JPS5919949A - Microencapsulated toner - Google Patents

Abstract

PURPOSE:To obtain a microencapsulated toner having superior pressure fixability, uniform dispersibility of additives into a core material, and easiness of manufacure, by preparing the toner with a resin wall film and the core material raised in viscosity. CONSTITUTION:The microencapsulated toner is obtained by dispersing a colorant, a magnetic material, etc. into the core material raised in viscosity by hardening reaction, and sealing it into microcapsules made of a resin wall film. As said core material, a reaction product of an epoxy compd. and an amine compd., an acid anhydride, or a Lewis acid, xanthate and amine compd., reaction products of metal salts of org. acids, metal halide, metal oxide, or org. peroxide, etc. are preferably used. As the resin wall film, products of polymerization reaction are preferable, an epoxy resin, a polyamide resin, a polyurethane resin, etc. are exemplified.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is used for developing electrostatic images and other latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc., and is particularly applicable to so-called pressure fixing toners. This invention relates to a microcapsule toner suitable as a microcapsule toner.

Conventionally, as an electrophotographic method, US Pat. No. 2,297,691
No. specification, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43
A number of methods are known, as described in Japanese Patent No. 24748 and others, but in general, a latent image is formed on a photoreceptor made of a photoconductive material by various means. Then, this latent image is developed using toner, and if necessary, the tonate image is transferred to a transfer material such as paper, and then fixed by applying heat, pressure, solvent vapor, etc. to obtain a copied image. It is something.

Further, as a method for developing a latent image using toner, for example, the a-air brush method described in U.S. Pat. No. 2,874,063, the cascade method described in U.S. Pat. No. 2,618,552, and the 2221776 Specification 1
Many other methods are known, including the powder cloud method described in mFK, the Arplash 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 pressure rollers, and a pressure fixing method in which toner is fixed on a support by pressure from a suppression roller or the like. The components of the toner are selected to suit the fixing method used, and the toner fixed by this fixing method is usually difficult to fix by other fixing methods.

Among the above fixing methods, the pressure fixing method is disclosed in U.S. Patent No. 3269.
No. 626 Specification*, VF Publication No. 15876/1976, and others, it consumes less energy, has no risk of pollution, does not require waiting time after the fuser starts driving, and can print the transfer paper. This method is advantageous in that there is no risk of burning, high-speed fixing is possible, and the structure of the fixing device is simple.

On the other hand, the pressure fixing method has drawbacks such as generally low toner fixing properties and an offset phenomenon in which a portion of the toner is transferred to the suppression roller and stains subsequent images.
Various studies have been conducted on pressure fixing toners. For example, for the purpose of improving pressure fixing properties,
Japanese Patent Publication No. 9880 discloses a toner for pressure fixing containing an aliphatic component and a thermoplastic resin component, and Japanese Patent Publication No. 57-6588 discloses a toner for pressure fixing using a 7-lock combination of a tenacious polymer and a soft texture polymer. A toner 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 microcapsule toner, which consists of a wall membrane that constitutes a microcapsule that is destroyed by pressure, and a relatively soft core material that is 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, the core material having a viscosity suitable for fixing is
A coloring agent that needs to be dispersed and contained in the core material,
The viscosity is too high for dispersing magnetic powder and other additives, making it difficult to disperse them uniformly.
When a step of dispersing the core material in a liquid that is incompatible therewith is included, it is difficult to sufficiently and uniformly disperse the core material in this step.

However, if a 6-material 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 feature of the present invention is that it is composed of a resin wall film and a core material whose viscosity has been increased by a curing reaction.

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 thickened by a curing reaction is encapsulated in microcapsules made of a resin wall film. Use as capsule 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, so this curing reaction 8
Since the additives can be evenly dispersed in the core material No. 11, the core material has a sufficiently uniform distribution of additives and has a high viscosity, making it suitable for pressure fixing. A microcapsule toner is obtained.

That is, according to the toner of the present invention, a toner image formed by developing a latent image is sufficiently transferred to paper using a pressure fixing method, specifically, a pressure fixing device comprising a pair of suppression rollers. It is possible to fix it on a support such as, and after ensuring this fixing property, the additive is evenly contained in the core material, so it is sufficient to achieve the desired purpose. As a result, if the additive is a colorant, the density of the color in the visible image can be sufficiently increased, and if the additive is a magnetic substance, it can impart sufficient magnetism to the toner. For example, magnetic brush development can be advantageously used, and the characteristics of the toner can be made uniform, so that excellent visible images can be formed.

