Living radical polymer, composition, resin-coated pigment, and method for producing living radical polymer

Abstract

Provided are: a living radical polymer that has a low molecular weight distribution and that has a specific functional group at at least one end; and a resin-coated pigment in which a resin composition including the living radical polymer has high dispersibility, the resin-coated pigment having exceptional properties such as storage stability, ejection stability, and color development in a dispersed state, and being suitable for use in a pigment dispersion.　The above-described problem was solved as follows. Specifically, the present invention provides: a living radical polymer having a specific functional group structure, the living radical polymer including, at an end or in the main chain thereof, a specific organic compound site derived from a polymerization initiator, and being obtained by reacting a radical generator having a specific functional group at at least one end, e.g., at an iodine end produced by a precursor; a living radical polymer composition including the living radical polymer; a resin-coated pigment coated with a living radical polymer composition; and a method for producing a living radical polymer having a specific functional group structure.

Description

[Technical Field]

[0001] The present invention relates to a living radical polymer having a narrow molecular weight distribution and a specific functional group at at least one polymer terminal, a composition thereof, a resin-coated pigment, and a method for producing the living radical polymer. [Background technology]

[0002] Living radical polymerization is a groundbreaking polymerization method that leverages the advantages of radical polymerization, such as its simplicity and versatility, while overcoming its drawback of heterogeneous molecular weight. Living radical polymerization is obtained by using a polymerization initiator composed of a dormant and an organic compound moiety that generate polymerization active ends in the presence of a catalyst, along with a radically polymerizable unsaturated monomer. The ends of the resulting polymer (hereinafter also called the precursor) are bonded to the organic compound moiety and the dormant in the polymerization initiator, respectively. Therefore, when a new radically polymerizable monomer is added to the precursor and polymerization is carried out, copolymers with different components are obtained (block copolymers with block-like bonding, graft copolymers with branch-like bonding, and star copolymers or ladder copolymers with star-like bonding). Since the primary structure of copolymers with such different bonding states greatly affects the chemical and physical properties of the polymer, living radical polymerization is an important technology both academically and industrially.

[0003] However, the resulting precursor dormants contain sulfides, halogens, or transition metals, and therefore have drawbacks such as odor, corrosiveness, toxicity, and discoloration, which significantly limits their application to various uses. For this reason, it is necessary to remove the resulting precursor dormants.

[0004] On the other hand, by attaching functional groups to the precursor ends, it becomes possible to exhibit new functions, for example, by segregating the functional groups near the surface of the thin film, reacting them with other polymers, or adsorbing or reacting them with the surface of organic or inorganic particles. There are two types of precursors with functional groups attached to their ends: (I) polymers in which the organic compound portion of a polymerization initiator containing functional groups is attached to the precursor end, and (II) polymers in which a functional group-containing compound is used to remove the dormant at the precursor end and simultaneously attach a new functional group to the end. In polymer (I) described above, a dormant end is present at one end of the polymer, which is undesirable from the standpoint of safety, such as toxicity, as mentioned earlier.

[0005] For example, Patent Document 1 describes a living radical polymer in which hydrolyzable silyl groups are bonded via nitrogen and sulfur as the polymer described in (II) above. Non-Patent Document 1 describes a polymer in which hydroxyl groups, thiol groups, or alkoxysilyl groups are bonded to a precursor via nitrogen. However, the polymers obtained in these documents had the problem that the desired chemical structure could not be bonded due to degradation caused by side reactions.

[0006] On the other hand, living radical polymers have the advantage of uniform molecular weight distribution, allowing for uniform adsorption and reaction with pigments, as well as ensuring uniform steric repulsion. In recent years, they have become extremely useful as pigment dispersants for dispersing nanometer (nm) sized pigments in ink compositions to form high-quality images.

[0007] The ink composition is first obtained by creating a pigment dispersion in which small-particle pigments are uniformly dispersed and stabilized in a solvent, and then adding a binder resin or the like to the pigment dispersion to fix it to a substrate such as paper or a plastic sheet. Examples of pigment dispersions include non-aqueous pigment dispersions used in solvent-based or ultraviolet (UV) curing ink compositions (Patent Document 2), and aqueous pigment dispersions used in aqueous ink compositions (Patent Documents 3 and 4).

[0008] In conventional pigment dispersions, the primary pigment particles tend to aggregate easily due to the reduction in pigment particle size and the decrease in viscosity of ink compositions associated with high-speed printing. Therefore, there has been a desire to realize a pigment dispersion with excellent properties necessary for ink compositions, such as pigment dispersibility, storage stability, discharge stability, and color development. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2011-74325 [Patent Document 2] Japanese Patent Publication No. 2013-064092 [Patent Document 3] Japanese Patent Publication No. 2011-225834 [Patent Document 4] Japanese Patent Publication No. 2016-160308 [Non-patent literature]

[0010] [Non-Patent Document 1] Macromolecules, (USA), 2016, No. 49, pp. 9425-9940 [Overview of the project] [Problems that the invention aims to solve]

[0011] The present invention has been made in view of the problems of the prior art described above, and provides a living radical polymer having a narrow molecular weight distribution and a specific functional group at at least one terminal, a composition containing the living radical polymer, a resin-coated pigment containing the living radical polymer, and a method for producing the living radical polymer. Furthermore, the present invention also provides resin-coated pigments and the like that have high pigment dispersibility, and that exhibit excellent storage stability, discharge stability, and color development properties in ink compositions containing a binder resin in the pigment dispersion, making them suitable for use in pigment dispersions. [Means for solving the problem]

[0012] The present invention includes the following. [1] A living radical polymer containing an organic compound moiety derived from a polymerization initiator at one end or in the main chain, A living radical polymer in which a terminal functional group structure represented by the following formula (1) or formula (2) is bonded to the main chain directly or through an ester moiety at at least one of the ends. [Chemical formula] (In formula (1), R 1 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R 2 and R 3 are each independently at least one group selected from hydrogen, an alkyl group of C 1~3 , and a cyano group, R 4 is an alkylene group of C 1~3 , an imino group, an N-alkylene carboxamide moiety, or an N-alkylene amidine moiety.) In the living radical polymer, the main chain of the polymer is arranged on the left side of C in formula (1), and the bond on the left side of C in formula (1) indicates the linking site with the main chain. [Chemical formula] <000028G> (In formula (2), R 5 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R 6 are each independently one or two groups selected from hydrogen, an alkyl group of C 1~3 , and an alkoxy group of C 1~3 .) In the living radical polymer, the main chain of the polymer is arranged on the left side of the benzene ring in formula (2), and the bond on the left side of the benzene ring in formula (2) indicates the linking site with the main chain. [1-1] In the terminal functional group structure represented by the formula (1), R 1 However, it is a carboxyl group or a hydroxyl group, R 2 and R 3 However, each is independently selected from hydrogen, cyano group, and methyl group. R 4 The living radical polymer according to [1] above, wherein the moiety is a methylene group, an imino group, an N-alkylene carboxylic acid amide moiety, or an N-alkylene amidine moiety. [1-2] In the terminal functional group structure represented by formula (2) above, R 5 is a carboxyl group or a hydroxyl group, R 6 The living radical polymer described in [1] or [1-1] above, wherein the group is hydrogen or a methoxy group. [1-3] A living radical polymer according to any one of the above [1], [1-1], and [1-2], wherein an ester moiety derived from an ethyl carboxylate is bonded. [1-4] A living radical polymer according to any of the above [1] and [1-1] to [1-3], wherein the molecular weight distribution value is 1.0 to 1.5. [2] The living radical polymer according to [1], wherein the terminal functional group structure represented by formula (1) or formula (2) is bonded to the main chain via the ester moiety. [3] A living radical polymer according to any one of [1] to [2] above, comprising an organic compound moiety derived from an organiodine compound as a polymerization initiator.

[0013] [4a] A living radical polymer composition comprising a living radical polymer described in any of [1] to [3] above and a polymer that does not contain the terminal functional group structure, wherein the living radical polymer is present in a proportion of 50 parts by weight or more of 100 parts by weight of all living radical polymers. [4b] A resin composition for pigment coating, The living radical polymer is included in any of the above [1] to [3], The living radical polymer contains an organic compound moiety derived from a polymerization initiator at one end or in the main chain, A resin composition for pigment coating, wherein at least one of the terminal ends of the living radical polymer is bonded to the main chain, either directly or via an ester moiety, by a terminal functional group structure represented by formula (1) or formula (2). [4-1] The composition according to [4a] or [4b] above, wherein the living radical polymer is a diblock copolymer comprising a hydrophilic block (A) and a hydrophobic block (B) that includes at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer. [4-2] The composition according to any one of [4a], [4b], and [4-1], wherein the living radical polymer is an ABA-type triblock copolymer having terminal functional group structures represented by formula (1) or formula (2) at both ends, and comprising a hydrophilic block (A) and a hydrophobic block (B) that include at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer. [4-3] The hydrophilic block (A) is R in formula (1) 1 Or R in formula (2) above 5 The composition according to any one of [4a], [4b], [4-1] and [4-2] above, which is a (co)polymer comprising at least one of a (meth)acrylate (co)polymer, a styrene (co)polymer, or an amine (co)polymer having a structural unit derived from the same functional group as above. [4-4] In the terminal functional group structure represented by formula (1) above, R 1 However, it is a carboxyl group or a hydroxyl group, R 2 and R 3 However, each is independently selected from hydrogen, cyano group, and methyl group. R 4The composition according to any one of [4a], [4b] and [4-1] to [4-3] above, wherein the moiety is a methylene group, an imino group, an N-alkylene carboxylic acid amide moiety, or an N-alkylene amidine moiety. [4-5] In the terminal functional group structure represented by formula (2) above, R 5 is a carboxyl group or a hydroxyl group, R 6 The composition according to any one of the above [4a], [4b] and [4-1] to [4-4], wherein the component is hydrogen or a methoxy group. [4-6] The composition according to any one of [4a], [4b], and [4-1] to [4-5], wherein the terminal functional group structure represented by formula (1) or formula (2) is bonded to the main chain via the ester moiety. [4-7] A composition according to any one of [4a], [4b], and [4-1] to [4-6], wherein an ester moiety derived from an ethyl carboxylate is attached. [4-8] A composition according to any one of [4a], [4b], and [4-1] to [4-7], comprising an organic compound moiety derived from the organiodine compound used as the polymerization initiator. [4-9] The composition according to any one of [4a], [4b], and [4-1] to [4-8], wherein the number average molecular weight of the living radical polymer is 1,000 to 50,000 and the molecular weight distribution value is 1.0 to 1.5.

[0014] [5] A resin-coated pigment in which at least a portion of the surface is coated with a composition comprising a living radical polymer as described in any of [1] to [3] above. [5-1] The resin-coated pigment according to [5], wherein the pigment comprises an amine-modified pigment, and the terminal functional group structure of the living radical polymer represented by formula (1) or formula (2) contains at least a carboxyl group. [5-2] The resin-coated pigment according to [5] or [5-1] above, wherein the pigment comprises a sulfonic acid-modified pigment, and the terminal functional group structure of the living radical polymer represented by formula (1) or formula (2) contains at least an amino group. [5-3] The resin-coated pigment according to any one of [5], [5-1], and [5-2] above, wherein the resin composition contains 50 parts by weight or more of a living radical polymer having a specific terminal functional group structure represented by formula (1) or formula (2) in proportion to 100 parts by weight of all the living radical polymers. [5-4] In the terminal functional group structure represented by formula (1) above, R 1 However, it is a carboxyl group or a hydroxyl group, R 2 and R 3 However, each is independently selected from hydrogen, cyano group, and methyl group. R 4 The resin-coated pigment according to any of the above [5], [5-1] to [5-3], wherein the moiety is a methylene group, an imino group, an N-alkylene carboxylic acid amide moiety, or an N-alkylene amidine moiety. [5-5] In the terminal functional group structure represented by formula (2) above, R 5 is a carboxyl group or a hydroxyl group, R 6 The resin-coated pigment according to any of the above [5], [5-1] to [5-4], wherein the pigment is a hydrogen or methoxy group. [5-6] A resin-coated pigment according to any one of the above [5], [5-1] to [5-5], wherein the terminal functional group structure represented by formula (1) or formula (2) is bonded to the main chain via the ester moiety. [5-7] A resin-coated pigment according to any of the above [5], [5-1] to [5-6], wherein an ester moiety derived from an ethyl carboxylate is bonded. [5-8] A resin-coated pigment according to any one of the above [5], [5-1] to [5-7], comprising an organic compound moiety derived from an organic iodine compound as a polymerization initiator. [6] The resin-coated pigment according to [5], wherein the living radical polymer is a diblock copolymer comprising a hydrophilic block (A) and a hydrophobic block (B) that includes at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer. [7] The resin-coated pigment according to any one of [5] to [6] above, wherein the living radical polymer is an ABA-type triblock copolymer having terminal functional group structures represented by formula (1) or formula (2) at both ends, and comprising a hydrophilic block (A) and a hydrophobic block (B) that comprises at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer. [8] The hydrophilic block (A) is R in formula (1) 1 Or R in formula (2) above 5 A resin-coated pigment according to either [6] or [7] above, which is a (co)polymer comprising at least one of a (meth)acrylate (co)polymer, a styrene (co)polymer, or an amine (co)polymer having a structural unit derived from the same functional group as above. [9] The resin-coated pigment according to any one of [5] to [8] above, wherein the number average molecular weight of the living radical polymer is 1,000 to 50,000 and the molecular weight distribution value is 1.0 to 1.5.

[0015]

[10] A resin-coated pigment dispersion comprising, in addition to the resin-coated pigment described in any of [5] to [9] above, a medium consisting of at least one selected from water, an oil-soluble organic solvent, and a polymerizable compound.

[11] An ink composition characterized by containing the resin-coated pigment dispersion described in

[10] above and a binder resin.

[12] An inkjet ink composition as described in

[11] above, characterized in that the resin viscosity at 25°C is 50 mPa·s or less.

