JP2757725B2 - Capsule toner and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a capsule toner for developing an electrostatic latent image, a magnetic latent image and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, there are a heat fixing method and a pressure fixing method as fixing methods used in electrophotography. Heat fixing method
When the power is turned on, a rise time is required to heat the fixing device to a predetermined temperature, and thereafter, energy is required to maintain the fixing device at a predetermined temperature. On the other hand, the pressure fixing method has an advantage that it does not require a rising time at power-on and does not require heating energy of a fixing device.However, the fixing strength is not sufficient, and the toner image is easily peeled off when rubbed. Requires high pressure.

[0003] The capsule toner is developed to solve the above-mentioned problem, and has a core material containing a fixing material, and the outside of the core material is completely covered with a hard shell.
When an external pressure is applied to the capsule toner by the pressure fixing method,
The outer shell is broken, and the fixing substance flows out and is fixed on an image forming support such as paper or OHP. When the capsule toner is used as a one-component developer, it contains magnetic particles for imparting magnetic properties, and also contains colorant particles for coloring. When the agent particles are contained, the viscosity of the core material increases,
Even when an external pressure is applied, the fixing substance does not flow out, and the fixing property is deteriorated.

[0004] In order to improve the fixability, it is preferable that the colorant particles and the magnetic particles are unevenly distributed on the outer shell. However, when the colorant particles and the magnetic particles are exposed on the outer shell surface, the resistance value of the portion decreases. Therefore, the insulating property of the surface of the capsule particles is reduced, causing leakage of the charged charges, and the charge amount is reduced.
In addition, when the colorant particles and the magnetic particles have hydrophilicity, the environment dependence of the electric resistance increases. Therefore, it is important not to expose the colorant particles and the magnetic particles to the outer shell surface. Further, if the fixing substance exudes from the capsule during the production or storage of the toner, the toner aggregates or the fixing property is significantly reduced. Therefore, the outer shell needs to prevent the permeation of the fixing substance. However, conventional capsule toners have not always been satisfactory.

For example, Japanese Patent Application Laid-Open No. 57-179860 proposes a capsule toner having a shell made of a polyurethane resin or a polyurea resin obtained by reacting isocyanate with water, amine or glycol.
No. 2,228,673 discloses a capsule toner having a shell made of a polyurea resin obtained by using one kind of bifunctional amine and one or more kinds of polyfunctional amines having three or more functions. However, in these capsule toners, when the number of magnetic particles is increased or the outer shell is made thinner as the particle size of the capsule is reduced, the concentration of the colorant particles and the magnetic particles in the outer shell increases and the surface of the outer shell increases. Exposed, the charge amount becomes small, the environmental dependence of the chargeability becomes large, and the colorant particles and magnetic particles penetrate the outer shell, and the fixing substance, especially the low molecular weight component, flows out from the outer shell. was there.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems, to maintain good chargeability of a capsule, and to reliably hold a fixing substance inside a capsule with an outer shell. It is an object of the present invention to provide a capsule toner excellent in image quality and fixability, and a method for producing the same.

[0007]

Means for Solving the Problems The present invention comprises (1) a core material containing a fixing component, an outer shell covering the core material, and a chargeable substance attached to the surface of the outer shell. The capsule toner, wherein the outer shell contains at least a polyurea resin obtained from an aliphatic polyamine and an aromatic polyamine, (2)
It comprises a core material containing a fixing component, an outer shell covering the core material, and a chargeable substance attached to the surface of the outer shell. The capsule toner containing at least a polyurea resin obtained from an aliphatic polyamine and an aromatic polyamine in the outer shell, and (3) at least colorant particles and After dispersing an oily substance containing magnetic particles, a fixing component, and a polyisocyanate in a solvent, an aliphatic polyamine and an aromatic polyamine are added to the dispersion, and the mixture is polymerized to form a polyurea resin. A method for producing a capsule toner, comprising forming an outer shell containing the toner and adhering a chargeable substance to the outer shell.

