JP2002226591A - Method for producing colored resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a colored resin particle which is stably dispersed in a nonaqueous solvent, not flocculated and has excellent redispersibility. SOLUTION: This method for producing the colored resin particle is characterized in that (i) an additive containing a colorant component and a resin component is added to an aqueous solvent (X), then (ii) in a nonaqueous solvent (Y) incompatible with the aqueous solvent (X), a monomer which is soluble in the nonaqueous solvent (Y) but is insolubilized by polymerization in the presence of a block or graft copolymer which is insoluble in the nonaqueous solvent (Y) and has self dispersibility is polymerized to give a resin particle (P) dispersed in the nonaqueous solvent (Y) and (iii) the resin particle (P) is added to a system obtained by the process (i), liquid drops containing the colorant component and the resin component are formed in the nonaqueous solvent (Y) and the aqueous solvent (X) is removed to produce the colored resin particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to colored resin fine particles and a method for producing the same. The present invention is particularly used for electrostatographic liquid developers, inks, paints, etc.
The present invention relates to colored resin fine particles dispersed in a non-aqueous solvent and a method for producing the same.

[0002]

2. Description of the Related Art A liquid developer for electrophotography (liquid toner) comprising colorant-containing resin particles dispersed in a highly insulating non-aqueous solvent can be used on demand, and can be a dry developer. Compared with the above, the particle size can be made smaller, so that the fixed image can have higher image quality, higher reproducibility, etc., and is expected to be used in fields such as industrial printers and high-speed high-performance copiers. is there.

Such a liquid developer includes a non-aqueous solvent having a high insulating property as a medium, various coloring agents such as carbon black, a coloring agent such as a dye, a resin component containing these coloring agents, or a coloring agent. A resin component that imparts charge control and fixability by adsorbing to the resin, a dispersant for dispersing the colorant-containing resin particles in a non-aqueous solvent, a charge control agent that adjusts the polarity and charge amount of the colorant-containing resin particles, And other components.

[0004] As a dispersion obtained by dispersing a colorant-containing resin particle in a non-aqueous solvent, for example, a kneaded product of a resin component and a colorant is dry-pulverized, and then ball milled together with a non-aqueous solvent in which the dispersant is dissolved. Using a wet disperser such as a paint shaker or a sand mill, a concentrated dispersion liquid that is dispersed to a target particle size to be a master batch is prepared, and the concentrated dispersion liquid is used as it is or diluted with a solvent. Yes,
A charge control agent is added as needed to obtain the desired polarity.

[0005] Alternatively, in the presence of a polymer soluble in the non-aqueous solvent in a non-aqueous solvent, resin particles are formed by polymerizing a monomer which is soluble in the non-aqueous solvent but becomes insoluble by polymerization. A method is also known in which a colorant is adsorbed to the resin particles, or a resin particle dispersion is added to a non-aqueous solvent containing a charge control agent together with a colorant separately dispersed.

However, these methods have a limitation in reducing the particle size, and require mechanical dispersion treatment or granulation treatment, and the resulting composition has insufficient dispersion stability of the resin particles. Was something.

[0007] Further, as a method for producing such a resin particle dispersion, (1) utilizing a change in the solubility of a polymer,
A method of microencapsulating carbon black and other pigments dispersed by adding a poor solvent to a polymer solution completely dissolved in a good solvent, by core solvation,
(2) a method in which an aqueous colorant is dispersed in a non-aqueous medium by a phase inversion method using an emulsifier (phase inversion method); (3) a semi-liquid self-dispersible graft-block polymer and carbon black. A method of kneading and dispersing with a three-roll mill and dispersing in a non-aqueous medium (JP-A-3-188469);
(4) A method of producing microcapsules by an interfacial polymerization method in a non-aqueous medium using a protective colloid comprising a block polymer having a hydrophobic block and a hydrophilic block (Japanese Patent Application Laid-Open No. 7-246329) is also known. .

However, in coacervation,
The solvent resistance of the polymer greatly depends on the temperature. At a high temperature, the polymer swells and dissolves in the solvent, so that the fusion of the polymer proceeds, and the colored particles aggregate and cannot be redispersed.

When a colorant is dispersed from an aqueous system to a non-aqueous system by the phase inversion method, the addition of an additive used for adjusting the electric resistance and the chargeability may destroy the dispersion system, and the electric resistance and the chargeability may be destroyed. Control becomes difficult.

The microencapsulation using the interfacial polymerization method has problems such as the synthesis of fine resin particles separately from the colorant in the polymerization process because the pigment as the colorant and the resin to be coated are not compatible. is there.

[0011]

Accordingly, an object of the present invention is to provide a novel colored resin particle and a method for producing the same. Another object of the present invention is to provide colored resin particles which are stably dispersed in a non-aqueous medium, do not cause aggregation, and have good redispersibility, and a method for producing the same. The present invention further provides a freely controllable colored resin particles and a manufacturing method thereof in the range of 10 ² micron order of particle size from sub-micron order. Another object of the present invention is to provide a colored resin particle capable of freely changing the ratio of a polymer component and a pigment such as carbon black contained in the particle, and a method for producing the same. Further, the present invention can control the particle surface, freely control the chargeability and the surface resistance, and in particular, contain a colorant having desired characteristics such as high resistance and good positive charge. Provided are colored resin particles capable of forming particles and a method for producing the same.

[0012]

Means for Solving the Problems In the present system, the present inventors have proposed a method of coating a coloring agent with nano-order fine particles as a stabilizer in order to increase the solvent resistance to a polymer as compared with core solvation. Further, it has been found that there is an improvement in the point that the type of additive that can be added and the concentration can be increased as compared with the phase inversion method using an emulsifier, and that the present invention is completed. It has been reached.

That is, the present invention which solves the above-mentioned problems,
(1) (i) An additive containing a colorant component and a resin component is disposed in water or a water-miscible solvent (hereinafter, these may be referred to as an aqueous solvent (X)), and then (ii) In the non-aqueous solvent (Y) immiscible with the aqueous solvent (X),
In the presence of a block or graft copolymer which is insoluble and self-dispersible in the non-aqueous solvent (Y), the monomer which is soluble in the non-aqueous solvent (Y) and becomes insoluble by polymerization is polymerized. Resin particles (P) dispersed in a non-aqueous solvent (Y) are obtained, and (iii) the resin particles (P) are added to the system obtained in (i), and the non-aqueous solvent (Y) is added. A droplet containing the coloring agent component and the resin component therein, and removing the aqueous solvent (X) to produce colored resin particles. 1 embodiment).