[0016]

[13] A method for producing a living radical polymer according to any of [1] to [3] above, A polymerization step to form a precursor of a living radical polymer using a polymerization initiator containing an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer, A method for producing a living radical polymer, comprising: an introduction step of reacting a functional group-containing radical generator with the dormant terminal derived from the dormant of the precursor to introduce a terminal functional group structure derived from the functional group-containing radical generator in place of the dormant terminal. [13-1] The method for producing a living radical polymer according to

[13] above, characterized in that, in the introduction step, the reaction temperature for producing the living radical polymer is within the range of +15°C to +35°C relative to the 10-hour half-life temperature of the functional group-containing radical generator. [13-2] A method for producing a living radical polymer according to

[13] or [13-1], wherein in the polymerization step, 0.1 to 50 moles of the polymerization initiator are used per 100 moles of the radical polymerizable unsaturated monomer. [13-3] A method for producing a living radical polymer according to any one of

[13] , [13-1], and [13-2], wherein in the introduction step, 1 to 50 moles of the functional group-containing radical generator are used per mole of the dormant terminal of the precursor.

[14] A method for producing a living radical polymer according to

[13] , wherein the functional group-containing radical generator is represented by any of the following formulas (3) to (5). [ka] (In formula (3), R 1 Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R 2 and R 3 These are, independently, hydrogen and C 1~3It is at least one group selected from alkyl groups and cyano groups, R 4 Each of them is independent of C 1~3 (This is the alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety.) [ka] (In formula (4), R 1 Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R 2 and R 3 These are, independently, hydrogen and C 1~3 It is at least one group selected from alkyl groups and cyano groups, R 4 Each of them is independent of C 1~3 (This is the alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety.) [ka] (In formula (5), R 5 Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R 6 These are, independently, hydrogen and C 1~3 alkyl and C 1~3 (One or two groups selected from the alkoxy groups.)

[15] A method for producing a living radical polymer according to any one of

[13] to

[14] above, wherein in the introduction step, a radical generator having a faster decomposition rate than the functional group-containing radical generator, and / or a nonmetallic compound having an ionic bond with an iodide ion is further used. [Effects of the Invention]

[0017] This invention describes the effects obtained by a living radical polymer having a specific functional group at least one terminal, a composition thereof, a resin-coated pigment thereof, and a method for producing the living radical polymer. While the detailed mechanism of action of this effect remains unclear, it is presumed to be as follows. However, the present invention does not have to be interpreted as being limited to this mechanism of action.

[0018] The polymer of the present invention is characterized by a narrow molecular weight distribution and the presence of a specific functional group with high purity at at least one end. This facilitates the segregation of the specific functional group near the surface of the thin film, and also enables uniform and efficient adsorption and reaction to the surfaces of other polymers or organic or inorganic particles. Therefore, the polymer of the present invention can be used to obtain additives such as compatibilizers and surface modifiers, polymer films or particles with functionalized surfaces, and pigments with modified surfaces.

[0019] The polymer of the present invention is obtained by applying heat to the dormant end of a polymer precursor, which is obtained by using a polymerization initiator composed of an organic compound and a dormant, and a radically polymerizable unsaturated monomer, in the presence of a specific functional group-containing radical generator. The reaction mechanism is presumed to be as follows: First, the functional group-containing radical generated from the radical generator abstracts the dormant present at the precursor end, thereby generating a precursor terminal radical. On the other hand, the functional group-containing radical derived from the functional group-containing radical generator, which is present in excess relative to the dormant at the precursor end, can diffuse rapidly in the reaction solution due to its low molecular weight and is present in excess. Therefore, the functional group-containing radical quickly binds to the precursor terminal radical, thereby obtaining a precursor to which the specific functional group-containing compound is bound in high purity. Furthermore, the functional group-containing radical inhibits the binding of precursor terminal radicals to each other, which would broaden the molecular weight distribution, so the obtained polymer can maintain the narrow molecular weight distribution of the precursor.

[0020] Therefore, according to the manufacturing method of the present invention, in addition to the effects described above, a polymer in which a desired specific functional group is bonded can be obtained without degrading the polymer.

[0021] Furthermore, according to the present invention, it is possible to provide a resin-coated pigment that can improve the dispersibility of a pigment dispersion by covering at least a portion of its surface with a resin composition containing the above-mentioned polymer, thereby improving the storage stability, discharge stability, color development, and other properties of an ink composition containing a binder resin in the pigment dispersion. [Brief explanation of the drawing]

[0022] [Figure 1] This figure shows the spectrum of JMS-S3000 SpiralTOF®, a living radical polymer (PMMA-SA) having a specific functional group-containing compound at its terminal end, obtained in Example 5 described later, and includes an explanation of the polymer sites from which the peaks in the spectrum originated. [Figure 2] This figure shows only the peaks of the SpiralTOF spectrum from Figure 1. [Figure 3] This figure shows the JMS-S3000 SpiralTOF spectrum of the precursor (PMMA-I) of the living radical polymer (PMMA-SA) obtained in Example 5, along with an explanation of the polymer sites from which the peaks in the spectrum originated. [Figure 4] This figure shows only the peaks of the SpiralTOF spectrum from Figure 3. [Figure 5] This figure shows the JMS-S3000 SpiralTOF spectrum of the polymer (PMMA-H) obtained by substituting the terminal iodine atoms with hydrogen atoms from the precursor (PMMA-I) of the living radical polymer (PMMA-SA) obtained in Example 5, along with an explanation of the polymer sites from which the peaks in the spectrum originated. [Figure 6] This figure shows only the peaks of the SpiralTOF spectrum from Figure 5. [Figure 7]This figure shows (a) the peak of the precursor (PMMA-I) in Figure 4, (b) the peak of the polymer (PMMA-H) in Figure 6, where the terminal iodine of the precursor is replaced with hydrogen, and (c) the peak of the living radical polymer (PMMA-SA) in Figure 2. [Modes for carrying out the invention]

[0023] The present invention will be described in detail below.

[0024] [1. Living radical polymers] (1-1. Structure of living radical derivatives) The living radical polymer of the present invention has a specific functional group at at least one end. That is, in the living radical polymer of the present invention, one end or the center (in the main chain) contains an organic compound moiety derived from a polymerization initiator, and a compound having a specific functional group represented by the following formula (1) or formula (2) is bonded to the end, either directly or via an ester moiety. The terminal functional group structure is bonded to the main chain of the living radical polymer via the left-hand bonding plug of the following formula (1) or formula (2). [ka] (In formula (1), R 1 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R 2 and R 3 These are, independently, hydrogen, methyl group, etc. 1~3 It is at least one group selected from alkyl groups and cyano groups, R 4 C 1~3 (This is the alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety.) [ka] (R in equation (2)) 5is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R 6 These are, independently, hydrogen, methyl group, etc. 1~3 C such as alkyl groups and methoxy groups 1~3 (One or two groups selected from the alkoxy groups.)

[0025] The structure of living radical polymers having the aforementioned functional groups differs mainly depending on the polymerization initiator, for example, the number of dormants in one molecule of the polymerization initiator. For example, in the case of a living radical polymer obtained from a monofunctional polymerization initiator having one dormant in one molecule, an organic compound fragment of the polymerization initiator is bonded to one end of the polymer as the main chain, and a compound having a specific functional group is bonded to the other end. On the other hand, in the case of a living radical polymer obtained from a polyfunctional polymerization initiator having 2 to 4 dormants in one molecule, an organic compound moiety derived from the polymerization initiator is located in the center of the main chain or in the center of the polymer molecule, resulting in a polymer with 2 to 4 branched chains flanking the organic compound moiety, and a compound having a specific functional group is bonded to the end of each branched chain of the polymer. In other words, when a monofunctional initiator represented by the formula CX (where C is the organic compound moiety and X is the dormant) is used, the structure of the resulting living radical polymer is exemplified by the formula CMX (where M is the main chain), C'-X 2~4 A polyfunctional initiator represented by (C' is the organic compound moiety, X 2~4 When using (which shows 2 to 4 dormants), the structure of the resulting living radical polymer is C'-(MX) 2~4 This is illustrated by the formula (where M is a branched chain that can form the main chain). And the above C'-(MX) 2~4 In the living radical polymer of the formula, since the lengths of each of the multiple branched chains represented by M are substantially uniform, the aforementioned organic compound moiety represented by C' is located approximately at the center of the living radical polymer. In other words, by using a polyfunctional initiator, it is possible to produce a living radical polymer in which the organic compound moiety is located in the center of a main chain having multiple branched chains. Regarding these structures in living radical polymers, the most suitable one can be selected depending on the desired application. For example, if only one end needs to be reacted, a polymer obtained from a monofunctional polymerization initiator without functional groups, to which a compound having a specific functional group is bonded, is suitable. If two or more ends need to be reacted, a polymer obtained from a monofunctional polymerization initiator with functional groups, or a living radical polymer obtained from a polyfunctional polymerization initiator, to which a compound having a specific functional group is bonded, is suitable.

[0026] Examples of living radical polymers before the bonding of compounds having specific functional groups, where a dormant is bonded to the terminal (hereinafter also referred to as a precursor), include homopolymers of one type of radically polymerizable unsaturated monomer, random copolymers, block copolymers, graft copolymers of two or more types of radically polymerizable unsaturated monomers, and even star-shaped (co)polymers and ladder-shaped (co)polymers of one or more types of radically polymerizable unsaturated monomers. However, the present invention is not limited to these examples.

[0027] (1-2. Radical polymerizable unsaturated monomers) Radical polymerizable unsaturated monomers are used in the production of living radical polymers and refer to monomers that have unsaturated bonds capable of radical polymerization in the presence of organic radicals. More specifically, monomers known as vinyl monomers can be used to form the main chain of living radical polymers. Vinyl monomers are a general term for monomers represented by formula (6). CHR 7 =CR 8 R 9 (6) (In formula (6), R 7 , R 8 and R 9 Each of these independently represents either a hydrogen atom or an organic group. In formula (6), the organic group includes optionally substituted alkyl groups having 1 to 12 carbon atoms, optionally substituted aryl groups having 6 to 18 carbon atoms, etc.

[0028] The following are examples of vinyl monomers represented by formula (6), but the present invention is not limited to these examples.

[0029] Examples of vinyl monomers include styrene and its derivatives (R 7 and R 8 is a hydrogen atom, R 9 (a phenyl group which may have substituents), acrylic acid (R 7 and R 8 is a hydrogen atom, R 9 (Carboxyl group) and its alkali metal salts, acrylamide (R 7 and R 8 is a hydrogen atom, R 9 (CONH2 group) and its derivatives, acrylates (acrylic acid esters or acrylic acid salts), methacrylic acid (R 7 is a hydrogen atom, R 8 is a methyl group, R 9 (Carboxyl group) and its alkali metal salts, methacrylamide (R 7 is a hydrogen atom, R 8 Examples include a methyl group (where R is a CONH2 group) and its derivatives, methacrylates (methacrylate esters or methacrylate salts), etc., but the present invention is not limited to these examples.

[0030] Specific examples of styrene and its derivatives include, for example, styrene (hereinafter also referred to as St), o-, m- or p-methoxystyrene, o-, m- or pt-butoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-chlorostyrene, o-, m- or p-hydroxystyrene, o-, m- or p-styrenesulfonic acid and its alkali metal salts, o-, m- or p-styreneboronic acid and its derivatives, but the present invention is not limited to these examples.

[0031] Specific examples of acrylamide and its derivatives include, for example, acrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, and N-hydroxyethylacrylamide, but the present invention is not limited to these examples.

[0032] Specific examples of acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate (hereinafter also referred to as BA), t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, nonyl acrylate, decanyl acrylate, lauryl acrylate, behenyl acrylate, and stearyl acrylate; aryl alkyl acrylates such as benzyl acrylate; epoxy alkyl acrylates such as tetrahydrofurfuryl acrylate and glycidyl acrylate; cycloalkyl acrylates such as cyclohexyl acrylate; alkoxyalkyl acrylates such as 2-methoxyethyl acrylate and 2-butoxyethyl acrylate; and hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Examples of polyalkylene glycol monoacrylates such as rilate, diethylene glycol monoacrylate, and polyethylene glycol monoacrylate; alkoxy polyalkylene glycol acrylates such as methoxytetraethylene glycol acrylate and methoxy polyethylene glycol acrylate; dialkylaminoalkyl acrylates such as 2-(dimethylamino)ethyl acrylate; 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate; fluoroalkyl acrylates in which a fluorine atom is substituted on the alkyl group of an alkyl acrylate; acrylates in which a tris(trialkylsiloxy)silyl group is substituted on the alkyl group of an alkyl acrylate; and acrylates in which an ethyl phosphorylcholine group is substituted on the alkyl group of an alkyl acrylate. However, the present invention is not limited to these examples.

[0033] Specific examples of methacrylamide and its derivatives include, for example, methacrylamide, N-isopropylmethacrylamide, N,N-dimethylmethacrylamide, N-methylolmethacrylamide, and N-hydroxyethylmethacrylamide, but the present invention is not limited to these examples.

[0034] Specific examples of methacrylates include, for example, methyl methacrylate (hereinafter also called MMA), ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, nonyl methacrylate, decanyl methacrylate, lauryl methacrylate, behenyl methacrylate, stearyl methacrylate, and other alkyl methacrylates, arylalkyl methacrylates such as benzyl methacrylate, epoxyalkyl methacrylates such as tetrahydrofurfuryl methacrylate and glycidyl methacrylate, cycloalkyl methacrylates such as cyclohexyl methacrylate, alkoxyalkyl methacrylates such as 2-methoxyethyl methacrylate and 2-butoxyethyl methacrylate, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, and Examples include polyalkylene glycol monomethacrylates such as ethylene glycol monomethacrylate, alkoxy polyalkylene glycol methacrylates such as methoxytetraethylene glycol methacrylate and methoxy polyethylene glycol methacrylate, dialkylaminoalkyl methacrylates such as 2-(dimethylamino)ethyl methacrylate, fluoroalkyl methacrylates such as 3-chloro-2-hydroxypropyl methacrylate and 2-hydroxy-3-phenoxypropyl methacrylate, fluoroalkyl methacrylates such as 2,2,3,4,4,4-hexafluorobutyl methacrylate in which a fluorine atom is substituted on the alkyl group of the alkyl methacrylate, 3-[[triethylsiloxy)silyl]propyl methacrylate in which a tris(trialkylsiloxy)silyl group is substituted on the alkyl group of the alkyl methacrylate, and ethyl phosphorylcholine methacrylate in which an ethyl phosphorylcholine group is substituted on the alkyl group of the alkyl methacrylate, but are not limited to these examples.

