A-B block co-polymer, A-B block co-polymer production method, resin treatment pigment composition, resin treatment pigment composition production method, pigment dispersion, and pigment dispersion solution

Patent metadata

Field	Value
Publication number	US-10982020-B2
Application number	US-201415313179-A
Country	US
Kind code	B2
Filing date	Jun 25, 2014
Priority date	Jun 25, 2014
Publication date	Apr 20, 2021
Grant date	Apr 20, 2021

Abstract

There is provided a resin-treated pigment that is useful as a coloring agent for color filters or inkjet inks, that can expand a hue range and improve performances such as color density, color developability, and transparency, and that is excellent in properties such as dispersibility and dispersion stability of pigments, re-dissolvability, and alkali-solubility. An A-B block copolymer 90% by mass or more of which is constituted by a methacrylate-based monomer or methacrylate-based monomers, in which the block A has a carboxy group-containing methacrylate as a constituent, and the block B has an ionic bond moiety represented by formula (1) as a constitutional unit, the ionic bond moiety containing a methacrylate, and an organic coloring matter having one or more sulfonate ions each being bonded thereto and each being a counter ion of a nitrogen cation of a quaternary ammonium salt.

First claim

The invention claimed is:

1. An A-B block copolymer, 90% by mass or more of which is constituted by a methacrylate-based monomer or methacrylate-based monomers, wherein:
a polymer block A comprises at least a carboxyl group-containing methacrylate as a constituent, provided that the polymer block A comprising an amino group- or quaternary ammonium salt group-containing methacrylate as a constituent is excluded;
a polymer block B comprises an ionic bond moiety represented by formula (1) as a constitutional unit,
the ionic bond moiety comprising:
a methacrylate; and
an organic coloring matter having one or more sulfonate ions:

wherein X represents an organic group, R1 to R3 each independently represent any one selected from the group consisting of C1 to C18 alkyl groups and a benzyl group, and a DSO 3 − group represents an organic coloring matter,
wherein the polymer block A is water-soluble when being neutralized with an alkali,
the polymer block B is capable of adsorbing to a pigment,
D in the DSO 3 − group of the formula (1) in the polymer block B is an organic coloring matter skeleton,
the DSO 3 − group in the polymer block B is a sulfonate-group-containing dye having at least one sulfonate group,
the sulfonate-group-containing dye dissolves in water,
the at least one sulfonate group in the DSO 3 − group in the polymer block B is ionically bonded to a quaternary ammonium cation that is bonded to X in the formula (1), and
a moiety represented by the formula (1) is contained in a range from 5 to 40% by mass in the A-B block copolymer and in a range from 20 to 80% by mass in the polymer block B.

2. The A-B block copolymer according to claim 1 , wherein the ionic bond moiety being contained in the polymer block B and comprising the organic coloring matter having one or more sulfonate ions each being bonded thereto is formed by subjecting:
an A-C block copolymer comprising the polymer block A and a polymer block C comprising a quaternary ammonium methacrylate represented by formula (2) as a constituent; and
the organic coloring matter having at least one structural moiety selected from the group consisting of alkali metal sulfonates, within a molecule thereof,
to a reaction to detach counter ions as an alkali metal halide:

wherein X represents an organic group, R1 to R3 each independently represent any one selected from the group consisting of C1 to C18 alkyl groups and a benzyl group, and Y − represents a halogen ion.

3. The A-B block copolymer according to claim 1 , wherein the polymer block A has a number average molecular weight in a range from 3000 to 20000 in terms of polystyrene in gel permeation chromatography, a degree of dispersion in a range of 1.5 or less, which is weight average molecular weight/number average molecular weight, and an acid value in a range from 30 to 250 mgKOH/g.

4. The A-B block copolymer according to claim 1 , obtained by utilizing living radical polymerization using a polymerization initiation compound.

5. The A-B block copolymer according to claim 4 , wherein, in the living radical polymerization, a total number of moles of a monomer or monomers for forming the polymer block B is in a range from 10 to 150 mol relative to 1 mol of the polymerization initiation compound.