The present invention also relates to (2) (i) dissolving in water or a water-miscible solvent (hereinafter, these may be referred to as an aqueous solvent (X)) in the aqueous solvent (X) or By polymerizing a monomer that is soluble in the aqueous solvent (X) and insoluble by polymerization in the presence of a self-dispersing resin component, the resin particles (P) dispersed in the aqueous solvent (X) are polymerized. ') And then (ii) a system in which the colorant component is dispersed in a non-aqueous solvent (Y) immiscible with the aqueous solvent (X). Adding, forming a droplet containing the coloring agent component and the resin component in the non-aqueous solvent (Y), and removing the aqueous solvent (X) to produce colored resin particles. This is a method for producing particles (hereinafter, may be referred to as a second embodiment).

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on specific embodiments.

(I) First Embodiment In the first embodiment of the present invention, the above-mentioned resin particles (P) form aqueous droplets dispersed in a non-aqueous solvent (Y). In doing so, it is based on the discovery that it functions as an extremely excellent dispersion stabilizer. According to the method according to the first embodiment of the present invention, the intended colored resin particles can be prepared using an extremely large variety of resin components and various colorant components that can be used in the phase transition method, Further, the ratio of the resin component and the colorant component in the colored resin particles can be set relatively arbitrarily, and the size of the obtained colored resin particles is determined by the stirring conditions, the concentration of the resin particles (P). It is possible to arbitrarily adjust comparatively by appropriately setting the above.

First, the system (i) of the aqueous solvent (X) comprising an additive containing a colorant component and a resin component will be described.

The aqueous solvent (X) used in the first embodiment of the present invention is not particularly limited, but may be water, a lower alcohol, aldehyde, or ketone solvent having about 1 to 5 carbon atoms. Among them, water or a water-lower alcohol mixture is particularly used.

Next, in the first embodiment of the present invention, a coloring agent component is blended in such an aqueous solvent (X).

The colorant component incorporated in the aqueous solvent (X) is not particularly limited, and may be an organic pigment, an inorganic pigment, or a mixture thereof.

Examples of the inorganic pigment include alumina, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Inorganic oxide pigments, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide,
Zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silica fine powder, silicon carbide, silicon nitride,
Examples include powders or particles of boron carbide, tungsten carbide, titanium carbide, cerium oxide, carbon black, and the like. Further, such an inorganic pigment may be treated with a known hydrophobizing agent such as a titanium coupling agent, a silane coupling agent, or a higher fatty acid metal salt.

The organic pigments include, for example, Navels Yellow, Naphthol Yellow S, Hanser Yellow G, Hanser Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake Yellow pigments, such as yellow pigments, orange pigments such as kilybdenum orange, permanent orange RK, benzidine orange G, indanthrene brilliant orange GK, permanent red 4R, lithol red, pyrazolone red 4R, watching red calcium salt, lake red D, brilliant carmine Red pigments such as 6B, Aeomin Lake, Rhodamine Lake B, Buzarin Lake, Brilliant Carmine B, and purple face such as Fast Violet B and Methyl Violet Lake , Alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, blue pigment such as indanthrene blue BC, Pigment Green B, Malachite Green Lake, Final Yellow Green G, etc. Green pigment and the like.

Further, the surface of the coloring agent component is modified with a polymer chain such as a block or graft copolymer so as to be stably dispersed during the addition in the aqueous solvent (X) as described above. It is desired to be a polymer-grafted colorant. More specifically, a block or graft having a segment (B) having an affinity for the aqueous solvent (X) and a segment (A) having a lower affinity than the segment (B) for the aqueous solvent (X). Desirably, it is a polymer-grafted colorant modified with a copolymer chain. It can be said that these polymer-grafted coloring agents simultaneously contain the coloring agent component and the resin component of the present invention.

In the following, specific examples of the polymer-grafted colorant which simultaneously contains the colorant component and the resin component of the present invention will be described focusing on the embodiment using carbon black obtained by grafting a polymer chain as described above. However, it goes without saying that the present invention should not be limited to these.

The carbon black used for producing the carbon black graft polymer according to the present invention is not particularly limited as long as it has a functional group such as a carboxyl group or a hydroxy group on its surface. Any type such as channel black, acetylene black, lamp black and the like can be used, and ordinary commercial products can be used as they are, but among them, those having a carboxyl group are preferable. Further, it is preferable to use carbon black having a pH of less than 7, particularly 1 to 5 as the carbon black. A carbon black having a carboxyl group can be easily obtained as an acidic carbon black, but a carbon black obtained by oxidizing a neutral or basic carbon black can also be suitably used as a raw material in the present invention. When the carbon black does not have a functional group such as a carboxyl group or has a pH of 7 or more, grafting may not be effectively performed. In addition, the test method of the pH of carbon black is based on JISK6211.

The average particle size of the carbon black is 0.0005 to 0.4 μm, especially 0.001 to 0.2 μm.
It is preferably within the range of m. Average particle size is 0.0
Since carbon black having a size of less than 005 μm cannot be easily obtained, it has little industrial significance. The average particle size is 0.4
If it exceeds μm, sufficient dispersibility may not be provided to the obtained carbon black graft polymer.

On the other hand, the polymer used to form a polymer portion by being grafted onto such carbon black is composed of a segment (A) having a reactive group capable of reacting with a functional group on the surface of carbon black; It is a block or graft type polymer having substantially no reactive group and a segment (B) having a higher affinity for the aqueous solvent used than the segment (A).

In such a block-type or graft-type polymer, the reactive group contained in the segment (A) reacts with a functional group present on the surface of carbon black to convert the polymer into carbon black. There is no particular limitation as long as it can contribute to grafting, and various reactive groups can be used.

Here, in order to make the grafting more reliable and stable, it is desired that the polymer portion be bonded to the carbon black via a covalent bond. Particularly, an ester bond, a thioester bond, an amide bond, At least one bond selected from the group consisting of an amino bond, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond and a sulfonyl bond, and at least one bond selected from the group consisting of an ester bond, a thioester bond and an amide bond Is desired.
Considering these points, the reactive group is an epoxy group,
It is desirable that at least one or two or more selected from the group consisting of a thioepoxy group, an aziridine group, an N-hydroxyacrylamide group and an oxazoline group. The reactive group for carbon black is not necessarily limited to these, but when a polymer having a group other than these reactive groups is used, the type of carbon black that can be used may be limited. The reason that the polymer preferably has the reactive group is that regardless of the type and state of the carbon black that can be used, the carbon black and the polymer are added with very high grafting efficiency even under mild conditions. To react. In particular, when the carbon black has a carboxyl group as a surface functional group as described above, the carboxyl group is an epoxy group, a thioepoxy group, an aziridine group,
An irreversible addition reaction is performed at a high yield by a thermal reaction with an N-hydroxyacrylamide group or an oxazoline group, and this addition reaction is desirable because the above-mentioned covalent bond is formed between the carbon black portion and the polymer portion.