[0035] R of the vinyl monomer represented by formula (6) 8 and R 9The group may also be a group having a carboxyl group or a carboxylate. Specifically, examples include itaconic acid such as itaconic acid, dimethyl itaconate, and monobutyl itaconate, as well as its monoalkyl esters and dialkyl esters, but the examples are not limited to these.

[0036] The vinyl monomer may be a vinyl monomer having two or more double bonds (vinyl groups, isopropenyl groups, etc.). Specifically, examples include diene compounds (e.g., butadiene, isoprene, etc.), compounds having two allyl groups (e.g., diallyl phthalate, etc.), compounds having two acrylic groups (e.g., ethylene glycol diacrylate, etc.), and compounds having two methacrylic groups (e.g., ethylene glycol dimethacrylate, etc.), but are not limited to these examples.

[0037] Other vinyl monomers besides those mentioned above can also be used. Specifically, examples include vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate), other styrene derivatives (e.g., α-methylstyrene), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone), N-vinyl compounds (e.g., N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, vinyloxazoline), acrylonitrile, methacrylonitrile, maleic acid and its derivatives (e.g., maleic anhydride), vinyl halides (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, vinyl fluoride, vinylidene fluoride), olefins (e.g., ethylene, propylene, 1 or 2-butene, 1-hexene, 1-octene, cyclohexene), etc., but are not limited to these examples.

[0038] Radical polymerizable unsaturated monomers may be used individually or in combination of two or more types.

[0039] The amount of radically polymerizable unsaturated monomer used can be adjusted as appropriate depending on the desired molecular weight and other factors.

[0040] (1-3. Properties of Living Radical Polymers) The number-average molecular weight of the living radical polymer composition is, for example, 1,000 to 200,000, preferably 1,000 to 100,000, and more preferably 1,000 to 50,000. The weight-average molecular weight of the living radical polymer composition is equal to or slightly greater than the number-average molecular weight, for example, 1,000 to 240,000, preferably 1,000 to 120,000, and more preferably 1,000 to 60,000.

[0041] Living radical polymers also have the characteristic of having a narrower molecular weight distribution compared to conventional radical polymerization. The molecular weight distribution is the value obtained by dividing the weight-average molecular weight of a polymer by the number-average molecular weight. Compared to the molecular weight distribution obtained by conventional radical polymerization, which is about 2 or more, the molecular weight distribution of the living radical polymer obtained in the present invention is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, even more preferably 1.0 to 1.25, and particularly preferably 1.0 to 1.24. However, the lower limit of the molecular weight distribution range of the living radical polymer may be 1.05, 1.10, etc.

[0042] The number-average molecular weight and weight-average molecular weight of the polymer are values ​​obtained by size exclusion chromatography in accordance with general rules (JIS K 7252-1 (2016) and ISO 16014-1 (2012)) under the following measurement conditions. [Number-average molecular weight and weight-average molecular weight of polymers] • Measuring instrument: EXTREMA size exclusion chromatography (GPC / SEC) system manufactured by JASCO Corporation. • Columns: SHODEX manufactured by Showa Denko K.K., Sample side: K-803, KF-804L, KF-806F (3 columns connected), Reference side: KF-800RH • Eluent: Tetrahydrofuran (hereinafter referred to as THF) Calibration curve standard materials: Polymethyl methacrylate (excluding styrene-based polymers), polystyrene (styrene-based polymer) • Preparation of the sample for measurement: Dissolve the polymer composition in the eluent (THF) to prepare a solution with a polymer concentration of 0.1% by weight, and use the filtrate after filtering the solution.

[0043] (1-4. Polymerization Initiators) The polymerization initiator used in the production of the aforementioned precursor (hereinafter also referred to as the polymerization initiator for precursor production) comprises an organic compound moiety and a dormant, and preferably consists only of the organic compound moiety and the dormant. Furthermore, while known methods can be used in the polymerization of precursors of living radical polymers, it is necessary to appropriately select the type of polymerization initiator depending on the polymerization method, as described below. For example, precursors of living radical polymers can be produced by nitroxide-mediated radical polymerization (NMP method) using a nitroxide compound (nitroxide group) as the dormant, atom transfer radical polymerization (ATRP method) using bromine as the dormant, radical polymerization (RAFT method) utilizing a reversible addition-cleavage reaction using a thiocarbonylthio compound (thiocarbonylthio group) as the dormant, radical polymerization using organic tellurium, organic antimony, or organic bismuth as the dormant (TERP method, represented by organic tellurium), and radical polymerization using iodine as the dormant (e.g., RCMP method).

[0044] Typical polymerization initiators in the NMP method using a nitroxide compound as a dormant include, for example, t-butyl(1-phenyl-2-methylpropyl)(1-phenylethoxy)amine, which has a 1-phenylethyl group as the organic compound moiety and a t-butyl(1-phenyl-2-methylpropyl)nitroxide group as a dormant. However, the present invention is not limited to these examples. The NMP method and the polymerization initiators used therein are summarized in Sigma-Aldrich's "Handbook of Precision Radical Polymerization," pp. 31-34, published in July 2012; please refer to it.

[0045] Typical polymerization initiators in the ATRP method using bromine as a dormant include, for example, monofunctional t-butyl-α-bromoisobutyrate having a t-butylisobutyrate group as the organic compound moiety, monofunctional 2-hydroxyethyl-2-bromoisobutyrate having a hydroxyl-containing 2-hydroxyethyl-2-isobutyrate group as the functional group-containing organic compound moiety, and bifunctional ethylenebis(2-bromoisobutyrate) having an ethylenebis(isobutyrate group) as the organic compound moiety. However, the present invention is not limited to these examples. Furthermore, examples of catalysts include amine compounds such as 2,2'-bipyridine, and examples of catalytic metal salts include halogenated transition metals such as copper(I) chloride. However, the present invention is not limited to these examples. The ATRP method and the polymerization initiators used therein are summarized on page 2-18 of Sigma-Aldrich's "Handbook of Precision Radical Polymerization," published in July 2012. Please refer to it.

[0046] Typical polymerization initiators in the RAFT polymerization method using thiocarbonylthio compounds as dormants include, for example, monofunctional cyanopropylbenzothianoates (hereinafter referred to as CPBS) having a phenyldithioester group as a dithioester dormant and a cyanoisopropyl group as an organic compound moiety, monofunctional cyanopentanoic acid benzothianoates having a carboxyl group such as a cyanopentanoic acid group as a functional group-containing organic compound moiety, monofunctional cyanopropyl-n-dodecyltrithiocarbonates having an n-dodecyltrithiocarbonate group as a trithiocarbonate dormant and a cyanoisopropyl group as an organic compound moiety, and bifunctional ethylenebis(cyanopentanoic acid-n-dodecylthiocarbonate) having an ethylenebiscyanopentanoic acid group as an organic compound moiety. However, the present invention is not limited to these examples. For information on the RAFT polymerization method and the polymerization initiators used therein, please refer to pp. 19-30 of Sigma-Aldrich's "Handbook of Precision Radical Polymerization," published in July 2012.

[0047] Typical polymerization initiators in the TERP method, which uses an organic tellurium compound as the dormant, include, for example, 2-methylteranylpropionitrile, which has a methyl tellurium group as the organic tellurium dormant and a cyanoisopropyl group as the organic compound moiety. However, the present invention is not limited to these examples. The TERP method and the polymerization initiators used therein are summarized in "Living Radical Polymerization 2. Polymerization Mechanism and Method 2," pp. 365-367, of the Journal of the Rubber Association of Japan (No. 82), published in August 2009. Please refer to this for further information.

[0048] Typical polymerization initiators in the RCMP method using iodine as a dormant include, for example, monofunctional 2-iodoisobutyronitrile (CP-I), 2-iodoisobutyrate ethyl, and 2-iodo-2-phenylethyl acetate (PAME), each having an isobutyronitrile group, an ethyl isobutyrate group, and an ethyl phenylethyl group as organic compound moieties; monofunctional 2-iodoisobutyric acid and 2-iodo-2-phenylacetic acid, each having a carboxyl-containing isobutyric acid group and a phenylacetic acid group as functional group-containing organic compound moieties; and bifunctional 2-iodoisobutyrate-2-hydroxyethyl and 2-iodo-2-phenylacetic acid-2-hydroxyethyl, each having an isobutyrate hydroxyethyl group and a phenylacetic acid hydroxyethyl group as organic compound moieties. However, the present invention is not limited to these examples. For details on the RCMP method and the polymerization initiators used therein, please refer to pages 6610-6618 of the journal Macromolecules (No. 47), published by ACS in September 2014.

[0049] From the viewpoint of polymerization control, the amount of polymerization initiator used to obtain a living radical polymer is preferably 0.1 to 50 moles, and more preferably 0.5 to 40 moles, per 100 moles of the radically polymerizable unsaturated monomer used. Furthermore, from the viewpoint of the degree of polymerization, it is even more preferable to use 0.5 to 10 moles of polymerization initiator per 100 moles of the radically polymerizable unsaturated monomer.

[0050] As for methods for obtaining living radical polymers, from the viewpoint of efficiency in abstracting dormants from the polymer ends and bonding functional group-containing organic compound fragments, the RAFT method using a thiocarbonylthio compound as the dormant, the TERP method using an organic tellurium compound, the ATRP method using a halogen (bromine or iodine), or the RCMP method are preferred. Among these, the ATRP method or the RCMP method using a halogen (bromine or iodine) are more preferred, and the RCMP method is most preferred from the viewpoint of low odor, low coloration, and low toxicity of the resulting polymer.

[0051] (1-5. Structure of the organic compound moiety) The living radical polymer of the present invention contains organic compound moieties derived from the polymerization initiator used for precursor production described above. That is, the organic compound moieties introduced into either one end of the precursor or into the main chain by the polymerization initiator are maintained in the living radical polymer even when a living radical polymer with altered terminal structures of the precursor is subsequently produced. Thus, the organic compound moieties contained in the living radical polymer are present in either one end or into the main chain of the living radical polymer. As is evident from the fact that the organic compound moieties originate from the polymerization initiators mentioned above, specific examples of organic compound moieties include the following: For example, organic compound moieties having structures derived from 1-phenylethyl group which can be introduced by the NMP method, for example t-butylisobutyrate group, 2-hydroxyethyl-2-isobutyrate group, ethylenebis(isobutyrate group) which can be introduced by the ATRP method, for example cyanoisopropyl group, cyanopentanoic acid group, cyanoisopropyl group, ethylenebiscyanopentanoic acid group which can be introduced by the RAFT polymerization method, for example cyanoisopropyl group which can be introduced by the TERP method, for example isobutyronitrile group, ethyl isobutyrate group, ethyl phenylethyl group, isobutyrate group containing a carboxyl group, phenylacetic acid group, hydroxyethyl isobutyrate group, hydroxyethyl phenylacetic acid group, etc. which can be introduced by the RCMP method. Examples of organic compound moieties exemplified in the above structure include alkyl or alkylate group residues (such as alkylene groups if included in the main chain of the polymer) with a total of 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, which may be substituted with phenyl groups, halogens, hydroxyl groups, cyano groups, etc., and may have organic acid groups such as carboxyl groups, acetate groups, and butyric acid groups; and aryl group residues (such as arylene groups if included in the main chain of the polymer) with a total of 6 to 24 carbon atoms, preferably 8 to 18 carbon atoms, which may be substituted with phenyl groups, halogens, hydroxyl groups, cyano groups, etc., and may have organic acid groups such as carboxyl groups, acetate groups, and butyric acid groups. Among these, residues such as organic compound moieties that can be introduced by the ATRP method, RCMP method, etc. using polymerization initiators containing halogens such as iodine, for example, t-butyl isobutyrate group, 2-hydroxyethyl-2-isobutyrate group, ethylenebis(isobutyrate group); isobutyronitrile group, ethyl isobutyrate group, ethyl phenylacetate group, carboxyl group-containing isobutyric acid group, phenylacetic acid group, 2-hydroxyethyl isobutyrate group, 2-hydroxyethyl phenylacetate group, etc. are preferable as the organic compound moiety.

[0052] (1-6. Structure of terminal functional groups) In the living radical polymer of the present invention, a specific functional group represented by the above formula (1) or formula (2) is bonded directly or via an ester moiety at at least one terminal, that is, at one terminal or both terminals. [Chemical formula] In formula (1), R 1 ~R 4 is as described above. That is, R 1 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, and preferably, R 1 is a carboxyl group or a hydroxyl group. R 2 and R 3 are each independently at least one group selected from hydrogen, an alkyl group of C 1~3 , and a cyano group, and preferably, hydrogen or a methyl group. R 4 is an alkylene group of C 1~3 , an imino group, an N-alkylenecarboxamide moiety, or an N-alkylenamidine moiety, and preferably, an imino group, an N-alkylenecarboxamide moiety, or an N-alkylenamidine moiety. The imino group is represented by =NH. In addition, the N-alkylene carboxylic acid amide moiety is represented by -C(=O)-NHRa- (Ra is an alkylene group having 1 to 3 carbon atoms), and Ra is preferably an ethylene group (having 2 carbon atoms). Furthermore, it is an N-alkylene amidine moiety, which is represented by -C(=NH)-NHRb- (Rb is an alkylene group having 1 to 3 carbon atoms), and Rb is preferably an ethylene group (having 2 carbon atoms). When the specific functional group in formula (1) is bonded to the end of the main chain of the living radical polymer via an ester moiety, the terminal moiety is -OC(=O)-CR 2 (R 3 )-R 4 -R 1 and is represented by.

Chemical formula

[0053] Examples of the terminal functional group structure of formula (1) include a structure in which a functional group-containing compound generated by denitrification of an azo compound having a specific functional group-containing compound is bonded, a structure in which an ester moiety is bonded to a compound generated from an aliphatic diacyl type organic peroxide having a specific functional group-containing compound, and a structure in which a functional group-containing compound obtained by decarboxylation of a compound (carbon dioxide derived from the ester moiety) generated from an aliphatic diacyl type organic peroxide having a specific functional group-containing compound is bonded.

