JPH07230183A - Encapsulated toner and its manufacture - Google Patents

Abstract

PURPOSE:To provide the electrophotographic encapsulated toner containing an attachable polymer superior in adhesiveness to original toner particles and good in the environmental stability of chargeability and to provide the manufacturing method of this toner having the unaffected chargeability of a colorant without impairing the fixing performance and mechanical strength of a binder resin. CONSTITUTION:The vinyl polymer is attached to the surfaces of the original toner particles through the product obtained by reaction of monomers having glycidyl groups with amino groups present on the surfaces of the encapsulated original toner particles followed by polymerization of the monomers to cover the surfaces of the particles with the vinyl polymer, and the monomer is represented by the formula in which X is H or methyl, and Y is methylene or carbonyl.

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 in an electrophotographic method and an electrostatic printing method, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, in a method of manufacturing a toner, a method of dispersing a charge control agent in a toner binder in order to control the charge of the toner has been used. That is, a charge control agent is charged together with a toner binder, a coloring material and other additives, and kneaded and pulverized to obtain a toner. However, this method has a drawback in that the chargeability varies depending on the degree of dispersion of the charge control agent present in the toner, and the chargeability is dominated by the charge control agent present on the surface of the toner, and A certain charge control agent hardly contributes to charging, but on the contrary, has a drawback that the fixing performance and mechanical strength that the binder resin should have are impaired. Further, since the charge control agent exists in a state of being mixed with the coloring material, it is affected by the charging property of the coloring material. Therefore, when producing toners of different colors, it is necessary to change the type and addition amount of each charge control agent, resulting in high cost. Furthermore, this method cannot be used for encapsulated toners having a core / shell structure.

Another method for producing a toner is disclosed in Japanese Patent Laid-Open No.
7-202547, JP-A-63-27853, and JP-A-63-27854, a toner containing a polymer containing a charge control agent is spray-dried or coated with heat or pressure to form a toner. The method of obtaining is described. However, the spray-drying method has a drawback in that the coating layer wraps a plurality of toner bases and the toner particle size becomes large. After that, even if the sieving operation is performed, the yield of the toner having the predetermined particle diameter is low. Furthermore, since a large amount of organic solvent is used, there are safety and health problems. The method of coating the toner base material by heat fusion also has a drawback of causing adhesion and aggregation of toner particles to increase the toner particle size. Also, the method of fusing the coating polymer on the toner base with pressure is preferable when the toner base particles to be heat-fixed are hard, but when this method is applied to liquid core capsule toner, the capsule is said to be destroyed. There was a flaw.

Further, in JP-A-60-173552, a toner is prepared by forming a coating layer consisting of a coloring agent or magnetic particles or a conductive agent and a binder resin on the surface of toner core particles using a jet mill. A method of making is described.
Further, Japanese Patent Laid-Open No. 63-49766 discloses a method in which toner base particles and a thermoplastic resin are mixed by applying a strain force and then coated. As described above, these methods can be applied when the toner base particles are hard, such as those intended for heat fixing, but for capsule toners having a liquid core intended for pressure fixing, The application of this method has the drawback that the capsules are destroyed.

In JP-A-57-45558, toner core particles formed by polymerization are dispersed in a latex aqueous solution, and a water-soluble inorganic salt is added to the surface of the toner core particles so that fine particles are allowed to settle and coated. A method of forming layers to make a toner is described. However, in this method, since the fine particles adhere to the core material to form the coating layer, the adhesion to the core material is poor and the coverage of the core material is insufficient. Further, there is a drawback in that the influence of the surfactant and the inorganic salt remaining on the toner greatly affects the environment of charging, and the amount of charge is reduced particularly under conditions of high temperature and high humidity.

JP-A-62-227161 and JP-A-62-227162 describe a method of attaching a polymer of a monomer having a charging function to a toner base. Here, a method is described in which a connecting molecule such as ethylene glycol dimethacrylate is first chemically bonded onto the toner surface by graft polymerization, and then a polymerizable monomer having a charge control group is polymerized. In this case, the charge control group is localized on the toner surface, so that the fixing property of the toner binder is not impaired and the effect of being less affected by the charging property of the coloring material is obtained, but the reaction is performed in two steps. Therefore, there is a drawback that not only many kinds of materials are required, but also time and labor are required and cost is increased.

