JPH0334062B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a microcapsule toner that is used for developing electrostatic images and other latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc., and is particularly suitable as a so-called pressure fixing toner. It is. Conventionally, as an electrophotographic method, U.S. Patent No.
Although many methods are known as described in Japanese Patent Publication No. 2297691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, and others, generally,
A latent image is formed on a photoreceptor made of a photoconductive substance by various means, this latent image is developed using toner, and the toner image is transferred to a transfer material such as paper as necessary. The image is then fixed by applying heat, pressure, solvent vapor, etc. to obtain a copied image. Further, as a method for developing a latent image using toner, for example, the magnetic brush method described in U.S. Pat. No. 2,874,063, the cascade method described in U.S. Pat. Many other methods are known, including the powder cloud method described in the specification, the fur brush method, and the liquid development method. On the other hand, methods for fixing toner images include a heating fixing method in which the toner is heated and melted using a heater or a heated roller, etc., and then fused and solidified to a support such as a transfer material; There are known methods such as a solvent fixing method in which toner is fixed on a support by using a pressure roller or the like, and a pressure fixing method in which the toner is fixed on a support by pressure using a pressure roller or the like. The components of toner are selected to suit the fixing method used, and toner that is fixed by one fixing method is usually difficult to fix by another fixing method. Among the above fixing methods, the pressure fixing method is patented in the US Patent No.
It is described in Specification No. 3269626, Japanese Patent Publication No. 46-15876, and others, and consumes less energy.
This method is advantageous in that there is no risk of pollution, no waiting time is required after the fuser starts driving, there is no risk of burning the transfer paper, high-speed fixing is possible, and the structure of the fuser is simple. It is. On the other hand, in the pressure fixing method, the toner fixing properties are generally low, and there are disadvantages such as an offset phenomenon in which a portion of the toner is transferred to the pressure roller and stains the subsequent image. research is being conducted. For example, for the purpose of improving pressure fixing properties, Japanese Patent Publication No. 44-9880 discloses a pressure fixing toner containing an aliphatic component and a thermoplastic resin component, and Japanese Patent Publication No. 57-6588 discloses a toner containing a tenacious polymer. A pressure fixing toner using a soft polymer block polymer is disclosed. However, to date, there is no known pressure fixing toner that has sufficient fixing properties and is practically satisfactory, and although some have been put into practical use, it is necessary to compensate for their low fixing properties. It is said that A suitable type of toner for pressure fixing is a microcapsule toner, which consists of a wall film forming a microcapsule that is destroyed by pressure, and a relatively soft core material encapsulated within the microcapsule. Various types are known. In order for this microcapsule toner to have good pressure fixing properties, it is necessary for the core material to have appropriate viscosity and elasticity. However, a core material having a viscosity suitable for fixing has a viscosity that is too high for the dispersion of colorants, magnetic powder, and other additives that need to be dispersed in the core material. If it is difficult to uniformly disperse the core material, and if the microcapsule formation process includes a step of dispersing the core material in a liquid that is incompatible with the core material, It is difficult to disperse the material sufficiently and uniformly. However, if a core material with low viscosity is used to eliminate such disadvantages, the pressure fixing properties will be reduced. The present invention has been made based on the above circumstances, and has excellent pressure fixing properties, additives such as colorants are sufficiently uniformly dispersed in the core material, and is easier to manufacture. The purpose of the present invention is to provide a microcapsule toner that can The present invention is characterized in that in a microcapsule toner comprising a resin wall film and a core material thickened by a curing reaction, the core material is a reaction product of an epoxy compound and an amine compound, a xanthate ester, etc. and an amine compound or an organic acid metal salt, and a reaction product of an isocyanate compound and an amine compound. The present invention will be specifically explained below. In the present invention, a core material in which colorants, magnetic substances, and other additives are dispersed and whose viscosity has been increased by a curing reaction is encapsulated in microcapsules made of a resin wall film. Use microcapsule toner. According to the present invention, the core material is thickened by a curing reaction, and the material of the core material naturally has a low viscosity before the curing reaction,