[0054] As a specific example of the structure of formula (1), as described above, one example is a structure in which a functional group-containing compound generated by denitrification is bonded to an azo compound having a specific functional group-containing compound, but the present invention is not limited to such examples. For example, 4,4-azobis(4-cyanobalic acid) (hereinafter referred to as ACVA), which has a carboxyl group as a specific functional group, has a half-life of 10 hours (hereinafter referred to as T 10h (Also known as) = ​​69℃) The carboxylic acid-3-cyanopropyl group (R 1 ;Carboxyl group, R 2 ; Methyl group, R 3 ;Cyano group, R 4 ; ethylene group), 2,2-azobis{N-(2-carboxyethyl)-2-methylpropionamidine}(T 10h The N-(2-carboxyethyl)-2-methylpropionamidine moiety (R =57℃) is generated by denitrification. 1 ;Carboxyl group, R 2 =R 3 ; Methyl group, R 4 Examples include the N-ethyleneamidine moiety. Also, for example, 2,2-azobis{2-methyl-N-(2-hydroxyethyl)propionamide}(T) which has a hydroxyl group as a specific functional group. 10h The 2-methyl-N-(2-hydroxyethyl)propionamide moiety (R =86℃) is generated by denitrification. 1 ;Hydroxyl group, R 2 =R 3 ; Methyl group, R 4Examples include the N-ethylene carboxylic acid amide moiety. Furthermore, for example, 2-2-azobis(2-methylpropionamidine)(T) which has an amino group as a specific functional group. 10h (R =56℃) is a 2-methylpropionamidine group (R 1 ; Amino group, R 2 =R 3 ; Methyl group, R 4 Examples include the imino group. The 10-hour half-life temperature is defined as the temperature at which the amount of the compound remaining is halved when the compound is dissolved in a more inert solvent to make a 0.1 mol / l (or 0.05 mol / l) solution, and then allowed to stand in a glass ampoule at a constant temperature under a nitrogen atmosphere for 10 hours due to decomposition. The 10-hour half-life temperatures for each compound mentioned above in this paragraph are values ​​obtained when water is used as the solvent.

[0055] Furthermore, specific structures of formula (1) include, as mentioned above, a structure in which an ester moiety is bonded to a compound generated from an aliphatic diacyl-type organic peroxide having a specific functional group, and a structure in which a functional group-containing compound is bonded to a compound obtained by decarboxylating carbon dioxide (derived from the ester moiety of a compound generated from an aliphatic diacyl-type organic peroxide having a specific functional group). More specifically, the following structures are examples, but the present invention is not limited to these examples. For example, a discustic acid peroxide having a carboxyl group as a specific functional group (hereinafter also referred to as SAPO, T 10h =66℃ (in acetone) generates an ethyl carboxylate group (R) via the ester moiety. 1 ;Carboxyl group, R 2 =R 3 ; Hydrogen, R 4 ; Methylene group) or ester moiety from which carbon dioxide has been decarboxylated into an ethyl carboxylate group, diglutanic acid peroxide (T 10h (R) propyl carboxylate group (R) generated via the ester moiety from approximately 60°C. 1 ;Carboxyl group, R 2 =R 3 ; Hydrogen, R4 ; propyl carboxylate group obtained by decarboxylating carbon dioxide derived from the ethylene group or ester moiety, diadipinic acid peroxide (T 10h (R) butyl carboxylate group (R) generated via the ester moiety from approximately 60°C. 1 ;Carboxyl group, R 2 =R 3 ; Hydrogen, R 4 Examples include butyl carboxylates obtained by decarboxylating carbon dioxide from a propylene group or ester moiety. Also, for example, di-(3-hydroxybutyroyl)peroxide (T) having a hydroxyl group as a specific functional group. 10h (R) 3-hydroxypropyl ester group (R) generated via the ester moiety from approximately 60°C 1 ;Hydroxy group, R 2 =R 3 ; Hydrogen, R 4 Examples include the isoethylene group (-C(CH3)-) or the 3-hydroxypropyl group obtained by decarboxylating carbon dioxide from the ester moiety. Furthermore, for example, di-(3-aminopropyl)peroxide (T) having an amino group as a specific functional group. 10h (R) 3-aminoethyl ester group (R) generated via the ester moiety from approximately 60°C. 1 ; Amino group, R 2 =R 3 ; Hydrogen, R 4 Examples include an aminoethyl ester group obtained by decarboxylating carbon dioxide derived from a methylene group or ester moiety.

[0056] On the other hand, examples of structures of formula (2) include a structure in which an ester moiety is attached to a compound generated from an aromatic diacyl-type organic peroxide having a specific functional group-containing compound, and a structure in which a functional group-containing compound is attached to a compound obtained by decarboxylating the ester moiety generated from an aromatic diacyl-type organic peroxide having a specific functional group-containing compound.

[0057] As specific structures of formula (2), as described above, the following structures can be cited as examples of structures in which an ester moiety generated from an aromatic diacyl-type organic peroxide having a specific functional group-containing compound is bonded, or a functional group-containing compound obtained by decarboxylating an ester group generated from an aromatic diacyl-type organic peroxide having a specific functional group-containing compound is bonded; however, the present invention is not limited to these examples. For example, di(2-carboxyl-1-benzoyl)peroxide (T) has a carboxyl group as a specific functional group. 10h (R) 2-carboxyl-1-phenyl ester group (R) generated via the ester moiety from approximately 75°C. 5 ;2-carboxyl group, R 6 Examples include a hydrogen atom or a phenyl carboxylate group obtained by decarboxylating the ester moiety. Also, for example, di-(4-hydroxy-3-methoxy-1-benzoyl)peroxide (T) having a hydroxyl group as a specific functional group. 10h (R) 4-hydroxy-3-methoxy-1-phenyl ester group (R) is generated via the ester moiety from approximately 60°C. 5 4-hydroxyl group, R 6 Examples include a 3-methoxy group or a 4-hydroxy-3-methoxy-1-phenyl group obtained by decarboxylation of the ester moiety. Furthermore, preferred ester moieties are those derived from alkyl carboxylates, such as ethyl carboxylates and methyl carboxylates.

[0058] As for the structure of formula (1) or formula (2) having the specific functional group-containing compound described above, from the viewpoint of obtaining a polymer to which the specific functional group-containing compound is bonded in high purity, a living radical polymer in which the functional group-containing compound is bonded via an ester moiety is preferred, and further R 1 is a carboxyl group (R 2 =R 3 ; Hydrogen, R 4 ; a methylene group) an ethyl carboxylate group, and R 1 is a hydroxyl group (R 2 =R 3 ; Hydrogen, R 4A living radical polymer to which an isoethylene group (-C(CH3)-)) is bonded to a 3-hydroxypropyl ester group is more preferred, R 1 is a carboxyl group, R 2 =R 3 ; Hydrogen, R 4 Living radical polymers in which a methylene group, specifically an ethyl carboxylate group, is bonded are most preferred.

[0059] [2. Living radical polymer composition] Next, the living radical polymer composition of the present invention will be described. The living radical polymer composition comprises at least the living radical polymer described above and a living radical polymer in which a compound having a specific functional group is not bonded to the terminal (a polymer that does not contain a specific terminal functional group).

[0060] Living radical polymers that do not have the aforementioned specific functional groups bonded to their ends include precursors and living radical polymers in which the dormant of the precursor is replaced with hydrogen by some reaction. The composition, primary structure, and molecular weight of these polymers that do not contain the specific terminal functional groups are almost identical to those of living radical polymers, with little variation. In other words, polymers that do not contain the aforementioned specific terminal functional groups mainly differ from living radical polymers only in their terminal structure, and specific examples include those that have hydrogen instead of the specific functional groups represented by formulas (1) and (2) above. In addition to those derived from precursors, polymers that may be included in living radical polymer compositions include known polymers that do not originate from precursors, such as thermoplastic resins, thermosetting resins, solvents that dissolve polymers derived from precursors, and antioxidants.

[0061] The living radical polymer having the specific terminal functional group described above is preferably present in a high proportion in the entire mixture of polymers derived from the precursor, i.e., in the mixture of the precursor in which a dormant such as a halogen, including iodine, is introduced at the terminal, the polymer in which the dormant at the precursor terminal is substituted with hydrogen, and the living radical polymer. That is, it is preferable that the living radical polymer having the specific terminal functional group structure represented by formula (1) or formula (2) is present in a proportion of 50 parts by weight or more, more preferably 70 parts by weight or more, even more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more, with almost all living radical polymers having the specific terminal functional group structure being represented by formula (1) or formula (2) per 100 parts by weight of the entire mixture of polymers derived from the precursor.

[0062] The living radical polymer composition may contain, in addition to the living radical polymer having the aforementioned specific terminal functional group and the polymer not having the aforementioned specific terminal functional group, a thermoplastic resin, a thermosetting resin, a solvent for dissolving the polymer derived from the precursor, an antioxidant, and the like, which are polymers not derived from the precursor. The content of the living radical polymer having the aforementioned specific terminal functional group in the living radical polymer composition is preferably 1 to 100 parts by weight per 100 parts by weight of the entire polymer composition. On the other hand, the content of the polymer not having the specific terminal functional group is preferably 0 to 50 parts by weight per 100 parts by weight of the entire polymer composition. Furthermore, the content of the thermoplastic resin, thermosetting resin, a solvent for dissolving the polymer derived from the precursor, an antioxidant, and the like, which are polymers not derived from the precursor, is preferably 0 to 99 parts by weight per 100 parts by weight of the entire polymer composition.

[0063] [3. Resin composition for pigment coating] The pigment coating resin composition is used to cover at least a portion of the surface of a pigment. The pigment coating resin composition can improve the dispersibility of a pigment dispersion, and can also improve the storage stability, discharge stability, and color development of an ink composition containing a binder resin in the pigment dispersion. The pigment coating resin composition contains at least the living radical polymer described above. Other components in the pigment coating resin composition include polymerization inhibitors and antioxidants.

[0064] In a pigment coating resin composition, it is preferable that the composition contains 50% by weight or more of living radical polymers, more preferably 70% by weight or more of living radical polymers, and particularly preferably 90% by weight or more of living radical polymers, based on the total weight of the composition. Alternatively, the pigment coating resin composition may consist solely of living radical polymers.

[0065] [4. Resin-coated pigments containing living radical polymer compositions] The resin-coated pigment of the present invention has at least a portion of its surface coated with a resin composition for pigment coating. In this way, the resin-coated pigment, whose surface is covered with the above-mentioned resin composition for pigment coating, has good properties such as dispersibility.

[0066] (4-1. Pigments) There are no particular limitations on the type of pigment used as a component of the resin-coated pigment of the present invention, but organic pigments or inorganic pigments can be used. Examples of organic pigments include azo, diazo, condensed azo, thioindigo, induthlon, quinacridone, anthraquinone, benzimidazolone, penylene, triphenylmethane, quinoline, anthraquinone, phthalocyanine, anthrapyridine, and dioxazine pigments. Examples of inorganic pigments include titanium dioxide, ultramarine, Prussian blue, zinc oxide, red iron oxide, lead yellow, transparent iron oxide, aluminum powder, zinc sulfide, lead white, zinc oxide, lithopone, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, silica, iron black, titanium black, cobalt violet, vermilion, molybdenum orange, red lead, red iron oxide, lead yellow, cadmium yellow, zinc chromate, yellow ochre, chromium oxide, ultramarine, Prussian blue, cobalt blue, carbon black, carbon fiber, carbon nanofiber, and carbon nanotubes (single-walled nanotubes, double-walled nanotubes, and multi-walled nanotubes). These pigments are preferably used by selecting the type of pigment, particle size, and processing method according to the purpose. For example, organic fine particle pigments are preferred except when opacity is required for the colored material. In particular, when it is desired to form a highly detailed and transparent colored material, it is desirable to finely mill the pigment by wet milling such as salt milling or dry milling. Furthermore, considering nozzle clogging when applying inkjet printing, it is desirable to remove organic pigments with a particle size exceeding 0.5 μm and make the average particle size 0.15 μm or less.

[0067] Furthermore, to give more specific examples of these pigments using their color index (hereinafter referred to as CI) numbers, we have: CIPigment blue 15, 15:1, 15:3, 15:4, 15:6, 22, 60, 64; CIPigment red 4, 5, 9, 23, 48, 49, 52, 53, 57, 97, 112, 122, 123, 144, 146, 147, 149, 150, 166, 168, 170, 177, 180, 184, 185, 192, 202, 207, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 238, 240, 242, 254, 255, 264, 272; CIPigment yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 97, 109, 110, 117, 120, 125, 128, 129, 137 , 138, 147, 148, 150, 151, 153, 154, 155, 166, 168, 175, 180, 181, 185, 191, CIPigment white 6, 18, 21, CIPigment black 7, 12, 27, 30, 31, 32, 37, CIPigment orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73, CIPigment violet 19, 23, 29, 30, 37, 40, 50, CIPigment green Examples include 7 and 36. Preferred examples of these pigments in terms of color development, dispersibility, and weather resistance include Pigment blue 15 and 15:3 for blue, Pigment red 122 for red, Pigment yellow 74 and 155 for yellow, and Pigment white 6 for white. These pigments may be used individually or in mixtures of two or more. Mixing methods include mixing powdered pigments, mixing paste pigments, and preparing solid solutions through pigment formation; any of these methods may be used. Furthermore, the pigment may be either surface-treated with a derivative or not surface-treated. Derivative treatment of the pigment surface refers to modifying the pigment surface with a compound that introduces a pigment-like skeleton during or after the pigment manufacturing process. Examples of pigments with modified surfaces include amine-modified and sulfonic acid-modified pigments. Amine-modified pigments are surface-treated with aliphatic amine compounds such as laurylamine, stearylamine, and rosinamine, while sulfonic acid-modified pigments are surface-treated with fuming sulfuric acid, concentrated sulfuric acid, chlorosulfuric acid, etc.

