JP2011057822A - Modified pigment and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified pigment showing high dispersion stability to an organic solvent, and to provide a production method for obtaining the modified pigment applied to a pigment for general purpose and showing high dispersion stability to an organic solvent. <P>SOLUTION: The modified pigment has a modified polyamine (B) formed by reacting a vinyl copolymer (B-1), having a functional group reacting with an amino group to form an amide bond in one terminal, with an amino group of a polyamine; and a polymer (P) obtained by polymerizing at least one polymerizable unsaturated monomer (C) soluble in a non-aqueous solvent and made insoluble or hardly soluble after polymerization; on the surface of a pigment (A). A method for producing the same is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a modified pigment having a polymer on the pigment surface. More specifically, the modified pigment can be used as a coloring material for paint, plastic, printing ink, rubber, leather, textile printing, color filter, jet ink, thermal transfer ink, and the like. And a manufacturing method thereof.

Since pigments are generally insoluble colorants, it is an important issue to uniformly disperse pigment particles in a medium such as a solvent or resin in the production of paints, printing inks, color filters, etc. and the coloring of plastics. Yes.
Since the dispersibility of the pigment greatly depends on the properties of the surface of the pigment particles, attempts have been made to improve the dispersibility by various surface treatments. These treatment methods include rosin treatment, various surfactant treatments such as cationic surfactants, anionic surfactants, nonionic surfactants, pigment derivative treatments, and polymer treatments.

Among these treatment methods, polymer treatment methods for improving dispersibility by coating a pigment surface with a polymer include an in-situ polymerization method, a phase separation (coacervation) method, and a submerged drying method. .
Among them, for example, Patent Documents 1 to 6 describe in-situ polymerization methods that do not use water as a solvent. All of these are subjected to in-situ polymerization in a non-aqueous solvent having a dielectric constant of 1.5 to 20 and a surface tension of 15 to 60 mN / m. However, none of the methods described in this document is general-purpose because it is essential to use a surface-treated pigment and stably disperse the pigment with a specific dispersion stabilizer.

  On the other hand, the present inventors have at least one kind of polymer containing a polymerizable unsaturated group soluble in a non-aqueous solvent and a non-aqueous solvent which is insoluble or hardly soluble after polymerization. It has already been found that a pigment characterized by having a polymer obtained by polymerizing a polymerizable unsaturated monomer is excellent in dispersibility (see Patent Document 7).

Japanese Patent Laid-Open No. 2004-2501 Japanese Patent Laid-Open No. 2004-18736 JP 2004-35592 A JP 2004-083660 A JP 2004-107523 A JP 2004-107524 A JP 2008-88211 A

  An object of the present invention is to provide a modified pigment exhibiting high dispersion stability with respect to an organic solvent, and a production method for obtaining a modified pigment that can be applied to a general-purpose pigment and exhibits high dispersion stability with respect to an organic solvent.

  As a result of intensive studies to solve the above problems, the present inventor has found that the surface of the pigment (A) is soluble in the modified polyamine (B) and a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization. In order to complete the present invention, a modified pigment characterized by having a polymer (P) obtained by polymerizing a kind of polymerizable unsaturated monomer (C) exhibits high pigment dispersibility. It came.

  That is, the present invention provides a modified polyamine obtained by reacting a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond on one end with the amino group of the polyamine on the surface of the pigment (A). (B) and a modified polymer (P) obtained by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and insoluble or hardly soluble after polymerization Provide pigments.

  The present invention is also obtained by reacting the pigment (A) with an amino group of a polyamine and a vinyl copolymer (B-1) having a functional group that reacts with the amino group to form an amide bond at one end. A method for producing a modified pigment comprising polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and insoluble or hardly soluble after polymerization in the presence of the modified polyamine (B). provide.

Since the modified pigment of the present invention exhibits high dispersion stability in an organic solvent, the color when an organic solvent such as paint, plastic, printing ink, rubber, leather, textile printing, color filter, jet ink, or thermal transfer ink is used as a solvent. It is very useful as a material.
In addition, the method for producing a modified pigment of the present invention can be applied to general-purpose pigments regardless of whether they are untreated pigments, treated pigments, or organic / inorganic.

(Pigment (A))
The pigment (A) used in the present invention is at least one pigment selected from known and commonly used organic pigments or inorganic pigments. In addition, the present invention can be applied to either an untreated pigment or a treated pigment.

Examples of organic pigments include perylene / perinone compound pigments, quinacridone compound pigments, phthalocyanine compound pigments, anthraquinone compound pigments, phthalone compound pigments, dioxazine compound pigments, isoindolinone compound pigments, methine / azomethine compounds Examples thereof include compound pigments, diketopyrrolopyrrole compound pigments, insoluble azo compound pigments, and condensed azo compound pigments. Specific examples of the organic pigment are as follows, for example.
Examples of perylene / perinone compound pigments include C.I. I. PigmentViolet 29, C.I. I. Pigment Red 123, 149, 178, 179, C.I. I. Pigment Black 31, 32, C.I. I. Pigment Orange 43 and the like.
Examples of quinacridone compound pigments include C.I. I. Pigment Violet 19, 42, C.I. I. Pigment Red 122, 202, 206, 207, 209, C.I. I. Pigment Orange 48, 49 and the like.
Examples of the phthalocyanine compound pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, C.I. I. Pigment Green 7, 36, 58 and the like.
Examples of the anthraquinone compound pigment include C.I. I. Pigment Blue 60, C.I. I. Pigment Yellow 24, 108, C.I. I. Pigment Red 168, 177, C.I. I. Pigment Orange 40 and the like.
Examples of the phthalone compound pigment include C.I. I. And pigments such as Pigment Yellow 138.
Examples of the dioxazine compound pigment include C.I. I. Pigment Violet 23, 37, and the like.
Examples of isoindolinone compound pigments include C.I. I. Pigment Yellow 109, 110, 173, C.I. I. Pigment Orange 61 and the like.
Examples of methine / azomethine compound pigments include C.I. I. Pigment Yellow 139, 185, C.I. I. Pigment Orange 66, C.I. I. Pigment Brown 38 and the like.
Examples of the diketopyrrolopyrrole compound pigment include C.I. I. Pigment Red 254, 255 and the like.
Examples of insoluble azo compound pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 55, 73, 74, 81, 83, 97, 130, 151, 152, 154, 156, 165, 166, 167, 170, 171, 172, 174, 175, 176, 180, 181, 188, C.I. I. Pigment Orange 16, 36, 60, C.I. I. Pigment Red5, 22, 22, 31, 112, 146, 150, 171, 175, 176, 183, 185, 208, 213, C.I. I. PigmentViolet 43, 44, C.I. I. Pigment Blue 25, 26 and the like.
Examples of the soluble azo compound pigment include C.I. I. Pigment Red 53: 1, 57: 1, 48 and the like.
Examples of the condensed azo compound pigment include C.I. I. Pigment Yellow 93, 94, 95, 128, 166, C.I. I. Pigment Orange 31C. I. Pigment Red 144, 166, 214, 220, 221, 242, 248, 262, C.I. I. Pigment Brown 41, 42 and the like.