Therefore, it is possible to disperse the additives sufficiently uniformly in the core material before the curing reaction, so that in the end, the additives are dispersed sufficiently uniformly and the viscosity is high, making it suitable for pressure fixing. A microcapsule toner having a core material is obtained. That is, according to the toner of the present invention, a toner image formed by developing a latent image is sufficiently transferred onto a support such as paper by a pressure fixing method, specifically, by a pressure fixing device consisting of a pair of pressure rollers. It is possible to fix it, and after securing this fixation,
Furthermore, since the additives are uniformly contained in the core material,
Sufficient amounts of additives can be included to achieve the intended purpose, so that if the additive is a colorant, the intensity of the color in the visible image can be sufficiently high, and if the additive is a colorant, the intensity of the color in the visible image can be sufficiently high, or if the additive is a colorant, If it is a solid material, sufficient magnetism can be imparted to the toner, making it possible to advantageously utilize, for example, magnetic brush development, as well as making the characteristics of the toner uniform, forming an excellent visible image. can do. The core material in the present invention is made by hardening and thickening the core material, and therefore, the core material only needs to be a liquid material that undergoes such a hardening reaction, and is made of a single material and is resistant to heat. Accordingly, they can be classified into those that cause a curing reaction, those that cause a curing reaction with or without heating with an appropriate curing agent, and others, but those that cause a curing reaction with a curing agent are particularly preferred for practical purposes. Preferred specific combinations of core materials in which a curing reaction occurs with such a curing agent include the following. Combination of epoxy compound and amine compound Examples of epoxy compounds Epoxy resin, epoxidized soybean oil, epoxidized linseed oil, epoxidized polyester, other liquid compounds containing epoxy groups Examples of amine compounds Ethylenediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, imidazoles, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, isophoronediamine, other primary and secondary or a tertiary amine A combination of a xanthate ester and an amine compound or an organic acid metal salt Examples of xanthate esters Chloroprene having an alkylzantate group at the end, such as alkyl Examples of xanthate-modified amine compounds - Same as the above examples of amine compounds - Examples of organic acid metal salts Naphthenic acid metal salts, stearic acid metal salts, other organic acid metal salts Combination of isocyanate compounds and amine compounds Isocyanate compounds Examples of toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene diisocyanate, and other polyisocyanate compounds Examples of amine compounds Polyamines listed in the examples of amino compounds above In each of the combinations listed above, generally the former The latter is said to be the main agent and the latter is said to be the curing agent, but this distinction may be convenient in some cases. The ratio of these combinations varies depending on the specific combination, so it cannot be stated in general. In addition, the resin wall film constituting the microcapsules is not limited, but is preferably formed by a polymerization reaction, such as epoxy resin, polyamide resin, polyurethane resin, polyurea resin, or vinyl resin. , and others are practically preferable resin wall membrane materials. Typical epoxy resins here are those obtained by curing the reaction product of bisphenol A and epichlorohydrin, and curing agents include ethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, hexamethylenediamine, imino Examples include bispropylamine, other aliphatic polyamine compounds, xylylene diamine, phenylene diamine, other aromatic polyamine compounds, and other generally known epoxy curing agents. Examples of polyamide resins include so-called polyamide resins obtained by the reaction