The core material in the present invention is a material obtained by hardening and thickening the core material. Therefore, the core material may be a liquid material that undergoes such a hardening reaction. 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.

L. Combination of epoxy compound and amine compound, acid anhydride or Lewis acid Examples of epoxy compounds Epoxy resin, epoxidized soybean oil, epoxidized linseed oil, epoxidized polyester, other liquid compounds containing epoxy groups ゛Amine Examples of compounds: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, imidazoles, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, isophoronediamine, and others. Examples of primary, secondary or tertiary amino acid anhydrides Phthalic anhydride, hexahydrophthalic anhydride, dodecynylsuccinic anhydride, pyromellitic anhydride, chlorenic anhydride, other acid anhydrides Examples of Lewis acids In addition to boron complex compounds and other Lewis acids, combinations of epoxy compounds and general epoxy resin curing agents are also effective.

(2) Combinations of xanthate esters and amine compounds, organic acid metal salts, metal halides, metal oxides, or organic peroxides Examples of xanthate esters Chloroprene having an alkylzantate group at the end, such as [Denka LCRJ ( Examples of alkyl xanthate modified amine compounds such as Denki Kagaku Kogyo M); Same as the amine compounds in I above; Examples of organic acid metal salts; Naphthenic acid metal salts, stearic acid metal salts, and other organic acid metal salts. Examples of metal halides Tin chloride, zinc chloride, iron chloride, and other metal halides Salts of metal oxides Zinc oxide and other metal oxides Examples of organic peroxides Benzoyl peroxide, lauroyl peroxide, and other organic Combination of acid metal salt isocyanate compound and amine compound or polyol Examples of isocyanate compounds Toluylene diisocyanate, diphenylmeth”-4
+ 4- Diisocyanate, naphthylene diisocyanate, and other polyisocyanate compounds Examples of amine compounds Examples of polyamine polyols listed in the example of amino compounds in I above Ethylene glycol, glycerin, and other polyols ■Natural or synthetic drying oil or semi-drying oil Combination of oil or unsaturated fatty acid ester with naphthenic acid metal salt or fatty acid metal salt Examples of natural drying or semi-drying oils: Tung oil, Nino oil, linseed oil, sesame oil, soybean oil, hemp seed oil,
Kapok oil, poppy oil, rice bran oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, safflower oil, and other natural drying or semi-drying oils Examples of copolymers, dicyclopentadiene oligomers, other drying oils or semi-drying oils of unsaturated fatty acid esters I) -luric acid, lylunic acid, oleic acid, dihydric acid,
Examples of eleostearic acid, lyrunelaidic acid, gadonic acid, erucic acid, and other unsaturated fatty acid ester naphthi/acid metal salts Cobalt naphthenate, naphthi/lead acid, iron naphthenate, calcium nanthenate, manganese naphthenate, etc. Naphthenic acid metal salt Examples of fatty acid metal salts Aluminum stearate, zinc stearate, and other fatty acid metal salts In each of the above-mentioned combinations, the former is generally used as the main agent and the latter as the curing agent, but the distinction is Sometimes it is convenient. The ratio of these combinations varies depending on the specific combination K, 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 resins, polyurea resins, vinyl resins, and others are practically preferred resin wall 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, hexamethylene diane, 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. can be used.