[0008]

When the outer shell of the capsule toner is formed using only the aromatic polyamine having a slow reaction, the coloring agent particles and the magnetic particles are taken into the outer shell, and these penetrate the outer shell. It cannot be held strong. In addition, when the outer shell is formed using only the aliphatic polyamine having a fast reaction, the colorant particles and the magnetic particles are not taken into the outer shell, the core is easily taken into the core material, and the viscosity of the core material is extremely increased. Even if pressure is applied, the fixable substance cannot flow out, and the fixability deteriorates.

The present invention solves the above-mentioned drawbacks,
When the outer shell of the capsule toner is formed by interfacial polymerization or the like, the fast-reacting aliphatic polyamine first reacts with the polyisocyanate to form the outermost layer of the outer shell, and then the aromatic polyamine becomes It is presumed that it reacts with the polyisocyanate while taking in the colorant particles and the magnetic particles to form an outer shell inside the polyisocyanate. As a result, the colorant particles and the magnetic particles are not exposed on the outer shell surface, the fixing material can be strongly held in the outer shell, and the chargeable substance is uniformly attached to the outer shell surface. As a result, the chargeability of the capsule toner was improved, and a copy image excellent in image quality, fixability and the like was made possible.

The aliphatic polyamine used in the present invention means a polyamine in which an amino group is not directly bonded to an aromatic ring, and specifically, ethylenediamine, hexamethylenediamine, diaminocyclohexane, piperazine, diethylenetriamine , Triethylenetetramine,
Tetramethylene pentamine, iminobispropylamine, diaminoethyl ether, 1,4-diaminobutane, pentamethylenediamine, 2-methylpiperazine,
Examples thereof include 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylaminopropylamine, diaminopropylamine, diaminopropane, 2-methylpentamethylenediamine, and xylenediamine. Among them, diethylenetriamine, diaminocyclohexane, and tetraethylenepentanamine are preferred. The above aliphatic amines may be used alone or as a mixture.

The aromatic polyamine used in the present invention means a polyamine in which an amino group is directly bonded to an aromatic ring, and specifically, m-phenylenediamine, triaminobenzene, 3,5 -Tolylenediamine, diaminodiphenylamine, diaminonaphthalene, t-butyltoluenediamine, diethyltoluenediamine, diaminophenol and the like. Among them, phenylenediamine, diaminophenol and triaminobenzene are preferred. The above aromatic amines may be used alone or in a mixture. The mixing ratio of the aliphatic polyamine and the aromatic polyamine is such that the aromatic polyamine is 2 to 95 wt%, preferably 5 to 80 wt% based on the total polyamine.
wt%.

Examples of the substance which reacts with the amine to give a polyurea resin include the following polyisocyanates. Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate,
3,3′-dimethyldiphenyl-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, m-phenylene diisocyanate,
p-phenylene diisocyanate, transcyclohexane-1,4-diisocyanate, diphenyl ether diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2,6-diisocyanate caproic acid, tetramethyl-m-xylylene diisocyanate, tetramethyl-p-xylylene Diisocyanate, trimethylhexamethylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, isocyanate alkyl-2,6-diisocyanate caproate,
6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,
Examples include 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and the like.

Further, urethane modified products using these polyisocyanates and monomer polyols, adducts of trimethylolpropane, urethane prepolymers using polyether polyols or polyester polyols, modified uretidiones, modified isocyanurates ,
A carbodiimide modified product, a uretonimine modified product, an allohanate modified product, and a buret modified product can also be used.

As the core substance of the capsule toner particles, a core substance mainly having a pressure fixing property is used for the purpose of pressure fixing, and a component having a heat fixing property is mainly used for the purpose of heat fixing. Is used. It is desirable to select the type of each component, the composition ratio, and the thickness of the outer shell according to the purpose.