The method for introducing these reactive groups into the polymer (segment (A)) will be described later.

The segment (A) having such a reactive group must have a low affinity for the target medium on the segment chain structure. In addition, since the low affinity here is a relative one by comparison with the other segment (B), the segment (A) may have various configurations depending on the configuration of the segment (B). Can not be specified. However, from a further perspective, said segment (A)
It is preferable that the compound has high affinity for carbon black because it shows better orientation to carbon black. From this point, the segment (A) has a main chain mainly containing a carbon-carbon bond, and more preferably contains an aromatic ring such as a benzene ring, a naphthalene ring or an indene ring in the main chain. The segment (B) has a skeleton structure having less aromatic rings than the segment (A), for example, a hydrophilic structure such as an ether structure, a carboxyl group, or a hydroxyl group. It is desirable to include a large amount of the structure of the nature.

As described above, the chain structure of the segment (A) can be appropriately selected according to the chain structure of the segment (B) selected from the viewpoint of dispersibility to be imparted to carbon black. , For example, a styrene monomer,
(Various vinyl polymers, polyesters, polyethers, etc. (having the above reactive group) by homo- or copolymerization of (meth) acrylic monomers, alkylene monomers, etc.
Among them, a vinyl polymer, particularly a vinyl monomer component having an aromatic ring, may be used as a polymer chain.
Since it is a vinyl-based polymer containing at least mol%, more preferably at least 60 mol%, and having a reactive group, a combination with various segments (B) selected according to a liquid medium to be used becomes possible. desirable.

In consideration of economic efficiency and the like, particularly, homo- or copolymers mainly composed of styrene-based monomers and (meth) acrylic-based monomers, especially styrene-based monomer components of 50 mol% or more, Is preferably a polymer chain containing 60 mol% or more (having the above reactive group).

On the other hand, the segment (B) is, for example, a polymer having a polyether-based structure such as a poly (meth) acrylic structure or a polyalkylene glycol in consideration of dispersibility in the aqueous solvent (X) to be used. An appropriate one is selected from the chains.

The method for obtaining a polymer having the segment (A) having a reactive group and the segment (B) having a high affinity for the aqueous solvent (X) to be used is not particularly limited. It can be produced by appropriately combining known techniques for polymerizing various block or graft polymers with techniques for producing reactive polymers.

As a method for obtaining a graft type polymer,
For example, a method of polymerizing a polymer to be a main chain by solution polymerization, emulsion polymerization, bulk polymerization or suspension polymerization of a polymerization initiator and a polymerizable monomer in the presence of a high molecular weight product to be a graft chain It has been known. However, if the high molecular weight polymer does not have a radical polymerizable functional group, the resulting graft copolymer contains a large amount of non-grafted polymer, and has a disadvantage that graft efficiency is low. I have. Therefore, it is preferable to use a radical polymerizable polymer as the polymer. Such a radical polymerizable polymer is generally referred to as a “macromonomer” and is a polymer having a radical polymerizable group at one end, such as a (meth) acryloyl group or a styryl group. It is obtained by reacting a polymer having a carboxyl group at one end with a radical polymerizable monomer having a glycidyl group in an organic solvent (for example, Japanese Patent Publication No. A method is disclosed in which a prepolymer obtained by radical polymerization of a radical polymerizable monomer in the presence of mercaptoacetic acid and glycidyl methacrylate are reacted in the presence of a dimethyllaurylamine catalyst).

Therefore, for example, in order to obtain the graft copolymer according to the present invention, the carbon black as described above is used in the presence of the above-mentioned radical polymerizable high molecular weight as a component forming the segment (B). A polymerizable monomer having a reactive group in the molecule and other polymerizable monomers forming the skeleton of the segment (A) to be blended as necessary may be polymerized.

Further, in the first embodiment of the present invention, a resin component is blended as an additive blended in the aqueous solvent (X) (however, the colorant component and the resin component are mixed together). It may be blended in the form of a polymer-grafted colorant that is included at the same time.) The aqueous solvent (X)
The resin component incorporated therein is not particularly limited, and is not limited to a hydrophilic resin, but may be hydrophobic resin fine particles dispersible and compoundable in the aqueous solvent (X), other oligomers, uncrosslinked. It may be a monomer component or the like. Specifically, for example, acrylic resin, alkyd resin, epoxy resin, polyester resin, various acrylic acid monomers, acrylate monomers,
Copolymers such as amino-based monomers may be used, but are not limited to these. (The case where the polymer is blended in the form of the polymer-grafted colorant has already been described above, and a description thereof will be omitted. I do.) These may be used alone or in combination of two or more. That is, the polymer-grafted colorant may be used in combination with another resin component or colorant component. When a colorant component other than the polymer-grafted colorant (for example, a conventionally known organic pigment or inorganic pigment) is used as the colorant component, a dispersion that is also useful as a dispersing resin or a dispersing aid is used. By blending a resin component having excellent properties, it is particularly effective and useful in that a colorant component such as a pigment can be finely dispersed. On the other hand, the polymer-grafted colorant containing the colorant component and the resin component simultaneously can be dispersed in the aqueous solvent (X) without a dispersant such as a dispersing resin or a dispersing aid. It is particularly advantageous in that it can be used alone without using an agent (resin component) in combination.

In the first embodiment of the present invention, the colorant component and the resin component may be mixed in the aqueous solvent (X) at an arbitrary ratio.
It is preferable that the colorant component is 1 to 100 parts by mass, preferably 1 to 50 parts by mass, and the resin component is 1 to 100 parts by mass with respect to 0 parts by mass. When the colorant component is set to 100 parts by mass or less, particularly 50 parts by mass or less with respect to 100 parts by mass of the aqueous solvent (X), there is no problem that the viscosity is increased and the phase conversion does not occur well. This is particularly advantageous in that colored resin particles can be stably dispersed in the resin, do not cause aggregation, and have good redispersibility.