Polyurethane resins are obtained by the reaction of polyisocyanates and polyols, and polyurea resins are obtained by the reaction of polyisonoanates and polyamines. Specific examples of polyisocyanates include the following 〇(14) l) Hexamethylene diisocyanate OCN (CHz) aOcN Commercial product 2 "Desmodur H" manufactured by Sumitomo Bayer Urethane Industries, Ltd. 2) COC6H12NCO Commercially available Product = "Desmodur N" Manufactured by Sumitomo Bayer Urethane Industries, Ltd. 3) Metaphenylene diisocyanate CO Commercial product: "Naphconate" Manufactured by Nanyonalanili/Co., Ltd. 4) Toluylene isocyanate Commercial product 2 U Desmodur T" Manufactured by Sumitomo Bayer Urethane Industries, Ltd. [Hylene TMJ DuPont Co., Ltd. 5) 2.4-) Rylene diisocyanate commercial product = [
DES MODULE ECO manufactured by Sumitomo Bayer Urethane Industries, Ltd. 6) Reaction product of toluylene incyanate and trimethylolpropane Commercial product manufactured by Sumitomo Bayer Urethane Industries, Ltd. = [Coronet) LJ Manufactured by Nippon Polyurethane Industries, Ltd. 7) 3,3-dimethyl -Diphenyl-4,4-diisocyanate Commercial product = [-Hylene (manufactured by DuPont 8) Diphenylmethane-4,4-diisocyanate Commercial product: "
Millionate MTJ Manufactured by Nippon Polyurethane Kogyo Co., Ltd. 9) 3,3'-dimethyl-diphenylmethane-4,4-
Commercially available diisocyanate: [Hiren DMMJ manufactured by DuPont 10)
) Riphenylmethane-triincyanate Commercial product: “
Desmodur R” manufactured by Sumitomo Bayer Urethane Industries, Ltd. (18) 11) Polymethylene phenyl isocyanate commercial product:
"Millionate MRJ Manufactured by Nippon Polyurethane Industries Co., Ltd. 12) Naphthalene-1,5-diisocyanate GO Commercial product: [Desmodur 15.] Manufactured by Sumitomo Elurethane Industries Co., Ltd. Reacts with the above polyisocyanates to form polyurethane resins or polyurea resins. Specific examples of the polyol or polyamine to be provided include the following.

l) Polyols ethylene glycol, diols such as fluoropylene glycol, butylene glycol, hexamethylene glycol, triols such as glycerin, trimethylolpropane, trimethyloleta 7.1,2.6-hex/triol, pen/ta Erythritol, water, etc. 2) Polyamide/ethylenediami/, hexamethylenediami/, diethyle/triamidiamine/, iminobispropylamine, phenylenediamine, xylenediamine, triethylene/tetramine, and other vinyl-based resins for obtaining nivinyl-based resins. Examples of polymerizable monomers include styrenes such as styrene, rosechlorostyrene, α-methylstyrene, t-butylstereno, methyl acrylate, ethyl acrylate, n-propyl acrylate, stearyl acrylate, and 2-ethylhexyl acrylate. , α-methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylaterile. , vinyl ethers such as vinyl methyl ether and vinyl inftyl ether, vinyl pyridine/Q such as 2-vinyl pyridine and 4-vinyl pyridine, N-vinyl cyclic compounds such as N-vinylpyrrolitono, vinyl methyl keto/, vinyl ethyl Ketones, methylimpropenylgtone, 1:: Which vinyl compounds, ethylene, propylene, itfutylene, butaje, inbre/, unsaturated monocarbons, halogen-containing unsaturated compounds such as chlorobreno, etc. [1 Hydrocarbons 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 diacrylate, trietele/glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neobenchi. Polyhydric alcohol methacrylates such as glycol dimethacrylate, diethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, be/taerythritol tetramethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, Polyhydric alcohol acrylates such as tetraethylene glycol diacrylate, neope/tyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pe/taerythritol tetraacrylate; polyfunctional pinylpe/zes such as divinylbe/ze/ /, and others can be used alone or in combination, and these polyfunctional monomers may also be used in combination with the monofunctional monomers mentioned above.

The microcapsule toner of the present invention is formed by appropriately combining the above-mentioned core material and resin wall material.
A coloring agent is usually contained in the core material or further in the resin wall film. Further, when the toner of the present invention is a magnetic toner, fine magnetic powder is contained in place of the colorant or together with the colorant. In addition to these, various additives may be included as necessary.

As a coloring agent, carbon black, nigrosine dye (
C, 1,450415B), aniline blue (C, ■.

450405), Calco Oil Blue (C,1,Aa
zoecBlue 3), chrome yellow (C, 1,
A14090), Ultramarine Blue (C, 1, Ya 7
7103), DuPont Oil Red (C, 1, A261
05), Quinoline Yellow (C, t, Bread 47005)
, methylene blue chloride (C,1,A32015)
, phthalocyanine blue (C, I.

474160), malachite green off-salate (c
, r, boiled 42000), lamp black (C, 1, mu 77266), rose bengal (C, 1, A 45435)
), mixtures thereof, and others.

These colorants need to be contained in a sufficient proportion to form a visible image of sufficient density, and are usually contained in toner 1.
00 parts by weight and 1 to 20 parts by weight.