Particularly, when the purpose is pressure fixing,
(1) Binder resin, one containing a high-boiling solvent and a colorant that dissolves it as a main component, (2) Binder resin, one containing an oligomer and a colorant that dissolve it as a main component, (3) Soft A magnetic powder is used in place of the colorant, if necessary, and an additive such as silicone oil can be added to improve the fixability. Further, as the above high boiling solvent, a high boiling solvent that does not dissolve the binder resin can be added. Further, it is desirable to change the types or composition ratios of the constituent components when the purpose is pressure fixing and when the purpose is heat fixing.

As the binder resin that can be used for the core material, a known fixing resin can be used. Specifically, acrylate polymers such as polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, 2-ethylhexyl polyacrylate, and lauryl polyacrylate; polymethyl methacrylate, polybutyl methacrylate, and poly (methyl methacrylate) Methacrylate polymers such as hexyl methacrylate, poly (2-ethylhexyl methacrylate), and poly (lauryl methacrylate); copolymers of acrylates and methacrylates; copolymers of styrene monomers and acrylates or methacrylates Coalescence: polyvinyl acetate, polyvinyl propionate,
Ethylene polymers such as polyvinyl butyrate, polyethylene and polypropylene and copolymers thereof; Styrene copolymers such as styrene / butadiene copolymer, styrene / isoprene copolymer, styrene / maleic acid copolymer; polyvinyl ether , Polyvinyl ketone, polyester,
Polyamide, polyurethane, rubbers, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin and the like can be used alone or in combination. In addition, the binder resin can be formed by polymerizing the monomer in the state of the monomer after completion of the encapsulation.

As the high boiling point solvent that dissolves the binder resin,
An oily solvent having a boiling point of 140 ° C. or higher, preferably 160 ° C. or higher can be used. Specifically, phthalic acid esters such as diethyl phthalate and dibutyl phthalate;
Aliphatic dicarboxylates such as diethyl malonate and dimethyl oxalate; Phosphates such as tricresyl phosphate and trixylyl phosphate; citrates such as o-acetyltriethyl citrate; butyl benzoate and hexyl benzoate Benzoic acid esters such as hexadecyl myristate, dioctyl adipate, linseed oil, castor oil, and eno oil; alkyl naphthalenes such as methyl naphthalene, dimethyl naphthalene, monoisopropyl naphthalene, diisopropyl naphthalene; o- Alkyl diphenyl ethers such as, m-, p-methyl diphenyl ether;
Amide compounds of higher fatty acids or aromatic sulfonic acids such as N, N-dimethyllauroamide and N-butylbenzenesulfonamide; trimellitic acid esters such as trioctyl trimellitate; diarylmethanes such as dimethylphenylphenylmethane; Diarylalkanes such as diarylethane such as 1-phenyl-1-methylphenylethane, 1-dimethylphenyl-1-phenylmethane and 1-ethylphenyl-1-phenylethane; saturated aliphatic hydrocarbons and unsaturated aliphatic hydrocarbons Hydrogen, chlorinated paraffins and the like can be mentioned.

The soft solid substance that can be used as the core substance of the capsule toner for pressure fixing is not particularly limited as long as it has flexibility at room temperature and has a fixing property. A polymer in the range of 60 ° C. to 5 ° C. or a mixture of the polymer and another polymer is preferred.

Examples of the colorant include inorganic pigments such as carbon black, red iron oxide, navy blue and titanium oxide; azo pigments such as fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, and para brown; copper phthalocyanine; and metal-free phthalocyanine. And condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, and dioxazine violet. Further, as the magnetic one-component toner, all or part of the black colorant can be replaced with magnetic powder. As the magnetic powder, magnetite, ferrite, a simple metal such as cobalt, iron, nickel or the like or an alloy thereof can be used.

When fixing the capsule by applying external pressure,
It is necessary to lower the viscosity of the core so that the fixing substance flows out of the capsule, and it is necessary that at least 20% of the total weight of the colorant particles or the magnetic particles be present in the outer shell. Incidentally, it is preferably at least 50%. Further, a surface treatment with a silane coupling agent, a coupling agent such as a titanate coupling agent, or an oil-soluble surfactant, or an acrylic-based agent so that the colorant particles and the magnetic particles are easily taken into the outer shell. It is also possible to coat the surface with a resin, a styrene resin, an epoxy resin, or the like.