In the case of a polymer-grafted colorant which simultaneously contains the colorant component and the resin component, it may be blended in the aqueous solvent (X) at an arbitrary ratio. X) The polymer-grafted colorant is used in an amount of 1 to 100 parts by mass, preferably 1 to 50 parts by mass, per 100 parts by mass. Polymer-grafted colorant aqueous solvent (X) 1
By 100 parts by mass or less, particularly 50 parts by mass or less with respect to 00 parts by mass, the viscosity is increased, and there is no problem that the phase change does not occur well. This is particularly advantageous in that colored resin particles having good redispersibility can be obtained.

Next, in the first embodiment of the present invention,
The system (ii) in which the resin particles (P) used as the dispersion stabilizer are dispersed in the non-aqueous solvent (Y) will be described.

The non-aqueous solvent (Y) that is immiscible with the above-mentioned aqueous solvent (X) used in producing the resin particles (P) is not particularly limited, and examples thereof include hydrocarbon solvents, Benzene, toluene, hexane, etc. can be used, but isoparaffin-based hydrocarbons having particularly high insulating properties, Isopar M, Isopar L, Isopar G
(All are trade names manufactured by Exxon).
These may be used alone or in combination of two or more.

As the block or graft copolymer which is insoluble in the non-aqueous solvent (Y) and has self-dispersibility used in the first embodiment of the present invention, an AB block copolymer is used. , AB-type graft copolymer, but not limited to those having a simple structure.
Various types such as a type block copolymer, a more advanced alternating block copolymer, a comb-shaped graft copolymer in which a plurality of B segments are grafted to an A segment, and a star-shaped graft copolymer are also available. included. Similarly, the graft copolymer also includes various forms.

"The block or graft copolymer is insoluble in the non-aqueous solvent (Y) and has self-dispersibility" means that the block or graft copolymer is dissolved in the non-aqueous solvent (Y) in a solid state. Means that particles are formed by dispersing in a solvent so as to dissolve spontaneously just by leaving it without using a means such as mechanical stirring when adding the block or graft copolymer. The average particle size of the dispersed particles in the combined non-aqueous solvent (Y) is
For example, those having a thickness of 5 to 400 nm, particularly about 5 to 150 nm are desirable. The dispersion stability of the obtained resin particles (P) in the non-aqueous solvent (Y) greatly depends on the dispersion particle diameter of the block or graft copolymer.

Specific examples of the block or graft copolymer which is insoluble and self-dispersible in the non-aqueous solvent (Y) greatly depend on the type of the non-aqueous solvent (Y) used. The polymer unit having an affinity for the non-aqueous solvent (Y) and the polymer unit having a non-affinity for the non-aqueous solvent (Y), for example, a hydrophilic polymer unit, which cannot be specified unconditionally. For example, when the above-mentioned isoparaffinic hydrocarbon is used as the non-aqueous solvent (Y), the former polymer unit may be, for example, a long-chain hydrocarbon having about 6 to 40 carbon atoms. For example, using a polymer of a monomer having a stearyl group, on the other hand, as the latter polymer unit,
Cyclic structures such as benzene, naphthalene, and indene rings;
For example, a polymer of a monomer having a styrene skeleton can be used. Similarly, a block resin or a graft copolymer which is insoluble in the non-aqueous solvent (Y) and has self-dispersibility can be obtained even with a silicone resin.

Specific examples of the former monomer forming the polymer unit include stearyl acrylate, stearyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, nonadecyl acrylate, and the like. Nonadecyl methacrylate, aralkyl acrylate, aralkyl methacrylate, behenyl acrylate, behenyl methacrylate, pentasil acrylate, pentasil methacrylate, heptayl acrylate, heptacil methacrylate, nonacil acrylate, nonacil methacrylate, doteracyl acrylate, methacrylic acid Doteria sill, etc. Of these, particularly preferred is stearyl acrylate,
Behenyl acrylate, behenyl methacrylate, pentasil acrylate, pentasil methacrylate and the like.

As the monomer for forming the latter polymer unit, specifically, for example, styrene, o-
Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p
-Tert-butylstyrene, p-phenylstyrene,
Styrene-based monomers such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene and the like can be mentioned.

However, as a matter of course, the monomers forming the former and the latter polymer units are exemplified above as long as the finally obtained block or graft copolymer can exhibit the desired properties. It is not limited to anything. For example, in any unit, as a comonomer, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, α- Methyl chloroacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylate
Non-crystalline acrylate or non-crystalline methacrylate monomers such as butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, diaminoethyl methacrylate; acrylonitrile, methacrylonitrile Acrylic or methacrylic monomers such as acrylamide and acrylamide; vinyl ether monomers such as vinyl methyl ether, vinyl isobutyl ether and vinyl ethyl ether; vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N-vinyl Pyrrole, N-vinylcarbazole, N
N-vinyl compound monomers such as -vinylindole, N-vinylpyrrolidone, 2-isopropenyl-2-oxazoline; and others, ethylene, propylene, butylene,
It is possible to use various vinyl monomers such as vinyl chloride and vinyl acetate.

The monomer used in the first embodiment of the present invention which is soluble in the non-aqueous solvent (Y) and becomes insoluble by polymerization depends on the non-aqueous solvent (Y) used. Although different, for example, when the above-mentioned isoparaffinic hydrocarbon is used as the non-aqueous solvent (Y), monomers such as various acrylic methacrylic esters, styrene, and vinyl acetate can be used.

The block or graft which is insoluble in the non-aqueous solvent (Y) and has self-dispersibility “in the presence of the copolymer” becomes soluble in the non-aqueous solvent (Y) and becomes insoluble by polymerization. Since the monomer is polymerized, the copolymer is blended in the non-aqueous solvent (Y) and is soluble in the non-aqueous solvent (Y) and polymerized as in the method for producing the resin particles (P) shown below. May be polymerized, but as shown in the preparation example of Synthesis Example 1 described below, each monomer component forming these copolymers is blended in a non-aqueous solvent (Y), A monomer that is soluble in (Y) and becomes insoluble by polymerization may be polymerized. That is, the term "in the presence of a copolymer" as used herein means that these copolymers may not be present from the initial stage of polymerization of monomers which are soluble in the non-aqueous solvent (Y) and become insoluble by polymerization. This includes the case where these copolymers will be present during the polymerization process of monomers which are soluble in the solvent (Y) and insoluble by polymerization.