of carboxylic acid chlorides such as sebacyl chloride, terephthalic acid chloride, and adipic acid chloride with aliphatic polyamines and aromatic polyamines exemplified as curing agents for the above-mentioned epoxy resins. Polyamide resin can be used. Polyurethane resins are obtained by reacting polyisocyanates with polyols, and polyurea resins are obtained by reacting polyisocyanates with polyamines. Specific examples of polyisocyanates include the following. (1) Hexamethylene diisocyanate OCN (CH ₂ ) ₆ OCN Commercial product: “Desmodyur H” manufactured by Sumitomo Bayer Urethane Industries, Ltd. (2) Commercial product: "Desmodyur N" manufactured by Sumitomo Bayer Urethane Industries (3) Metaphenylene diisocyanate Commercial product: "Naphconate" manufactured by National Aniline (4) Toluylene isocyanate

[Formula] and

Mixture with [Formula] Commercial products: "Desmodyur T" manufactured by Sumitomo Bayer Urethane Industries, Ltd. "Hiren TM" manufactured by DuPont (5) 2.4-Tolylene diisocyanate Commercial product: "Desmodyur T" manufactured by Sumitomo Bayer Urethane Industries (6) Reaction product of toluylene isocyanate and trimethylolpropane Commercial product: "Desmodyur L" manufactured by Sumitomo Bayer Urethane Industries, Ltd. Commercial product: "Coronate L" manufactured by Nippon Polyurethane Industries, Ltd. (7) 3,3'-dimethyl-diphenyl-4,4'-diisocyanate Commercial product: "Hyren H" manufactured by DuPont (8) Diphenylmethane-4,4'-diisocyanate Commercial product: "Millionate MT" manufactured by Nippon Polyurethane Industries (9) 3,3'-dimethyl-diphenylmethane-4,
4′-diisocyanate Commercial product: “Hiren DMM” manufactured by Dupont (10) Triphenylmethane-triisocyanate Commercial product: "Desmodyur R" manufactured by Sumitomo Bayer Urethane Industries, Ltd. (11) Polymethylene phenyl isocyanate Commercial product: "Millionate MR" manufactured by Nippon Polyurethane Industries (12) Naphthalene-1,5-diisocyanate Commercial product: "Desmodyur 15" manufactured by Sumitomo Bayer Urethane Industries, Ltd. Specific examples of polyols or polyamines that react with the above polyisocyanates to produce polyurethane resins or polyurea resins include the following. (1) Polyol Diols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,
Triols such as 2,6-hexanetriol, pentaerythritol, water, others (2) Polyamines Ethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, phenylenediamine, xylenediamine, triethylenetetramine, and others Vinyl-based Vinyl polymerizable monomers for obtaining the resin include styrenes such as styrene, parachlorostyrene, α-methylstyrene, and t-butylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, and stearyl acrylate. , 2-ethylhexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, α-methylene aliphatic monocarboxylic acid esters, acrylonitrile, methacrylate Vinyl nitriles such as lonitrile, vinyl methyl ether,
Vinyl ethers such as vinyl isobutyl ether, vinyl pyridines such as 2-vinylpyridine and 4-vinylpyridine, N-vinyl cyclic compounds such as N-vinylpyrrolidone, vinyl methyl ketone, vinyl ethyl ketone, methyl isopropenyl ketone, etc. Vinyl ketones, unsaturated hydrocarbons such as ethylene, propylene, isobutylene, butadiene, and isoprene, halogen-containing unsaturated hydrocarbons such as chloroprene, and other monofunctional vinyl monomers can be used alone or in combination. In addition to the above monofunctional monomers, polyfunctional vinyl monomers can also be used, and these polyfunctional monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol. Polyhydric alcohol methacrylates such as dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol tetramethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neo Polyhydric alcohol acrylates such as pentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pentaerythritol tetraacrylate, polyfunctional vinylbenzenes such as divinylbenzene, and others can be used alone or in combination. Furthermore, these polyfunctional monomers may be used in combination with the monofunctional monomers described above. The microcapsule toner of the present invention is formed by an appropriate combination of the above-mentioned core material and resin wall material, but a coloring agent is usually contained in the core material or further in the resin wall material. It will be done. When the toner of the present invention is a magnetic toner, fine magnetic powder is contained instead of or together with the colorant. In addition to these, various additives may be included as necessary. Coloring agents include carbon black, nigrosine dye (CI No. 50415B), and aniline blue (CI No.
50405), Calco Oil Blue (CINo.
azoecBlue3), Chrome Yellow (CINo.14090),
Ultramarine Blue (CI No. 77103), DuPont Oil Red (CI No. 26105), Quinoline Yellow (CI No. 47005), Methylene Blue Chloride (CI
No.52015), Phthalocyanine Blue (CINo.