As a method for producing the capsule toner, a known interfacial polymerization method is preferable. For example, as a method for incorporating one component in the core material into a capsule, a method is known in which another core material component is previously charged together with a low-boiling solvent and a shell-forming component in a polymer state, and a shell is formed by interfacial polymerization. And then forming a shell by interfacial polymerization in the state of a monomer, and then polymerizing the monomer to form a core material. (For example, Japanese Patent Application Laid-Open No. 57-179860,
66948, JP-A-59-148066,
JP-A-59-162562)

As the low boiling point solvent, those having a boiling point of 100 ° C. or less can be used. Specifically, n-pentane, methylene chloride, ethylene chloride, carbon disulfide, acetone, methyl acetate, ethyl acetate, chloroform, methyl alcohol, ethyl alcohol, tetrahydrofuran, n-hexane, carbon tetrachloride, methyl ethyl ketone, benzene, ethyl Ether and petroleum ether can be exemplified. These may be used alone or in combination. The average particle size of the capsule toner of the present invention is preferably in the range of 1 to 30 μm, particularly preferably 2 to 18 μm.

The chargeable substance on the outer surface of the capsule toner is a polymerizable monomer having a functional group such as an amino group, an imidazole group, pyridine or piperazine as a positive charge, and a halogen atom or a nitro group as a negative charge. , A polymer composed of a polymerizable monomer having a functional group such as a cyano group, a sulfonic acid group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, or a known material such as fine particles having the above functional group on the surface Can be used. Known methods such as a graft polymerization method, a phase separation method, a dry mixing method, and a wet mixing method can be used as a method for attaching the chargeable substance. Among them, the graft polymerization method is preferred in view of durability and uniformity.

In the case of performing pressure transfer simultaneous fixing, it is preferable to attach lubricating particles to the surface of the capsule toner. As the lubricant particles, one kind selected from a fatty acid, a fatty acid metal salt, an aliphatic alcohol, an aliphatic amide, an aliphatic bisamide, and a fatty acid ester, or a mixture of two or more kinds is used.

Examples of the fatty acid include lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, arachiic acid, behenic acid, lignoceric acid, seracoleic acid, and the like, and mixtures thereof. Fatty acid metal salts include stearic acid and zinc, cadmium, barium, lead, iron, nickel, cobalt, copper,
Metal salts such as aluminum and magnesium; dibasic lead stearate, metal salts such as oleic acid and zinc, magnesium, iron, cobalt, copper, lead and calcium; metal salts such as palmitic acid and aluminum or calcium; lead caprylate , Lead caproate, zinc linoleate, cobalt linoleate, calcium ricinoleate, metal salts such as ricinoleic acid and zinc or cadmium, and mixtures thereof.

The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol, and typical examples thereof include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol and the like. . Fatty acid amides include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, oleic acid amide, linoleic acid amide, linolenic acid amide, cadrenic acid amide, erucic acid amide, selacolein Acid amide and the like can be mentioned.

Examples of the fatty acid bisamide include bislauric amide, bismyristic amide, bispalmitic amide, bisstearic amide and the like. Fatty acid esters include esters of fatty acids and monohydric alcohols, esters of fatty acids and polyhydric alcohols, and partial esters of fatty acids and polyhydric alcohols.

The lubricant particles may be added to the toner by any known method. The slurry may be mixed and dried, or may be mixed as a dry powder. Alternatively, the slurry may be dried while spraying the slurry on the dry powder. In order to mix the lubricant fine particles as a dry powder, it is necessary to dry them in advance. As the dryer, a through-air dryer, a spray dryer, a rotary dryer, a flash dryer, a fluidized-bed dryer, a heat transfer heating dryer, a freeze dryer, or the like can be used. For the solid mixing, various types of rotary container type mixers, fixed container type mixers, and composite type mixers thereof can be used.