[0068] (4-2. Living radical polymer compositions for resin-coated pigments) The living radical polymer used for resin-coated pigments is preferably a diblock copolymer or triblock copolymer containing a hydrophilic block (A) and a hydrophobic block (B). In the case of an aqueous ink composition in which water is selected as the medium for the pigment dispersion, the hydrophilic block (A) has the effect of dissolving in the water medium, and in the case of a solvent-based ink composition in which an oil-soluble organic solvent is selected as the medium for the pigment dispersion, or an ultraviolet-curable ink composition in which a radically polymerizable monomer is selected as the medium for the pigment dispersion, the hydrophilic block (A) has the effect of adsorbing onto the pigment. A specific example of a hydrophilic block (A) is R in equation (1) above. 1 Or R in equation (2) 5 It is preferable to include at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer having structural units derived from the same functional group. Furthermore, it is more preferable that it be a (co)polymer of (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxystyrene, 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 4-vinylpyridine, etc. In the case of an aqueous ink composition in which water is selected as the medium for the pigment dispersion, the hydrophobic block (B) has the effect of adsorbing to the pigment, and in the case of a solvent-based ink composition in which an oil-soluble organic solvent is selected, or an ultraviolet-curable ink composition in which a radically polymerizable monomer is selected as the medium for the pigment dispersion, the hydrophobic block (B) has the effect of dissolving in the oil-soluble organic solvent or the radically polymerizable monomer that is the medium. Specific examples of the hydrophobic block (B) include (co)polymers such as benzyl (meth)acrylate and styrene. In the triblock copolymer, it is more preferable that it is an ABA-type triblock copolymer containing a hydrophilic block (A) and a hydrophobic block (B). Furthermore, in the triblock copolymer, it is particularly preferable that the living radical polymer has terminal functional group structures represented by formula (1) or formula (2) at both ends.

[0069] In the hydrophilic block (A) and hydrophobic block (B) constituting the above-mentioned AB-type diblock copolymer and ABA-type triblock copolymer, in addition to the radical-reactive unsaturated monomers constituting the aforementioned specific (meth)acrylic (co)polymers, styrene (co)polymers, and amine (co)polymers, at least one radical-polymerizable unsaturated monomer, described later, may be copolymerized to adjust their hydrophilicity or hydrophobicity. In the above-mentioned AB-type diblock copolymer or ABA-type triblock copolymer, there exists an appropriate acid value, amine value, and / or hydroxyl value, from the viewpoint of increasing the saturation of the coating film of the ink composition containing the pigment dispersion. Preferred values ​​for the acid value, amine value, and / or hydroxyl value are 20 mg KOH / g or more, more preferably 20 to 200 mg KOH / g, even more preferably 40 to 100 mg KOH / g, and particularly preferably 60 to 95 mg KOH / g, for example, 70 to 95 mg KOH / g, 80 to 90 mg KOH / g, etc.

[0070] The number-average molecular weight of the above-mentioned AB-type diblock copolymer or ABA-type triblock copolymer is, for example, 1,000 to 50,000, preferably 1,000 to 30,000, more preferably 1,000 to 10,000, and particularly preferably 1,000 to 8,000. The weight-average molecular weight of the above-mentioned AB-type diblock copolymer or ABA-type triblock copolymer is equal to or slightly greater than the number-average molecular weight, for example, 1,000 to 60,000, preferably 1,000 to 35,000, more preferably 1,000 to 15,000, and particularly preferably 1,000 to 10,000.

[0071] [5. Resin-coated pigment dispersion] The resin-coated pigment dispersion of the present invention comprises at least the resin-coated pigment described above, and further contains a medium selected depending on the form of the final ink composition. Specifically, as the medium of the pigment dispersion, for example, water is selected for aqueous ink compositions, an oil-soluble organic solvent for solvent-based ink compositions, and a polymerizable compound for UV-curable ink compositions.

[0072] (5-1.Wed) The water that may be included in the resin-coated pigment dispersion can be purified water, deionized water, distilled water, etc., but it is preferable to use deionized water from which divalent metal ions, which tend to inhibit pigment dispersibility, have been removed in advance. Examples of divalent metal ions include magnesium ions, calcium ions, strontium ions, barium ions, iron ions, cobalt ions, and nickel ions. It is also possible to add a water-soluble organic solvent to water. Specific examples of water-soluble organic solvents include alkyl alcohols with 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; alkylene glycols containing 2 to 6 carbon atoms in the alkylene group, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, and diethylene glycol; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; and N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazoline. The water and water-soluble organic solvent content in the resin-coated pigment dispersion is, for example, 50% or more by weight and 70% or more by weight, respectively, based on the total weight of the dispersion.

[0073] (5-2. Oil-soluble organic solvents) Oil-soluble organic solvents that may be contained in the resin-coated pigment dispersion include: ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and tetralin; hydrocarbon solvents such as cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether. Examples include glycol ether solvents such as tripropylene glycol monobutyl ether; glycol ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene glycol diacetate; and vegetable oils such as linseed oil, soybean oil, and castor oil. Any of the above organic solvents may be used individually or as a mixture of two or more.

[0074] The content of oil-soluble organic solvents in the resin-coated pigment dispersion is, for example, 50% or more by weight, 70% or more by weight, based on the total weight of the dispersion.

[0075] (5-3. Polymerizable compound) Polymerizable compounds are polymerizable compounds that crosslink or polymerize upon irradiation with ultraviolet light. Examples of polymerizable compounds include radical polymerizable compounds, cationic polymerizable compounds, or mixtures thereof.

[0076] Radical polymerization compounds include (meth)acrylate compounds, etc. (Meth)acrylate compounds include monofunctional unsaturated monomers, difunctional unsaturated monomers, or polyfunctional unsaturated monomers with three or more functions.

[0077] Examples of monofunctional unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomiristyl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate (hereinafter, IDA, IDMA), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-(ethoxyethoxy)ethyl (meth)acrylate (hereinafter, EEEA, EEEMA), cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobolonyl (meth)acrylate, and β-carboxyethyl (meth)acrylate.

[0078] Examples of difunctional unsaturated monomers include polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate (hereinafter referred to as NPGDA, NPGDMA), 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, and neopentyl glycol diglycidyl ether di(meth)acrylate.

[0079] Examples of polyfunctional unsaturated monomers with three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tricyclodecanil(meth)acrylate.

[0080] Cationic polymerizable compounds include styrene derivatives, vinyl ether compounds, oxirane compounds, oxetane compounds, and the like. Examples of vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexyl vinyl ether, benzyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, 4-hydroxyethyl vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, trimethylolethane trivinyl ether, and the like. Examples of oxirane compounds include known epoxy compounds such as phenylglycidyl ether, pt-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylhexene oxide, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and 1,1,3-tetradecadienone dioxide.

[0081] The total content of radically polymerizable monomers in a resin-coated pigment dispersion is, for example, 10-95% by weight or 30-90% by weight, based on the total weight of the dispersion.

[0082] (5-4. Method for producing dispersions) The method for producing the resin-coated pigment dispersion of the present invention is not particularly limited, and it can be produced by mixing the above-mentioned resin-coated pigment, water, organic solvent, and radical polymerizable monomer using a known disperser or kneader.

[0083] For example, resin-coated pigment dispersions can be produced by dispersing a mixture consisting of resin-coated pigment, water, organic solvent, and radical polymerizable monomer using a paint shaker, kneader, roll mill, bead mill, sand mill, attritor, dissolver, extruder, homomixer, high-pressure homogenizer, etc. Among the above-mentioned dispersers and kneaders, media-type dispersers such as sand mills and bead mills are particularly preferred.

[0084] [6. Ink Composition] The ink composition of the present invention comprises the resin-coated pigment dispersion described above and a binder resin.

[0085] (6-1. Binder resin) Examples of binder resins that may be included in the ink composition include modified rosin resins such as lime rosin and maleated rosin, rosin-modified phenolic resins, rosin, rosin polymers, rosin esters, rosin derivatives such as hydrogenated rosin, (meth)acrylic resins, styrene-(meth)acrylic acid resins (P(S / MAA)), styrene-maleic acid resins, ethylene-vinyl acetate resins, coumarone indene resins, terpene phenolic resins, phenolic resins, urethane resins, melamine resins, urea resins, epoxy resins, cellulose resins, vinyl acetate resins, xylene resins, alkyd resins, aliphatic hydrocarbon resins, butyral resins, maleic acid resins, fumaric acid resins, and the like. Any of the above-mentioned binder resins may be used individually or as a mixture of two or more. Urethane resins and styrene-(meth)acrylic acid are preferably used as binder resins.

[0086] In the ink composition, the binder resin is preferably present in an amount of 1 to 30% by weight, and more preferably in an amount of 3 to 20% by weight, based on the total weight of the dispersion.

[0087] (6-2. Other ingredients) In the ink composition of the present invention, components other than the aforementioned binder resin may be added as needed. In particular, photopolymerization initiators are examples of components included in the UV-curable ink composition.

[0088] Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Acetophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, benzoylbenzoate methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2- Thioxanthone-based photopolymerization initiators such as lorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis( Examples of triazine-based photopolymerization initiators include dichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bischloromethyl-(piperonyl)-6-triazine, and 2,4-bischloromethyl(4'-methoxystyryl)-6-triazine.

[0089] The content of the photopolymerization initiator in the resin-coated pigment dispersion is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 3 parts by weight, based on the total weight of the dispersion.

[0090] Furthermore, various additives such as photosensitizers, photoacid generators, plasticizers, surface modifiers, UV inhibitors, antioxidants, hydrolysis inhibitors, and drying accelerators can be used as needed. The content of these additives is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less, based on the total weight of the resin-coated pigment dispersion.

[0091] The additive content in the ink composition is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less, based on the total weight of the ink composition.

[0092] (6-3. Method for producing ink compositions) There are no particular limitations on the method of manufacturing the ink composition; it can be manufactured by mixing the above-mentioned resin-coated pigment dispersion, binder resin, etc., using a known disperser or kneader.

[0093] The ink composition can be used, for example, as a printing ink composition such as an inkjet ink composition, or as a color resist for color filters. When the ink composition is used as a printing ink, it can be applied to inkjet printing, gravure printing, flexographic printing, screen printing, offset printing, etc., but as mentioned above, it is particularly suitable for use in inkjet printing.

[0094] Furthermore, in the case of an ink composition, such as an inkjet ink composition, the resin viscosity at 25°C is preferably 50 mPa·s or less, more preferably 30 mPa·s or less, even more preferably 20 mPa·s or less, and particularly preferably 10 mPa·s or less. Furthermore, in the ink composition, the resin viscosity at 25°C is preferably 0.5 mPa·s or higher, more preferably 1.0 mPa·s or higher, even more preferably 2.0 mPa·s or higher, and particularly preferably 3.0 mPa·s or higher.

[0095] [7. Method for producing living radical polymers] Next, a method for producing the living radical polymer of the present invention will be described. This method is characterized by the ability to obtain a polymer with a narrow molecular weight distribution and having a specific functional group at at least one polymer terminal in high purity.

[0096] The present invention provides a method for producing a polymer, comprising a polymerization step to form a precursor of a living radical polymer and an introduction step to introduce a specific functional group structure to the terminal end of the precursor. In the polymerization step, the precursor is polymerized using a polymerization initiator containing an organic compound moiety and a dormant, or preferably a polymerization initiator consisting only of an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer. In the introduction step, a specific functional group-containing radical generator is reacted with the dormant terminal end of the precursor obtained in the polymerization step at a predetermined temperature to introduce a terminal functional group structure derived from the functional group-containing radical generator. Each step will be described below.

[0097] (7-1. Polymerization process) In the polymerization process, the aforementioned NMP method, ATRP method, RAFT polymerization method, TERP method, or RCMP method may be used. As polymerization initiators for precursor production, the polymerization initiators described in the explanations of these production methods can be used. In particular, it is preferable to use an organiodine compound as the polymerization initiator, which can efficiently detach and bond the dormant at the precursor terminal using a specific functional group-containing radical generator. Therefore, the RCMP method, which uses at least an organiodine compound as the polymerization initiator, will be explained in more detail.

[0098] While organiodine compounds that can be suitably used as polymerization initiators for precursor production were described in detail in the previous section, in addition to methods using already manufactured polymerization initiators, it is also possible to use polymerization initiator raw materials, such as azo compounds and iodine, by introducing them into the initial stages of polymerization and generating an in-situ polymerization initiator consisting of an organiodine compound through the reaction of the two.

[0099] Examples of azo compounds used to produce organoiodine compounds include functional group-free azo compounds such as 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis(isobutyronitrile) (AIBN), 2,2-azobis(2-methylbutyronitrile), 1,1-azobis(cyclohexane-1-carbonnitrile), and 2,2-azobis(2,4,4-trimethylpentane), as well as functional group-containing azo compounds such as 4,4-azobis-4-cyanovaleric acid (ACVA) having a carboxyl group, 2,2-azobis{2-methyl-N-(2-hydroxyethyl)propionamide} having a hydroxyl group, and 2-2-azobis{2-(2-imidazolin-2-yl)propane} having an amino group. However, the present invention is not limited to these examples.

[0100] The amount of azo compound used to generate the polymerization initiator described above is preferably 1 to 5 moles, and more preferably 1.3 to 3 moles, per mole of iodine.

[0101] To efficiently polymerize the aforementioned polymerization initiator, it is desirable to use a catalyst in addition to the polymerization initiator. Examples of catalysts include known compounds that coordinate to and abstract iodine, but the present invention is not limited to such examples.

[0102] Examples of catalysts include organic amine compounds and nonmetallic compounds having ionic bonds with iodide ions, where the nonmetallic atoms in the nonmetallic compound are in a cationic state and form ionic bonds with iodide ions. However, the present invention is not limited to these examples.

[0103] Examples of catalysts consisting of organic amine compounds include triethylamine, tributylamine, 1,1,2,2-tetrakis(dimethylamino)ethene, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, ethylenediamine, tetramethylethylenediamine, tetramethyldiaminomethane, tris(2-aminoethyl)amine, tris(2-(methylamino)ethyl)amine, and hematoporphyrin. These catalysts may be used individually or in combination of two or more types.

[0104] Catalysts that have an ionic bond with an iodide ion, wherein the nonmetallic atom in the nonmetallic compound is in a cationic state and forms an ionic bond with the iodide ion, include, specifically, ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, sulfonium salts, and iodonium salts. More specifically, examples include tetrabutylammonium iodide, tetrabutylammonium triiodide, tetrabutylammonium bromodiodide, 1-methyl-3-methylimidazolium iodide, 2-chloro-1-methylpyridinium iodide, methyltributylphosphonium iodide (hereinafter also referred to as PMBI), tetraphenylphosphonium iodide, tributylsulfonium iodide, and diphenyliodonium iodide. These catalysts may be used individually or in combination of two or more types.

[0105] From the viewpoint of increasing the polymerization rate and reducing the amount of unreacted monomers remaining, the amount of catalyst is preferably 0.01 to 50 moles, more preferably 0.05 to 30 moles, even more preferably 0.1 to 20 moles, and even more preferably 0.5 to 10 moles per 100 moles of the above-mentioned organic iodine compound.

