중합체의 제조 방법 및 공중합체 전구체
JP2012510554A JP5615351B2 (ja) 2010-04-14 2011-04-08 ブロック共重合体の製造方法及び共重合体前駆体
CN201180017897.3A CN102858826B (zh) 2010-04-14 2011-04-08 嵌段共聚物的制造方法及共聚物前体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010092952 2010-04-14
JP2010-092952 2010-04-14

Publications (1)

Publication Number Publication Date
WO2011129077A1 true WO2011129077A1 (fr) 2011-10-20

Family

ID=44798464

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/002083 WO2011129077A1 (fr) 2010-04-14 2011-04-08 Procédé de production pour copolymère séquencé et précurseur de copolymère

Country Status (5)

Country Link
JP (1) JP5615351B2 (fr)
KR (1) KR101454096B1 (fr)
CN (1) CN102858826B (fr)
TW (1) TWI425012B (fr)
WO (1) WO2011129077A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013185005A (ja) * 2012-03-06 2013-09-19 Dic Corp 重合体の製造方法
JP2013203887A (ja) * 2012-03-28 2013-10-07 Dainichiseika Color & Chem Mfg Co Ltd 顔料着色剤組成物、カラーフィルター用着色剤、高分子分散剤及び該高分子分散剤の製造方法
JP2016029176A (ja) * 2015-09-18 2016-03-03 大日精化工業株式会社 顔料着色剤組成物及び顔料分散剤

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI606071B (zh) * 2016-12-23 2017-11-21 財團法人工業技術研究院 雙團塊共聚物與分散液

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06128336A (ja) * 1990-07-21 1994-05-10 Hoechst Ag 親水性共重合体およびリプログラフィーにおけるそれらの用途
WO2002031010A1 (fr) * 2000-10-13 2002-04-18 Kansai Paint Co., Ltd. Resine pour dispersion de pigment
JP2009024165A (ja) * 2007-06-19 2009-02-05 Dainichiseika Color & Chem Mfg Co Ltd 顔料分散剤、その製造方法、およびその利用
WO2010013651A1 (fr) * 2008-07-28 2010-02-04 大日精化工業株式会社 Dispersion aqueuse de pigment et ses applications
JP2010039060A (ja) * 2008-08-01 2010-02-18 Mitsubishi Chemicals Corp インクジェット法カラーフィルタ用着色硬化性樹脂組成物、カラーフィルタ、液晶表示装置および有機ｅｌディスプレイ

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5272201A (en) * 1990-04-11 1993-12-21 E. I. Du Pont De Nemours And Company Amine-containing block polymers for pigmented ink jet inks
GB0418124D0 (en) * 2004-08-13 2004-09-15 Asahi Chemical Ind Polymers useful as medical materials
JP5553957B2 (ja) * 2007-03-15 2014-07-23 富士フイルム株式会社 顔料分散組成物、光硬化性組成物、並びに、カラーフィルタ及びその製造方法
JP5413016B2 (ja) 2008-07-31 2014-02-12 東京エレクトロン株式会社 基板の洗浄方法、基板の洗浄装置及び記憶媒体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06128336A (ja) * 1990-07-21 1994-05-10 Hoechst Ag 親水性共重合体およびリプログラフィーにおけるそれらの用途
WO2002031010A1 (fr) * 2000-10-13 2002-04-18 Kansai Paint Co., Ltd. Resine pour dispersion de pigment
JP2009024165A (ja) * 2007-06-19 2009-02-05 Dainichiseika Color & Chem Mfg Co Ltd 顔料分散剤、その製造方法、およびその利用
WO2010013651A1 (fr) * 2008-07-28 2010-02-04 大日精化工業株式会社 Dispersion aqueuse de pigment et ses applications
JP2010039060A (ja) * 2008-08-01 2010-02-18 Mitsubishi Chemicals Corp インクジェット法カラーフィルタ用着色硬化性樹脂組成物、カラーフィルタ、液晶表示装置および有機ｅｌディスプレイ

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013185005A (ja) * 2012-03-06 2013-09-19 Dic Corp 重合体の製造方法
JP2013203887A (ja) * 2012-03-28 2013-10-07 Dainichiseika Color & Chem Mfg Co Ltd 顔料着色剤組成物、カラーフィルター用着色剤、高分子分散剤及び該高分子分散剤の製造方法
JP2016029176A (ja) * 2015-09-18 2016-03-03 大日精化工業株式会社 顔料着色剤組成物及び顔料分散剤

Also Published As

Publication number Publication date
KR20120138796A (ko) 2012-12-26
CN102858826A (zh) 2013-01-02
KR101454096B1 (ko) 2014-10-22
JPWO2011129077A1 (ja) 2013-07-11
TWI425012B (zh) 2014-02-01
CN102858826B (zh) 2015-05-20
JP5615351B2 (ja) 2014-10-29
TW201204754A (en) 2012-02-01

Similar Documents

Publication Publication Date Title
JP5778686B2 (ja) 新規共重合体
US9562128B2 (en) Copolymer
JP5615918B2 (ja) 新規共重合体
JP5652923B2 (ja) 新規共重合体
JP5615351B2 (ja) ブロック共重合体の製造方法及び共重合体前駆体
JP5616445B2 (ja) ブロック共重合体の製造方法及び共重合体前駆体
JP5785047B2 (ja) ブロック共重合体の製造方法
JP5996751B2 (ja) 新規共重合体

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180017897.3

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11768602

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012510554

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20127025835

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11768602

Country of ref document: EP

Kind code of ref document: A1