  Examples of inorganic pigments include titanium oxide, zinc sulfide, lead white, zinc white, lithbon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, silica, carbon black, and iron black. , Cobalt violet, vermillion, molybdenum orange, red lead, bengara, yellow lead, cadmium yellow, zinc chromate, yellow ocher, chromium oxide, ultramarine, bitumen, cobalt blue and the like.

  In the present invention, an organic pigment is particularly preferable because the effects of the present invention can be more exerted. The quinacridone compound pigment, the phthalocyanine compound pigment, the insoluble azo compound pigment, the condensed azo compound pigment, It is particularly preferable to use a diketopyrrolopyrrole compound pigment or a dioxazine compound pigment.

(Non-aqueous solvent)
The non-aqueous solvent used in the present invention is an organic solvent in which an aliphatic and / or alicyclic hydrocarbon solvent is essential. Examples of the aliphatic and / or alicyclic hydrocarbon solvents include n-hexane, n-heptane, “Loose” or “Mineral Split EC” manufactured by Shell Chemicals, and “Isopar C” manufactured by ExxonMobil Chemical. , “Isopar E”, “Isopar G”, “Isopar H”, “Isopar L”, “Isopar M”, “Naphtha 3”, “Naphtha 5” or “Naphtha 6”, products of Idemitsu Petrochemical Co., Ltd. “Solvent No. 7”, “IP solvent 1016”, “IP solvent 1620”, “IP solvent 2028” or “IP solvent 2835”, “Whitesol” of Japan Energy Co., Ltd., and the like.

Moreover, you may mix and use another organic solvent in the range which does not impair the effect of this invention. Specific examples of such organic solvents include “Swazole 100 or 150” manufactured by Maruzen Petroleum Corporation, aromatic hydrocarbon solvents such as toluene or xylene; methyl acetate, ethyl acetate, acetic acid-n. Esters such as butyl or amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; or alcohols such as methanol, ethanol, n-propanol, i-propanol or n-butanol Kind.
When mixed and used, the amount of the aliphatic and / or alicyclic hydrocarbon solvent used is preferably 50% by mass or more, and more preferably 60% by mass or more.

(Modified polyamine (B))
The modified polyamine (B) used in the present invention is a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at one end (hereinafter referred to as “reacting with an amino group to form an amide bond. The vinyl copolymer (B-1) having a functional group to be formed at one end is simply referred to as vinyl copolymer (B-1)) and is a modified polyamine (B) obtained by reacting the amino group of the polyamine. . Polyamines are generally known to have high adsorptivity to pigments, and the modified polyamine (B) of the present invention improves the dispersion stability of pigments in a hydrophobic solvent. As a result, it is considered preferable because the dispersed particle diameter of the modified pigment (D) obtained by polymerizing the polymerizable unsaturated monomer (C) described later on the pigment surface becomes finer.

(Polyamine)
The polyamine used in the present invention is a polymer having a repeating unit having a primary or secondary amino group. Such a polyamine is preferably at least one selected from the group consisting of polyallylamine, polyvinylamine and polyethyleneimine. Further, it may be a copolymer of polyallylamine, polyvinylamine, or polyethyleneimine and another polymerizable monomer.
When polyallylamine, polyvinylamine, or a copolymer of polyethyleneimine and another polymerizable monomer is used, the amine value of the polyamine of the present invention is preferably 50 or more, more preferably 300 or more. When the amine value is less than 50, the dispersibility of the modified pigment obtained due to insufficient adsorbing power to the pigment may be lowered. These polyamines may be used alone or in combination. Among these, from the viewpoint of industrial availability, polyallylamine or polyethyleneimine is preferable. Among them, polyallylamine is most preferable. The reason for this is that polyethyleneimine generally has a branched polymer structure, whereas polyallylamine has a linear polymer structure, so the amine has a high anchoring effect on the pigment. ing.
The number average molecular weight of the polyamine in the present invention is preferably 150 to 100,000, more preferably 600 to 20,000. If the number average molecular weight of the polyamine used in the present invention is less than 150, there is a risk that the pigment will be difficult to disperse due to insufficient adsorptive power to the pigment, whereas if it exceeds 100,000, the viscosity during reaction with the vinyl polymer may be increased. May increase or the gelation of the polymer, and the molecular weight of the polymer becomes too large, and the dispersibility may be lowered due to aggregation of the pigments.

(Polyallylamine)
The polyallylamine used in the present invention may be obtained by polymerizing allylamine in the presence of a polymerization initiator, optionally in the presence of a chain transfer catalyst, by a known method, or a commercially available product may be used. As a commercial item, it sells as polyallylamine series, such as PAA-01, PAA-03, PAA-05, PAA-15, PAA-10C, from Nitto Boseki Co., Ltd., for example.

(Polyvinylamine)
The polyvinylamine used in the present invention is, for example, a variety of known polymers such as N-vinylformamide polymerized by a known method in the presence of a polymerization initiator, optionally in the presence of a chain transfer catalyst, and then subjected to a hydrolysis reaction. It can be obtained by the method.

(Polyethyleneimine)
The polyethyleneimine used in the present invention may be obtained by polymerizing ethyleneimine by a known method, or a commercially available product may be used. As a commercial item, it is marketed as a polyethyleneimine series, such as SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000, from Nippon Shokubai Co., Ltd., for example.

(Vinyl copolymer (B-1))
In the vinyl copolymer (B-1) used in the present invention, functional groups that react with amino groups to form amide bonds include carboxyl groups, haloformyl groups such as chloroformyl groups, and oxycarbonyl groups such as methoxycarbonyl groups. Is mentioned. Among these, a carboxyl group is preferable because it can be easily introduced into a vinyl copolymer.
In order to obtain a vinyl copolymer having a carboxyl group at one end, for example, a method of coexisting a chain transfer agent having a carboxyl group at the time of polymerization can be mentioned. Examples of the chain transfer agent having a carboxyl group include thiocarboxylic acids such as mercaptoacetic acid, 2-mercaptopropionic acid, and 3-mercaptopropionic acid. It can also be obtained by a method of synthesizing a polymerizable monomer by a living radical polymerization method using a polymerization initiator having a carboxyl group such as 4,4′-azobis-4-cyanopentanoic acid.