[0106] In addition to the catalysts mentioned above, a small amount of a general-purpose radical polymerization initiator may be used as needed to accelerate the polymerization rate. The type of general-purpose radical polymerization initiator does not need to be selected as strictly as the type of polymerization initiator used for precursor production mentioned above; one can be used as appropriate depending on the polymerization temperature and polymerization time.

[0107] Examples of general-purpose radical polymerization initiators include azo compounds and organic peroxides, but the present invention is not limited to these examples. These general-purpose radical polymerization initiators may be used individually or in combination of two or more types.

[0108] Examples of azo compounds include those similar to those mentioned above. These azo compounds may be used individually or in combination of two or more types.

[0109] Examples of organic peroxides include, in addition to the aforementioned diacyl peroxides containing specific functional groups, general-purpose organic peroxides that do not contain functional groups, such as diacyl peroxides like di-(3,5,5-trimethylhexanoyl) peroxide and benzoyl peroxide, peroxy dicarbonates like di-n-propyl peroxy dicarbonate and di-isopropyl peroxy dicarbonate, dialkyl peroxides like dicumyl peroxide and di-t-butyl peroxide, peroxy esters like t-butyl peroxy pivalate and t-butyl peroxy-2-ethylhexanoate, and peroxyketals like 1,1-bis(t-butylperoxy)cyclohexane. However, the present invention is not limited to these examples. These organic peroxides may be used individually or in combination of two or more types.

[0110] Furthermore, if it is not necessary to use a general-purpose radical polymerization initiator, it is preferable to substantially omit the use of a general-purpose radical polymerization initiator, and more preferably to omit it entirely, from the viewpoint of avoiding adverse effects caused by the general-purpose radical polymerization initiator. Here, "substantially omitted" means an amount of general-purpose radical polymerization initiator such that there is substantially no influence on the polymerization reaction by the polymerization initiator. More specifically, the amount of general-purpose radical polymerization initiator per mole of catalyst is preferably 10 mmol or less, more preferably 1 mmol or less, and even more preferably 0.1 mmol or less.

[0111] The amount of general-purpose radical polymerization initiator per 100 moles of total radical polymerizable unsaturated monomer components is preferably 0.005 to 30 moles, more preferably 0.01 to 20 moles, and even more preferably 0.02 to 15 moles, from the viewpoint of increasing the polymerization rate and reducing the amount of unreacted radical polymerizable unsaturated monomers remaining.

[0112] As described in detail in the previous section, the polymerization conditions for polymerizing radically polymerizable unsaturated monomers are not particularly limited and can be set appropriately according to the polymerization method of the radically polymerizable unsaturated monomer. The polymerization temperature is preferably room temperature to 200°C, more preferably 30 to 140°C. Furthermore, the atmosphere when polymerizing radically polymerizable unsaturated monomers is preferably an inert gas such as nitrogen gas or argon gas. The reaction time should be set appropriately so that the polymerization reaction of the radically polymerizable unsaturated monomer is completed.

[0113] Polymerization of radically polymerizable unsaturated monomers may be carried out by bulk polymerization without the use of solvents, or by solution polymerization using a solvent that dissolves in the radically polymerizable unsaturated monomer or the polymer obtained thereby. Furthermore, emulsion polymerization, dispersion polymerization, suspension polymerization, etc., can be carried out by using a solvent that does not dissolve in the radically polymerizable unsaturated monomer or the polymer obtained thereby.

[0114] Solvents used in solution polymerization of radically polymerizable unsaturated monomers include, for example, aromatic solvents such as water, benzene, toluene, xylene, and ethylbenzene; alcoholic solvents such as methanol, ethanol, isopropanol, n-butanol, and t-butyl alcohol; halogen-containing solvents such as dichloromethane, dichloroethane, and chloroform; linear or branched aliphatic ether solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellsolve, butyl cellsolve, diglyme, and propylene glycol monomethyl ether acetate; alicyclic ether solvents such as tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane; esteric solvents such as ethyl acetate, butyl acetate, cellosolve acetate, and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diacetone alcohol; amide solvents such as dimethylformamide; and sulfoxide solvents such as dimethyl sulfoxide. However, the present invention is not limited to these examples. These solvents may be used individually or in combination of two or more. The amount of solvent should be determined appropriately, taking into account the polymerization conditions, monomer composition, and the concentration of the resulting polymer.

[0115] (7-2.Introduction process) In the introduction step of the polymer production method of the present invention, a polymer with a modified terminal structure is obtained by applying heat to the dormanth end of a precursor obtained from a living radical polymerization initiator and a radically polymerizable unsaturated monomer in the presence of a specific functional group-containing radical generator. Suitable examples of the specific functional group-containing radical generator include symmetric azo compounds containing a specific functional group represented by formula (3), which is formed by linking two identical compounds having a specific functional group represented by formula (1) or formula (2) via an azo group, and symmetric diacyl peroxides containing a specific functional group represented by formula (4) or formula (5) linked via a diacyl peroxide group. [ka] In formula (3), R 1Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, preferably a carboxyl group or a hydroxyl group. R 2 and R 3 Each of these is independently at least one group selected from hydrogen, a methyl group, and a cyano group, preferably hydrogen or a methyl group. Also, R 4 Each of them is independent of C 1~3 It is an alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety. [ka] In formula (4), R 1 Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, preferably a carboxyl group or a hydroxyl group. R 2 and R 3 Each of these is independently at least one group selected from hydrogen, a methyl group, and a cyano group, preferably hydrogen or a methyl group. Also, R 4 Each of them is independent of C 1~3 It is an alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety. [ka] In formula (5), R 5 Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, and is preferably a carboxyl group or a hydroxyl group. Also, R 6 Each of these is independently one or two groups selected from hydrogen, a methyl group, and a methoxy group, preferably hydrogen or a methoxy group. Note that each benzene ring in formula (5) contains 1 to 5 R 5 , or 1 to 4 R 6 (They may be joined together.)

[0116] For example, in the presence of a functional group-containing radical generator represented by formula (3), formula (4), or formula (5), radicals that efficiently abstract the dormant at the precursor terminal and bind to the resulting precursor terminal radical are alkyl radicals having specific functional groups, acyloxy radicals, etc. Of these, acyloxy radicals react particularly rapidly with the precursor terminal radical, so as the functional group-containing radical generator, diacyl peroxides represented by formula (4) or formula (5) are preferred, and among them, from the balance between the dormant abstraction rate and the reaction rate with the precursor terminal radical, aliphatic diacyl peroxides such as SAPO (discussic acid peroxide), di-(3-hydroxybutyroyl) peroxide, or di-(3-aminopropyl) peroxide are more preferred, with SAPO being the most preferred.

[0117] The amount of radical generator added is preferably 1 to 50 moles, more preferably 1 to 40 moles, even more preferably 1 to 35 moles, and most preferably 1 to 30 moles, per mole of the precursor terminal dormant.

[0118] The reaction conditions for reacting a specific functional group-containing radical generator with the precursor terminal dormant can be set appropriately according to the conditions for the decomposition of the functional group-containing radical generator, and are not particularly limited. However, the reaction temperature is preferably +15°C to +35°C, more preferably +25°C to +35°C, relative to the 10-hour half-life temperature of the functional group-containing radical generator. Furthermore, the atmosphere during the reaction is preferably an inert gas such as nitrogen or argon. The reaction time can be set appropriately to ensure the complete decomposition of the functional group-containing radical generator, but can be selected from ranges such as 50°C to 200°C, 60°C to 150°C, 70°C to 120°C, or 80°C to 100°C. A solvent can also be used to ensure a homogeneous reaction. Any solvent capable of dissolving living radical polymers can be used; for example, the same solvents used when polymerizing the radically polymerizable unsaturated monomers described above can be suggested.

[0119] As mentioned above, the reaction mechanism of the polymer production method of the present invention is presumed to be as follows. First, a radical generated from the functional group-containing radical generator abstracts a dormant present at the precursor terminal, thereby generating a precursor terminal radical. Meanwhile, functional group-containing radicals present in excess of the dormant at the precursor terminal rapidly bind to the precursor terminal radical. In this way, a precursor with a specific functional group-containing compound bound to its terminal is obtained in high purity. That is, the functional group-containing radical polymerization initiator in this method simultaneously plays two roles: abstracting a dormant present at the precursor terminal and causing the generated precursor radical to bind with radicals generated from further functional group-containing radical polymerization initiators present in excess in the reaction system. Therefore, if precursor radicals are generated at an earlier stage than radicals are generated from such functional group-containing radical generators, functional groups can be bonded to the ends of the precursors more efficiently than described above, and as a result, living radical polymers having terminal structures derived from functional group-containing compounds can be obtained with even higher purity. For this reason, it is desirable to use a compound that abstracts the dormant at the end of the precursor faster and more rapidly than the radical generation by the radical polymerization initiator, in addition to the radical generator (functional group-containing radical polymerization initiator) containing a functional group-containing compound.

[0120] As described above, examples of compounds that extract radicals from precursors include radical generators that decompose faster than the decomposition rate of radical generators containing functional groups (functional group-containing radical polymerization initiators), or nonmetallic compounds that have an ionic bond with iodide ions.

[0121] Examples of radical generators that decompose faster than functional group-containing radical generators include already known radical generators, but it is also possible to use radical generators with a 10-hour half-life temperature that is 20°C or more lower than that of radical generators containing functional group compounds.

[0122] Examples of nonmetallic compounds having an ionic bond with iodide ions include ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, sulfonium salts, and iodonium salts. More specifically, examples include tetrabutylammonium iodide, tetrabutylammonium triiodide, tetrabutylammonium bromodiodide, 1-methyl-3-methylimidazolium iodide, 2-chloro-1-methylpyridinium iodide, methyltributylphosphonium iodide (hereinafter also referred to as BMPI), tetraphenylphosphonium iodide, tributylsulfonium iodide, and diphenyliodonium iodide. These catalysts may be used individually or in combination of two or more types.

[0123] From the viewpoint of increasing the reaction rate, the amount of compound used to extract radicals from the aforementioned precursor is 0.5 to 20 moles, preferably 1 to 10 moles, per mole of terminal dormant of the living radical polymer precursor. [Examples]

[0124] The present invention will be described in more detail below with reference to examples. First, an example of precursor production is shown below.

[0125] Manufacturing Example 1-1 6.007 g of methyl methacrylate (MMA; distilled and purified by conventional methods from Fujifilm Wako Pure Chemical Industries, Ltd.), 0.174 g of 2-iodo-2-phenylethyl acetate (PAME; manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.2066 g of methyl tributylphosphonium iodide (BMPI; manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 30 ml Schlenk tube, and the internal space of the Schlenk tube was purged with nitrogen gas. The contents of the Schlenk tube were stirred at 70°C for 4 hours, then rapidly cooled to room temperature, and 20 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was added to dissolve it. To remove unreacted BMPI, the toluene solution was placed in a centrifuge tube and centrifuged at 2000 rpm for 15 minutes. The supernatant was reprecipitation by dropwise adding it to 500 g of hexane (manufactured by Kanto Chemical Co., Ltd.), and the resulting solution was filtered through a PTFE membrane filter (pore size: 0.45 μm). The resulting powder was then vacuum-dried at 50°C for 8 hours to obtain an MMA polymer (hereinafter referred to as PMMA) having iodine at one of its molecular ends. This reaction is represented by the following equation (i). [ka] The number-average molecular weight of the obtained polymer was 7,800, and the molecular weight distribution (weight-average molecular weight / number-average molecular weight, hereinafter referred to as Mw / Mn) was 1.13. Furthermore, the obtained polymer was dissolved in deuterated chloroform (containing TMS). 1 Analysis by 1H-NMR revealed that the integral of the methine proton (number of hydrogens: 2) of the ethyl ester in PAME and the integral of the methyl proton (number of hydrogens: 3) of the methyl ester in the MMA1 molecule located immediately next to the iodine atom had a ratio of 2:2.96, confirming that 98.7% of the iodine present at the polymer terminals was introduced. The results are shown in Table 1.

[0126] Manufacturing Example 2 PMMA having iodine at one molecular end was obtained using the same method as in Production Example 1-1, except that the polymerization conditions were changed from 70°C for 4 hours to 70°C for 1 hour. The number-average molecular weight of the obtained polymer was 2,900, and the Mw / Mn ratio was 1.15. Furthermore, 1¹H-NMR results confirmed that 98.7% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0127] Manufacturing Example 3 PMMA with iodine at one molecular end was obtained using the same method as in Production Example 1-1, except that the amount of PAME added was changed from 0.174 g to 0.044 g, the amount of BMPI added was changed from 0.2066 g to 0.4132 g, and the polymerization conditions were changed from 70°C for 4 hours to 70°C for 24 hours. The number-average molecular weight of the obtained polymer was 56,000, and the Mw / Mn ratio was 1.19. Furthermore, 1 ¹H-NMR results confirmed that 98.3% of the iodine present at the polymer ends was incorporated. The results are shown in Table 1.

[0128] Manufacturing Example 4 Except for using 6.007 g of MMA as the radical polymerizable unsaturated monomer, instead of 7.692 g of n-butyl acrylate (BA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and distilled and purified by conventional methods), instead of 0.174 g of PAME as the organiodine compound, instead of 0.117 g of 2-iodoisobutyronitrile (CP-I, manufactured by Tokyo Chemical Industry Co., Ltd.), the amount of BMPI added was changed from 0.2066 g to 0.8264 g, and the polymerization conditions were changed from 70°C for 4 hours to 110°C for 48 hours, a BA polymer having iodine at one molecular end (hereinafter referred to as PBA) was obtained by the same method as in Production Example 1-1. The number-average molecular weight of the obtained polymer was 7,600, and the Mw / Mn ratio was 1.25. Furthermore, the obtained polymer was dissolved in deuterated chloroform. 13 Analysis by 1C-NMR revealed that the integral value of the quaternary carbon (1 carbon atom) in CP-I and the integral value of the tertiary carbon (1 carbon atom) in the BA1 molecule immediately adjacent to the iodine atom were 1:0.98, confirming that 98.0% of the iodine present at the polymer terminals was introduced. The results are shown in Table 1.