The magnetic material may be a metal or alloy exhibiting ferromagnetism such as iron including ferrite and magnetite, conortite, or nickel, 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 exhibit ferromagnetic properties, such as manganese-copper-
Aluminum, a type of alloy called Heusler alloy containing manganese and copper such as manganese-copper-tin, or hichrome diacid, and others can be mentioned. 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 thereof is 920 to 70 parts by weight, preferably 4 parts by weight per 100 parts by weight of toner.
It is 0 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 fine magnetic powder are uniformly dispersed is cured to obtain a core material, and monomers and a polymerization initiator, etc. that provide the resin for the wall film are dissolved. [7] Dispersing the core material substance as fine particles in a medium,
A method in which the system is placed under polymerization conditions in this state, and a polymer made of the monomer is precipitated on the surface of the particles of the 1-substance substance.

(1) Disperse the U material, in which additives such as colorants and fine magnetic powders are uniformly dispersed, in a medium that does not dissolve it, and then heat it in that state to form the core material. After curing, monomers and polymerization initiators, etc. that provide the resin for the wall film are dissolved in a medium, and then
A method of subjecting the system to polymerization conditions to cause a polymer of the monomer to precipitate on the surface of microparticles that are hardened and become the core material.

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 colorant and magnetic fine powder into the solution to form a toner composition. The toner composition is dispersed as fine particles in a medium, and in this state the system is placed under polymerization conditions to form a polymer layer on the surface of each fine particle, and at the same time, the core material is cured. How to coerce.

2) Microcapsules in which a polymer wall film is formed on the surface of microparticles of core material in which additives such as colorants and magnetic fine powder are uniformly dispersed, and the core material inside is not yet hardened. A method in which 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 of pre-curing the core material and then microcapsulating it;
There are two main methods: a method in which the core material is hardened and microencapsulated at the same time, and a method in which the core material is hardened after being microencapsulated. Practically speaking, method c) above is advantageous.

The method c) above will be explained in detail.

A mixture of core materials in combination as described above, monomers that can be combined with this to provide a polymer for wall membrane materials, and polymerization aids such as polymerization initiators and crosslinking agents as necessary. A liquid toner composition is prepared by adding additives such as a colorant and uniformly mixing and dispersing the mixture, and then adding this toner composition to a dispersion medium that does not dissolve the core material and monomers. Disperse and suspend in fine particles. The particle size of the dispersed fine particles can be determined by monitoring the particle size and dispersion state by observation using a microscope, etc., and then controlling the rotation speed of a stirrer such as a homomixer used for suspension dispersion.
It can be controlled to a desired size. In this 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 microcapsule toner of the present invention is then cured to produce the microcapsule toner of the present invention.

In the above, the component ratio of the toner composition is 1. - The proportion occupied by the fiber material is selected to be within the range of 30 to 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 that 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 gelatin and gelatin! Conductors, water-soluble polymer substances such as polyvinyl alcohol, polystyrene sulfonic acid, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyglobil cellulose, sodium carboxymethylcellulose, sodium polyacrylate, anionic surfactants, nonionic surfactants, Effective use of surfactants such as cationic surfactants, hydrophilic inorganic colloidal substances such as colloidal silica, alumina, tricalcium phosphate, ferric hydroxide, titanium hydroxide, aluminum hydroxide, and others. I can do it. 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 azobisvaleronitrile. can be mentioned. The amount of the polymerization initiator is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the monomer component v of the toner composition.

In addition, when containing magnetic fine powder to make a magnetic toner, it may be treated in the same way as the colorant, but up to i, the affinity for organic substances such as core materials and monomers must be Since the magnetic powder has low properties, if it is used 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 powder can be uniformly dispersed. You can force it.

The microcapsule toner of the present invention can be used as a two-component developer by being mixed with a carrier such as iron powder or glass beads, 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 the in-situ polymerization method, numbers 4 to 6 are suitable for the interfacial polymerization method, and number 7 is suitable for the submerged drying method.

Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, ``human'' represents a core material, B represents a monomer, C represents a polymerization initiator, and D represents an additive.