[0007]

In order to solve the above-mentioned drawbacks, one of the inventors of the present invention has already proposed a method in which a polymer is attached to the surface of toner base particles (Japanese Patent Laid-Open No. 4-260).
055 publication). However, in this case, although the polymer can be easily attached to the surface of the toner base particles, there is a drawback that a large amount of polymer fine particles not attached to the surface are also generated. That is, it has been found that when the polymer fine particles are mixed with the toner, the polymer fine particles adhere to the developing roll to deteriorate the formation of the toner layer, and as a result, the image quality of the copy is deteriorated.
In order to prevent this, it was necessary to repeat washing many times in order to separate the polymer fine particles from the toner particles.

The present invention aims to eliminate the above drawbacks. That is, an object of the present invention is to provide an electrophotographic capsule toner having an adhesion polymer having excellent adhesion to toner base particles and having good environmental stability of charging. Another object of the present invention is not to impair the fixing performance mechanical strength that the binder resin should have,
An object of the present invention is to provide a method for producing an electrophotographic capsule toner that is not affected by the charging property of a color material. Another object of the present invention is to provide a method for producing a capsule toner which can be applied to a capsule toner having a liquid core without requiring a special reaction device or a complicated operation.

[0009]

The capsule toner of the present invention is obtained by reacting a glycidyl group-containing polymerizable monomer represented by the following formula (1), which is reacted with an amino group existing on the surface of the base particles of the capsule toner. The vinyl polymer is attached to the surface of the base particles of the capsule toner.

[Chemical 3] (Here, X represents a hydrogen atom or a methyl group, and Y represents a methylene group or a carbonyl group.) In the method for producing a capsule toner of the present invention, an amino group is allowed to exist in the capsule toner base particles, and the above formula (1) is used. ) A glycidyl group-containing polymerizable monomer represented by the formula (1) is reacted with the amino group to bond it, and then a vinyl monomer is polymerized to adhere the polymer to the surface of the toner base particle. .

Next, the present invention will be described in detail.
In the present invention, the encapsulated toner base particles to be treated are required to have at least a primary amino group or a secondary amino group on the surface. Among them, in particular, capsule particles produced by interfacial polymerization are preferable in that an amino group can be easily introduced to the surface.
Examples of the method for causing an amino group to exist on the surface of the toner base particles include, for example, a method of dissolving or dispersing a resin having the above group in a solvent and coating the core substance by a method such as spray drying, or An example is a method in which a polyamine is present in an aqueous medium and interfacial polymerization is used to coat the core substance. In particular, the second method is preferable because the amino group can be easily introduced to the surface of the mother toner particles at the same time when the mother toner particles of the capsule toner are formed.

A method for producing microcapsules by the interfacial polymerization method is disclosed, for example, in Japanese Examined Patent Publication No. 38-19574 and No. 42.
No. 4-446, Japanese Examined Patent Publication No. 2-31381, JP-A-58-66948, JP-A-59-148066, and JP-A-59-162562, the first present in a solvent. This is a method in which the capsule shell forming monomer and the second capsule shell forming monomer present in the oily droplets react at the interface of the oily droplets to form capsule shells. The first capsule shell forming monomer can be selected from an isocyanate, an acid halide and an epoxy compound. Particularly, from the viewpoint of electric resistance, it is preferable that at least isocyanate is contained. Specifically, metaphenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 3,3′-dimethyl-diphenyl-4,4′-diisocyanate,
Diisocyanates such as 3,3′-dimethyl-diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, or so-called burette type, adduct type, isocyanurate Examples include polyisocyanates known as molds. Examples of acid halides include dibasic acid halides such as adipoyl dichloride, phthaloyl dichloride, terephthaloyl dichloride, and 1,4-cyclohexanedicarbonyl chloride. Examples of the epoxy compound include epoxy compounds known as bisphenol A type, resorcin type, bisphenol F type, tetraphenylmethane type, novolac type, polyalcohol type, polyglycol type, and glycerin triether type.