[0129] Manufacturing Example 5 As a radically polymerizable unsaturated monomer, instead of using 6.007 g of MMA, 6.249 g of styrene (St; distilled and purified by a conventional method from Fuji Film Wako Pure Chemical Corporation) was used. As an organic iodine compound, instead of using 0.174 g of PAME, 0.152 g of iodine and 0.0985 g of 2,2 - azobis(isobutyronitrile) (AIBN, manufactured by Fuji Film Wako Pure Chemical Corporation) were used. A polymer of St having iodine at one molecular terminal (hereinafter referred to as PSt) was obtained in the same manner as in Production Example 1 - 1, except that the polymerization conditions were changed from 70 °C for 4 hours to 80 °C for 18 hours. The number average molecular weight of the obtained polymer was 7,700, and Mw / Mn was 1.23. Further, the obtained polymer was dissolved in heavy chloroform, 13 When analyzed by C - NMR, the integral value of the quaternary carbon (carbon number: 1) in CP - I and the integral value of the tertiary carbon of the St1 molecule immediately adjacent to iodine (carbon number of carbon (hydrogen number: 1)) were 1:0.98. From this, it was confirmed that 98.0% of the iodine at the polymer terminal was introduced. The results are shown in Table 1.

[0130] Production Example 6 Instead of using 0.174 g of PAME, an organic iodine compound, 0.133 g of cyanopropylbenzothioate (manufactured by Sigma - Aldrich Japan, hereinafter referred to as CPBS), a RAFT agent, was used, and AIBN was changed to 0.328 g. A PMMA having a phenyldithioester group at one molecular terminal was obtained in the same manner as in Production Example 1 - 1. The number average molecular weight of the obtained polymer was 7,900, and Mw / Mn was 1.21. Also, 1 From the results of H - NMR, it was confirmed that 98.4% of the phenyldithioester present at the polymer terminal was introduced. The results are shown in Table 1.

[0131]

Table 1

[0132] In addition, the identification and purity of the polymer having a specific functional group-containing compound obtained in the examples described below were examined based on the following methods. (Sample preparation) The obtained polymer was weighed to 0.1 g, and 0.1 g of trans-2-{3-(4-t-butylphenyl)-2-methyl-2-propenylidene} malononitrate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as DCTB) as a matrix was added thereto, and the mixture was ground in a mortar while mixing. Then, a very small amount of sodium trifluoroacetate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as NaTFA), which is an ionizing agent, was spotted on a sample plate in advance, and the obtained mixture of the polymer and DCTB was added. (Identification of polymer end groups) Using JMS-S3000 SpiralTOF manufactured by JEOL Ltd., the MS spectrum obtained by irradiating a laser of 50 kV on a polymer sample was analyzed. The MS spectrum of the sample was compared with the MS spectra of PMMA-I as a precursor and PMMA-H from which iodine at the precursor end had been removed. In the MS spectrum of the sample, there was a spectrum that did not match the spectra of PMMA-I and PMMA-H, and the total molecular weight thereof was consistent with the total molecular weight obtained by adding the molecular weight of the carboxylic acid ethyl ester group added to PMMA and the Na molecular weight of the ionizing agent. Therefore, it was confirmed that the carboxylic acid ethyl ester group was directly bonded to the PMMA end. (Measurement of purity of polymer having specific functional group-containing compound) The content of PMMA-H in the sample was calculated by dividing the area of the MS spectrum derived from PMMA-H present in the sample by the area of the main spectrum of PMMA-H. The purity was calculated by subtracting the percentage of the PMMA-H content in the sample from 100 to obtain the purity of the polymer having a specific functional group-containing compound in the sample (the content rate of the polymer having a functional group-containing compound in the polymer composition).

[0133] Examples 1 to 3 In a 30 ml Schlenk tube, 0.6 g of the polymer obtained in Production Example 1-1 was added, along with a carboxyl-containing discustic acid peroxide (SAPO; manufactured by NOF Corporation, T) as a radical generator. 10h 0.180 g of (=66°C) and 2 g of toluene (manufactured by Kanto Chemical Co., Ltd.) as a solvent were added and dissolved, and then the internal space of the Schlenk tube was replaced with nitrogen gas. The contents of the Schlenk tubes were then measured in each case, and in Example 1, 97°C (SAPO T 10h (66℃) + 31℃) for 2 hours, in Example 2 92℃ (SAPO's T 10h In Example 3, 4 hours at +26℃, and in Example 3, 87℃ (SAPO's T 10h After stirring at +21°C for 8 hours, the mixture was rapidly cooled to room temperature. To remove the SAPO decomposition residue, 200 g of 60°C warm water was added, and the mixture was allowed to stand in a separatory funnel to collect the upper oil phase. Reprecipitation was performed by adding the oil dropwise to 150 g of hexane, and the resulting solution was filtered through a PTFE membrane filter (pore size: 0.45 μm) to obtain a powder. This powder was then vacuum-dried at 50°C for 8 hours, which removed the dormant at the polymer ends and yielded a polymer with a structure containing a carboxyl group. The number-average molecular weight, Mw / Mn, and purity of the polymer with the ethyl carboxylate group attached were calculated, and the results are shown in Table 2.

[0134] Examples 4-6 In Example 2, polymers were produced in the same manner as in Example 2, except that BMPI, a nonmetallic compound having an ionic bond with an iodide ion that abstracts the iodine at the precursor terminal faster than a radical generator containing a specific functional group, was added in the same amounts as in Example 4 (0.5 moles), Example 5 (5 moles), and Example 6 (10 moles) per mole of the iodine terminal of the precursor. As a result, the dormant at the precursor terminal was eliminated, and a polymer with a structure containing a carboxyl group was obtained. This reaction is represented by the following formula (ii). [ka] The number-average molecular weight, Mw / Mn ratio, and purity of the polymers to which the ethyl carboxylate groups were bonded were calculated, and the results are shown in Table 2.

[0135] Examples 7-8 As in Example 5, in a system using BMPI, a nonmetallic compound having an ionic bond with an iodide ion that abstracts iodine from the precursor terminal faster than a radical generator containing a specific functional group, the polymer was produced in the same manner as in Example 2, except that SAPO was added at a rate of 1 mole in Example 7 and 30 moles in Example 8 per mole of iodine terminal of the precursor. As a result, the dormant at the polymer terminal was eliminated, and a polymer with a structure containing a carboxyl group was obtained. The number-average molecular weight, Mw / Mn, and purity of the polymer with the obtained ethyl carboxylate group were calculated and the results are shown in Table 2.

[0136] Examples 9-10 In Example 2, the precursor Mn was changed to 2,900 g / mol in Example 9 and 56,000 g / mol in Example 10, except that the preparation method was the same as in Example 2. As a result, the dormant at the polymer end was eliminated, and a polymer with a carboxyl group-containing compound structure was obtained. The number-average molecular weight, Mw / Mn, and purity of the polymer with the obtained ethyl carboxylate group were calculated and the results are shown in Table 2.

[0137] Example 11 As in Example 5, in a system using BMPI, a nonmetallic compound having an ionic bond with an iodide ion that abstracts iodine from the precursor terminal faster than a radical generator containing a specific functional group, Example 11 used a radical generator containing a specific functional group. That is, in Example 11, the polymer was produced in the same manner as in Example 2, except that an azo compound (AVCA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with the structure of a carboxylic acid-containing compound as a functional group was used as the radical generator containing a specific functional group. As a result, a polymer composition was obtained in which the dormant at the polymer terminal was removed and a structure containing a carboxyl group was bonded. The number-average molecular weight, Mw / Mn, and purity of the polymer with the bonded ethyl carboxylate group were calculated and the results are shown in Table 2.

[0138] Examples 12-13 In Example 2, polymers were produced in the same manner as in Example 2, except that the precursor radical polymerizable unsaturated monomer was changed to BA in Example 12 and to St in Example 13. As a result, a polymer composition was obtained in which the dormant at the polymer terminus was eliminated and a structure containing a carboxyl group was bonded. The number-average molecular weight, Mw / Mn, and purity of the polymer to which the ethyl carboxylate group was bonded were calculated, and the results are shown in Table 2.

[0139] Comparative Example 1 RAFT polymerization was adopted as the living radical polymerization method for producing the precursor, and dilauroyl peroxide (LPO; manufactured by NOF Corporation), a radical generator containing a compound without specific functional groups, was used, with polymerization conditions set to 90°C (T of LPO). 10h The polymer was prepared in the same manner as in Example 2, except that the incubation time was changed to 4 hours at 62°C (in benzene) + 28°C. As a result, the dormant at the polymer terminals was removed, and a polymer composition was obtained in which a structure containing a carboxyl group was bonded. The number-average molecular weight, Mw / Mn, and purity of the polymer to which the ethyl carboxylate group was bonded were calculated, and the results are shown in Table 2.

[0140] [Table 2]

[0141] The results in Table 2 show that living radical polymers in which a structure having a specific functional group-containing compound is introduced on the dormant side of the polymer terminals in the present invention, that is, living radical polymers in which a specific functional group is bonded in place of the detached dormant, have a narrow molecular weight distribution and high purity. Furthermore, according to the production method of the present invention, by reacting a radical polymerization initiator having a specific functional group-containing compound with the terminal dormant of the precursor, a living radical polymer with a narrow molecular weight distribution and high purity can be obtained.

[0142] Next, we present a manufacturing example of a resin-coated pigment in which at least a portion of the surface is coated with a living radical polymer composition having a specific functional group at one end.

[0143] Manufacturing Example 1-2 When the reaction of formula (i) described above was carried out under the same conditions as in Production Example 1-1, an iodine-containing polymer (precursor) was obtained, with a number-average molecular weight of 7,200 and a molecular weight distribution (weight-average molecular weight / number-average molecular weight, hereinafter referred to as Mw / Mn) of 1.16. Next, 0.6 g of the iodine-containing polymer mentioned above is placed in a 30 ml Schlenk tube, along with a carboxyl-group-containing discustic acid peroxide (SAPO; manufactured by NOF Corporation, T) as a radical generator. 10h 0.180 g of (=66°C), 0.1323 g of BMPI, and 2 g of 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.) as a solvent were added and dissolved, and then the internal space of the Schlenk tube was replaced with nitrogen gas. The contents of the Schlenk tube were then heated to 92°C (SAPO T 10h(66 °C) + 26 °C), stirred for 4 hours, then rapidly cooled to room temperature. To remove the decomposition residue of SAPO, 200 g of warm water at 60 °C was added, and the mixture was allowed to stand in a separatory funnel. The upper oil phase was taken out. Reprecipitation was carried out while dropping it into 150 g of hexane. The obtained powder was filtered through a PTFE membrane filter (pore size: 0.45 μm), and then vacuum dried at 50 °C for 8 hours. As a result, the dormant group at the polymer terminal was desorbed, and a polymer having a structure with a carboxyl group-containing compound bonded thereto was obtained. This reaction is also represented by the above formula (ii). The number average molecular weight of the obtained polymer, Mw / Mn, and the purity (terminal reaction rate) of the polymer having an ethyl carboxylate group bonded thereto were calculated, and the results are shown in Table 3.

[0144] Production Example 7 The polymerization conditions were changed from MMA 6.007 g to benzyl methacrylate (BzMA; distilled and purified by a conventional method from FUJIFILM Wako Pure Chemical Corporation) 10.572 g, and the reaction temperature was changed from 70 °C for 4 hours to 70 °C for 2 hours. Otherwise, the same method as in Production Examples 1-2 was used to obtain a polymer of a hydrophobic block (B) having iodine at one molecular terminal. The number average molecular weight of the obtained polymer was 3,500, and Mw / Mn was 1.14. Next, the entire amount of the polymer described above was placed in a 30 ml Schlenk tube, and 4.806 g of MMA and 1.034 g of MAA (methacrylic acid), which constitute the copolymer of the hydrophilic block (A), were added. Then, 0.2066 g of BMPI was added, the mixture was purged with nitrogen, stirred at 70°C for 2 hours, rapidly cooled to room temperature, and 20 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was added to dissolve it. To remove unreacted BMPI, the toluene solution was placed in a centrifuge tube and centrifuged at 2000 rpm for 15 minutes. The supernatant was reprecipitation by dropping it into 500 g of hexane (manufactured by Kanto Chemical Co., Ltd.), and the resulting powder was filtered through a PTFE membrane filter (pore size: 0.45 μm). The resulting powder was vacuum dried at 50°C for 8 hours to obtain an AB-type diblock copolymer in which the hydrophilic block (A) is introduced into the hydrophobic block (B) and iodine is present at one of the molecular ends. The number-average molecular weight of the hydrophilic block (A), calculated by subtracting the number-average molecular weight and weight-average molecular weight of the polymer in the hydrophobic block (B) from the number-average molecular weight and weight-average molecular weight of the obtained polymer, was 7,500, and the Mw / Mn ratio was 1.16. Furthermore, the same procedure as in Production Example 1-2 was performed, except that 0.6 g of the iodine-containing AB-type diblock copolymer described above was placed in a 30 ml Schlenk tube, to obtain an AB-type diblock copolymer in which a structure having a carboxyl group-containing compound at the end of a hydrophilic block (A) was bonded to a hydrophobic block (B). The number-average molecular weight, Mw / Mn, and purity (end reaction rate %) of the polymer to which the obtained ethyl carboxylate groups were bonded were calculated, and the results are shown in Table 3.

[0145] Manufacturing Example 8 Except for changing the polymerization conditions for the polymer of hydrophobic block (B) and the copolymer of hydrophilic block (A) from 2 hours at 70°C to 1 hour at 70°C, an AB-type diblock copolymer was obtained in which a structure having a carboxyl group-containing compound at the end of the hydrophilic block (A) was bonded to the hydrophobic block (B) using the same method as in Production Example 7. The number-average molecular weight, Mw / Mn, and purity of the polymer to which the obtained ethyl carboxylate groups were bonded were calculated, and the results are shown in Table 3.

[0146] Manufacturing Example 9 Except for changing the polymerization conditions for the polymer of hydrophobic block (B) and the copolymer of hydrophilic block (A) from 2 hours at 70°C to 4 hours at 70°C, an AB-type diblock copolymer was obtained in the same manner as in Production Example 7, in which a structure having a carboxyl group-containing compound at the end of the hydrophilic block (A) was bonded to the hydrophobic block (B). The number-average molecular weight, Mw / Mn, and purity of the polymer to which the obtained ethyl carboxylate groups were bonded were calculated, and the results are shown in Table 3.