Example I A: Alkyl xanthate-terminated liquid chloroprene [
Denka LCRX-50J (manufactured by Denki Kagaku Kogyo Co., Ltd., viscosity 40000CPS)
150g Amine curing agent for epoxy resins -) B-
001J (manufactured by Yuka Shell Epoxy Co., Ltd.) 201 B: Ethylene glycol dimethacrylate
100F styrene
50gC: Azobisisobutyronitrile
7.5gD:M iron trioxide rBt, -tool
(Manufactured by Chita Y Kogyo Co., Ltd.) 3oo, p lecithin
A toner composition is prepared by uniformly mixing 1.5 g or more of the substance at room temperature using a sand grinder disperser, and the dispersion stabilizer colloidal tricalcium phosphate 12I! The toner composition was dispersed in water 3 containing 0.2.9 tons of sodium dodecylbenzenesulfonate using a homojetter, 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-eye flask, and the temperature was raised to 70C.
The core material was kept for a period of time to harden and thicken, and at the same time, a polymer layer was formed on the surface of each dispersed fine particle. Thereafter, hydrochloric acid was added to remove the dispersion stabilizer, and the wholesaler particles were separated, washed with water, and dried to produce a microcapsule toner of the present invention having an average particle size of 15 μm and a wall thickness of about 1 μm. This is referred to as "toner 1".

Example A: Epoxidized soybean oil ADK C1zer 0-1
30PJ (manufactured by Adeka Argus Chemical Co., Ltd., viscosity 250CP
S) 150g hardening agent for epoxy resin [
Epicure UJ (Yuka Shell Epoxy Co., Ltd. J)
15.9B (2) 100.9 Styrene 50FC: Azobisisobutyronitrile 7.
59D: Triiron tetroxide [BL-100J
3001I lecithin
A microcapsule toner of the present invention was produced in exactly the same manner as in Example 1 using 1.5 g or more of the substance. This will be referred to as "toner 2".

Example 3 A: Alkyl xanthate-terminated liquid chloroprene “Denka LCRX-501 (viscosity 40,000 CPS)
150. P Cobalt naphthenate (curing agent) 15y B: Polyincyanate [Desmodur LJ (manufactured by Sumitomo Bayer Urethane Industries) 30ID Triiron ditetraoxide [B
L-100J 200f Lecithin 1.59 or more substances mixed uniformly using a kneaded grinder disperser [
7 to prepare a toner composition, and add 20. The toner composition was dispersed in water 3 containing F and 0.7511 of ophtadecyltetramethylammonium chloride using a homojetter, and the average particle diameter of the dispersed fine particles was adjusted to 10 to 15 μm.

A 200vt aqueous solution in which 8fI of triethylenetetramine as a polymerization initiator was dissolved was added dropwise into this suspended dispersion over 1 hour, and the dispersion was then continued to be stirred for 3 hours.
1) Form a urea wall film on the surface of the dispersion particles, and then raise the temperature of the system to 601? The core material was cured by raising the temperature to 100 ml and maintaining the temperature for 5 hours with continuous stirring. 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 is called 1 toner 3.

Example 4 A: Argylzantate-terminated liquid chlorobrene [Denka LCRX-50J (viscosity 40,000 CPS)
150I! Cobalt naphthenate (curing agent) 15
y B = Polyisocyanate [Desmodur LJ (Sumitomo Bayer Urethane Industries, Ltd. JjJ)
30I! D: Triiron tetroxide [BL-1,0Ql
200Il lecithin
A toner composition is prepared by uniformly mixing 1.5 g or more of the substance using a sand grinder disperser, 20 g of colloidal silica as a dispersion stabilizer, and 0.75 g of ophtadecyltetramethylammonium chloride, f/
Using a homojetter, the toner composition is dispersed in water 3 containing
It was set to 15μ.

While stirring this suspended dispersion with a stirrer, the temperature of the system was raised to 60C, and then 200 u of an aqueous solution in which 8 g of the polymerization initiator triethylenetetramine was dissolved was added dropwise over 1 hour. Stirring of the dispersion was continued for 5 hours while maintaining the temperature of the system to harden the core material and at the same time form a wall film of polyurea on the surface of the dispersion particles. Thereafter, the solid particles were 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 is called f "toner 4".

Example 5 A: Alkyl xanthate-terminated liquid chloroprene
Denka LCRX-50J (viscosity 40000CPS)
150. @Cobalt naphthenate (hardening agent)
xsgB: Polyincyanate
Desmodule LJ (manufactured by Sumitomo Bayer Urethane Industries)
309D = triiron tetroxide [BL-100J
20011 lecithin
A toner composition is prepared by uniformly mixing 1.51 J or more of the substance using a sand grinder disperser, and 3 parts of water containing 2 (l) of colloidal silica as a dispersion stabilizer and 0.7 l of ophtadecyltetramethylammonium chloride. The toner composition was dispersed therein using a homojetter, and the average particle diameter of the dispersed fine particles was set to 10 to 15 μm.