Examples of the polymerizable monomer used as a raw material for the vinyl copolymer (B-1) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Homopolymers of (meth) acrylic acid alkyl esters such as these, or between these esters or these esters, alkenyl benzenes such as styrene, α-methyl styrene, vinyl toluene, vinyl acetate, vinyl pyridine, acrylamide, methacryl Examples include amides, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and the like. Among these, one kind or two or more kinds can be used.
However, it is preferable not to use a polymerizable monomer that has a functional group that reacts with an amino group to form an amide bond, for example, a functional group that is equivalent to or more highly reactive with an amino group than a carboxyl group. The vinyl polymer containing the polymerizable monomer as a raw material is not only the terminal of the vinyl copolymer but also the functional group is randomly grafted to the main chain of the copolymer, so that it reacts with polyallylamine. There is a possibility of gelling inside, and the performance of the resulting modified pigment may be deteriorated. Specifically, polymerizable monomers such as butadiene, isoprene, chloroprene, (meth) acrylic acid, itaconic acid, and maleic anhydride have groups that are highly reactive with amino groups. It is preferable not to use it as a raw material for the union (B-1).

  The vinyl copolymer (B-1) can be obtained by heating the above various polymerizable monomers in a reaction vessel in the presence of a polymerization initiator and aging as necessary. The reaction conditions vary depending on, for example, the polymerization initiator and the solvent, but the reaction temperature is 30 to 150 ° C, preferably 60 to 120 ° C. The polymerization can be carried out in the presence of a non-reactive solvent.

  Examples of the polymerization initiator include peroxides such as t-butyl peroxybenzoate, di-t-butyl peroxide, cumene perhydroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide; azobisisobutylnitrile, Examples thereof include azo compounds such as azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.

  Non-reactive solvents include, for example, aliphatic hydrocarbon solvents such as hexane and mineral spirits; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as butyl acetate; methanol, butanol and the like And alcohol solvents such as: aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and pyridine. These solvents may be used in combination. As these solvents, those capable of dissolving the obtained vinyl copolymer (B-1) can be appropriately selected and used.

  The molecular weight of the vinyl copolymer (B-1) used in the present invention is preferably in the range of number average molecular weight of 500 to 100,000, and more preferably in the range of 1000 to 20,000. If the number average molecular weight is less than 500, sufficient steric repulsion effect as a pigment dispersant may not be maintained, and if it exceeds 100,000, the viscosity of the vinyl polymer is increased and the solvent solubility is decreased. In some cases, the performance of the modified pigment is reduced.

Further, the modified polyamine (B) in the present invention is one or more selected from the group consisting of the vinyl copolymer (B-1) and the following (B-2) to (B-5) as the polyamine. It is preferable to react with the above compound.

  (B1) A vinyl copolymer having a functional group that reacts with an amino group at one end, wherein the amount of the functional group that reacts with an amino group, the copolymer composition, or the copolymer composition ratio is the vinyl copolymer (B A vinyl copolymer (B-2) different from -1).

  As the vinyl copolymer (B-2), a vinyl copolymer (B-2-1) is preferable. The vinyl copolymer (B-2-1) includes a weight% of a functional group that reacts with an amino group at one end of the vinyl copolymer (B-1), and the vinyl copolymer (B-2-1). 1) The ratio by weight of the functional group that reacts with the amino group at one end is in the range of 0.4 to 0.8, and the molar ratio (B) with the vinyl copolymer (B-1) -1) / (B-2-1) is preferably reacted with the modified polyamine so that (B-1) / (B-2-1) = 0.25 to 4.0. (Hereinafter referred to as vinyl copolymer (B-2-1))

  Moreover, as said vinyl copolymer (B-2), a vinyl copolymer (B-2-2) is preferable. The vinyl copolymer (B-2) is a vinyl copolymer obtained by polymerizing a plurality of vinyl monomers. The Tg of the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2) ) Has a Tg difference of 20 ° C. or more, and a molar ratio (B-1) / (B-2) between the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2). -2) is preferably reacted with the modified polyamine such that (B-1) / (B-2-2) = 0.25-4.0. (Hereinafter referred to as vinyl copolymer (B-2-2))

  (B2) (Meth) acrylate (B-3) having a polyalkylene glycol chain. (Hereinafter referred to as (meth) acrylate (B-3)). Among them, it is preferable that the polyalkylene glycol chain reacts with the modified polyamine so as to have a ratio of 1 to 30% by weight with respect to the whole molecule.

  (B3) Polyester having a functional group that reacts with an amino group at one end, Polyamide having a functional group that reacts with an amino group at one end, or Polyesteramide having a functional group that reacts with an amino group at one end (B-4) (Hereinafter referred to as polymer (B-4)). In particular, the modified polyamine is preferably reacted with the modified polyamine so that these residues have a ratio of 1 to 50% by weight based on the whole molecule.

  (B4) Monocarboxylic acid or (meth) acrylate (B-5). Among these, it is preferable to react with the modified polyamine so that these residues have a ratio of 1 to 30% by weight based on the whole molecule.

((B1) Vinyl copolymer (B-2-1))
The vinyl copolymer (B-2-1) is a copolymer having a functional group that reacts with an amino group at one end and is different from the vinyl copolymer (A). Weight% of functional group reacting with amino group at one end of compound (B-1), and weight% of functional group reacting with amino group at one end of vinyl copolymer (B-2-1) The molar ratio (B-1) / (B-2-1) with the vinyl copolymer (B-1) is (B-1). ) / (B-2-1) = 0.25-4.0 It is preferable that it reacts with the modified polyamine.
Specifically, the vinyl copolymer (B-2-1) is a vinyl copolymer having a carboxyl group, and a copolymer having a molecular weight different from that of the vinyl copolymer (B-1). The molecular weight is adjusted by the content of the carboxyl group at one end of the vinyl copolymer. The weight percentage of the carboxyl group in the vinyl copolymer is preferably in the range of 1 to 10, and the vinyl copolymer ( The ratio of the weight percent of the carboxyl group at one end of B-1) to the weight percent of the carboxyl group at one end of the vinyl copolymer (B-2-1) is 0.4 to 0.8. A range is preferred. (However, it is assumed that the vinyl copolymer (B-2-1) at this time has a higher molecular weight than the vinyl copolymer (B-1).)
In addition, the vinyl polymer (B-2-1) residual chain (the vinyl polymer (B-2-1) residual chain as used herein refers to the remaining portion reacted with the carboxyl group) and the vinyl copolymer (B -1) The ratio of the residual chain is such that the molar ratio (B-1) / (B-2-1) with the vinyl copolymer (B-1) is (B-1) / (B-2-1) = 0.25 to 4.0 is preferable.

((B1) Vinyl copolymer (B-2-2))
The vinyl copolymer (B-2-2) is obtained by polymerizing a plurality of vinyl monomers, and the difference between the Tg of the vinyl copolymer (B-1) and the Tg of the vinyl copolymer (B2) is It is a vinyl copolymer having a temperature of 20 ° C or higher. Here, Tg is defined as a value measured by DSC (Differential Scanning Calorimetry) or tB-1nδ peak of dynamic viscoelasticity.
As described above, the molar ratio (B-1) / (B-2-2) between the vinyl copolymer (B-1) and the vinyl copolymer (B-2-2) is (B-1 ) / (B-2-2) = 0.25-4.0 It is preferable that it reacts with the modified polyamine.
Specifically, the Tg of the vinyl copolymer (B-2-2) is preferably 100 ° C. to −50 ° C., and it varies depending on the Tg of the vinyl copolymer (B-1). It is particularly preferred that the temperature is from -50 ° C to -50 ° C.