When the encapsulation by interfacial polymerization is used, it is preferable to mix the second capsule shell-forming monomer in the aqueous medium. As the second capsule shell forming monomer, water, ethylene glycol, 1,4-butanediol, catechol, resorcinol, hydroquinone,
polyols such as o-dihydroxymethylbenzene, 4,4′-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) propane, and ethylenediamine, tetramethylenediamine, hexamethylenediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, Diethylaminopropylamine, polyamines such as tetraethylenepentamine, and piperazine, 2-methylpiperazine, and piperazine compounds such as 2,5-dimethylpiperazine can be mentioned. However, in the present invention, at least an amino group is present so that at least an amino group is present. It is necessary to add polyamine or piperazine compounds. The shell material of the toner base particles having a capsule structure obtained by this method is generally a polyurea resin, a polyurethane resin, a polyamide resin, a polyester resin, an epoxy resin, an epoxy urea resin, or an epoxy urethane resin. Among them, especially polyurea resin or polyurethane resin alone or a mixture of both,
Alternatively, the epoxy urea resin or the epoxy urethane resin alone or a mixture of both is preferable from the viewpoints of the retention of the core substance and the environmental dependence of charging. Also,
It is preferable to change the thickness of the outer shell for the purpose of pressure fixing and the purpose of heat fixing, but the kind or composition ratio of the constituent components may be changed.

The present invention relates to a method for producing a toner in which a vinyl polymer is adhered to the surface of a base particle of a capsule toner, after reacting a glycidyl group-containing polymerizable monomer represented by the above formula (1) and then adhering to the surface. It is characterized in that the vinyl monomer to be allowed to polymerize is polymerized to adhere the polymer to the surface of the toner base particle. The reason for this is that by reacting a glycidyl group-containing polymerizable monomer, the amino group on the surface of the toner base particle is converted into a polymerizable functional group. It is considered that the amino group is hydrophilic, and since it is hydrophobized, the amount of adsorbed monomer increases and the generation of polymer fine particles that do not adhere to the surface is suppressed. Further, in the present invention, since the amino group is converted into a polymerizable functional group, the effect of suppressing the environmental dependence (humidity dependence) of charging due to the amino group, ozone decomposes the amino group to generate NO _x. It also has the effect of preventing this.

In the present invention, the vinyl polymer composed of a vinyl monomer to be attached to the surface is a polymer which should be called a charge controllable polymer, and the toner is positively charged by contact or friction with a charging member. Means a vinyl polymer capable of imparting a chargeability or a negative chargeability. Specific examples of the positive charge imparting agent include nitrogen-containing vinyl polymers such as vinyl polymers having an amino group, a pyridyl group, a dialkylamino group or a quaternary ammonium salt structure. For negative chargeability, a vinyl polymer having a carboxyl group, a sulfonic acid group, a group having a salt structure thereof, or a fluorinated alkyl group can be used. In addition, compounds conventionally known as charge control agents, for example, nigrosine dye,
It may be a compound itself such as a gold-containing chromium dye or a phthalocyanine dye, or a vinyl polymer containing an analogue thereof. Of these, a dialkylamino group or a group having a quaternary ammonium salt structure, a carboxyl group,
A vinyl polymer having a fluorinated alkyl group is preferred in terms of charging stability and manufacturability.

As the vinyl monomer containing a group having a quaternary ammonium salt structure, a polymerizable monomer represented by the following formula (2) is preferred.

[Chemical 4] (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂
R ₄ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, W represents —COO—, —CONH— or 1,4-phenylene group, and Z ⁻ represents an anion;
n represents an integer of 1 to 8. )

Specific examples of the polymerizable monomer represented by the above formula (2) include the following. That is, examples of the cation moiety include those represented by the following structural formula.