The additives to be mixed in the non-aqueous solvent (Y) include diethylene glycol dimethacrylate, ethylene glycol dimethacrylate,
It is also possible to mix 2-hydroxy-3-acryloyloxypropyl methacrylate and other crosslinking components such as hydrophilic crosslinking monomers. These may be used alone or in an appropriate combination of two or more. These crosslinking components and the like may be appropriately used as needed when polymerizing a monomer which is soluble in the non-aqueous solvent (Y) and becomes insoluble by polymerization. The amounts of these additives are not particularly limited as long as the effects of the present invention are not impaired as long as the performance of each additive can be sufficiently exhibited.

Similarly, in the first embodiment of the present invention, as an additive compounded in the non-aqueous solvent (Y), a polymerization initiator and other additives soluble in the non-aqueous solvent (Y) are used. In addition, various additives required for the polymerization of the monomer which becomes insoluble by the polymerization can be blended. The polymerization initiator is appropriately selected from known azo-based and peroxide-based ones according to the monomer which is soluble in the non-aqueous solvent (Y) to be used and becomes insoluble by polymerization, and an appropriate amount thereof is used. Can be. These may be used alone or in an appropriate combination of two or more. In addition, as the amount of these components, as long as the effects of the present invention are not impaired, the polymerization initiator and other additives are particularly required as long as the performance of the various additives required for the polymerization of the above monomer components can be sufficiently exhibited. It should not be restricted.

In the method for producing the resin particles (P) according to the first embodiment of the present invention, the resin particles (P) are soluble in the non-aqueous solvent (Y) in 100 parts by mass of the non-aqueous solvent (Y). And a monomer which becomes insoluble by polymerization, for example, 1 to 100 parts by mass, more preferably 10 to 100 parts by mass.
50 parts by mass of a block or graft copolymer insoluble in the non-aqueous solvent (Y) and having a self-dispersibility of 1 to 1
00 parts by mass, more preferably 5 to 30 parts by mass, and the temperature is adjusted or heated to a temperature of about 20 to 100 ° C., which is the polymerization temperature, and a polymerization initiator such as a known azo-based or peroxide-based The polymerization can be carried out by adding a predetermined amount, for example, 0.1 to 15 parts by mass to 100 parts by mass of the monomer.

The resin particles (P) obtained as a result of such a polymerization reaction have a block or graft copolymer bonded to the surface thereof and are stably dispersed in the non-aqueous solvent (Y). It has a very small particle diameter of 50 nm to 10 μm, particularly 50 nm to 5 μm.

Next, in the first embodiment of the present invention, such resin particles (P) are mixed with the non-aqueous solvent (Y).
It is used as it is in a state of being dispersed therein, or, if necessary, by further adding a desired amount of a non-aqueous solvent (Y), or once separated and then re-dispersed in the non-aqueous solvent (Y). This is gradually added to an aqueous solvent (X) containing the above-mentioned coloring agent component and resin component (which may be in the form of a polymer-grafted coloring agent containing them at the same time). By causing the transition, colored resin particles are obtained. Further, after the phase transition, the aqueous solvent (X) in the colored resin particles is removed, whereby the desired colored resin particles can be obtained. The conditions for removing the aqueous solvent (X) are not particularly limited, and the aqueous solvent (X) may be removed by heating. Preferably, the temperature is equal to or lower than the temperature at which the non-aqueous solvent (Y) evaporates under reduced pressure. It is desirable to remove the aqueous solvent (X) by heating to a temperature at which the aqueous solvent (X) can be removed.

(II) Second Embodiment In the second embodiment of the present invention, a colorant component (including a form of a polymer-grafted colorant containing a colorant component and a resin component simultaneously. When it is not in the form of a color-forming agent, an appropriate dispersing agent, for example, one containing a dispersing resin such as a grafted resin and a dispersing aid is included.)
It is based on the discovery that it functions as an extremely excellent dispersion stabilizer in forming aqueous droplets dispersed in the non-aqueous solvent (Y). According to the method according to the second embodiment of the present invention, the intended colored resin particles can be prepared using a very large variety of resin components and various colorant components that can be used in the phase transition method, In addition, the ratio of the resin component and the colorant component in the colored resin particles can be set relatively arbitrarily, and the size of the obtained colored resin particles is controlled by the stirring conditions, the resin particle (P ′). It is possible to arbitrarily adjust comparatively by appropriately setting the concentration and the like.

First, the system (i) of the aqueous solvent (X) containing the resin particles (P ') will be described.

The aqueous solvent (X) used in the second embodiment of the present invention is not particularly limited, and is the same as the aqueous solvent (X) used in the first embodiment described above. Are available.

As the resin component soluble or self-dispersed in the aqueous solvent (X) used in the second embodiment of the present invention, the resin particles (P ′) obtained by polymerization may be the aqueous solvent (X). The dispersant is not particularly limited as long as it can be stably dispersed in (1), and various dispersants conventionally known, for example, dispersants such as grafted resins and dispersants can be used. And
Not only hydrophilic resins, but also oligomers, uncrosslinked monomer components and the like may be used. Specifically, for example, acrylic resins, alkyd resins, epoxy resins, polyester resins, and various acrylic acid monomers, acrylate monomers, and copolymers of amino monomers may be used. It is not limited.

The “resin component that is self-dispersible in the aqueous solvent (X)” among the resin components described above means that when the resin component is added in a solid state to the non-aqueous solvent (Y), it is subjected to mechanical stirring or the like. It means that the particles (cores) are dispersed in the aqueous solvent (X) so as to dissolve spontaneously simply by leaving it without using any means.

In the second embodiment of the present invention, the resin component may be mixed in the aqueous solvent (X) at an arbitrary ratio. It is preferable that the component has a ratio of 1 to 100 parts by mass.

Next, the monomer which is soluble in the aqueous solvent (X) and becomes insoluble by polymerization depends on the aqueous solvent (X) used. For example, styrene, o-methyl Styrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-
Methoxystyrene, p-tert-butylstyrene, p
Styrene monomers such as -phenylstyrene, o-chlorostyrene, m-chlorostyrene and p-chlorostyrene; acrylic monomers such as hydroxy-2-ethyl methacrylate, methacrylic acid, acrylic acid, methacrylamide and acrylamide; acrylonitrile; ) Acrylate-based monomers, for example, monomers such as methyl methacrylate, ethyl methacrylate, and butyl acrylate can be used.

The additives to be mixed in the aqueous solvent (X) include diethylene glycol dimethacrylate, ethylene glycol dimethacrylate,
It is also possible to incorporate a crosslinking component such as -hydroxy-3-acryloyloxypropyl methacrylate and other hydrophilic crosslinking monomers. These may be used alone or in an appropriate combination of two or more. These crosslinking components and the like may be appropriately used as needed when polymerizing a monomer that is soluble in the aqueous solvent (X) and becomes insoluble by polymerization. The amounts of these additives are not particularly limited as long as the effects of the present invention are not impaired as long as the performance of each additive can be sufficiently exhibited.