In order to impart fluidity to the encapsulated toner, fine particles such as metal oxides such as silicon oxide and aluminum oxide, metal salts, ceramics, resins and carbon black may be added. As a method for adding the fine particles, after the capsule toner is dried, it may be adhered to the dry toner surface using a mixer such as a V blender or a Henschel mixer, or the fine particles may be dispersed in an aqueous liquid such as water or alcohol. The toner may be added to the slurry-state capsule toner, dried, and an external additive may be attached to the toner surface.

[0030]

【Example】

Example 1 (Preparation of Capsule Particles) In a mixed solution of 60 g of diethyl phthalate and 60 g of ethyl acetate, 30 g of a polyisobutyl methacrylate polymer (Mw = 16 × 10 ⁴ ) and styrene-
n-butyl methacrylate copolymer (Mw = 6 × 1
0 ⁴⁾ was dissolved 40 g, the magnetic powder (manufactured by Nippon Chemical Industrial Co., Ltd.: E
PT-1000) and dispersed in a ball mill for 16 hours. Next, isocyanate (Takenate D110 manufactured by Takeda Pharmaceutical Co., Ltd.) was added to 200 g of the dispersion.
N) 30 g and ethyl acetate 24 g were added and mixed well. (This solution is referred to as solution A.) On the other hand, 10 g of hydroxypropyl methylcellulose (Metroze 65SH50 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 200 g of ion-exchanged water to obtain 5
Cooled to ° C. (This solution is referred to as solution B.)

While stirring the solution B with an emulsifying machine (manufactured by Tokushu Kika Kogyo Co., Ltd .: auto homomixer), the solution A was slowly charged to emulsify. Thus, an O / W emulsion having an average particle size of the oil droplet particles of about 15 μm in the emulsion was obtained. Next, instead of an emulsifier, a stirrer equipped with a propeller type stirring blade (manufactured by Shinto Kagaku Co., Ltd .: Three One Motor) was used.
The mixture was stirred at 400 rpm. After 10 minutes, a 5% aqueous diaminocyclohexane solution as an aliphatic amine was added thereto.
A mixture of 00 g and 20 g of a 5% aqueous solution of triaminobenzene as an aromatic amine was dropped. After dropping, 60
℃, and the encapsulation reaction was performed for 3 hours. After completion of the reaction, the mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After sedimentation of the capsule particles, the supernatant was removed. This operation was repeated seven more times to wash the capsule particles. Thus, capsule particles containing an oily binder were obtained. Ion exchange water was added to the capsule particles to prepare a suspension having a solid content of 40%.

(Preparation of Toner) 125 g of ion-exchanged water was added to 125 g of the above capsule particle suspension (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller type stirring blade (Three One Motor manufactured by Shinto Kagaku) 200 revolutions /
Stir in minutes. After adding 5 g of 1N nitric acid and 4 g of a 10% cerium sulfate aqueous solution, 0.5 g of ethylene glycol dimethacrylate was added thereto and reacted at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule was allowed to settle, the supernatant was removed. This operation was repeated twice more to wash the capsule.

Thus, capsule particles obtained by graft-polymerizing ethylene glycol dimethacrylate on the outer surface of the capsule shell were obtained. This was suspended again in ion-exchanged water and stirred at 200 rpm using a stirrer equipped with a propeller type stirring blade (Three One Motor manufactured by Shinto Kagaku). Next, 0.4 g of potassium persulfate, 0.1 g of dimethylaminoethyl methacrylate, and 1 g of methyl methacrylate were added thereto.
g and sodium hydrogensulfite 0.16 g are added successively.
The reaction was performed at 5 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 2 liters of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule was allowed to settle, the supernatant was removed. This operation was repeated four more times to wash the capsule particles. The obtained capsule suspension was poured into a stainless steel pad and dried at 60 ° C. for 10 hours using a dryer (manufactured by Yamato Kagaku). Next, 1 part of hydrophobic silica (RA-200H manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the toner and mixed well.