[Chemical 5]

Further, the anion portion Z ^- The include those represented by the following structural formulas. Cl ^-, Br ^-, I ^-
Halogen ion such as CH ₃ COO ⁻ , C _{2
^{H 5 COO -, C 3 H}} 7 COO -, C 7 H 15 COO -,
An aliphatic carboxylic acid group such as C ₁₁ H ₂₃ COO ⁻ ,

[Chemical 6] Aromatic carboxylic acid groups and the like or ^{_{CH 3 SO 3, -, C}} 2
_{^{H 5 SO 3 -, C 3}} H 7 SO 3 -, C 7 H 15 SO 3 -,
C ₁₁ H ₂₃ SO ₃ ^- aliphatic sulfonic acid such as,

[Chemical 7] And other aromatic sulfonic acid groups. Also, Z
^- is, Acid Red, Acid Orange, Acid Violet, may be an anion residue of acid dyes such as Acid Blue.

In the present invention, the vinyl monomer represented by the above formula (2) may form a polymer by itself, or may be present as one component of the copolymer. The content of the vinyl monomer represented by the above formula (2) when it is present as one component of the copolymer is 1 mol% to 8 with respect to the total amount of the polymer.
It is desirable that the amount is 0 mol%, preferably 5 mol% to 60 mol%.

Examples of the monomer copolymerizable with the vinyl monomer represented by the above formula (2) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth). Propyl acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2
-(Meth) acrylic acid esters such as ethylhexyl, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and phenyl (meth) acrylate. Fatty acid vinyl esters such as vinyl acetate, vinyl acetate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl caproate, vinyl caprylate and vinyl stearate, or ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, Vinyl ethers such as 2-ethylhexyl vinyl ether and phenyl vinyl ether, vinyl ketones such as methyl vinyl ketone and phenyl vinyl ketone, styrene, chlorostyrene,
Examples thereof include vinyl aromatic compounds such as hydroxystyrene and α-methylstyrene. One or two or more of these may be mixed and copolymerized with the above monomer. Among these, (meth) acrylic acid esters are particularly preferable.

When the above vinyl polymer is adhered to the toner base particles, the fluidity of the toner is generally improved as compared with the toner base particles before being adhered, in order to further impart fluidity or chargeability to the toner. External additives such as silicon oxide, aluminum oxide, titanium oxide and carbon black may be added. The external additive may be added by drying the capsule toner and then adhering it to the toner surface using a mixer such as a V blender or a Henschel mixer, or by adding the external additive to water or a water-based liquid such as water / alcohol. After dispersion, the method may be added to a capsule toner in a slurry state and dried to attach an external additive to the toner surface.

As the core substance of the encapsulated toner particles, a core substance mainly composed of a component having a pressure fixing property is used for the purpose of pressure fixing, and a component having a heat fixing property for the purpose of heat fixing. A core material mainly composed of is used. Particularly for the purpose of pressure fixing, it is preferable that the core substance is mainly composed of a binder resin and a high-boiling-point solvent that dissolves the binder resin and a coloring material, or that is mainly composed of a soft solid substance and a coloring material. If necessary, a magnetic powder may be added in place of the coloring material, or an additive such as silicone oil may be added for the purpose of improving fixability. Further, a high boiling point solvent which does not dissolve the binder resin can be added to the high boiling point solvent which dissolves the binder resin. It is desirable to change the type or composition ratio of the constituents for the purpose of pressure fixing and the purpose of heat fixing.

As the binder resin, a known fixing resin can be used. Specifically, acrylic acid ester polymers such as polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, 2-ethylhexyl polyacrylate and lauryl polyacrylate, polymethyl methacrylate, polybutyl methacrylate, polymethacryl Methacrylic acid ester polymers such as acid hexyl, poly (2-ethylhexyl methacrylate), poly (lauryl methacrylate),
Copolymer of styrene monomer and acrylic ester or methacrylic ester, polyvinyl acetate, vinyl polypropionate, polyvinyl butyrate, ethylene-based polymers and copolymers such as polyethylene and polypropylene, styrene-butadiene copolymer Styrene-based copolymers such as styrene / isoprene copolymer, styrene / maleic acid copolymer, polyvinyl ether, polyvinyl ketone, polyester, polyamide, polyurethane, rubbers, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene Resins, phenolic resins and the like can be used alone or in combination. It is also possible to prepare a binder resin by polymerizing after charging and encapsulation in a monomer state.