74160), malachite green oxalate (CI
No. 42000), lamp black (CI No. 77266), rose bengal (CI No. 45435), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image with sufficient density, and are usually contained in a proportion of about 1 to 20 parts by weight per 100 parts by weight of toner. The magnetic material may be a ferromagnetic metal or alloy such as iron, cobalt, or nickel, including ferrite and magnetite, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. Alloys that become ferromagnetic, such as manganese-copper-aluminum,
Mention may be made of a type of alloy called a Heusler alloy containing manganese and copper, such as manganese-copper-tin, or chromium dioxide, among others. These magnetic substances are uniformly dispersed in the fluid core material in the form of fine powder with an average particle size of 0.1 to 1 micron. The content is 20 to 70 parts by weight per 100 parts by weight of toner.
Preferably it is 40 to 70 parts by weight. The toner of the present invention can be manufactured by the following method. (b) A core material in which additives such as a colorant and magnetic fine powder are uniformly dispersed is cured to obtain a core material, and a monomer and a polymerization initiator, etc. that provide a resin for the wall film are added. A method in which the core material substance is dispersed as fine particles in a dissolved medium, and in this state, the system is placed under polymerization conditions to precipitate a polymer made of the monomers on the surface of the particles of the core material material. (b) A core material in which additives such as a coloring agent and fine magnetic powder are uniformly dispersed is dispersed as fine particles in a medium that does not disintegrate, and in that state, the core material is heated, etc. After curing, monomers and polymerization initiators that provide the resin for the wall film are dissolved in a medium, and the system is placed under polymerization conditions to form microparticles that are cured and become the core material. A method of depositing a polymer of the monomer on the surface. (c) Prepare a solution of the core material, a monomer that provides the resin for the wall film, a polymerization initiator, etc., and uniformly disperse additives such as a coloring agent and fine magnetic powder into this solution to form a toner. A composition is prepared, this toner composition is dispersed in a medium as microparticles, and in this state, the system is placed under polymerization conditions to form a polymer layer on the surface of each microparticle, and at the same time, the core material is cured. How to coerce. (d) A polymer wall film is formed on the surface of microparticles of core material in which additives such as colorants and fine magnetic powders are uniformly dispersed, and the core material inside is not yet hardened. A method in which a capsule is formed and then the core material inside is hardened by heating, etc. As described above, the method for producing the toner of the present invention includes a method in which the core material is pre-cured and then microencapsulated, a method in which curing and microencapsulation of the core material are simultaneously performed, and a method in which the core material is microencapsulated and then microencapsulated. Methods for curing materials can be broadly classified into methods, but method (c) above is actually advantageous. The method (c) above will be explained in detail. A mixture of core materials in combination as described above,
A monomer that provides a polymer for wall membrane material that can be combined with this is mixed with polymerization aids such as a polymerization initiator and a crosslinking agent as necessary, and additives such as a coloring agent are added. A liquid toner composition is prepared by uniformly mixing and dispersing the toner composition, and this toner composition is dispersed and suspended in the form of fine particles in a dispersion medium that does not dissolve the core material, monomers, etc. The particle size of the dispersed fine particles can be determined by, for example, controlling the rotation speed of a stirrer such as a homomixer used for suspension dispersion while monitoring the particle size and dispersion state by observation using a microscope, etc. It can be controlled to a desired size. In such a state, the system is placed under polymerization conditions in which the monomer is polymerized, thereby forming a polymer layer on the surface of each fine particle to perform microencapsulation, and at the same time, the core material is The material is cured to produce the microcapsule toner of the present invention. In the above, the component proportions of the toner composition are:
The proportion of core material in the final toner is 30~
It is selected to be within the range of 80% by weight. Furthermore, in carrying out the above-mentioned method, the monomer is often lipophilic, and it is therefore advantageous to use a lipophilic core material as well, so in most cases the toner composition is It becomes lipophilic as a whole. Therefore, water or a non-lipophilic liquid may be used as the dispersion medium.