(Evaluation) 3 g of the obtained capsule toner and 100 g of an iron powder carrier coated on the surface with a phenol resin were mixed in an environment at a temperature of 20 ° C. and a humidity of 50%, and the charge amount of the capsule toner was measured by a blow-off method. However, 14μ
C / g, which was good. The thermogravimetric measurement of the obtained capsule toner showed that diethyl phthalate was contained in the same amount as the charged amount. When a copy test was performed on this toner using a copying machine in which FX2700 manufactured by Fuji Xerox Co., Ltd. was modified for use as a capsule toner, both image quality and fixing were good.

Comparative Example 1 The procedure of Example 1 was repeated, except that 100 g of a 5% aqueous solution of diaminocyclohexane and 20 g of a 5% aqueous solution of triaminobenzene were replaced with 120 g of a 5% aqueous solution of triaminobenzene. Thus, a capsule toner was obtained, and a developer was prepared in the same manner. When the charge amount of the obtained capsule toner was measured, it was 2 μC / g, which was much lower than in Example 1. In addition, the thermogravimetric measurement showed that no diethyl phthalate was contained. Further, a copy test was performed in the same manner as in Example 1. As a result, fogging occurred, many white spots were present in the image area, and the fixing property was poor.

Comparative Example 2 The procedure of Example 1 was repeated except that 100 g of a 5% aqueous solution of diaminocyclohexane and 20 g of a 5% aqueous solution of triaminobenzene were replaced with 10 g of a 5% aqueous solution of diethylenetriamine and 110 g of 5% xylylenediamine. A capsule toner was obtained in the same manner as in Example 1, and a developer was further prepared in the same manner. When the charge amount of the obtained capsule toner was measured, it was 3 μC / g, which was much lower than that in Example 1. In addition, the thermogravimetric measurement showed that no diethyl phthalate was contained. Further, a copy test was performed in the same manner as in Example 1. As a result, fogging occurred, many white spots were present in the image area, and the fixing property was poor.

Example 2 (Preparation of Capsule Particles) 70 g of a styrene-n-butyl methacrylate copolymer (Mw = 10 × 10 ⁴ ) was dissolved in a mixed solution of 60 g of dibutyl adipate and 60 g of ethyl acetate. Magnetic powder (made by Toda Industries: EPT-1000)
120 g was added and dispersed in a ball mill for 16 hours. Then, 25 g of isocyanate (Sumitomo Bayer Urethane Co., Ltd .: Sumidur HT) was added to 200 g of this dispersion.
And 24 g of ethyl acetate was added and mixed well. (This solution is referred to as solution A.) On the other hand, 10 g of hydroxypropylmethylcellulose (Metroze 65SH50 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 200 g of ion-exchanged water and cooled to 5 ° C. (This solution is referred to as solution B.)

While stirring the solution B with an emulsifying machine (manufactured by Tokushu Kika Kogyo Co., Ltd .: auto homomixer), the solution A was slowly charged to emulsify. Thus, an O / W emulsion having an average particle diameter of the oil droplet particles in the emulsion of about 7 μm was obtained.
Next, instead of the emulsifier, a stirrer equipped with a propeller type stirring blade (manufactured by Shinto Kagaku Co., Ltd .: Three One Motor) was used.
The mixture was stirred at 0 rotation / minute. Ten minutes later, 110 g of a 5% aqueous solution of diethylenetriamine as an aliphatic amine was added thereto.
And a mixture of 30 g of a 5% aqueous solution of phenylenediamine as an aromatic amine was added dropwise. After completion of the dropwise addition, the mixture was heated to 60 ° C., and an encapsulation reaction was performed for 3 hours. After the reaction, 2
The mixture was poured into 1 liter of ion-exchanged water, stirred sufficiently, and allowed to stand. After sedimentation of the capsule particles, the supernatant was removed. This operation was repeated seven more times to wash the capsule particles. Thus, capsule particles containing an oily binder were obtained. Add ion exchange water to the capsule particles,
A suspension having a solid content of 40% was prepared.