As the high boiling point solvent for dissolving the binder resin, an oily solvent having a boiling point of 140 ° C. or higher, preferably 160 ° C. or higher can be used. For example, Modern
Plastics Encyclopedia (19
75 to 1976) and those described in Plasticizers can be selected. Alternatively, a high-boiling-point solvent known as a core substance of a pressure fixing capsule toner (for example, JP-A-58-145964, 63-1).
63373 publication).

Specifically, phthalic acid esters (eg, diethyl phthalate, dibutyl phthalate); aliphatic dicarboxylic acid esters (eg, diethyl malonate, dimethyl oxalate); phosphoric acid esters (eg, tricresyl) Phosphates, trixylyl phosphates); citric acid esters (eg, o-acetyltriethyl citrate); benzoic acid esters (eg, butylbenzoate, hexylbenzoate); fatty acid esters (eg, hexadecylmyristate, dioctyl adipate) Alkylnaphthalenes (eg, methylnaphthalene, dimethylnaphthalene, monoisopropylnaphthalene, diisopropylnaphthalene); alkyldiphenyl ethers (eg, o-,
m-, p-methyldiphenyl ether); amide compounds of higher fatty acid or aromatic sulfonic acid (eg, N, N-
Dimethyllaurylamide, N-butylbenzenesulfonamide); trimellitic acid esters (eg, trioctyl trimellitate); diarylalkanes (eg, diarylmethane such as dimethyldiphenylmethane, 1-phenyl-1-methylphenylethane) , 1-dimethylphenyl-1-phenylethane, 1-ethylphenyl-1-phenylethane, etc.); and chlorinated paraffins. When a polymer having a long-chain alkyl group such as lauryl methacrylate homopolymer or copolymer is used as the binder polymer, an aliphatic saturated hydrocarbon or an organic solvent containing an aliphatic saturated hydrocarbon as a main component (for example, Exxon Chemical Co. Isopar-
G, Isopar-H, Isopar-L, Isopa
r-M etc.) can be used.

Examples of the coloring material include inorganic pigments such as carbon black, red iron oxide, dark blue, titanium oxide, fast yellow, disazo yellow, pyrazolone red, chelate red, azo pigments such as brilliant carmine and para brown, copper phthalocyanine, metal-free phthalocyanine. And condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, and dioxazine violet. Further, disperse dyes, oil-soluble dyes and the like can also be used. Furthermore, as the magnetic one-component toner, all or part of the black coloring material can be replaced with magnetic powder. As the magnetic powder, magnetite, ferrite, a simple metal such as cobalt, iron, nickel, or an alloy thereof can be used. Also, a silane coupling agent,
It may be a magnetic powder which is surface-treated with a coupling agent such as a titanate coupling agent or an oil-soluble surfactant, or whose surface is coated with an acrylic resin, a styrene resin or an epoxy resin. Furthermore, the coloring material or magnetic powder charged as one component of the core substance may be present at the interface between the core and the outer shell or in the outer shell after capsule formation.

The soft solid substance is not particularly limited as long as it has flexibility and fixability at room temperature, but a polymer having a Tg in the range of -60 ° C to 5 ° C or its weight is preferable. Mixtures of coalesce and other polymers are preferred. As a method of incorporating it into the capsule as one component in the core substance, it is charged in advance in the form of a polymer together with other core substance component, a low boiling point solvent and an outer shell forming component, and at the same time as forming the outer shell by interfacial polymerization or the outer shell. After completion of shell formation, a method of driving the low boiling point solvent out of the system to form a core substance can be used. In addition, a method may be used in which a core substance is formed by polymerizing a monomer after forming an outer shell by charging interfacial polymerization in a monomer state. An external additive such as silicon oxide, aluminum oxide, titanium oxide or carbon black may be added to the toner in order to impart fluidity or chargeability. As the method for adding the external additive, after the capsule toner is dried, it may be dry-adhered to the toner surface using a mixer such as a V blender or a Henschel mixer, or the external additive may be added in water or water / alcohol. After being dispersed in an aqueous liquid, it may be added to a capsule toner in a slurry state, dried and then attached to the toner surface.