Similarly, in the second embodiment of the present invention, as an additive compounded in the aqueous solvent (X),
A polymerization initiator and other various additives required for the polymerization of a monomer which is soluble in the aqueous solvent (X) and insoluble by polymerization can be blended. The polymerization initiator may be appropriately selected from known azo-based and peroxide-based ones according to the monomer which is soluble in the aqueous solvent (X) to be used and becomes insoluble by polymerization, and an appropriate amount thereof may be used. it can. These may be used alone or in an appropriate combination of two or more.
In addition, as the amount of these components, as long as the effects of the present invention are not impaired, the polymerization initiator and other additives are particularly required as long as the performance of the various additives required for the polymerization of the above monomer components can be sufficiently exhibited. It should not be restricted.

In the method for producing the resin particles (P ′) according to the second embodiment of the present invention, the aqueous solvent (X) is mixed with 100 parts by mass of the aqueous solvent (X) as described above.
1 to 100 parts by mass, more preferably 10 to 50 parts by mass of a monomer which becomes soluble in water and becomes insoluble by polymerization, and a resin component which is self-dispersed in the aqueous solvent (X) is 1
To 100 parts by mass, more preferably 5 to 30 parts by mass, and the temperature is adjusted or heated to a temperature of about 20 to 100 ° C., which is the polymerization temperature, and a polymerization initiator such as a known azo-based or peroxide-based Etc. in a predetermined amount, for example, monomer 10
Polymerization can be carried out by adding about 0.1 to 15 parts by mass to 0 parts by mass.

The resin particles (P ′) obtained as a result of such a polymerization reaction have a resin component that is self-dispersed in the aqueous solvent (X) bonded to the surface thereof and is stably dispersed in the aqueous solvent (X). All of which have an average particle diameter of 50 nm.
It has a very small particle size of 10 to 10 μm, especially 50 nm to 5 μm.

Next, in a second embodiment of the present invention,
In the non-aqueous solvent (Y) that is immiscible with the aqueous solvent (X), the colorant component (including the form of a polymer-grafted colorant containing both the colorant component and the resin component. If not in a form, a suitable dispersant such as
It contains a dispersing resin such as a grafted resin and a dispersing aid. ) Will be described.

The non-aqueous solvent (Y) that is immiscible with the aqueous solvent (X) is not particularly limited, and the non-aqueous solvent used in the first embodiment of the present invention as described above. The same thing as (Y) can be used.

Further, in the second embodiment of the present invention, the colorant component is dispersed in such a non-aqueous solvent (Y). As such a dispersion method, for example,
It may be dispersed as a form of a polymer-grafted colorant that simultaneously contains a dispersible colorant component and a resin component, or when not in the form of a polymer-grafted colorant,
An appropriate dispersing agent may be added to the colorant component for dispersion.

The colorant component and the polymer-grafted colorant simultaneously containing the colorant component and the resin component are the same as those described in the first embodiment of the present invention. The same as the colorant can be used (however, as shown below,
It must be prepared by changing the one used as the segment (B) to one having high affinity for the non-aqueous solvent (Y)). Also, regarding the dispersant,
Resin components used in the first embodiment of the present invention as described above, for example, the same ones as dispersing resins such as grafted resins and dispersing aids can be used (details will be described below).

In particular, the colorant component to be mixed in the non-aqueous solvent (Y) is preferably in the form of the above-mentioned polymer-grafted colorant. Specifically, it is added to the non-aqueous solvent (Y), self-disperses, and functions as a kind of polymerization stabilizer used in the first embodiment. It is desired to be a surface-modified polymer-grafted colorant. The polymer-grafted colorant described as the polymer-grafted colorant disposed in the aqueous solvent (X) in the first embodiment of the present invention is the same as that used as the segment (B). Non-aqueous solvent (Y)
Having high affinity for, for example, 6 to 4 carbon atoms
It can be prepared in the same manner except that it is changed to a polymer of a monomer having a long chain hydrocarbon of about 0, for example, stearyl group.

Further, in the second embodiment of the present invention,
As other additives blended in the non-aqueous solvent (Y), conventionally known various dispersants, for example, a dispersing resin such as a grafted resin, a dispersing aid, and the like may be appropriately blended.
These may be used alone or in combination of two or more. In particular, other colorant components other than the polymer-grafted colorant having excellent dispersibility useful as a dispersing resin and a dispersing aid as the above-mentioned coloring agent component (for example, conventionally known organic pigments and inorganic pigments) In the case of using these, it can be said that it is desirable to use these dispersing resins and dispersing aids in combination.
The amounts of these additives are not particularly limited as long as the effects of the present invention are not impaired as long as the performance of each additive can be sufficiently exhibited.

Next, in the second embodiment of the present invention, a system in which a coloring agent component is dispersed in a non-aqueous solvent (Y) is prepared by dispersing the resin particles (P ′) described above. Colored resin particles are obtained by gradually adding to the aqueous solvent (X) system to cause phase transition. Further, after the phase transition, the aqueous solvent (X) in the colored resin particles is removed, whereby the desired colored resin particles can be obtained. Aqueous solvent (X)
The conditions for removing are not particularly limited, and the aqueous solvent (X) may be removed by heating. Preferably, the aqueous solvent (X) is removed at a temperature lower than the temperature at which the non-aqueous solvent (Y) evaporates under reduced pressure. ) Is desirably removed by heating to a temperature at which the aqueous solvent (X) can be removed.

In the second embodiment of the present invention, since the non-aqueous solvent (Y) containing the colorant component is used as described above, the finally obtained colored resin particles are used in the non-aqueous solvent (Y). Since the coloring agent component contained in ()) is concentrated near the interface of the finally obtained colored resin particles, it is excellent in that it can be efficiently colored.

(III) Regarding Colored Resin Particles Obtained As described above, the colored resin particles of the present invention obtained as a result of the phase transition produced by the method as shown in the first and second embodiments of the present invention, The particle size can be adjusted arbitrarily arbitrarily by the production conditions, and the average particle size is 50 nm to 1
The particle size can be individually set to 0 μm, particularly 200 nm to 5 μm, which is the optimum material for the electrophotographic liquid developer and other uses.

For this reason, for example, it can be suitably used as a raw material in the production of a liquid developer for electrophotography.