((B2) (Meth) acrylate (B-3))
In the (meth) acrylate (B-3), having a polyalkylene glycol chain means a state of polyalkylene glycol (meth) acrylate. Specific examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, and mixtures thereof. Among them, polyethylene glycol and polypropylene glycol are preferable.
The (meth) acrylate (B-3) is preferably reacted with the modified polyamine so that the polyalkylene glycol chain has a ratio of 1 to 30% by weight with respect to the whole molecule.

((B3) Polymer (B-4))
Specifically, the polymer (B-4) is any one of the following polymers (b3-1) to (b3-3).
(B3-1) polyester having a functional group that reacts with an amino group at one end;
(B3-2) Polyamide having a functional group that reacts with an amino group at one end (b3-3) Polyesteramide having a functional group that reacts with an amino group at one end

(B3-1) The polyester having a functional group that reacts with an amino group at one end is specifically a polyester having a carboxyl group at the end. This can be synthesized by various methods as follows.
(B-1) an addition reaction for adding a lactone compound to a monocarboxylic acid compound, (b) an addition reaction for adding a lactone compound to a hydroxycarboxylic acid compound, (c) a monocarboxylic acid compound, a hydroxycarboxylic acid compound, and a lactone compound Examples thereof include a condensation reaction in which three components are condensed.

  (B3-2) The polyamide having a functional group that reacts with an amino group at one end is specifically a polyamide having a carboxyl group at the end. This is prepared from lactams such as ε-caprolactam and ω-laurolactam, and aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid.

  (B3-3) The polyesteramide having a functional group that reacts with an amino group at one end is specifically a co-condensate of an ester and an amide having a carboxyl group at the end. This can be prepared by co-condensing hydroxycarboxylic acid, lactone and the like used in the production of the polyester and polyamide with aminocarboxylic acid and lactam.

  The polymer (B-4) is preferably reacted with the modified polyamine so that these residues have a ratio of 1 to 50% by weight based on the whole molecule. Here, the residue represents the remaining polymer portion reacted with the carboxyl group.

((B4) monocarboxylic acid or (meth) acrylate (B-5))
The monocarboxylic acid is not particularly limited as long as it is a compound having one carboxylic acid group in one molecule, and specifically, acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, octylic acid, lauric acid, Examples include aliphatic monocarboxylic acids such as myristic acid, palmitic acid, stearic acid, isononanoic acid, and arachidic acid, and aromatic monocarboxylic acids such as benzoic acid and p-butylbenzoic acid.

The (meth) acrylate used in the present invention is, for example, (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Homopolymers of acid alkyl esters, or between these esters or these esters with alkenylbenzene such as styrene, α-methylstyrene, vinyltoluene, and vinyl acetate, vinylpyridine, acrylamide, methacrylamide, dimethylamino methacrylate Examples thereof include copolymers with ethyl, N-methylolacrylamide, N-butoxymethylacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
It is preferable that the monocarboxylic acid and the (meth) acrylate react with the modified polyamine so as to have these residues in a proportion of 1 to 30% by weight with respect to the whole molecule. Here, the residue represents the remaining monocarboxylic acid or (meth) acrylate reacted with the carboxyl group.

(Reaction between polyamine and vinyl copolymer (B-1))
The reaction between the polyamine and the vinyl copolymer (B-1) or the mixture of the vinyl copolymer (B-1) to the compound (B-5) is, for example, 200 ° C. or less under a nitrogen gas stream. Can be done. For the reaction, a known polymerization catalyst such as tin-based or titanium-based may be used. If necessary, a non-reactive solvent such as toluene, xylene, or solvesso that does not participate in the reaction can be used. It is not always necessary to remove the solvent used.

  The graft ratio of the vinyl copolymer (B-1) to the polyamine is preferably in the range of about 20 to 95%, and in the range of 30 to 90%, the affinity with the diluting solvent and the film-forming resin. And is particularly preferred because of its excellent balance of affinity with the pigment. Here, the graft ratio represents the reaction amount of the carboxyl group of the vinyl copolymer (B-1) with respect to the total amount of amino groups of the polyamine, and is through the amide bond of the modified polyamine of the present invention. Vinyl copolymer (B-1) Remaining chain (here, vinyl copolymer (B-1) The remaining chain refers to the remaining portion where the carboxyl group has reacted).

  When the residual chain of the vinyl copolymer (B-1) of the modified polyamine is less than 20%, the pigments are likely to aggregate with each other, and the insufficient viscosity reduction effect and the ink film may be affected. Further, when the residual chain of the vinyl copolymer (B-1) possessed by the modified polyamine exceeds 95%, the amino group which is a functional group that adsorbs to the pigment is insufficient, and dispersion stability tends to decrease depending on the pigment. In some cases, the effect of lowering the viscosity is insufficient and the ink film is defective.

(Reaction of polyamine with one or more compounds selected from the group consisting of (B-2) to (B-5))
The reaction between the polyamine and one or more compounds selected from the group consisting of (B-2) to (B-5) can be performed, for example, at 200 ° C. or lower under a nitrogen gas stream. For the reaction, a known polymerization catalyst such as tin-based or titanium-based may be used. If necessary, a non-reactive solvent such as toluene, xylene, or solvesso that does not participate in the reaction can be used. The solvent used is not necessarily removed and can be used as it is as one component of the pigment dispersant.
The reaction between the polyamine and one or more compounds selected from the group consisting of (B-2) to (B-5) is sequentially performed even at the same time as the vinyl copolymer (B-1). It doesn't matter.

(Other ingredients)
The modified polyamine (B) used in the present invention may contain a non-reactive solvent used in the production of the modified polyamine (B), and after the non-reactive solvent used in the production is distilled off, A new solvent may be added.

  In order to give the modified polyamine (B) used in the present invention a crosslinking point with the polymer (P) obtained by polymerizing the polymerizable unsaturated monomer (C) described later, a polymerizable unsaturated group It is also preferable to introduce. This is because the surface of the pigment can be more firmly coated by crosslinking the polymer (P) and the modified polyamine (B). As a method for introducing a polymerizable unsaturated group into the modified polyamine (B), for example, after reacting a polyamine and a vinyl copolymer (B-1), a glycidyl methacrylate is added to introduce a polymerizable unsaturated group. There are ways to do it.

(Polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization)
The polymerizable unsaturated monomer (C) used in the present invention that is soluble in the non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is specifically exemplified by methyl (meth) acrylate, ethyl ( Such as olefins such as (meth) acrylate, n-propyl (meth) acrylate or i-propyl (meth) acrylate, or (meth) acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride, Vinyl monomers having no so-called reactive polar groups (functional groups); (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide , Dimethylaminopropylacrylamide or alkoxylated N-methyl Amide bond-containing vinyl monomers such as rolled (meth) acrylamides; dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates, or dialkyl [(meth) acryloyloxy Alkyl] phosphites or (meth) acryloyloxyalkyl acid phosphites; alkylene oxide adducts of the above (meth) acryloyloxyalkyl acid phosphates or acid phosphites, glycidyl (meth) acrylates, methyl glycidyl (meta ) Ester compounds of epoxy group-containing vinyl monomers such as acrylate and phosphoric acid or phosphorous acid or their acidic esters, as well as 3-chloro-2-acid phosphoxypropipropylene Phosphorus atom-containing vinyl monomers such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-2-hydroxyethyl monobutyl fumarate Alternatively, polymerizable unsaturated carbo such as polypropylene glycol or polyethylene glycol mono (meth) acrylate, or “Placcel FM, FA monomer” (a caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.) Hydroxyalkyl esters of acids or their adducts with ε-caprolactone, and unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid In addition, polymerizable unsaturated carboxylic acids such as monoesters of these dicarboxylic acids and monohydric alcohols, or the above-mentioned polymerizable unsaturated carboxylic acid hydroxyalkyl esters and maleic acid, succinic acid, phthalic acid, hexa Various unsaturations such as adducts with anhydrides of polycarboxylic acids such as hydrophthalic acid, tetrahydrophthalic acid, hensentricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynyl succinic acid Carboxylic acids and “Cardura E”, palm oil fatty acid group Monoglycidyl esters of monovalent carboxylic acids such as sidyl esters or glycidyl octyl esters or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide, or adducts thereof with ε-caprolactone or Hydroxyl-containing polymerizable unsaturated monomers such as hydroxy vinyl ether; Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Glycidyl (meth) acrylate, (β- Methyl) glucidyl (meth) acrylate, (meth) allyl glycidyl ether or polymerizable unsaturated carboxylic acids or mono-2- (meth) acryloyloxymonoethyl phthalate, etc. Various unsaturated carboxylic acids such as an equimolar adduct of an acid group-containing vinyl monomer and the polycarboxylic acid anhydride are added to “Epicron 200”, “Epicron 400”, “Epicron 441”, “Epicron 850” or “Epicron”. "Epicron 1050" (epoxy resin manufactured by DIC Corporation), or "Epicoat 828", "Epicoat 1001" or "Epicoat 1004" (epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.), "Araldite 6071" or "Araldite 6084" ( 1 such as “Chissonox 221” (epoxy compound manufactured by Chisso Corporation) or “Denacol EX-611” (epoxy compound manufactured by Nagase Kasei Co., Ltd.) Has at least two epoxy groups in the molecule Epoxy group-containing polymerizable unsaturated monomers such as an epoxy group-containing polymerizable compound obtained by addition reaction of various polyepoxy compounds at an equimolar ratio; 2-hydroxyethyl (meth) acrylate-hexamethylene diisocyanate, etc. Isocyanate group-containing α, β-ethylenically unsaturated monomers such as molar adducts and monomers having an isocyanate group and a vinyl group such as isocyanate ethyl (meth) acrylate; vinyl ethoxysilane, α-methacryloxypropyl Alkoxysilyl group-containing polymerizable unsaturated monomers such as silicon monomers such as trimethoxysilane, trimethylsiloxyethyl (meth) acrylate, “KR-215, X-22-5002” (product of Shin-Etsu Chemical Co., Ltd.) And (meth) acrylic acid, crotonic acid, maleic acid , Α, β-ethylenically unsaturated carboxylic acids such as unsaturated mono- or dicarboxylic acids such as fumaric acid, itaconic acid or citraconic acid, monoesters of these dicarboxylic acids with monohydric alcohols, or 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, such as 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol mono (meth) acrylate -Unsaturated cal Acid hydroalkyl esters and polyacids such as maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid", tetrachlorophthalic acid or dodecynyl succinic acid Examples include carboxyl group-containing α, β-ethylenically unsaturated monomers such as adducts of carboxylic acid anhydrides.
Of these, the use of C3 or lower alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate is preferred. Furthermore, in order to change the surface characteristics of the pigment surface and enhance the interaction with the pigment dispersant or pigment dispersion resin, at least one kind of carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, dimethylamino group, etc. It is preferable to copolymerize a polymerizable unsaturated monomer containing a functional group.

  In order to prevent the modified polyamine (B) and the polymer (P) from eluting from the pigment (A) when the modified pigment is used, it is more preferable that the polymer is crosslinked. Examples of the polyfunctional polymerizable unsaturated monomer used as the crosslinking component include divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri Ethoxytri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Sa (meth) acrylate or allyl methacrylate, and the like.

  Further, in a use range in which a polymer having an essential component of a polymerizable unsaturated monomer (C) which is soluble in at least one non-aqueous solvent and becomes insoluble or hardly soluble after polymerization is not dissolved in the non-aqueous solvent system. Other polymerizable unsaturated monomers may be used. Examples of other polymerizable unsaturated monomers include polymerizable unsaturated monomers that can be used other than the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms and the alkyl (meth) acrylate described above. A monomer is mentioned.

The modified pigment of the present invention is at least one polymerizable unsaturated monomer that is soluble in a non-aqueous solvent and insoluble or hardly soluble after polymerization in the presence of the pigment (A) and the modified polyamine (B). It is obtained by polymerizing the body (C).
The pigment (A) and the modified polyamine (B) are preferably mixed before polymerization. By mixing, the surface of the pigment (A) is wetted with the modified polyamine (B), and the interface formed by this (the pigment (A) and the modified polyamine (B)) is considered to be the place of polymerization. After mixing the pigment (A) and the modified polyamine (B), the polymerizable unsaturated monomer (C) is further mixed and polymerized to be coated with the modified polyamine (B) and the polymer (P). Modified pigments are obtained. In this method, that is, the case where the pigment (A) is finely and stably dispersed with the dispersion stabilizer is not essential, and therefore the surface treatment of the pigment (A) to form a finely dispersed state is always necessary. Rather, it can be applied to a wide variety of pigments.