In practice, it is necessary to mix a dispersion stabilizer into this dispersion medium, so that the toner composition can be maintained in a stably dispersed and suspended state during the polymerization reaction. Examples of dispersion stabilizers include water-soluble polymer substances such as gelatin, gelatin derivatives, polyvinyl alcohol, polystyrene sulfonic acid, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, and sodium polyacrylate, and anionic surfactants. Surfactants such as surfactants, nonionic surfactants, and cationic surfactants, hydrophilic inorganic colloids such as colloidal silica, alumina, tricalcium phosphate, ferric hydroxide, titanium hydroxide, and aluminum hydroxide. Substances and others can be used effectively. Of course, two or more of these can be used in combination, or a suitable auxiliary agent can be used at the same time. Specific examples of the polymerization initiator used in the polymerization reaction system include organic peroxides such as benzoyl peroxide and lauroyl peroxide, and azobis-based polymerization initiators such as azobisisobutyronitrile and azobisparellonitrile. can be mentioned. The amount of this polymerization initiator is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the monomer components of the toner composition. Note that when containing magnetic fine powder to make a magnetic toner, it can be treated in the same way as the colorant, but as it is, the affinity for organic substances such as core materials and monomers will decrease. Therefore, if the magnetic fine powder is used together with a so-called coupling agent such as a titanium coupling agent, a silane coupling agent, or lecithin, or after being treated with a coupling agent, the magnetic fine powder can be uniformly dispersed. The microcapsule toner of the present invention can be used as a two-component developer by being mixed with a carrier made of iron powder, glass beads, etc., or can be used as is as a one-component developer when it contains a magnetic material. Some specific examples of combinations of core material, wall material, etc., which can suitably carry out the present invention, along with their conditions, are as shown in the following table. Note that numbers 1 to 3 are suitable for in-situ polymerization, number 4 is suitable for interfacial polymerization, and number 5 is suitable for in-liquid drying.

[Table] Items marked with * are product names.
Examples of the present invention will be described below, but the present invention is not limited thereto. Further, A represents a core material, B represents a monomer, C represents a polymerization initiator, and D represents an additive. Example 1 A: Alkylzantate-terminated liquid chloroprene “Denka LCR X-50” (manufactured by Denki Kagaku Kogyo Co., Ltd.,
Viscosity 40000CPS) 150g Amine curing agent for epoxy resin "Epomate B"
-001" (manufactured by Yuka Ciel Epoxy Co., Ltd.) 20g B: Ethylene glycol dimethacrylate 100g styrene 50g C: Azobisisobutyronitrile 7.5g D: Triiron tetroxide "BL-100" (manufactured by Titan Kogyo Co., Ltd.)
300g Lecithin A toner composition is prepared by uniformly mixing 1.5g or more of the substance at room temperature using a sand grinder disperser.
The above toner composition was dispersed in water 3 containing 12 g of colloidal tricalcium phosphate as a dispersion stabilizer and 0.2 g of sodium dodecylbenzenesulfonate using a homogeator, and the average particle size of the dispersed fine particles was adjusted to 10 to 15 μm. . This suspended dispersion was placed in a four-necked flask, heated to 70°C, and kept at this temperature for 8 hours to harden and thicken the core material and form a polymer layer on the surface of each dispersed fine particle. I forced it. Then, add hydrochloric acid to remove the dispersion stabilizer, separate the solid particles, wash with water and dry to obtain an average particle size.
A microcapsule toner of the present invention having a thickness of 15μ and a wall thickness of about 1μ was produced. This is referred to as "toner 1". Example 2 A: Epoxidized soybean oil “ADK CizerO-130P”
(manufactured by Adeka Argus Chemical Co., viscosity 250CPS)
150g Hardening agent for epoxy resin "Epiquure U" (manufactured by Yuka Ciel Epoxy Co., Ltd.) 15g B: Ethylene glycol dimethacrylate 100g Styrene 50g C: Azobisisobutyronitrile 7.5g D: Triiron tetroxide "BL-100" 300g Lecithin 1.5g A microcapsule toner of the present invention was produced in exactly the same manner as in Example 1 using the above substances.This is referred to as "Toner 2".Example 3 A: Alkylzantate-terminated liquid chloroprene "Denka LCR -50” (viscosity 40000CPS)
150g Cobalt naphthenate (curing agent) 15g B: Polyisocyanate "Desmodyur L"
(Manufactured by Sumitomo Bayer Urethane Industries, Ltd.) 30g D: Triiron tetroxide "BL-100" 200g Lecithin 1.5g or more are mixed uniformly using a sand grinder disperser to make a toner composition, and a dispersion stabilizer is used. The above-mentioned toner composition was dispersed in water 3 containing 20 g of colloidal silica and 0.75 g of ophtadecyltetramethylammonium chloride using a homogeator, and the average particle size of the dispersed fine particles was adjusted to 10 to 10.