[0077]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. In the following, “parts” means parts by mass unless otherwise specified.

Synthesis Example 1 Preparation Example of System (ii) in which Resin Particles (P) are Dispersed in Nonaqueous Solvent (Y) Preparation of Graft Polymer Ultrafine Particle Dispersion Emulsion

[0079]

[Table 1]

In the above Table 1, a macromonomer of stearyl methacrylate; a block or graft copolymer which is insoluble and non-dispersible in the non-aqueous solvent (Y) (hereinafter, also simply referred to as “block / graft copolymer”) ) Forming monomer, • Styrene; Block graft copolymer forming monomer, • 2-Isopropenyl-2-oxazoline;
A graft copolymer-forming monomer; diaminoethyl methacrylate; a monomer that is soluble in the nonaqueous solvent (Y) and insoluble by polymerization (hereinafter, referred to as
Simply referred to as “insoluble polymer-forming monomer”), toluene: a non-aqueous solvent.

Ultrafine graft polymer particles (resin particles (P)) were prepared by the solution polymerization using the compositions shown in Table 1 above.

Specifically, using the compositions shown in Table 1 above,
Azobisisobutyronitrile 1 as a polymerization initiator
The polymerization was carried out at 70 ° C. for 10 hours under a nitrogen atmosphere. Polymerization was performed at a polymer solid content of 50% by mass. Thereafter, toluene was degassed by an evaporator and dried under reduced pressure to purify it as solid graft polymer ultrafine particles.

Thereafter, isopar (non-aqueous solvent (Y))
The ultrafine particles of the solid graft polymer were dispersed in the resulting mixture to obtain a dispersant-dispersed emulsion.

In the dispersant-dispersed emulsion, the graft polymer ultrafine particles are not completely dissolved in the isopar, and the system (ii) in which the graft polymer ultrafine particles are dispersed in the isopar has a translucent bluish color. Was.
Dynamic light scattering device (DLS700, manufactured by Otsuka Electronics Co., Ltd.)
Was found to have an average particle diameter of 57.4 nm.

Synthesis Example 2: Preparation example of a system (i) in which a colorant component and a resin component are simultaneously contained in an aqueous solvent (X) in the form of a polymer-grafted colorant Grafted carbon black used in the phase inversion method Synthesis of Dispersion The composition of an ethanol-dispersed graft carbon black (polymer grafting colorant; hereinafter, also simply referred to as GCB) dispersion used in the phase inversion method is shown in Table 2 below.

[0086]

[Table 2]

Method for Producing Ethanol-Dispersed GCB Dispersion A separable flask equipped with a temperature sensor, stirring blades, and a cooling tube was charged with the composition shown in Table 2 above and 700 parts by mass of zirconia beads, and reacted at 700 rpm. After stirring at a temperature of 70 ° C. for 5 hours, the zirconia beads and the liquid were separated by filtration to obtain an ethanol-dispersed GCB dispersion.

Table 3 below shows the monomer composition of the graft polymer for GCB in Table 2 above.

[0089]

[Table 3]

Preparation of Graft Polymer for GCB In a separable flask equipped with a temperature sensor, stirring blades, and a cooling tube, the monomer composition shown in Table 3 was dissolved in 100 parts of ethyl acetate, and azobisisobutyro was used as an initiator. 80 ° C under a nitrogen atmosphere in a system containing 1 part of nitrile
For 12 hours. After removing the solvent with an evaporator, the obtained resin solution was heated at 80 ° C.
After drying for 4 hours, the graft polymer for GCB was purified.

Example 1 GCB dispersion liquid (synthesized above) in a 500 ml flask
50 parts were added, and 100 parts of the dispersant dispersion emulsion (prepared above) was slowly dropped with a dropping pipette while stirring at 500 rpm, and then 80 parts of Isopar was dropped. Thereafter, ethanol was degassed from the dispersion using an evaporator to produce colored resin fine particles (1). In the measurement using a dynamic light scattering device (DLS700, manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the colored resin fine particles (1) obtained was 4.
It was 1 μm.

Example 2 GCB dispersion in 500 ml flask (synthesized above)
30 parts were added, and 120 parts of the dispersant dispersion emulsion (prepared above) was slowly dropped with a dropping pipette while stirring at 600 rpm, and then 22.4 parts of Isopar was dropped. Thereafter, ethanol was degassed from the dispersion using an evaporator to produce colored resin fine particles (2). In the measurement using a dynamic light scattering device (DLS700, manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the obtained colored resin fine particles (2) was 2.3 μm.

Example 3 A terpolymer (stearyl macromonomer-styrene-isopropyloxazoline copolymer) having the composition shown in Table 5 below was placed in toluene in a separable flask equipped with a temperature sensor, stirring blades, and a cooling tube. Was synthesized.

Thereafter, using this terpolymer as a stabilizer, polyvinyl acetate particles (resin particles (P)) were synthesized by polymerization of vinyl acetate in the composition shown in Table 4 below. The temperature of the polymerization system was 75 ° C., and the polymerization time was 8 hours. The polymerization initiator azoisobutyronitrile was directly added after the temperature of the system was raised.

[0095]

[Table 4]

In the above Table 4, vinyl acetate; insoluble polymer-forming monomer; terpolymer; polymer unit of block graft copolymer; isopar M; non-aqueous solvent (Y); vinyl pyrrolidone A comonomer component of the polymer unit of the terpolymer.

[0097]

[Table 5]

A composition similar to that of Example 2 was used except that the system in which the polyvinyl acetate particles prepared in this example were dispersed in Isopar M was used in place of the dispersant dispersion emulsion (prepared above) of Example 2. In the same manner as in Example 2, colored resin fine particles (3) were produced. Dynamic light scattering device (DLS70
0, manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the obtained colored resin fine particles (3) was 8.3 μm.

From the above, stable colorant-containing particles could be produced by using polyvinyl acetate particles as a stabilizer.

Comparative Example 1 For comparison with the ultrafine particles of the graft polymer of Synthesis Example 1 (the above dispersant = resin particles (P)), the graft polymer was soluble in the nonaqueous solvent (Y) under the composition and conditions shown in Table 6 below. A fine polymer was synthesized and colored resin fine particles were prepared using a dispersion stabilizer.

The polymer soluble in the non-aqueous solvent (Y) is a hydrophilic unit (more specifically, a polymer which is insoluble and self-dispersible in the non-aqueous solvent (Y) which is one of the constituents of the resin particles (P)). In the block or graft copolymer having a non-aqueous solvent (H), there is no hydrophilic polymer unit having no affinity for the non-aqueous solvent (Y). (Y) was dissolved in the isopar.