[0027]

【Example】

Example 1 (Preparation of Capsule Particles) Saturated aliphatic hydrocarbon (Isop
er-M: manufactured by Exxon Co., Ltd.) and a mixed solution of 40 g of ethyl acetate and 60 g of ethyl acetate were added to a lauryl methacrylate polymer (Mw = 3 × 1).
0 ⁴ ) 30 g, lauryl methacrylate / 2-ethylhexyl methacrylate copolymer (Mw = 6 × 10 ⁴ ) 4
0 g was added and dissolved. Magnetic powder (EPT-100
0: made by Toda Kogyo Co., Ltd.) 120g, 1 in ball mill
Dispersed for 6 hours. Next, to 200 g of this dispersion, 30 g of isocyanate (Sumijour L: manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 24 g of ethyl acetate were added and thoroughly mixed (this liquid is referred to as liquid A). On the other hand, 200 deionized water
Dissolve 10 g of hydroxypropylmethyl cellulose (Metroses 65SH50: manufactured by Shin-Etsu Chemical Co., Ltd.) in 5 g, and 5 ° C.
It cooled to this (this liquid is set to B liquid). The liquid B was stirred with an emulsifying machine (auto homomixer: specially manufactured by Kiki Kako Co., Ltd.), and the liquid A was slowly charged into the liquid to emulsify the liquid. Thus, the average particle diameter of the oil droplet particles in the emulsion is about 12 μm.
A / W emulsion was obtained. Next, instead of the emulsifier, a stirrer equipped with a propeller-type stirring blade (three-one motor:
It was changed to Shinto Kagaku Co., Ltd.) and stirred at 400 rpm. 1
After 0 minutes, a 5% aqueous solution of diethylenetriamine 20
0 g was added dropwise. After completion of the dropping, the mixture was heated to 60 ° C. 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 the capsule particles settled, the supernatant was removed. This operation was repeated 7 more times to wash the capsule particles. In this way, capsule particles containing the oily binder were obtained. Ion-exchanged water was added to the capsule particles to prepare a suspension having a solid content concentration of 40%.

(Tonerization) 125 g of ion-exchanged water was added to 125 g of the prepared 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 Co., Ltd.) ) At 200 rpm. 4 g of glycidyl methacrylate was added and the reaction was carried out at 20 ° C. for 3 hours. Furthermore, 0.2 g of ethyltrimethylammonium chloride chloride and 2.0 g of methyl methacrylate were added to the reaction mixture, and 0.2 g of a polymerization initiator (VA-O4 manufactured by Wako Pure Chemical Industries, Ltd.).
4) was added and the reaction was carried out at 50 ° C. for 3 hours. After the completion of the reaction, vacuum filtration was performed with 2 liters of ion-exchanged water for washing.

Next, 2 g of a 5% aqueous solution of sodium 4-naphtholsulfonate was added to this capsule particle suspension, and
The ion exchange reaction was performed by stirring for 0 minutes at room temperature. After the reaction was completed, the capsule particles were filtered under reduced pressure with 1 liter of ion-exchanged water and washed. Thus, the capsule toner of the present invention in which the polymer was attached to the surface of the capsule shell was obtained. The cake of the obtained capsule toner was placed in a stainless steel vat and dried at 60 ° C. for 20 hours with a dryer (Yamato Scientific Co., Ltd.). To 100 parts of the obtained capsule toner, 0.1 part of carbon black (REGAL330R: manufactured by Cabot) was added and mixed well.

Using the above toner, the temperature is 25 ° C. and the humidity is 4
Image quality was evaluated under 0% environment. The copying machine used was a Fuji Xerox 2700 modified for capsule toner to obtain a copy sample. When copying up to the 20,000th sheet, a stable copy was obtained. When the developing roll and the toner layer forming blade were examined, polymer fine particles were not attached.