As a mixing method, for example, a homogenizer, a disper, a bead mill, a paint shaker, a kneader, a roll mill, a ball mill, an attritor, a sand mill and the like can be used. In the present invention, the form of the pigment to be used is not limited, and any form of slurry, wet cake, and powder may be used. That is, in the production method of the present invention, even a pigment containing water such as a wet cake can be used.
After the pigment (A) and the modified polyamine (B) are mixed, the polymerizable unsaturated monomer (C) and a polymerization initiator described later are further mixed and polymerized to obtain a modified pigment.
At that time, the amount of the modified polyamine (B) is not particularly limited since it is appropriately optimized depending on the purpose, but usually 1 to 200 parts is used with respect to 100 parts of the pigment (A), more preferably. 2 to 50 parts, more preferably 3 to 30 parts.
Further, the amount of the polymerizable unsaturated monomer (C) used is not particularly limited because it is appropriately optimized depending on the purpose, but usually 1 to 200 parts per 100 parts of the pigment (A). More preferably 2 to 50 parts, still more preferably 3 to 30 parts.

  The amount of the modified polyamine (B) and polymer (P) finally coated on the pigment is preferably 2 to 400 parts, more preferably 4 to 100 parts, relative to 100 parts of the pigment (A). More preferably, it is 6-60 parts. In that case, it is preferable to use at least 1 sort of said polymerizable unsaturated monomer (C) normally in the ratio of 10-400 parts with respect to 100 parts of said modified polyamine (B), Preferably 30- 400 parts, more preferably 50 to 200 parts.

The method of polymerizing the polymerizable unsaturated monomer (C) in the presence of the pigment (A), the non-aqueous solvent, and the modified polyamine (B) may be performed by a known and conventional polymerization method. Usually, it is carried out in the presence of a polymerization initiator. Such polymerization initiators include azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylbutyronitrile), benzoyl peroxide, t-butyl perbenzoate, t-butyl-2-ethylhexano A radical generating polymerization catalyst such as ate, t-butyl hydroperoxide, di-t-butyl peroxide, or cumene hydroperoxide may be used alone or in combination of two or more.
Since some polymerization initiators are difficult to dissolve in the non-aqueous solvent system, a method in which the polymerization initiator is dissolved in the polymerizable unsaturated monomer (C) and added to the mixed system of the pigment (A) and the modified polyamine (B) is preferable. .
The polymerizable unsaturated monomer (C) or the polymerizable unsaturated monomer (C) in which the polymerization initiator is dissolved can be added by a dropping method in a state where the polymerization temperature is reached. A method of adding the polymer at a normal temperature before warming, heating the polymer after sufficiently mixing, and polymerizing is stable and preferable.
The polymerization temperature is usually in the range of 60 ° C to 130 ° C. In addition, when the pigment (A) is an organic pigment, if the polymerization temperature is too high, the pigment may undergo significant changes in form such as alteration and crystal growth. In that case, it is preferable to polymerize at 70 to 100 ° C.

  After the polymerization, the nonaqueous solvent used for the polymerization is removed by filtration, followed by drying and pulverization to obtain a powdery polymer-coated pigment. Nutsche, filter press, etc. can be used for the filtration method. Moreover, it can dry with well-known drying apparatuses, such as a box-type dryer, a vacuum dryer, a band dryer, and a spray dryer. For the pulverization, a known pulverizer such as a mortar, a hammer mill, a disk mill, a pin mill, or a jet mill can be used.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “parts” and “%” are based on mass.

<Synthesis Example 1 Synthesis of Vinyl Polymer (X1)>
100 parts of xylene and 10 parts of thioglycolic acid were kept at 80 ° C. in a nitrogen stream, and while stirring, 54 parts of methyl methacrylate, 36 parts of butyl acrylate, and a polymerization initiator (“Perbutyl (registered trademark) O” [active ingredient A mixture consisting of 2 parts of peroxy 2-ethylhexanoate t-butyl, manufactured by Nippon Oil & Fats Co., Ltd.] was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, xylene was added to adjust the nonvolatile content to obtain a xylene solution (X1) of a vinyl copolymer having a nonvolatile content of 50% and having a carboxyl group at one end. The resin had a mass average molecular weight of 5000 and an acid value of 60.5 mgKOH / g.

<Synthesis Example 2 Synthesis of Vinyl Polymer (X2)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream, 68 parts of ethyl methacrylate, 29 parts of 2-ethylhexyl methacrylate, 3 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl (registered trademark) O” [ The active ingredient peroxy 2-ethylhexanoate t-butyl, manufactured by Nippon Oil & Fats Co., Ltd.]) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, xylene was added to adjust the non-volatile content to obtain a xylene solution of a vinyl copolymer (X2) having a non-volatile content of 50% and having a carboxyl group at one end. The weight average molecular weight of the resin was 7000, the acid value was 18.0 mgKOH / g, and the glass transition temperature Tg was 38 ° C.

<Synthesis Example 3 Synthesis of Vinyl Polymer (X3)>
While maintaining 100 parts of xylene at 80 ° C. in a nitrogen stream, stirring, 66 parts of ethyl methacrylate, 28 parts of 2-ethylhexyl methacrylate, 6 parts of thioglycolic acid, and a polymerization initiator (“Perbutyl (registered trademark) O” [ The active ingredient peroxy 2-ethylhexanoate t-butyl, manufactured by NOF Corporation] was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 part of “Perbutyl (registered trademark) O” was added every 4 hours and stirred at 80 ° C. for 12 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the non-volatile content to obtain a xylene solution of a vinyl copolymer (X3) having a non-volatile content of 50% and having a carboxyl group at one end. The weight average molecular weight of the resin was 4000, the acid value was 36.0 mgKOH / g, and the glass transition temperature Tg was 38 ° C.

<Synthesis Example 4 Synthesis of Vinyl Polymer (X4)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 30 parts of ion-exchanged water and 30 parts of isopropyl alcohol are kept at 80 ° C. in a nitrogen stream, and 40 parts of N-vinylformamide are added while stirring. A mixture consisting of 8 parts of mercaptoethanol and 0.8 part of a polymerization initiator (“Perbutyl (registered trademark) O” [active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation)] takes 4 hours. And dripped. After completion of the reaction, an appropriate amount of ion-exchanged water was added to adjust the nonvolatile content to obtain a vinyl polymer (X4) having a nonvolatile content of 40%.

<Synthesis Example 5 Synthesis of Polyvinylamine Copolymer (PA-1)>
A flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer was 125 parts of the vinyl polymer (X4) having a non-volatile content of 40% obtained in Synthesis Example 4 and 141 parts of a 20% sodium hydroxide solution. In addition, the mixture was reacted at 80 ° C. for 16 hours with stirring. After completion of the reaction, acetone was added to precipitate the resin component, followed by separation and drying to obtain a solid content of the polyvinylamine copolymer (PA-1). The amine value of the polyvinylamine copolymer (PA-1) was 1174 mg KOH / g, and the hydrolysis rate of N-vinylformamide calculated from the amine value was 90%.