(Preparation of Toner) 125 g of ion-exchanged water was added to 125 g of the above-mentioned suspension of capsule particles (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller type stirring blade (Three One Motor manufactured by Shinto Kagaku) 200 revolutions /
Stir in minutes. After adding 5 g of 1N nitric acid and 4 g of a 10% cerium sulfate aqueous solution, 0.5 g of ethylene glycol dimethacrylate was added thereto and reacted at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred, and allowed to stand. After the capsule was allowed to settle, the supernatant was removed. This operation was repeated twice more to wash the capsule.

In this manner, capsule particles obtained by graft-polymerizing ethylene glycol dimethacrylate on the capsule shell surface were obtained. This was suspended again in ion-exchanged water and stirred at 200 rpm using a stirrer equipped with a propeller type stirring blade (Three One Motor manufactured by Shinto Kagaku). Next, 0.4 g of potassium persulfate, 3 g of sodium allyl sulfonate, and 0.16 g of sodium bisulfite were sequentially added thereto, and reacted at 25 ° C. for 3 hours. After the reaction,
The mixture was poured into 2 liters of ion-exchanged water, stirred sufficiently, and allowed to stand. After the capsule was allowed to settle, the supernatant was removed.
This operation was repeated four more times to wash the capsule particles. Thus, a capsule toner in which pentafluoropropyl methacrylate was graft-copolymerized on the capsule outer shell surface was obtained. The obtained capsule suspension was poured into a stainless steel pad, and dried at 60 ° C. with a dryer (Yamato Kagaku).
For 10 hours. Next, hydrophobic silica (R972 manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts of the toner.
Was added and mixed well.

(Evaluation) 3 g of the obtained capsule toner and 100 g of an iron powder carrier whose surface was coated with a phenol resin were mixed in an environment at a temperature of 20 ° C. and a humidity of 50%, and the charge amount of the capsule toner was measured by a blow-off method. However, -15
μC / g, which was good. In addition, thermogravimetry of the obtained capsule toner revealed that dibutyl adipate was contained in the same amount as the charged amount. When a copy test was performed by reversal development on this toner using a copying machine in which FX2700 manufactured by Fuji Xerox Co., Ltd. was modified for a capsule toner, both image quality and fixing were good.

Comparative Example 3 A capsule toner was prepared in the same manner as in Example 2 except that 110 g of a 5% aqueous solution of diethylenetriamine and 30 g of a 5% aqueous solution of phenylenediamine were replaced with 140 g of a 5% aqueous solution of phenylenediamine. Was obtained, and a developer was prepared in the same manner, and the amount of charge was measured. The result was −3 μC / g, which was much lower than that in Example 2. In addition, thermogravimetry revealed that dibutyl adipate was not contained at all. Further, when a copying test was performed in the same manner as in Example 2, fogging occurred, many white spots were present in the image area, and the fixing property was poor.

[0043]

According to the present invention, by adopting the above structure, good chargeability can be maintained without exposing the colorant particles and the magnetic particles from the outer shell of the capsule, and the image quality and fixability can be maintained. It is possible to provide excellent copy image quality.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-222867 (JP, A) JP-A-60-222868 (JP, A) JP-A-61-120160 (JP, A) 220561 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03G 9/093

Claims (3)

(57) [Claims] 1. A capsule toner comprising a core material containing a fixing component, an outer shell covering the core material, and a chargeable substance attached to the surface of the outer shell, wherein at least an aliphatic toner is used. A capsule toner comprising the outer shell containing a polyurea resin obtained from a polyamine and an aromatic polyamine. 2. A colorant particle and / or a magnetic material comprising a core material containing a fixing component, an outer shell covering the core material, and a chargeable substance attached to the surface of the outer shell. An encapsulated toner containing particles in an outer shell, wherein the outer shell contains at least a polyurea resin obtained from an aliphatic polyamine and an aromatic polyamine. 3. An oily substance containing at least colorant particles and / or magnetic particles, a fixing component, and a polyisocyanate is dispersed in a solvent, and then the aliphatic polyamine and the aromatic polyamine are added to the dispersion. And polymerizing to form an outer shell containing a polyurea resin, and attaching a chargeable substance to the outer shell.