It was set to 15μ. Into this suspended dispersion, 200 ml of an aqueous solution in which 8 g of triethylenetetramine, a polymerization initiator, was dissolved was added dropwise over 1 hour, and the dispersion was continued to be stirred for 3 hours to coat the surface of the dispersion particles. After forming a urea wall film, the temperature of the system was raised to 60° C. and maintained at that temperature with continued stirring for 5 hours to cure the core material. Then, the solid particles were separated, washed with water and dried to produce a microcapsule toner of the present invention having an average particle size of 13 μm and a wall thickness of about 1 μm. This will be referred to as "toner 3." Example 4 A: Alkylzantate-terminated liquid chloroprene "Denka LCR X-50" (viscosity 40000CPS)
150g Cobalt naphthenate (curing agent) 15g B: Polyisocyanate "Desmodyur L"
(Manufactured by Sumitomo Bayer Urethane Industries, Ltd.) 30g D: Triiron tetroxide "BL-100" 200g Lecithin 15g A toner composition is prepared by uniformly mixing 15g or more of the substances using a sand grinder disperser, and a dispersion stabilizer colloid. The toner composition was dispersed in water 3 containing 20 g of silica and 0.75 g of ophtadecyltetramethylammonium chloride using a homogeator, and the average particle size of the dispersed fine particles was 10 to 10.
It was set to 15μ. While stirring this suspended dispersion with a stirrer, the temperature of the system was raised to 60°C, and then 200 ml of 8 g of triethylenetetramine, a polymerization initiator, was dissolved.
Add an aqueous solution dropwise over 1 hour, then continue stirring the dispersion for 5 hours while maintaining the temperature of the system to harden the core material and at the same time form a wall film made of polyurea on the surface of the dispersion particles. I forced it. After that, the solid particles were separated, washed with water and dried to obtain an average particle size of 13 μm.
A microcapsule toner of the present invention having a wall thickness of about 1 μm was produced. This will be referred to as "toner 4". Example 5 A: Alkylzantate-terminated liquid chloroprene "Denka LCR X-50" (viscosity 40000CPS)
150g Cobalt naphthenate (curing agent) 15g B: Polyisocyanate "Desmodyur L"
(manufactured by Sumitomo Bayer Urethane Industries, Ltd.) 30g D: Triiron tetroxide "BL-100" 200g Lecithin 1.5g or more are mixed uniformly using a sand grinder disperser to make a toner composition, and a dispersion stabilizer is used. The above-mentioned toner composition was dispersed in water 3 containing 20 g of colloidal silica and 0.75 g of ophtadecyltetramethylammonium chloride using a homogeator, and the average particle size of the dispersed fine particles was adjusted to 10 to 10.
It was set to 15μ. While stirring this suspended dispersion with a stirrer, the temperature of the system was raised to 60°C, and stirring of the dispersion was continued for 5 hours while maintaining that temperature to harden the core material, and then the polymerization initiator was triturated. 200 ml of an aqueous solution in which 8 g of ethylenetetramine was dissolved was added dropwise to the system over 1 hour while stirring, and stirring was continued for 3 hours to form a wall film made of polyurea on the surface of the dispersion particles. Ta. After that, the solid particles were separated, washed with water and dried to obtain an average particle size of 13 μm and a wall thickness of approximately
A 0.7μ microcapsule toner of the present invention was produced. This is referred to as "toner 5". Example 6 A: Alkylzantate-terminated liquid chloroprene "Denka LCR X-50" 150g Amine curing agent for epoxy resin "Epomate B
-001'' 20g B: Methyl methacrylate-styrene copolymer (9:1) 150g D: Triiron tetroxide ``BL-100'' 300g Lecithin 5g Dissolve B in 1 part of methylene chloride, then dissolve A, and then add lecithin. was added, triiron tetroxide was added while stirring using a sand grinder disperser while maintaining the temperature at 10° C., to prepare a toner composition, and the mixture was stirred for 1 hour. This was dispersed in an aqueous solution prepared by dissolving 40 g of polyvinyl alcohol in 10 parts of water using a homogeator, so that the average particle size of the dispersed fine particles was 10 to 15 μm. This suspended dispersion was placed in a four-necked flask equipped with a distillation device, and the temperature of the system was adjusted while stirring.