<Synthesis Example 6 Synthesis of Polyvinylamine Copolymer (PA-2)>
A flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, 125 parts of the vinyl polymer (X4) having a non-volatile content of 40% obtained in Synthesis Example 4 and 42 parts of a 20% sodium hydroxide solution In addition, the mixture was reacted at 80 ° C. for 2 hours with stirring. After completion of the reaction, acetone was added to precipitate the resin component, followed by separation and drying to obtain a solid content of the polyvinylamine copolymer (PA-2). The amine value of the polyvinylamine copolymer (PA-2) was 305 mg KOH / g, and the hydrolysis rate of N-vinylformamide calculated from the amine value was 23%.

<Synthesis Example 7 Synthesis of Modified Polyamine (BJ-1)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 100 parts of xylene and 20% aqueous solution of polyallylamine (“PAA-05” manufactured by Nittobo Co., Ltd., number average molecular weight of about 5,000) A mixture consisting of 37.5 parts was charged, stirred at 140 ° C. with stirring under a nitrogen stream, water was distilled off using a separator, and xylene was returned to the reaction solution while being mixed with Synthesis Example 1 The vinyl copolymer (X1) obtained in (1) (used as the vinyl copolymer (B-1) in the present application) 168.8 parts of which was heated to 140 ° C was added, and the reaction was carried out at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-1) having a nonvolatile content of 40%. The resin had a mass average molecular weight of 7,500 and an amine value of 32.5 mg KOH / g.

<Synthesis Example 8 Synthesis of Modified Polyamine (BJ-2)>
In a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube and a thermometer, 54.5 parts of xylene, the vinyl copolymer (X2) obtained in Synthesis Example 2 (the vinyl copolymer (B-1 in this application)) )) 19.0 parts, vinyl copolymer (X2) obtained in Synthesis Example 3 (used as vinyl copolymer (B-2-1) in the present application) 38.0 parts, and polyallylamine 20% aqueous solution (Nittobo Co., Ltd. “PAA-05”, number average molecular weight of about 5,000) was charged with a mixture of 7.5 parts, stirred at 140 ° C. while stirring under a nitrogen stream, and water was removed using a separator. The reaction was carried out at 140 ° C. for 8 hours while returning xylene to the reaction solution.
After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-2) having a nonvolatile content of 40%. The resin had a weight average molecular weight of 10,000 and an amine value of 22.0 mg KOH / g.

<Synthesis Example 9 Synthesis of Modified Polyamine (BJ-3)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube, and thermometer, 10.5 parts of 20% aqueous solution of polyallylamine “PAA-03” and polyethylene glycol-polypropylene glycol monomethacrylate (manufactured by NOF Corporation) "Blemmer 70PEP-350B", average ethylene glycol chain number 5, average propylene glycol chain number 2) (used as (meth) acrylate (B-3) in the present application) 1.5 parts, and stirring at 50 ° C under a nitrogen stream And stirred for 3 hours. Next, 35.2 parts of xylene and 52.8 parts of the vinyl copolymer (X3) obtained in Synthesis Example 3 (used as the vinyl copolymer (B-1) in the present application) were charged, and the mixture was stirred at 140 ° C. under a nitrogen stream. The reaction was carried out at 140 ° C. for 8 hours while returning water to the reaction solution while distilling off water using a separator. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-3) having a nonvolatile content of 40%. The weight average molecular weight of the resin was 8,000, and the amine value was 31.0 mg KOH / g.

<Synthesis Example 10 Synthesis of Modified Polyamine (BJ-4)>
To a flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube and a thermometer, 100 parts of the modified polyamine (BJ-3) having a nonvolatile content of 40% obtained in Synthesis Example 9 and 1.6 parts of glycidyl methacrylate were added. , And reacted at 80 ° C. for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-4) having a nonvolatile content of 40% and having a methacryloyl group.

<Synthesis Example 11 Synthesis of Modified Polyamine (BJ-5)>
In a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 11 parts of xylene and 7.5 parts of polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., average molecular weight of about 600) In addition, the mixture was stirred at 140 ° C. while stirring under a nitrogen stream, and water was distilled off using a separator, while the xylene was returned to the reaction solution, and the vinyl copolymer obtained in Synthesis Example 1 ( X1) (Used as vinyl copolymer (B-1) in the present application) 168.8 parts of a mixture heated to 140 ° C were added, and the reaction was carried out at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the nonvolatile content to obtain a modified polyamine (BJ-5) having a nonvolatile content of 40%.

<Synthesis Example 12 Synthesis of Modified Polyamine (BJ-6)>
To a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube and thermometer, 11 parts of xylene and 7.5 parts of the polyvinylamine copolymer (PA-1) obtained in Synthesis Example 5 were added, While stirring, the mixture is stirred at 140 ° C., and water is distilled off using a separation device. While returning xylene to the reaction solution, the vinyl copolymer (X1) obtained in Synthesis Example 1 (in this application) (Used as vinyl copolymer (B-1)) 152 parts heated to 140 ° C were added and reacted at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the water content in the reaction solution to obtain a nonvolatile content, to obtain a modified polyamine (BJ-6) having a nonvolatile content of 40%.

<Synthesis Example 13 Synthesis of Modified Polyamine (BJ-7)>
To a flask equipped with a stirrer, reflux condenser, nitrogen blowing tube, and thermometer, 11 parts of xylene and 7.5 parts of the polyvinylamine copolymer (PA-2) obtained in Synthesis Example 6 were added. While stirring, the mixture is stirred at 140 ° C., and water is distilled off using a separation device. While returning xylene to the reaction solution, the vinyl copolymer (X1) obtained in Synthesis Example 1 (in this application) (Used as vinyl copolymer (B-1)) 42.2 parts heated to 140 ° C were added and reacted at 140 ° C for 8 hours. After completion of the reaction, an appropriate amount of xylene was added to adjust the water content in the reaction solution to obtain a non-volatile content, thereby obtaining a modified polyamine (BJ-7) having a non-volatile content of 40%.

<Comparative Synthesis Example 1 Synthesis of Polymer (BH-1)>
A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 800 parts of heptane and 170 parts of butyl acetate, and the temperature was raised to 90 ° C. A mixture comprising 950 parts of 2-ethylhexyl acid, 50 parts of dimethylaminoethyl methacrylate, and 7 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 5 hours, and the same temperature was maintained after completion of the addition. For 10 hours to continue the reaction. Thereafter, a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 15 parts of butyl acetate was added, and further 15 parts of glycidyl methacrylate and 30 parts of dimethylaminoethanol were added, and the temperature was raised to 80 ° C. By performing the reaction at the same temperature for 10 hours, a polymer (BH-1) solution containing a polymerizable unsaturated group soluble in a non-aqueous solvent was obtained.