[0102]

[Table 6]

The GCB dispersion used was the one synthesized in Synthesis Example 2 (above).

In Comparative Example 1, colored fine particles could be produced, but polymer particles soluble in the non-aqueous solvent (Y) settled and then formed aggregates and could not be redispersed. In this comparative example, when a polymer soluble in Isopar, which is a non-aqueous solvent (Y), is used as a stabilizer instead of the graft polymer ultrafine particles (prepared above) of Synthesis Example 1 as a dispersion stabilizer, the intended colored resin fine particles are It turned out that it could not be obtained.

Example 4 Preparation of Blue Pigment CB-Containing Fine Particles The commercially available copper phthalocyanine blue (average particle diameter 300 nm) dispersion (pigment of pigment) Colored resin microparticles (4) were produced in the same manner as in Example 2 except that a resin component for dispersion was used to disperse copper phthalocyanine blue. In the measurement using a dynamic light scattering device (DLS700, manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the obtained colored resin fine particles (4) was 1 μm.
Met.

In Examples 1 to 4 described above, the graft polymer ultrafine particles (prepared above) of Synthesis Example 1 were used as a stabilizer. Conversely, finely dispersed GCB dispersed particles (polymer grafted color) were used. The following Example 5 specifically explains that it is possible to synthesize colored resin fine particles having a target particle diameter even when the agent is used as a stabilizer.

Example 5 (1) Preparation of a system (ii) in which an isopar dispersed GCB in the form of a polymer-grafted colorant was dispersed as a colorant component in a non-aqueous solvent (Y) (ii) Temperature sensor, stirring blade, cooling A composition shown in Table 7 below and 700 parts by mass of zirconia beads were added to a separable flask equipped with a tube, and the mixture was stirred at a rotation speed of 700 rpm and a reaction temperature of 100 ° C. for 5 hours. Then, the zirconia beads and the liquid were filtered. To obtain a graft carbon black dispersion (GCB DNI) (a system in which isoper-dispersed GCB is dispersed in a nonaqueous solvent (Y)).

[0108]

[Table 7]

The average particle diameter of the obtained finely dispersed isoper-dispersed GCB was 103 nm.

(2) Resin particles (P) in aqueous solvent (X)
Preparation of System (i) Dispersing ')) Monodisperse polystyrene fine particles (resin) having an average particle size of 1.2 µm in ethanol (aqueous solvent (X)) by polymerization with the raw material compositions shown in Table 8 below by dispersion polymerization. Particles (P ′)) were dispersed to obtain a system (i).

Synthesis of Polystyrene Fine Particle Dispersion

[0112]

[Table 8]

In the above Table 8, styrene; a monomer which is soluble in the aqueous solvent (X) and becomes insoluble by polymerization; polyvinyl pyrrolidone K-90; a resin component soluble in the aqueous solvent (X); ethanol; Aqueous solvent (X), Azobisisobutyronitrile; a polymerization initiator.

More specifically, the raw material components for synthesizing the polystyrene fine particles shown in Table 8 above were mixed in a separable flask equipped with a temperature sensor, a stirring blade, and a cooling tube at a stirring speed of 120 rpm under a nitrogen atmosphere at 70 ° C. for 24 hours. Polymerization was performed for a time to obtain a polystyrene fine particle dispersion. The average particle diameter of the polystyrene fine particles dispersed in the polystyrene fine particle dispersion was 1.2 μm.

(3) Preparation of Colored Resin Fine Particles In a 500 ml flask, 50 parts of the polystyrene fine particle dispersion obtained in the above (2) is placed, and the dispersion of the isoper dispersed GCB obtained in the above (1) is stirred while stirring at 500 rpm. 100 parts of the liquid was slowly dropped with a dropping pipette, and then 80 parts of Isopar was dropped. Thereafter, ethanol was degassed from the dispersion using an evaporator to produce colored resin fine particles (5). The average particle diameter of the obtained colored resin fine particles (5) was 20.5 μm.

[0116]

As described above, according to the present invention, it is possible to obtain colored resin particles which do not aggregate in a non-aqueous solvent and have good redispersibility. Further, according to the method of the present invention, even if an additive such as a charge controlling agent is added, the dispersion state of the particles is good and the electrical resistivity and the chargeability of the obtained colored resin particles can be easily controlled. Furthermore, because of the good dispersibility, the viscosity of the dispersion is also very low. Therefore, for example, it is a raw material that can be suitably used in the preparation of a liquid developer for electrophotography.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Tomoyuki Kuwamoto, Inventor 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Hayato Ikeda 5-8, Nishi-Otabi-cho, Suita-shi, Osaka Company N-catalyst F term (reference) 4F070 AA32 AA35 AB08 AE04 DA33 DC13 4J011 PA03 PA65 PA69 PA83 PB25 PC02 4J026 AC15 AC16 BA05 BA20 BA27 BA32 FA04 GA06

Claims (2)

[Claims] (I) disposing an additive containing a colorant component and a resin component in water or a water-miscible solvent (hereinafter, these may be referred to as an aqueous solvent (X)); ii) In a non-aqueous solvent (Y) that is immiscible with the aqueous solvent (X), the non-aqueous solvent (Y) is insoluble in the non-aqueous solvent (Y) and a self-dispersible block or graft copolymer is used. By polymerizing a monomer which is soluble in the aqueous solvent (Y) and becomes insoluble by polymerization, resin particles (P) dispersed in the non-aqueous solvent (Y) are obtained, and (iii) the resin particles (P) ) Is added to the system obtained in the above (i) to form droplets containing the coloring agent component and the resin component in the nonaqueous solvent (Y), and the aqueous solvent (X) is removed for coloring. A method for producing colored resin particles, comprising producing resin particles. 2. (i) In water or a water-miscible solvent (hereinafter sometimes referred to as an aqueous solvent (X)), a resin component soluble or self-dispersed in the aqueous solvent (X) In the presence, by polymerizing a monomer that is soluble in the aqueous solvent (X) and becomes insoluble by polymerization, resin particles (P ′) dispersed in the aqueous solvent (X) are obtained. (Ii) a system in which a colorant component is dispersed in a non-aqueous solvent (Y) that is immiscible with the aqueous solvent (X), and is added to the system obtained in (i). A method for producing colored resin particles, comprising forming droplets containing the coloring agent component and the resin component in a solvent (Y), and removing the aqueous solvent (X) to produce colored resin particles.