While stirring this suspended dispersion with a stirrer, the temperature of the system was raised to 60 tlC, 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. An aqueous solution of 200 Tnt in which 8.9% of ethylenetetramine was dissolved was added dropwise over 1 hour while stirring the system, and stirring was continued for 3 hours to form a wall film made of polyurea on the surface of the dispersion particles. was formed. 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 0.7 μm was produced. This will be referred to as "toner 5."

Example 6 A: Alkyl xanthate-terminated liquid chlorobrene [
Denka LCRX-50J
Amine curing agent for 15o9 epoxy resin “Ebome” B-001J
209B: Methyl methacrylate-styrene copolymer (9:1) 150gD=triiron tetroxide [BL-
100J 300g lecithin 5g methylene chloride 11
A toner composition is prepared by dissolving B in water, then dissolving A, further adding lecithin, and adding triiron tetroxide while stirring using a sand grinder disperser while maintaining the temperature at IOC, 1. Stir for hours. This was dispersed using a homojetter in an aqueous solution containing 4 (l) of polyvinyl alcohol dissolved in 10 tK of water, and the average particle size of the dispersed fine particles was adjusted to 1.
It was set to 0-15μ. This suspended dispersion was placed in a four-eye flask equipped with a distillation device, and while stirring, the temperature of the system was gradually raised to 40C and maintained for 1 hour, and then raised to 50C for 3 hours.
The particles were kept for a certain period of time, thereby curing the core material and at the same time depositing the wall film material on the surface of the particles to form a wall film. After the odor of methylene chloride had 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: Alkyl xanthate-terminated liquid chlorobrene
Denka LCRX-50J
150g Amine curing agent for epoxy resin [Ebome] B-001J
20. PB = Methyl methacrylate-styrene copolymer (9:1) 150gD: Triiron tetroxide "BI, -100J 3
00# Lecithin 5y Methylene chloride 1 tKB'! A toner composition was prepared by dissolving A, then adding lecithin, and adding triiron tetroxide while stirring using a sand grinder disperser while maintaining the temperature at IOC for 9.1 hours. Stirred. This was dispersed in an aqueous solution of 40.9% polyvinyl alcohol dissolved in 107% water using a homojetter,
The average particle diameter of the dispersed fine particles was set to 10 to 15 μm. This suspended dispersion was placed in a four-eye flask equipped with a distillation device and stirred at room temperature for 4 days to harden the core material. After that, while continuing to stir, the temperature of the system was gradually raised to 40°C.
After that, the temperature was raised to 50°C and kept for 3 hours, thereby causing the wall film material to precipitate on the human flesh of the particles of the core material to form a wall film. After the methine chloride/odor has completely disappeared, the solid particles are separated from each other, washed with water and dried, with an average particle size of 13.
A microcapsule toner having a thickness of about 1 μm and a wall thickness of about 1 μm was produced and designated as “Toner 7”.

Comparative Examples 1 to 7 In each of Examples 1 to 7, the hardening agent of the core material (A) was excluded, and the other parts were exactly the same as in the corresponding examples, and the hardening was carried out in the same manner as in the corresponding examples. A total of 7 types of microcapsule toners with core materials for comparison were manufactured.These are respectively designated as 1 to 1 to 7.

Examples Each of Toner 1 to Toner 7 and Comparative Toner 1 to Comparative Toner 7 obtained as described above was used as a sweet developer. The toner image was developed using a modified toner (manufactured by Manufacturer), and the toner image was transferred to a transfer paper made of plain paper. 1 line.Visible image 1# thus obtained!
When rubbed with a plastic eraser or with paper V of the same type as the transfer paper, almost no change was observed in the visible images of Toners 1 to 7, and good visible images were formed. On the other hand, according to Comparative Toner 1 to Comparative Toner 7, the visible images 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. 2) The core material is a reaction product of an epoxy compound and an amine compound, an acid anhydride or a Lewis acid, a xanthate ester and an amine compound, an organic acid metal salt, a metal halide, a metal oxide, or an organic peroxide. reaction products of isocyanate compounds with amine compounds or polyols, and reaction products of natural or synthetic drying or semi-drying oils or unsaturated fatty acid esters with naphthenic acid metal salts or fatty acid metal salts. The microcapsule toner according to claim 1, comprising at least one selected type. 3) The microcapsule toner according to claim 1 or 2, wherein the resin wall film is formed by a polymerization reaction.