Comparative Example 1 Except that glycidyl methacrylate was not added, the same treatment as in Example 1 was carried out to obtain a comparative capsule toner. Similarly, using the obtained capsule toner, the temperature of 25
The image quality was evaluated under the environment of ° C and humidity of 40%. The copying machine used was a Fuji Xerox 2700 modified for capsule toner to obtain a copy sample. As a result, 2
From the 000th sheet, white streaks occurred in the copy transport direction.
When the developing roll and the toner layer forming blade were examined, polymer fine particles were attached to the developing roll, and lumps of polymer fine particles and broken toner were attached to the toner layer forming blade. It was confirmed that the toner was not conveyed onto the developing roll at that location and streaks were formed.

Example 2 125 g of ion-exchanged water was added to 125 g of the capsule particle suspension prepared in Example 1 (corresponding to 50 g of capsule particles), and a stirrer equipped with a propeller-type stirring blade (Three One Motor: Shinto). Stirring was carried out at 200 revolutions / minute (manufactured by Kagaku). A mixture of 0.5 g of allyl glycidyl ether (Epiol A manufactured by NOF CORPORATION), 1.0 g of trifluoroethyl methacrylate and 2.0 g of methyl methacrylate was added thereto and stirred for 3 hours. Next, 0.3 g of 4,4'-azobiscyanovaleric acid was sequentially added to this, and the reaction was carried out at 50 ° C for 6 hours. After the completion of the reaction, vacuum filtration was performed with 2 liters of ion-exchanged water for washing. The obtained capsule cake was placed in a stainless vat and dried at 60 ° C. for 20 hours with a dryer (manufactured by Yamato Scientific Co., Ltd.). Thus, the capsule toner of the present invention in which the polymer was attached to the surface of the capsule shell was obtained. To 100 parts of the obtained capsule toner, carbon black (REGAL330
R: made by Cabot Co.) was added to 0.1 part and mixed well.

Using the above toner, the temperature is 25 ° C. and the humidity is 4
Image quality was evaluated under 0% environment. The copying machine used was a 2700 manufactured by Fuji Xerox Co., Ltd. modified for capsule toner, and reverse development was performed to obtain a copy sample. 20
When copying was performed up to the 000th sheet, a stable copy was obtained. When the developing roller and the toner layer forming blade were examined, polymer fine particles were not attached.

Comparative Example 2 The same treatment as in Example 2 was carried out except that allyl glycidyl ether was not added to obtain a comparative capsule toner. A copy sample was similarly obtained using the obtained capsule toner. As a result, streaks occurred in the copy transport direction from the 2000th sheet. When the developing roll and the toner layer forming blade were examined, polymer fine particles were attached to the developing roll, and lumps of polymer fine particles and broken toner were attached to the toner layer forming blade. It was confirmed that the toner was not conveyed onto the developing roll at that location and streaks were formed.

[0035]

As described above, the encapsulated toner of the present invention is prepared by binding the glycidyl group-containing polymerizable monomer represented by the above formula (1) to the amino group present on the surface of the toner base particles, Since the vinyl polymer is attached to the toner base particles via the, the adhesiveness between the vinyl polymer and the toner base particles is significantly improved, and good copy image quality can be maintained for a long period of time.

Claims (4)

[Claims] 1. A vinyl polymer is obtained through a reaction product of a glycidyl group-containing polymerizable monomer represented by the following formula (1), which has reacted with an amino group present on the surface of a capsule toner base particle. A capsule toner characterized in that it adheres to. [Chemical 1] (Here, X represents a hydrogen atom or a methyl group, and Y represents a methylene group or a carbonyl group.) 2. The encapsulated toner according to claim 1, wherein the encapsulated toner base particles are formed by interfacial polymerization. 3. The capsule toner according to claim 1, wherein the vinyl polymer contains a quaternary ammonium salt-containing vinyl monomer represented by the following formula (2) as a monomer component. [Chemical 2] (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂
R ₄ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, W represents —COO—, —CONH— or 1,4-phenylene group, and Z ⁻ represents an anion;
n represents an integer of 1 to 8. ) 4. A glycidyl group-containing polymerizable monomer represented by the above formula (1), wherein an amino group is present in the capsule toner base particles in a method for producing a capsule toner in which a polymer is attached to the surfaces of the capsule toner base particles. Is reacted with the amino group to bond it, and then a vinyl monomer is polymerized,
A method for producing a capsule toner, which comprises depositing a polymer on the surface of the toner base particles.