[0147] Manufacturing Example 10 An ABA-type triblock copolymer with iodine at the molecular termini was obtained using the same method as in Production Example 7, except that 0.330 g of ethylene glycol-bis(2-iodo-2-phenylacetate) (BPDG) was used instead of 0.174 g of PAME as the living radical polymerization initiator, BMPI was changed from 0.2066 g to 0.4132 g, and the polymerization conditions were changed from 70°C for 2 hours to 70°C for 1 hour. Next, an ABA-type triblock copolymer in which structures having carboxyl group-containing compounds at the ends of hydrophilic blocks (A) were bonded to hydrophobic blocks (B) was obtained using the same method as in Production Example 2, except that BMPI was changed from 0.1323 g to 0.2646 g. The number-average molecular weight, Mw / Mn, and purity of the polymer to which the obtained ethyl carboxylate groups were bonded were calculated, and the results are shown in Table 3.

[0148] Manufacturing Example 11 Except for replacing 4.806 g of MMA and 1.034 g of MAA, which constitute the copolymer of hydrophilic block (A), with 4.806 g of MMA and 1.888 g of 2-(dimethylamino)ethyl methacrylate (DMEMA; manufactured by Tokyo Chemical Industry Co., Ltd. and distilled and purified by conventional methods), and replacing 0.180 g of SAPO with 0.135 g of di-(3-aminopropyl)peroxide (APPO), an AB-type diblock copolymer was obtained in which structures having amino group-containing compounds at the ends of hydrophilic block (A) were bonded to hydrophobic block (B) using the same method as in Production Example 7. The number-average molecular weight, Mw / Mn, and purity of the polymer bonded with the obtained 3-aminoethyl ester groups were calculated, and the results are shown in Table 3.

[0149] Manufacturing Example 12 Except for replacing 4.806 g of MMA and 1.034 g of MAA, which constitute the copolymer of hydrophilic block (A), with 4.806 g of MMA and 1.563 g of 2-hydroxyethyl methacrylate (2-HEMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and distilled and purified by conventional methods), and replacing 0.180 g of SAPO with 0.157 g of di-(3-hydroxybutyroyl) peroxide (HBPO), an AB-type diblock copolymer was obtained in which structures having amino group-containing compounds at the ends of hydrophilic block (A) were bonded to hydrophobic block (B) using the same method as in Production Example 7. The number-average molecular weight, Mw / Mn, and purity of the polymer bonded with the obtained 3-hydroxypropyl ester groups were calculated, and the results are shown in Table 3.

[0150] Comparative Manufacturing Example 1 Similar to Production Example 1-2, an MMA polymer (hereinafter referred to as PMMA) with iodine at one of its molecular ends was obtained. The number-average molecular weight and Mw / Mn of the obtained copolymer are shown in Table 3.

[0151] Reference manufacturing example A polymer with a carboxyl group-containing compound was obtained using the same method as in Production Example 1, except that 0.180 g of SAPO was changed to 0.018 g. The number-average molecular weight, Mw / Mn, and purity of the polymer with the obtained ethyl carboxylate group were calculated, and the results are shown in Table 3.

[0152] Comparative Manufacturing Example 2 6.007 g of methyl methacrylate (MMA; distilled and purified by conventional methods from Fujifilm Wako Pure Chemical Industries, Ltd.), 0.318 g of 3-mercaptopropionic acid (MPAP; manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.328 g of AIBN were added to a 30 ml Schlenk tube, and the internal space of the Schlenk tube was purged with nitrogen gas. The contents of the Schlenk tube were stirred at 70°C for 4 hours, then rapidly cooled to room temperature, and 20 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was added to dissolve the mixture. To remove unreacted BMPI, the toluene solution was placed in a centrifuge tube and centrifuged at 2000 rpm for 15 minutes. The supernatant was reprecipitation by dropwise adding it to 500 g of hexane (manufactured by Kanto Chemical Co., Ltd.), and the resulting solution was filtered through a PTFE membrane filter (pore size: 0.45 μm). The obtained powder was then vacuum-dried at 50°C for 8 hours to obtain an MMA polymer (hereinafter referred to as PMMA) having a carboxyl group at at least one molecular end. The number-average molecular weight, Mw / Mn, and purity of the polymer to which the obtained ethyl carboxylate groups were bonded were calculated, and the results are shown in Table 3.

[0153] [Table 3]

[0154] Next, examples of pigment dispersions and the like coated with (co)polymers having specific functional group-containing compounds obtained in the above-described manufacturing examples will be explained below.

[0155] The evaluation of the pigment dispersions, etc., obtained in the examples described later is shown in the following items.

[0156] <1. Pigment dispersion particle size (size of dispersed pigment particles)> The pigment dispersion particle size is the value obtained by dynamic light scattering method in accordance with general rules (JIS Z 8828 (2019) and ISO 22412 (2017)) under the following measurement conditions. For each obtained pigment dispersion, the average particle size (D50: the cumulative 50% value calculated from the smallest particle side in the frequency distribution of scattering intensity) was measured. The average particle size was measured immediately after the preparation of the pigment dispersion and after standing at 70°C for 7 days. Average particle size was measured by diluting the pigment dispersion in various media and measuring the D50 at 25°C using a zeta potential, particle size, and molecular weight measurement system (ELSZ-2000Z, manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 2. Note that a smaller average particle size of the pigment dispersion immediately after dispersion indicates superior initial dispersibility, and a smaller change in the average particle size after 7 days indicates superior long-term stability.

[0157] <2. Viscosity of pigment dispersions> The viscosity of the pigment dispersion is the value obtained by measuring it under the following conditions using the viscosity measurement method in accordance with the general rule (JIS K 5101-6-2 (2004)). Specifically, the viscosity of each pigment dispersion was measured immediately after preparation using a BM-type rotational viscometer (rotation speed 6 rpm, 25°C). The results are shown in Table 4.

[0158] <3. Saturation of ink composition coating> The saturation of the ink composition coating film is the value obtained when the coating film was prepared and measured under the following measurement conditions using a colorimeter in accordance with the general rule (JIS K 5101-2-2 (2004)). Samples of each pigment dispersion were applied to a 100 μm thick PET film (product name: Lumirror 100-T60, manufactured by Toray Industries, Inc.) using a bar coater (No. 6, winding diameter 0.15 mm) to a wet film thickness of 2 μm, and dried at 25°C to produce a coating film. The reflected hue and chroma of the obtained coating film were measured using a spectrophotometer (product name: SE 6000, manufactured by Nippon Denshoku Industries, Ltd.). A white plate was placed on the underside of the PET film, and the reflected hue was measured using the Hunter Lab color system with light source C (halogen lamp 12V 50W), a viewing angle of 2°, and a measurement area of ​​30 mmφ. From the obtained a and b values, the chroma C* value was calculated using the following formula. For the white board used, light source C was used, with a viewing angle of 2°, and tristimulus values ​​X, Y, and Z in the XYZ color system were 90≦X≦96, 92≦Y≦98, and 100≦Z≦116. The results are shown in Table 4. Saturation C*=(a 2 +b 2 ) 1 / 2

[0159] Example 14 5.5 parts by weight of a PMMA polymer having a carboxylic acid functional group-containing compound at one end, obtained in Production Example 1-2, was dissolved in 30 parts by weight of ethyl acetate. 13.5 parts by weight of unmodified phthalocyanine copper (CIPigment 15, FASTOGEN BLUE TGR-SD, manufactured by DIC Corporation) was added to this mixture, and the mixture was dispersed in a disperser for 30 minutes to prepare a mill base. After thoroughly dispersing the pigment in the mill base using a horizontal media disperser, 51 parts by weight of ethyl acetate was added to obtain a blue solvent-based dispersion (resin-coated pigment dispersion) with a pigment concentration of 13.5%. The average particle size of the pigment dispersion obtained was 128 nm. The viscosity at 25°C was 3.6 mPa·s. When this pigment dispersion was stored at 70°C for one week, the average particle size of the pigment in the dispersion was 140 nm, and the rate of change was 9.4%. Next, 7 parts by weight of a styrene-methacrylic acid copolymer, which is a binder resin, was added to this pigment dispersion and dispersed in a disperser to obtain a solvent-based ink composition. The saturation of the ink composition coating film was measured and found to be 72. The results are shown in Table 4.

[0160] Examples 15-24, 26-29, Comparative Examples 2 and 3, and Reference Examples A pigment dispersion (resin-coated pigment dispersion) and an ink composition coating film were obtained in the same manner as in Example 14, except that the conditions shown in Table 4 were changed. The results are shown in Table 4.

[0161] Example 25 The pigment dispersion and ink composition coating were obtained in the same manner as in Example 14, except that the conditions shown in Table 4 were changed, and 2.5 parts by weight each of 1-hydroxycyclohexylphenyl ketone and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one were added as photopolymerization initiators to 100 parts by weight of the polymerizable compound, and the resin was cured using an ultraviolet irradiation device (high-pressure mercury lamp). The results are shown in Table 4.

[0162] [Table 4]

[0163] The results in Table 4 show that the pigment coating resin composition of the present invention, which has a specific functional group at at least one end of the living radical copolymer, when used to cover at least a portion of the surface of the pigment, improved the pigment dispersibility of the pigment dispersion. Furthermore, it was confirmed that the pigment coating resin composition can improve the storage stability, discharge stability, and color development of an ink composition containing a binder resin in the pigment dispersion.

Claims

1. A resin-coated pigment in which at least a portion of the surface is coated with a composition containing a living radical polymer, The living radical polymer contains an organic compound moiety derived from a polymerization initiator at one end or in the main chain of the living radical polymer. A resin-coated pigment in which a terminal functional group structure represented by formula (1) or formula (2) below is directly or via an ester moiety bonded to the main chain at at least one of its terminal ends. 【Chemistry 1】 (In formula (1), R1 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R2 and R3 are each independently at least one group selected from hydrogen, C1-3 alkyl groups, and cyano groups. R4 is a C1-3 alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety. 【Chemistry 2】 (In formula (2), R 5 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R6 is one or two groups independently selected from hydrogen, a C1-3 alkyl group, and a C1-3 alkoxy group.

2. The resin-coated pigment according to claim 1, wherein the living radical polymer is a diblock copolymer comprising a hydrophilic block (A) and a hydrophobic block (B) that includes at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer.

3. The resin-coated pigment according to claim 1, wherein the living radical polymer is an A-B-A type triblock copolymer having terminal functional group structures represented by formula (1) or formula (2) at both ends, and comprising a hydrophilic block (A) containing at least one of a (meth)acrylic (co)polymer, a styrene (co)polymer, and an amine (co)polymer, and a hydrophobic block (B).

4. The hydrophilic block (A) is R in formula (1) １ Or R in formula (2) above ５ The resin-coated pigment according to any one of claims 2 and 3, which is a (co)polymer comprising at least one of a (meth)acrylate (co)polymer, a styrene (co)polymer, or an amine (co)polymer having a constituent unit derived from the same functional group as the above.

5. The resin-coated pigment according to any one of claims 1 to 4, wherein the number-average molecular weight of the living radical polymer is 1,000 to 50,000 and the molecular weight distribution value is 1.0 to 1.

5.

6. The resin-coated pigment according to any one of claims 1 to 5, wherein the terminal functional group structure represented by formula (1) or formula (2) is bonded to the main chain via the ester moiety.

7. The resin-coated pigment according to any one of claims 1 to 6, comprising an organic compound moiety derived from the organic iodine compound as the polymerization initiator.

8. A resin-coated pigment according to any one of claims 1 to 7, wherein a portion of the surface is coated with a living radical polymer composition comprising the living radical polymer and a living radical polymer that does not contain the terminal functional group structure, wherein the living radical polymer is present in a proportion of 50 parts by weight or more of the living radical polymer in 100 parts by weight of all living radical polymers.

9. A resin-coated pigment dispersion comprising, in addition to the resin-coated pigment described in any one of claims 1 to 8, a medium comprising at least one selected from water, an oil-soluble organic solvent, and a polymerizable compound.

10. An ink composition characterized by containing a resin-coated pigment dispersion according to claim 9 and a binder resin.

11. A method for producing a living radical polymer, The living radical polymer contains an organic compound moiety derived from a polymerization initiator at one end or in the main chain of the living radical polymer. At least one of the terminals, a terminal functional group structure represented by the following formula (1) or formula (2) is attached to the main chain directly or via an ester moiety, 【Transformation 3】 (In formula (1), R1 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R2 and R3 are each independently at least one group selected from hydrogen, C1-3 alkyl groups, and cyano groups. R4 is a C1-3 alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety. 【Chemistry 4】 (In formula (2), R 5 is at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R6 is one or two groups independently selected from hydrogen, a C1-3 alkyl group, and a C1-3 alkoxy group. A polymerization step to form a precursor of a living radical polymer using a polymerization initiator containing an organic compound moiety and a dormant, and a radically polymerizable unsaturated monomer, A method for producing a living radical polymer, comprising: an introduction step of reacting a functional group-containing radical generator with the dormant terminal derived from the dormant of the precursor to introduce a terminal functional group structure derived from the functional group-containing radical generator in place of the dormant terminal.

12. A method for producing a living radical polymer according to claim 11, wherein the functional group-containing radical generator is represented by any of the following formulas (3) to (5). 【Transformation 5】 (In formula (3), R １ Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R ２ and R ３ These are, independently, hydrogen and C １～３ It is at least one group selected from alkyl groups and cyano groups, R ４ Each of them is independent of C １～３ (This is the alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety.) 【Transformation 6】 (In formula (4), R １ is, independently of each other, at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, R ２ and R ３ These are, independently, hydrogen and C １～３ It is at least one group selected from alkyl groups and cyano groups, R ４ Each of them is independent of C １～３ (This is the alkylene group, imino group, N-alkylene carboxylic acid amide moiety, or N-alkylene amidine moiety.) 【Transformation 7】 (In formula (5), R ５ Each of these is independently at least one functional group selected from a carboxyl group, a hydroxyl group, and an amino group. R ６ These are, independently, hydrogen and C １～３ alkyl and C １～３ (One or two groups selected from the alkoxy groups.)

13. A method for producing a living radical polymer according to any one of claims 11 to 12, wherein in the introduction step, a radical generator having a faster decomposition rate than the functional group-containing radical generator, and / or a nonmetallic compound having an ionic bond with an iodide ion are further used.

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