6. A process for producing the A-B block copolymer according to claim 1 , the process comprising:
conducting living radical polymerization in the presence of at least a polymerization initiation compound and a catalyst, wherein:
the polymerization initiation compound is at least any one of iodine and iodine compounds,
the catalyst is at least one compound selected from the group consisting of phosphorus halides, phosphite-based compounds, phosphinate-based compounds, imide-based compounds, phenol-based compounds, diphenylmethane-based compounds, and cyclopentadiene-based compounds, and
a polymerization temperature is in a range from 30 to 50° C.

7. A resin-treated pigment composition obtained by treating a pigment with the A-B block copolymer according to claim 1 ,
wherein the pigment is treated within a range from 10 to 200 parts of the A-B block copolymer relative to 100 parts of the pigment.

8. A process for producing the resin-treated pigment composition according to claim 7 , the process comprising:
subjecting (i) the organic coloring matter having at least one structural moiety selected from the group consisting of alkali metal sulfonates within a molecule thereof, the organic coloring matter being the sulfonate-group-containing dye that dissolves in water, and
(ii) an A-C block copolymer comprising:
the polymer block A that is water-soluble when being neutralized with an alkali and comprises at least the carboxyl group-containing methacrylate as a constituent, provided that the polymer block A comprising the amino group- or quaternary ammonium salt group-containing methacrylate as a constituent is excluded; and
a polymer block C comprising: a quaternary ammonium methacrylate represented by formula (2) as a constituent:

wherein X in the formula (2) represents an organic group, R1 to R3 in the formula (2) each independently represent any one group selected from the group consisting of C1 to C18 alkyl groups and a benzyl group, and Y − in the formula (2) represents a halogen ion,

to a reaction to detach counter ions as an alkali metal halide, in the presence of the pigment in an aqueous medium, thereby turning the pigment into a pigment treated with the A-B block copolymer, the A-C block copolymer reacting with the organic coloring matter in the reaction to form the A-B block copolymer.

9. The process for producing the resin-treated pigment composition according to claim 8 , wherein the organic coloring matter and the A-C block copolymer are subjected to the reaction to detach the counter ions as the alkali metal halide in the presence of the aqueous medium comprising the pigment dispersed therein with a sulfonate group-containing surface active agent, thereby turning the pigment into a pigment treated with the A-B block copolymer.

10. A pigment dispersion obtained by dispersing the resin-treated pigment composition according to claim 7 .

11. A pigment dispersion comprising at least:
a pigment; and
a pigment dispersant,
wherein the pigment dispersant is the A-B block copolymer according to claim 1 , and
the pigment dispersion is an aqueous solution in which the polymer block B of the A-B block copolymer adsorbs to the pigment so that the pigment is dispersed in the aqueous solution.

12. A pigment dispersion liquid obtained by dispersing the pigment dispersion according to claim 10 in at least one dispersion medium selected from the group consisting of water, organic solvents, and polymerizable monomers.

13. A pigment dispersion obtained by dispersing a resin-treated pigment composition that is obtained by the process for producing the resin-treated pigment composition according to claim 8 .

14. The A-B block copolymer according to claim 1 , wherein the sulfonate-group-containing dye comprises at least one dye selected from the group consisting of acid dyes having a xanthene structure, pyranine derivatives, coumarin derivatives, oxazole derivatives, thiazole derivatives, imidazole derivatives, imidaz

Assignees

• Dainichiseika Color Chem

Inventors

• Shimanaka Hiroyuki
• Tagi Yoichi
• Murakami Yoshikazu
• Aoyagi Shinichiro
• Arai Kazutaka
• Yoshikawa Sachio

Classifications

• C09D17/00

  Pigment pastes, e.g. for mixing in paints (artists' paints C09D5/06) · CPC title

• C09C3/10

  Treatment with macromolecular organic compounds {(C09C3/006 takes precedence)} · CPC title

• C08F2438/00

  Living radical polymerisation · CPC title

• C08F293/00 Primary

  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 (on to polymers modified by introduction of unsaturated end groups C08F290/02) · CPC title

• C08F220/46

  with carboxylic acids, sulfonic acids or salts thereof · CPC title