Gradually raise the temperature to 40℃ and keep it for 1 hour, then 50℃
The temperature was raised to .degree. C. and maintained for 3 hours, thereby curing the core material and at the same time precipitating the wall material on the surface of the particles to form a wall film. After the odor of methylene chloride completely disappeared, the solid particles were separated, washed with water and dried to produce a microcapsule toner of the present invention having an average particle size of 13 μm and a wall thickness of about 1 μm. This will be referred to as "toner 6". Example 7 A: Alkylzantate-terminated liquid chloroprene "Denka LCR X-50") 150g Amine curing agent for epoxy resin "Epomate B
-001'' 20g B: Methyl methacrylate-styrene copolymer (9:1) 150g D: Triiron tetroxide ``BL-100'' 300g Lecithin 5g Dissolve B in 1 part of methylene chloride, then dissolve A, and then add lecithin. was added, triiron tetroxide was added while stirring using a sand grinder disperser while maintaining the temperature at 10° C., to prepare a toner composition, and the mixture was stirred for 1 hour. This was dispersed in an aqueous solution prepared by dissolving 40 g of polyvinyl alcohol in 10 parts of water using a homogeator, so that the average particle size of the dispersed fine particles was 10 to 15 μm. This suspended dispersion was placed in a four-necked flask equipped with a distillation device and stirred at room temperature for 4 days to harden the core material. Thereafter, while continuing to stir, the temperature of the system was gradually raised to 40°C and held for 1 hour, then raised to 50°C and held for 3 hours, thereby coating the surface of the core material particles with the wall film material. A wall film was formed by precipitation. After the odor of methylene chloride completely disappeared, the solid particles were separated, washed with water and dried to produce a microcapsule toner having an average particle size of 13 μm and a wall thickness of about 1 μm. This will be referred to as "toner 7". Comparative Examples 1 to 7 In each of Examples 1 to 7, a comparative microorganism of an uncured core material was prepared in exactly the same manner as in the corresponding example except that the curing agent of the core material (A) was excluded. A total of seven types of capsule toners were manufactured. These are referred to as "comparison toner 1" to "comparison toner 7", respectively. Experimental example Toner 1 to Toner 7 obtained as above
Using each of Comparative Toner 1 to Comparative Toner 7 as a developer, an electrophotographic copying machine "U-
BixT" (manufactured by Konishiroku Photo Industry Co., Ltd.) was used to develop the electrostatic charge image, and the toner image was transferred to transfer paper made of plain paper.
Fixing was carried out by a pressure fixer having a linear pressure of cm. When the visible image thus obtained was rubbed with a plastic eraser or with paper of the same type as the transfer paper, almost no change was observed in any of the visible images created by Toner 1 to Toner 7, indicating that a good visible image was formed. Ta. On the other hand, comparative toners 1~
According to Comparative Toner 7, the visible image had low density.

Claims (1)

[Scope of Claims] 1. A microcapsule toner comprising a resin wall film and a core material thickened by a curing reaction, wherein the core material is a reaction product of an epoxy compound and an amine compound, a xanthate ester, and an amine. A microcapsule toner comprising at least one selected from a reaction product with a compound or an organic acid metal salt, and a reaction product between an isocyanate compound and an amine compound. 2. The microcapsule toner according to claim 1, wherein the resin wall film is formed by a polymerization reaction.