Example 1 Synthesis of Modified Pigment (1)
208 parts of a wet cake (pigment content 48%) of Fast Gen Blue FGF (DIC Corporation blue pigment), 20 parts of the modified polyamine (BJ-1) obtained in Synthesis Example 1 (in terms of solid content). 300 parts of 25 mm zirconia beads and 300 parts of heptane were placed in a polyethylene jar and mixed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.). After dilution with 200 parts of heptane, the zirconia beads were removed to prepare a pigment mixture.
400 parts of the obtained pigment mixed solution was charged into a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, and then t-butylacrylamidesulfonic acid as a polymerizable monomer (C). 2 parts dissolved in 20 parts of ion-exchanged water are added, and 2 parts of 2,2′-azobis (2-methyl) are added to a polymerizable monomer composition of 3 parts of methyl methacrylate and 5 parts of ethylene glycol dimethacrylate. A solution of 2 parts of butyronitrile was added. After stirring for 30 minutes at room temperature, the temperature was raised to 80 ° C., and the reaction was continued for 15 hours at the same temperature. After cooling, the modified pigment and the polymerization solvent were separated by filtration. The obtained modified pigment was dried with a hot air dryer at 100 ° C. for 5 hours and then pulverized with a pulverizer to obtain a modified pigment (1).

<Examples 2 to 17 and Comparative Example 1 Synthesis of Modified Pigments (2) to (17) and Comparative Modified Pigment (1)>
A pigment mixture was prepared in the same manner as in Example 1 except that the pigment (A) and the modified polyamine (BJ-1) used were changed to the pigment (A) and the modified polyamine described in Tables 2 to 4.
A modified pigment was obtained in the same manner as in Example 1 except that 400 parts of the obtained pigment mixed solution was used and the polymerizable monomer (C) was changed to the polymerizable monomers shown in Tables 2 to 4. (2) to (17) and comparative modified pigment (1) were obtained.

In Table 1,
Fast Gen Blue FGF (wet cake) C.I. I. Pigment Blue 15: 3 (blue pigment manufactured by DIC Corporation) Pigment component 48.0%
Shimla First Red 4590 (powder) C.I. I. Pigment Red 146 (Red Pigment manufactured by DIC Corporation)
Shimla First Yellow 4400T (powder) C.I. I. Pigment Yellow 14 (yellow pigment manufactured by DIC Corporation)
Fast Gen Green S (wet cake) C.I. I. Pigment Green 7 (Green pigment manufactured by DIC Corporation) Pigment component 46%
Typeke CR-93 (powder) titanium oxide (rutile titanium oxide pigment made by Ishihara Sangyo Co., Ltd.)

In Table 2,
Fast Gen Blue FGF (wet cake) C.I. I. Pigment Blue 15: 3 (blue pigment manufactured by DIC Corporation) Pigment component 48.0%

In Table 3,
Fast Gen Blue FGF (wet cake) C.I. I. Pigment Blue 15: 3 (blue pigment manufactured by DIC Corporation) Pigment component 48.0%

<Application example 1>
4.75 parts of the modified pigment (1) obtained in Example 1, 0.25 parts of Solspers 5000 (Lubrisol Co., Ltd. product), 2 of Azisper PB-821 (Ajinomoto Fine Techno Co., Ltd. pigment dispersant) A solution obtained by dissolving 1 part in 21.4 parts of ethyl acetate was charged with 125 parts of 1.25 mm zirconia beads in a polyethylene jar and dispersed for 2 hours using a paint shaker (Toyo Seiki Co., Ltd.). After adding 7.1 parts of ethyl acetate and removing the zirconia beads, the bar coater no. 6 was applied to the glass plate. As a result of measuring 60 ° gloss with a haze gloss meter (BYK Gardner product) after drying at room temperature for 10 hours, it was 95. The cyan density (OD value) measured by SpectroEye (product of GretagMacbeth) was 2.0, and the coated film showed good transparency and good pigment dispersibility. It was confirmed that

<Application examples 2 to 17>
Pigment dispersion, coating, and evaluation were performed in the same manner as in Application Example 1 except that the modified pigment (1), the pigment dispersant, and the solvent were changed as shown in Tables 4 to 6.

<Comparative Application Examples 1-6>
Pigment dispersion, coating, and evaluation were performed in the same manner as in Application Example 1 except that the pigment, pigment dispersant, and solvent were changed as shown in Table 7.

In Table 4,
Azisper PB-821 Pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd. 100% active ingredient
Pigment dispersant 2: Disper BYK2050 Pigment dispersant manufactured by BYK, Inc. 52% active ingredient

In Table 5,
Pigment dispersant 1: Ajisper PB-821 Pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd. 100% active ingredient
Pigment dispersant 2: Disper BYK2050 Pigment dispersant manufactured by BYK, Inc. 52% active ingredient

In Table 6,
Pigment dispersant 1: Ajisper PB-821 Pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd. 100% active ingredient

In Table 7,
Pigment dispersant 1: Ajisper PB-821 Pigment dispersant manufactured by Ajinomoto Fine Techno Co., Ltd. 100% active ingredient
Pigment dispersant 2: Disper BYK2050 Pigment dispersant manufactured by BYK, Inc. 52% active ingredient
Fast Gen Blue FGF C.I. I. Pigment Blue 15: 3 (Blue pigment manufactured by DIC Corporation)
Shimla First Red 4590 C.I. I. Pigment Red 146 (Red pigment manufactured by DIC Corporation)
Shimla First Yellow 4400T C.I. I. Pigment Yellow 14 (yellow pigment manufactured by DIC Corporation)
Fast Gen Green S C.I. I. Pigment Green 7 (Green pigment manufactured by DIC Corporation)
Taipei CR-93 (Ishihara Sangyo Co., Ltd. Rutile type titanium oxide pigment)

From the above results, it is suggested that the modified pigment of the present application has a particularly high OD value and is excellent in pigment dispersibility. The OD value is an index indicating the light absorptance in the wavelength ranges of complementary colors (red, blue, and green) of cyan, yellow, and magenta. The higher the absorptance, the higher the value. The lower the dispersibility of the pigment, that is, the more coarse pigment particles are present in the coating film, the more white scattered light is generated on the surface of the colored coating film, and the light absorption rate of the complementary color of the colored coating film decreases. The value drops. Therefore, it can be generally said that the higher the OD value, the higher the dispersibility of the pigment.

Claims (5)

On the surface of the pigment (A),
A modified polyamine (B) obtained by reacting a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at one end with an amino group of the polyamine;
At least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization
A modified pigment comprising a polymer (P) obtained by polymerizing The modified pigment according to claim 1, wherein the polyamine is at least one selected from the group consisting of polyallylamine, polyvinylamine, and polyethyleneimine. The modified pigment according to claim 1 or 2, wherein the non-aqueous solvent includes an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent. Pigment (A);
In the presence of a modified polyamine (B) obtained by reacting an amino group of a polyamine with a vinyl copolymer (B-1) having a functional group that reacts with an amino group to form an amide bond at one end,
At least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and becomes insoluble or hardly soluble after polymerization
A process for producing a modified pigment, characterized in that The method for producing a modified pigment according to claim 4, wherein the non-aqueous solvent includes an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent.