JPH07175260A - Production of thermocompression fixing capsule toner and capsule toner - Google Patents

Abstract

PURPOSE:To manifest appropriately the function of each additive without problems such as the generation of contamination in the inside of a developing device by the stripping of the various additives with the agitation of the device since the various additives does not exist on the outside shell surface of a toner. CONSTITUTION:In the producing method of a thermocompression fixing capsule toner constituted of a hot-melt core material containing at least a thermoplastic resin and the outside shell provided so as to cover the surface of the core material, the shell in which the additives are dispersed is formed by covering the surface of the core material with the resin, in which at least one or more kind of the additives selected from a group composed of an electroconductive material, a charge controlling agent, a wax component, a coloring material and a magnetic powder are previously dispersed, by in situ polymerization and the thermocompression fixing capsule toner is obtained by this method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat and pressure fixing capsule toner used for developing an electrostatic latent image formed in an electrophotographic method, an electrostatic printing method, an electrostatic recording method and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventional electrophotographic methods include US Pat. Nos. 2,297,691 and 235780.
As described in the specification of No. 9, etc., an electric latent image is formed by uniformly charging a photoconductive insulator layer, then exposing the layer, and dissipating the charge on the exposed portion. Was formed, and further, a fine powder having a colored charge called toner was attached to the latent image to make it visible (developing step), and the obtained visible image was transferred to a transfer material such as transfer paper. The subsequent (transfer step) comprises a step of permanently fixing (fixing step) by heating, pressure, or any other suitable fixing method. As described above, the toner must have the functions required not only in the developing step but also in the transfer step and the fixing step.

Generally, toner is subjected to a mechanical frictional force due to a shearing force and an impact force received during mechanical operation in a developing device,
It deteriorates during the copying of thousands to tens of thousands of sheets. In order to prevent such toner deterioration, a tough resin having a large molecular weight that can withstand mechanical frictional force may be used, but these resins generally have a high softening point and are not suitable for oven fixing, which is a non-contact fixing method. Since the thermal efficiency is poor, the fixing cannot be performed sufficiently. In addition, since the heat efficiency is good, it is necessary to raise the temperature of the heat roller even in the heat pressure fixing method using a heat roller, which is a widely used contact fixing method. Invite. Further, when such a resin is used, the pulverizability is poor, so that the production efficiency is significantly reduced when the toner is produced. Therefore, a binder resin having a too high degree of polymerization and a softening point cannot be used.

On the other hand, the thermal pressure fixing method using a heat roller or the like has a remarkably high thermal efficiency and is widely used from low speed to high speed. When the heating roller surface and the toner image surface come into contact with each other, the toner is applied to the heating roller surface. A so-called offset phenomenon, in which the toner adheres and is transferred to the subsequent transfer paper or the like, is likely to occur. In order to prevent this phenomenon, the surface of the heating roller is processed with a material with excellent mold release properties, and a mold release agent such as silicone oil is applied to the surface to deal with this problem. It is easy to cause high cost and device trouble.

Also, Japanese Patent Publication No. 57-493 and Japanese Patent Laid-Open No. 504484.
As described in JP-A-57-37357 and JP-A-57-37357, there is a method of improving the offset phenomenon by making the resin asymmetric and cross-linking, but the fixing property is not improved.

Generally, since the lowest fixing temperature is between the low temperature offset and the high temperature offset, the usable temperature range is between the lowest fixing temperature and the high temperature offset, and the lowest fixing temperature should be lowered as much as possible and the high temperature offset generation temperature should be as high as possible. By raising the temperature, the fixing temperature can be lowered and the usable temperature range can be widened, energy saving, high speed fixing and paper curl can be prevented. Therefore, there is always a demand for a toner having good fixability and offset resistance.

Conventionally, there has been proposed a technique for attaining low-temperature fixability by using a capsule toner composed of a core material and an outer shell provided so as to cover the surface of the core material as the toner.

Among them, when a low melting point wax which is easily plastically deformed is used as the core material (US Pat. No. 3,269,626, Japanese Patent Publication No. 46-15876, etc.), fixing can be performed only by pressure, but the fixing strength is high. Inferior and limited in application. Further, when a liquid material is used as the core material, the shell material may be broken in the developing device to stain the inside of the machine, which makes it difficult to adjust the strength of the shell material.

Therefore, when used alone as a core material for heat and pressure fixing, blocking occurs at high temperatures, but a resin having a low glass transition point which improves fixing strength is used, and blocking resistance and the like are provided as an outer shell. For this purpose, a heat roller fixing capsule toner in which a resin wall having a high melting point is formed by interfacial polymerization has been devised.

Such capsule toner has been disclosed in Japanese Patent Laid-Open No. Sho 61-61.
No. 56352, JP-A No. 58-205162, JP-A No. 58-205163, JP-A No. 63-128357, and JP-A No. 63-128357 have been proposed.
No. 128358, No. 63-128359, No. 63-128360, No. 63-128361, No. 63-128362), because the manufacturing method is a spray-dry method, while burdening the manufacturing equipment, Since the shell material has not been devised, the performance of the core material has not been fully achieved.

Therefore, a capsule toner using a compound having a heat dissociation property as a shell material (JP-A-4-212169)
Alternatively, a capsule toner (Japanese Patent Application No. 4-259088) using amorphous polyester as a shell material has been proposed. When these capsule toners are manufactured, a polymerizable monomer is suspended in a dispersion medium and its outer shell is formed by interfacial polymerization or in situ method in consideration of the shortening of steps, simplification of equipment and the like. Is advantageous, and the capsule toner is manufactured by these methods.

On the other hand, conventionally, in the core material of the encapsulated toner, a conductive substance has been used for the purpose of improving the cleaning property and stabilization of the charge, and a charge control agent for controlling the charge to either positive or negative polarity. A wax component, a colorant pigment as a colorant, and a magnetic powder for the purpose of imparting magnetism to the toner are appropriately added to improve offset resistance.

Many of these additives are generally solid and do not dissolve in the polymerizable monomer, and particles such as the charge control agent and the coloring material pigment are usually present as aggregates. Therefore, in the case of producing a toner by the suspension polymerization method, after the polymerizable monomer and the above additives are sufficiently crushed into particles using a dispersing machine such as a ball mill or a sand stirrer, solid-liquid dispersion is performed. A method for producing a toner by carrying out polymerization is used. However, originally, the charge control agent added for the purpose of stabilizing the charge, and the additive such as a conductive substance added for the purpose of improving the cleaning property are greatly present when they are present in the vicinity of the toner surface. When the additive is dispersed by the above-mentioned dispersion method, there is a problem that the effect is not exhibited because the additive is easily taken into the toner and hardly exists on the toner surface.

In order to solve these problems, Japanese Patent Laid-Open No. 1-1
In JP-A-85652, JP-A-1-185659 and JP-A-1-185665, an additive or resin fine particles containing the additive is fixed on a toner surface to a toner obtained by a suspension polymerization method. By doing so, a manufacturing method is disclosed in which an additive is allowed to exist on the surface of the toner so as to have its function. However, such a manufacturing method is costly in manufacturing equipment, the dispersibility of the additives is poor, and the manufacturing stability is also poor. Further, since all the additives are not firmly adhered to the toner surface, the adhesion of the adhesive does not occur during printing. There was also a problem that sufficient additives were released and the inside of the machine was contaminated.

The present invention has been made based on the above circumstances, and its purpose is to allow an additive that is not soluble in a polymerizable monomer to exist in the vicinity of the toner surface with good dispersibility and efficiency. It is an object of the present invention to provide a heat-pressure fixing capsule toner capable of suitably exhibiting the function of an additive and free from in-machine contamination and capable of low-temperature fixing, and a method for producing the same.

[0016]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have used a resin in which various additives such as a conductive substance are dispersed in the outer shell of a capsule toner. Found that the above problems can be solved by
The present invention has been completed.

That is, the gist of the present invention is (1) a capsule for heat and pressure fixing comprising a heat-fusible core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material. In the toner manufacturing method, by performing in situ polymerization using a resin in which one or more additives selected from the group consisting of a conductive substance, a charge control agent, a wax component, a coloring material pigment, and a magnetic powder are previously dispersed. A method for producing a capsule toner for heat and pressure fixing, which comprises coating the resin on the surface of a core material to form an outer shell in which the additive is dispersed, (2) a main component of a resin constituting the outer shell Is an amorphous polyester, (3) The production method according to (1) above, wherein (3) the amorphous polyester comprises one or more divalent alcohol monomers and 1 as a constituent monomer.
One obtained by polycondensation using at least one divalent carboxylic acid monomer, at least a trivalent or more polyvalent alcohol monomer and / or a trivalent or more polyvalent carboxylic acid monomer. And a glass transition point of 50 to 80 ° C. and an acid value of 3 to 5
0 (KOHmg / g), the production method according to (2) above, (4) comprising a heat-meltable core material containing at least a thermoplastic resin, and an outer shell provided so as to cover the surface of the core material. In heat and pressure fixing capsule toner,
Capsule toner for heat and pressure fixing, characterized in that at least a conductive substance is dispersed in the outer shell resin, (5)
In a heat-and-pressure fixing capsule toner composed of a heat-meltable core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material, at least a coloring material pigment is contained in the outer shell resin. A heat and pressure fixing capsule toner characterized by being dispersed, and (6) a heat-meltable core material containing at least a thermoplastic resin, and an outer shell provided so as to cover the surface of the core material. A capsulated toner for heat and pressure fixing, wherein at least magnetic powder is dispersed in the outer shell resin.

The capsule toner for heat and pressure fixing of the present invention comprises:
A capsule toner for heat and pressure fixing comprising a heat-meltable core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material, wherein various additives are dispersed in the outer shell resin. It is characterized by what is done. Here, as the various additives, at least one selected from the group consisting of a conductive substance, a charge control agent, a wax component, a coloring material pigment, and a magnetic powder is used. That is, these are 2
You may use together 1 or more types.

In the present invention, since the additive which is normally dispersed in the core material of the capsule toner is dispersed in the outer shell resin as described above, the function of the additive is suitably exhibited as described below. be able to. Therefore, in the present invention, it is only necessary to disperse an additive appropriately selected within the range in which the function as the outer shell is not lost, and other additives can be dispersed in the core material. Specifically, regarding the distribution of various additives, for example, there are the following modes, but the present invention is not limited thereto.

A core material: charge control agent, wax component, color material pigment, magnetic powder shell material: conductive material b core material: conductive material, charge control agent, wax component, magnetic powder shell material: color material pigment c Core material: conductive material, charge control agent, wax component, color material pigment Shell material: magnetic powder d Core material: charge control agent, wax component, color material pigment Shell material: conductive material e Core material: conductive material, Charge control agent, wax component Shell material: color material pigment f Core material: conductive substance, charge control agent, color material pigment, magnetic powder Shell material: wax component g Core material: charge control agent, wax component, magnetic powder shell material : Conductive substance, color pigment h Core material: conductive substance, color pigment, magnetic powder Shell material: charge control agent, wax component i Core material: charge control agent, color pigment, magnetic powder Shell material: conductive Substance, wax component

First, these additives will be described in detail below.

The conductive substance (low resistance substance) that can be used in the present invention is not particularly limited as long as it has a resistivity of 10 ⁻³ to 10 ³ Ω · cm, and examples thereof include carbon black and triacid oxide. It is possible to use iron, iron tetraoxide iron oxide, tin oxide, titanium oxide and the like. Among them, carbon black has a small particle size, and thus can be suitably used in the present invention. The carbon black is not particularly limited as long as it is manufactured by an ordinary manufacturing method such as a channel method or a furnace method.

The pH value of these carbon blacks is usually 3.0 to 10, preferably 5.0 to 9.0, and the volatilization loss is usually 5% or less, preferably 3% or less. To be done. Generally, a resin has a high resistivity of 10 ¹² to 10 ¹⁷ Ωcm because it is electrically insulating in nature, but the resistivity of the resin is 10 ⁶ to 10 ⁶ by dispersing a conductive substance as in the present invention. It becomes ¹¹ Ωcm.

Conventionally, the toner obtained by the suspension polymerization method has a shape close to a sphere, and when the copying speed and the printing speed are high, even if the untransferred toner remaining on the photoreceptor is cleaned with a blade, However, there is a problem that the untransferred toner is not completely removed due to the strong adhesion between the toner and the toner, leaving black streaks in the final image.

It is considered that one of the causes of the increase in the adhesive force is the electrostatic increase in the adhesive force due to the high electric resistance of the toner. That is, the capsule toner produced by the above-described polymerization method has a tendency that the toner surface is covered with the shell material resin and thus the electric resistance of the toner tends to increase.

As a method of lowering the electric resistance of such toner, there is known a method of mechanically attaching a conductive substance such as carbon black onto the toner surface as described above. However, such a method has a problem that the adhered conductive substance is peeled off by stirring in the developing machine, resulting in contamination inside the machine. In addition, it is difficult to control the resistance, and particularly when the toner resistance is 10 ⁵ Ωcm or less, it becomes difficult to electrostatically transfer the toner after development onto the transfer paper onto the transfer paper by means of corona transfer, bias transfer or the like. was there.

Therefore, as in the present invention, by using a resin in which a conductive substance is dispersed in advance as an outer shell, it becomes possible to control the electric resistance of the surface of the capsule toner obtained by the polymerization method, and it is possible to control the transfer of the untransferred toner. Even when the cohesive force is lowered and the copying speed and the printing speed are high, it is possible to completely remove it by the blade cleaning and prevent the generation of black stripes.

In the heat and pressure fixing capsule toner of the present invention, the conductive substance is dispersed in the outer shell resin, but more specifically, it is not normally exposed on the outer shell surface and It is dispersed in the whole or a part from the vicinity of the surface of the shell to the vicinity of the interface between the outer shell and the core material. in this way,
In the present invention, the conductive substance is present in the outer shell resin and does not normally appear on the outer shell surface. Therefore, the conductive substance is coated on the toner surface, or only the core material of the capsule toner has the conductive substance. It is clearly distinguished from the conductive toner containing the.

The dispersion concentration of the conductive substance is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the outer shell resin. If it is less than 5 parts by weight, the resistance value is not sufficiently lowered and the effect on the cleaning property is small, and if it is more than 50 parts by weight, the resistance value is too low and the charging property is lowered.

The charge control agent that can be used in the present invention includes
Both of the following negatively chargeable charge control agents and positively chargeable charge control agents can be mentioned. The negatively chargeable charge control agent is not particularly limited, and examples thereof include metal-containing azo dyes “Varifast Black 3804” and “Bontron S.
-31 "," Bontron S-32 "," Bontron S-
34 "(above, manufactured by Orient Chemical Co., Ltd.)," Aizen spirone black TRH "," Aizen spirone black T "
-77 "(above, manufactured by Hodogaya Chemical Co., Ltd.), copper phthalocyanine dye, metal complex of alkyl derivative of salicylic acid, for example," Bontron E-81 "," Bontron E-8 ".
2 "," Bontron E-85 "(above, manufactured by Orient Chemical Company), quaternary ammonium salt, for example," COPY CHARGE NX "
VP434 ”(manufactured by Hoechst), nitroimidazole derivatives and the like. Of these, preferred is "Aizen spirone black T-77",
"Aizen spirone black TRH" is mentioned.

The positively chargeable charge control agent is not particularly limited, and examples thereof include nigrosine dye "Nigrosine base EX", "oil black BS", "oil black SO", "bontron N-01", and "bontron". N-07 "," Bontron N-09 "," Bontron N "
-11 "(above, manufactured by Orient Chemical Co., Ltd.) triphenylmethane dye containing a tertiary amine as a side chain, quaternary ammonium salt compound, for example," Bontron P-51 ".
(Orient Chemical Co., Ltd.), cetyl trimethyl ammonium bromide, “COPY CHARGE PX VP435” (Hoechst Co.), polyamine resins such as “AFP-B” (Orient Chemical Co., Ltd.), and imidazole derivatives. Among these, preferred are "Bontron N-01", "Bontron N-07", "Bontron N-09", and "AFP-B".

It is possible to provide sufficient charge stability without adding a charge control agent in the toner for heat and pressure fixing, but in the case where the toner fog occurs on the photoconductor especially at high temperature and high humidity. was there. To solve such problems, a method of adding a charge control agent to the toner to stabilize the charging property is known. However, if the added charge control agent is present near the center of the toner, it is not so effective. On the contrary, when it exists on the outermost surface of the toner, in particular, in the two-component developer, the charge control agent migrates to the carrier, the charge amount level of the toner is greatly lowered, and the problem that the fog increases is likely to occur. When the charge control agent is added by the method of the present invention, the charge control agent exists in the outer shell resin and therefore exists near the toner surface, but does not deposit on the outermost surface of the toner. A stable charge amount can be obtained, transfer to a carrier does not occur, and good results satisfying all of them can be obtained.

The dispersion concentration of the charge control agent is usually 0.05 to 20 with respect to 100 parts by weight of the shell resin.
Parts by weight, preferably 0.1 to 10 parts by weight. 0.0
If it is less than 5 parts by weight, image quality deterioration such as fogging tends to occur, and if it is more than 20 parts by weight, the charge amount level becomes too high and the image density tends to decrease.

Examples of the wax component usable in the present invention include polyolefin, fatty acid metal salt, fatty acid ester, partially saponified fatty acid ester, higher fatty acid, higher alcohol, paraffin wax, amide wax, polyhydric alcohol ester, silicone varnish, Any one or more kinds of offset preventing agents such as aliphatic fluorocarbon, silicone oil, microcrystalline wax, and sazol wax may be contained. Of these, preferred are polyolefin, silicone oil, microcrystalline wax, and sazol wax.

It is possible for the heat and pressure fixing toner to have sufficient offset resistance without the addition of a wax component, but especially the copying speed and printing speed are high,
When the diameter of the fixing roller is large, the releasability from the fixing roller is poor, and nail marks may occur in a solid image.

In order to solve such a problem, there is known a method of adding a wax component to the toner to improve the releasability, but if the added wax component is present near the center of the toner, it is not so much. When the wax component is not present on the outermost surface of the toner, the wax component migrates to the photoconductor to contaminate the print.

When the wax component is added by the method of the present invention, since the wax component is present in the outer shell resin,
Although it exists in the vicinity of the toner surface, it is not deposited on the outermost surface of the toner, so that a large releasing effect is obtained and transfer to the photosensitive member does not occur, and good results satisfying all are obtained.

The dispersion concentration of the wax component is usually
The wax component is 5 to 100 relative to 100 parts by weight of the outer shell resin.
Parts by weight, preferably 10 to 70 parts by weight. If it is less than 5 parts by weight, the releasing effect is low, and if it is more than 100 parts by weight, contamination of the photoconductor is likely to occur.

As the coloring material pigment that can be used in the present invention, various organic or inorganic pigments and dyes of various colors can be used.

That is, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like. As yellow pigments, yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, bunzer yellow G, bunzer yellow 10G, benzidine yellow G, benzidine yellow G
R, quinoline yellow rake, permanent yellow NC
G, Tartrazine rake, etc.

Examples of orange pigments include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, induslen brilliant orange RK, benzidine orange G and induslen brilliant orange GK. Examples of red pigments include red iron oxide, cadmium red, red lead, mercury sulfide, quinacridone, cadmium, permanent red 4R, resole red, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake. B, Alizarin Rake, Brilliant Carmine 3B, etc.

Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake. Examples of blue pigments include dark blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated compound, fast sky blue, and indanthrene blue BC.

Examples of green pigments include chrome green, chrome oxide, pigment green B, mica light green lake, and final yellow green G. As white pigments, zinc white, titanium oxide, antimony white,
For example, zinc sulfide.

Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

Among these coloring material pigments, preferred are benzidine yellow G, benzidine yellow GR,
Brilliant carmine 6B, quinacridone, rhodamine lake B, phthalocyanine blue, metal-free phthalocyanine blue, and phthalocyanine blue partially chlorinated compounds can be mentioned. These pigments may be used alone or in combination of two or more.

When the coloring material pigment is added by the method of the present invention, it becomes ubiquitous in the shell material of the toner surface layer, so that the transparency of the fixed toner, that is, the transmission when developed and fixed on the OHP film is observed. It is possible to improve the color reproduction and the color reproducibility when the colors are overlapped in a full-color image. Further, since it is not a method of mechanically adhering it on the surface of the toner, it is possible to provide a developer free from contamination in the machine.

The dispersion concentration of the coloring material pigment is usually 3 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the outer shell resin. If the amount is less than 3 parts by weight, the coloring power is weak and the color is light, and if the amount is more than 50 parts by weight, the coloring power is too strong, resulting in poor halftone reproducibility in printed images and poor density gradation. The image becomes a standing image and the image quality deteriorates.

The magnetic powder that can be used in the present invention includes, for example, ferrite, magnetite and other iron, cobalt, nickel and other ferromagnetism metals or alloys, compounds containing these elements, or ferromagnetic elements. Alloys that do not have a ferromagnetism when subjected to a suitable heat treatment, for example, manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, or chromium dioxide. , And others. The average particle size of these magnetic materials is 0.1
Dispersed in the shell resin in the form of a fine powder of ˜1 μm. Of these, preferred are ferrite and magnetite.

When the fine magnetic powder is added to the toner to make it a magnetic toner, it may be treated in the same manner as in the case of the colorant, but as it is, it has a low affinity for organic substances such as outer shell resin. When the magnetic fine powder is used together with a so-called coupling agent such as a titanium coupling agent, a silane coupling agent, and lecithin or after being treated with the coupling agent, the magnetic fine powder can be uniformly dispersed.

If magnetic powder is added by the method of the present invention,
Since it becomes ubiquitous in the shell material of the toner surface layer, it is possible to increase the magnetic force of the toner with a small amount of magnetic powder, and particularly in a two-component developing system, it effectively acts to prevent toner scattering.

The dispersion concentration of the magnetic powder is usually 5 to 100 parts by weight, preferably 10 to 70 parts by weight, with respect to 100 parts by weight of the outer shell resin. If it is less than 5 parts by weight, the magnetic force is weak and there is no effect of addition, and if it is more than 100 parts by weight, the magnetic powder is likely to appear on the outermost surface and the fixing property is deteriorated.

The resin constituting the outer shell of the encapsulated toner of the present invention is not particularly limited as long as it has higher hydrophilicity than the thermoplastic resin used for the core material in the case of in situ polymerization. , Polyesters, polyesteramides, polyamides, polyureas, or polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate / diethylaminoethyl methacrylate or copolymers thereof with styrene or unsaturated carboxylic acid esters, or acrylic An unsaturated carboxylic acid / unsaturated dibasic acid / unsaturated dibasic acid anhydride polymer such as an acid or methacrylic acid, or a copolymer of the same and a styrene-based monomer is used. Among them, when amorphous polyester is used as the main component of the outer shell, it can be preferably used in the present invention because the obtained toner has excellent low-temperature fixability.

Such an amorphous polyester is usually
As a constituent monomer, one or more divalent alcohol monomers and one or more divalent carboxylic acid monomers, and at least a trivalent or more polyhydric alcohol monomer and / or a trivalent or more polyvalent carboxylic monomer. What is obtained by polycondensation using an acid monomer is used. Such an amorphous polyester is usually 50 to 100% by weight based on the total weight of the resin in the outer shell.
As the other resin component contained and contained in the outer shell, polyamide, polyesteramide, polyurea or the like can be used in an amount of 0 to 50% by weight.

Examples of the dihydric alcohol monomer include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3).
-2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0)-
Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,
Alkylene oxide adducts of bisphenol A such as 2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A , Bisphenol A
Propylene adduct, bisphenol A ethylene adduct, hydrogenated bisphenol A and the like.

Examples of the trihydric or higher polyhydric alcohol monomers include, for example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1, 2,4
-Butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxy Methylbenzene etc. are mentioned. Trivalent alcohol is preferably used. In the present invention, these two
A single monomer or a plurality of monomers may be used from the polyhydric alcohol monomer and the trihydric or higher polyhydric alcohol monomer.

The acid component may be a divalent carboxylic acid monomer such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid. , Sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, n-dodecylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, and anhydrides or lower alkyl esters of these acids. Can be mentioned.

Examples of trivalent or higher polycarboxylic acid monomers include 1,2,4-benzenetricarboxylic acid and 2,5,7-
Naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxylic) methane, 1,2,7,8-octanetetracarboxylic acid,
Pyromellitic acid, enpol trimer acid and their acid anhydrides, lower alkyl esters and the like can be mentioned. Preferably, a trivalent carboxylic acid or its derivative is used. In the present invention, these divalent carboxylic acid monomers and trivalent or higher polyvalent carboxylic acid monomers may be used alone or in combination.

The method for producing the amorphous polyester in the present invention is not particularly limited, and it can be produced by esterification or transesterification reaction using the above-mentioned monomer. Here, amorphous is one which does not have a definite melting point, and when crystalline polyester is used in the present invention, the amount of energy required for melting is large and the toner fixability cannot be improved, which is not preferable.

The amorphous polyester thus obtained preferably has a glass transition point of 50 to 80 ° C. If it is less than 50 ° C, the storage stability of the toner will be poor, and if it exceeds 80 ° C, the fixing property of the toner will be poor.
In the present invention, the glass transition point is a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd.) and the temperature rising rate is 10 ° C./min.
The temperature at the intersection of the extension line of the base line below the glass transition point and the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak, when measured by.

The acid value of the amorphous polyester is 3
It is preferably -50 (KOHmg / g), more preferably 10-30 (KOHmg / g). Three
If it is less than (KOHmg / g), it becomes difficult for the amorphous polyester as the shell material to come out to the interface during the in-situ polymerization, so that the storage stability of the toner becomes poor, and 50 (KOHmg / g)
If it exceeds g), the polyester tends to move into the aqueous phase, resulting in poor production stability. Here, the acid value is measured according to JIS
This is due to K0070.

The resin used as the main component of the heat-fusible core material of the capsule toner of the present invention includes polyester resin, polyester-polyamide resin, polyamide resin,
Examples of the thermoplastic resin such as vinyl resin, preferably,
Vinyl resin may be used. The glass transition point derived from the thermoplastic resin which is the main component of such a heat-meltable core material is 1
It is preferably 0 to 50 ° C, but the glass transition point is 1
If the temperature is lower than 0 ° C, the storage stability of the capsule toner deteriorates, and
If the temperature exceeds 0 ° C, the fixing strength of the capsule toner deteriorates, which is not preferable.

Among the above-mentioned thermoplastic resins, examples of the monomer constituting the vinyl resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene and p-ethylstyrene. , 2,4-
Styrene or styrene derivatives such as dimethylstyrene, p-chlorostyrene, vinylnaphthalene, etc., ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene, etc., such as vinyl chloride,
Vinyl esters such as vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl formate, vinyl caproate, etc., such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, N-Butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, acrylic acid Stearyl, methoxyethyl acrylate, acrylic acid 2-
Hydroxyethyl, glycidyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloromethyl acrylate, methacrylic acid, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, methacrylic acid. Decyl, lauryl methacrylate, methacrylic acid 2
-Ethylhexyl, stearyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate,
Ethylenic monocarboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like, and esters thereof such as ethylenic monocarboxylic acid substitution products such as acrylonitrile, methacrylonitrile, acrylamide, etc., such as ethylenic acid such as dimethyl maleate. Dicarboxylic acids and their substitution products, vinyl ketones such as vinyl methyl ketone, vinyl ethers such as vinyl methyl ether, vinylidene halides such as vinylidene chloride, eg N-
Examples thereof include N-vinyl compounds such as vinylpyrrole and N-vinylpyrrolidone.

Among the components constituting the resin for the core material according to the present invention, 50 to 90% by weight of styrene or a styrene derivative is used to form the main skeleton of the resin, and ethylenic is used to adjust the thermal characteristics such as the softening temperature of the resin. It is preferable to use 10 to 50% by weight of monocarboxylic acid or its ester because the glass transition point of the resin for core material can be easily controlled.

When a crosslinking agent is added to the monomer composition constituting the resin for the core material according to the present invention, for example, divinylbenzene, divinylnaphthalene, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diethylene Acrylate, 1,3-
Butylene glycol dimethacrylate, 1,6-hexylene glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) propane, 2 General crosslinking such as 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dibromoneopentyl glycol dimethacrylate, diallyl phthalate Appropriate agent (2 if necessary
A combination of two or more species can be used.

The amount of these crosslinking agents used is 0.001 to 15% by weight, preferably 0.1 to 10% by weight, based on the polymerizable monomer. The amount of these crosslinkers used is 15
If it is more than 5% by weight, the toner is less likely to be melted by heat, resulting in poor heat fixing property or heat pressure fixing property. Also the amount used
If the amount is less than 0.001% by weight, it is difficult to prevent the offset phenomenon in which a part of the toner adheres to the roller surface without being completely fixed to the paper and is transferred to the next paper in the heat and pressure fixing. Further, the above monomer may be polymerized in the presence of unsaturated polyester to give a graft or crosslinked polymer, which may be used as a resin for the core material.

Further, as the polymerization initiator used for producing the thermoplastic resin for the core material, 2,2'-azobis (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4
-Dimethylvaleronitrile, other azo or diazo polymerization initiators: benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, dicumyl peroxide Examples thereof include peroxide-based polymerization initiators such as oxides.

Two or more kinds of polymerization initiators may be mixed and used for the purpose of controlling the molecular weight and molecular weight distribution of the polymer, the reaction time or the like. The amount of the polymerization initiator used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymerized monomer.

Next, the method for producing the heat and pressure fixing capsule toner of the present invention will be described in detail. The encapsulated toner of the present invention can be suitably produced by the in situ polymerization method from the viewpoint of simplifying production equipment and production process. The method for producing a capsule toner for heat and pressure fixing of the present invention is a capsule for heat and pressure fixing comprising a heat-fusible core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material. In the method for producing a toner, in situ polymerization is carried out by using an outer shell resin in which the above-mentioned various additives are dispersed in advance to coat the surface of the core material with the resin to form an outer shell in which the additives are dispersed. It is characterized by doing.

In this manufacturing method, the shell is formed by utilizing the property that the mixed liquid of the core material and the shell constituent is dispersed in the dispersion medium, and the shell constituent is unevenly distributed on the surface of the droplet. Can be done by That is, due to the difference in the solubility index, the core constituent material and the outer shell constituent material are separated in the droplets of the mixed liquid, and in that state, the polymerization of the core constituent material proceeds to form the core resin and The resin used as the shell constituting material becomes the outer shell as it is, and a capsule structure is formed. According to this method, since the outer shell is formed as a layer having a substantially uniform thickness, the charging property of the toner becomes uniform.

By the way, in general encapsulation by in-situ polymerization, a monomer of a resin as an outer shell, an initiator and the like are supplied from one of an inner phase and an outer phase of a dispersed phase to form an outer shell by polymerization. This is performed by obtaining an encapsulated product (“Microcapsule” Sankyo Publishing Co., Ltd. 1987).
Year, Yasushi Kondo, Naozumi Koishi). On the other hand, in
The in situ polymerization is different from the general encapsulation by in situ polymerization, because the monomers of the core resin, the initiator and the like are polymerized inside the outer shell resin to form the core resin. Since the two are common in that the monomers and the like are supplied only from the inner phase of the dispersed phase, the method of the present invention is also included in the in-situ polymerization in a broad sense.

In the present invention, in such an in situ polymerization method, by dispersing various additives in the outer shell resin in advance, the outer shell in which various additives are dispersed can be formed. According to this method, the various additives are dispersed and present in the outer shell constituent components and do not exist on the outer shell surface of the toner. Therefore, various additives are peeled off by stirring in the developing machine, resulting in in-machine contamination. There is no problem. In addition, as described above, the functions of various additives can be appropriately exhibited.

The method of dispersing the additive in the outer shell resin is as follows:
A known method is generally used, and for example, it may be melt-kneaded and dispersed by a biaxial kneading, a Banbury mixer, a kneader, or the like, or may be melt-blended and dispersed at the time of manufacturing the outer shell resin.

In the present invention, when the mixed liquid of the core constituent material and the outer shell constituent material is dispersed in the dispersion medium, a dispersion stabilizer is contained in the dispersion medium in order to prevent aggregation and coalescence of the dispersoids. Keep it. Examples of the dispersion medium include water, methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, acetonitrile, acetone, isopropyl ether, tetrahydrofuran, dioxane and the like. It is also possible to use these individually or in mixture.

Examples of the dispersion stabilizer include gelatin, gelatin derivatives, polyvinyl alcohol, polystyrene sulfonic acid, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate. , Sodium pentadecyl sulfate, sodium octyl sulfate, sodium allyl-alkyl-polyether sulfonate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, 3,3 -Disulfone diphenylurea-4,4-diazo-bis-amino-β-
Naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-
Tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-sodium disulfonate, colloidal silica, alumina, tricalcium phosphate, ferric hydroxide, titanium hydroxide, aluminum hydroxide and others are used. can do. Two or more kinds of these dispersion stabilizers may be used in combination.

In the production method of the present invention, the amount of the amorphous polyester added is usually 3 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the core material. If it is less than 3 parts by weight, the film thickness of the outer shell becomes too thin and the storage stability deteriorates. If it exceeds 50 parts by weight, the viscosity becomes high and atomization becomes difficult and the production stability deteriorates.

In the present invention, the encapsulated toner obtained as described above may be used as a precursor particle, and a heat-pressure fixing encapsulated toner further subjected to seed polymerization may be used. Therefore, in the present invention, the encapsulated toner includes not only those obtained by the in situ polymerization method alone as described above but also those obtained by combining the in situ polymerization and the seed polymerization.

That is, seed polymerization is carried out by adding at least a vinyl polymerizable monomer and a vinyl polymerization initiator to an aqueous suspension of the capsule toner (hereinafter sometimes referred to as precursor particles) obtained as described above. After being absorbed in the precursor particles, the monomer components in the precursor particles are polymerized. For example, after the production of the precursor particles by the above-mentioned in situ polymerization method, at least the vinyl polymerizable monomer and the vinyl polymerization initiator are immediately added to the precursor particles in a suspended state so as to be absorbed in the precursor particles. Seed the monomer component in the particles
It may be polymerized. By doing so, the manufacturing process can be further simplified. The vinyl polymerizable monomer or the like to be absorbed in the precursor particles may be added in advance as a water emulsion.

The water emulsion to be added is obtained by emulsifying and dispersing a vinyl polymerizable monomer and a vinyl polymerization initiator in water together with a dispersion stabilizer, and further includes a crosslinking agent, an offset preventing agent, a charge control agent, etc. Can also be included.

The vinyl polymerizable monomer used in the seed polymerization may be the same as that used in the production of the above-mentioned precursor particles. Further, as the vinyl polymerization initiator, the cross-linking agent and the dispersion stabilizer, the same ones as those used in the production of the precursor particles can be used. seed
The amount of the crosslinking agent used in the polymerization is 0.001 to 15% by weight, preferably 0.1 to 15% by weight based on the vinyl polymerizable monomer.
It is recommended to use 10% by weight. When the amount of these cross-linking agents used is more than 15% by weight, the toner obtained is less likely to be melted by heat, resulting in poor heat fixing property or heat pressure fixing property.
When the amount used is less than 0.001% by weight, it is difficult to prevent the offset phenomenon in which a part of the toner adheres to the roller surface without being completely fixed to the paper and is transferred to the next paper during thermal pressure fixing.

Further, in order to further improve the storage stability of the toner, the hydrophilic shell material such as the above-mentioned amorphous polyester may be added to the water emulsion. The amount added at that time is usually 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the core material. In the present invention, at this time,
In the outer shell resin to be added, the above-mentioned various additives may be dispersed in advance, and in that case, similarly selected from the group consisting of a conductive substance, a charge control agent, a wax component, a color material pigment, and a magnetic powder. One or more additives are used.

In addition to the amorphous polyester as the hydrophilic shell material, for example, a vinyl resin having a hydrophilic functional group such as a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an ammonium ion, or an amorphous polyester. An amide, an amorphous polyamide, an epoxy resin or the like can also be used in combination.
Such a water emulsion can be prepared by uniformly dispersing it with an ultrasonic oscillator or the like.

The acid value of the amorphous polyester used in the seed polymerization is 3 to 50 as in the case of the first step reaction.
It is preferably (KOHmg / g), and more preferably 10 to 30 (KOHmg / g). 3 (KOH
If it is less than 100 mg / g), the amorphous polyester as the shell material is less likely to come out at the interface during seed polymerization, and the storage stability of the obtained toner is poor. Phase transition easily occurs and manufacturing stability deteriorates. Here, the acid value is measured according to JIS K007.
It is due to 0.

The water emulsion is added in such an amount that the vinyl polymerizable monomer is used in an amount of 10 to 20 relative to 100 parts by weight of the precursor particles.
Adjust so that it is 0 parts by weight. If it is less than 10 parts by weight, the fixing property is not improved, and if it exceeds 200 parts by weight, it becomes difficult to uniformly absorb the monomer in the precursor particles.

By the addition of the water emulsion, the vinyl polymerizable monomer is absorbed in the precursor particles and the precursor particles swell. Then, in this state, the monomer component in the precursor particles is polymerized. That is, it is seed polymerization using the precursor particles as seed particles.

When seed polymerization is further carried out in this way, the following points are further improved as compared with the capsule toner produced by the in situ polymerization method alone. That is, the capsule toner produced by the in situ polymerization method is superior to the conventional one in terms of low-temperature fixability and storage stability, but by further performing the seed polymerization method, a more uniform outer shell is formed in terms of interface science. Further, the storage stability is further improved. In addition, since the polymerizable monomer of the core material can be polymerized in two stages (in situ polymerization reaction and seed polymerization reaction), the thermoplastic monomer in the core material can be further prepared by appropriately using a crosslinking agent. The molecular weight of the resin can be easily controlled, and the low temperature fixability and the offset resistance can be improved. In particular, it is possible to provide a toner suitable not only for high-speed fixing but also for low-speed fixing.

The particle size of the capsule toner of the present invention is not particularly limited, but the average particle size is usually 3 to 30 μm. The thickness of the outer shell of the capsule toner is 0.
01 to 1 μm is preferable, and if it is less than 0.01 μm, blocking resistance is deteriorated, and if it exceeds 1 μm, heat melting property is deteriorated, which is not preferable.

If desired, the capsule toner of the present invention may contain a fluidity improver, a cleaning improver, and the like. Examples of the fluidity improver include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, and chromium oxide. , Cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. Fine silica powder is particularly preferable.

The fine silica powder is Si--O--Si.
It is a fine powder having a bond and may be produced by a dry method or a wet method. In addition to anhydrous silicon dioxide, aluminum silicate, sodium silicate,
It may be any of potassium silicate, magnesium silicate, zinc silicate, etc., but those containing 85% by weight or more of SiO ₂ are preferable. Further, a fine powder of silica surface-treated with a silane coupling agent, a titanium coupling agent, a silicone oil, a silicone oil having an amine in a side chain, or the like can be used.

Examples of the cleaning property improver include metal salts of higher fatty acids typified by zinc stearate, fine particles of fluorine-based high molecular weight particles, and the like. Further additives for adjusting the developability, for example, methacrylic acid methyl ester,
Fine particles of a polymer such as methacrylic acid butyl ester may be used. Further, a small amount of carbon black may be used for toning and resistance adjustment. As the carbon black, conventionally known ones, for example, various ones such as furnace black, channel black and acetylene black can be used.

The heat and pressure fixing capsule toner of the present invention comprises:
When it contains magnetic fine powder, it is used alone as a developer, and when it does not contain magnetic fine powder, it is a non-magnetic one-component developer or a two-component system mixed with a carrier. The developer can be prepared and used. The carrier is not particularly limited, but iron powder,
Ferrite, glass beads, etc., or those coated with a resin thereof, as well as magnetite fine powder, resin carrier obtained by kneading ferrite fine powder into resin, and the like are used, and the mixing ratio of the toner to the carrier is 0.5 to 20% by weight. The carrier has a particle size of 15 to 500 μm.

The heat and pressure fixing capsule toner of the present invention gives good fixing strength by fixing to a recording material such as paper by using heat and pressure together.
If heat and pressure are used in combination, a known heat roller fixing method, or an unfixed toner image on a recording material is heated by a heating section and a heat-resistant sheet, as described in, for example, JP-A-2-190870. By means of a fixing method in which the heat-melting sheet is heated and melted via the heat-resistant sheet to fix, or, for example, as described in JP-A-2-162356, a fixedly supported heating element, and the film is pressed against the heating element, and a film is formed. A method such as a method of heating and fixing the visible image of the toner on the recording material by a pressure member that brings the recording material into close contact with the heating body via the method is suitable for fixing the capsule toner of the present invention.

[0092]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples.

Resin Production Example 1 Propylene oxide adduct 36 of bisphenol A
7.5 g, bisphenol A ethylene oxide adduct 146.4 g, terephthalic acid 126.0 g, dodecenyl succinic anhydride 40.2 g, trimellitic anhydride 77.
7 g was placed in a glass 2-liter four-necked flask, equipped with a thermometer, a stainless stirrer, a downflow condenser, and a nitrogen introduction tube, and allowed to react at 220 ° C. in a mantle heater under a nitrogen stream. .

The degree of polymerization was traced from the softening point according to ASTM E28-67, and the reaction was terminated when the softening point reached 110 ° C. This resin is called resin A. Resin A measured with a differential scanning calorimeter (Seiko Denshi Kogyo)
The glass transition point value of was 65 ° C. Also, JIS
The acid value measured by the method according to K0070 is 18
(KOHmg / g).

Resin Production Example 2 Propylene oxide adduct 51 of bisphenol A
4.5 g, 204.8 g of ethylene oxide adduct of bisphenol A, 226.6 g of terephthalic acid, and 48.0 g of trimellitic acid anhydride were placed in a glass 2-liter four-necked flask, and a thermometer, a stainless steel stirring rod, and a downflow were used. A type condenser and a nitrogen introducing tube were attached, and the reaction was carried out at 220 ° C. under a nitrogen stream in a mantle heater.

The degree of polymerization was traced from the softening point according to ASTM E28-67, and the reaction was terminated when the softening point reached 105 ° C. This resin is called resin B. The glass transition point of the resin B measured by a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo KK) was 63 ° C. Also JIS
The acid value measured by the method according to K0070 is 12
(KOHmg / g).

Resin Production Example 3 Propylene oxide adduct of bisphenol A 525
g, terephthalic acid 136.5 g, dodecenyl succinic anhydride 1
Put 60.8g into a glass 2 liter 4-neck flask,
A thermometer, a stirring rod made of stainless steel, a downflow condenser, and a nitrogen introduction tube were attached, and the reaction was carried out at 220 ° C. under a nitrogen stream in a mantle heater.

The degree of polymerization was traced from the softening point according to ASTM E28-67, and the reaction was terminated when the softening point reached 110 ° C. This resin is called resin C. The glass transition point of the resin C measured by a differential scanning calorimeter (manufactured by Seiko Instruments Inc.) was 63 ° C. Also JIS
The acid value measured by the method according to K0070 is 10
(KOHmg / g).

Example 1 100 parts by weight of Resin A and carbon black "Monarch 88"
Twenty-five parts by weight of "0" (manufactured by Cabot Co., Ltd.) were mixed well with a Henschel mixer, then kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product A. The resin A and the kneaded material A each have a resistivity of 5 × 10 ¹³ Ωc.
m was 2.2 × 10 ⁷ Ωcm.

The resistivity was measured according to the following procedure. First, as a sample, the coarsely crushed product was filled in a tablet molding machine, and a load of 10 tons was applied to produce pellets having a thickness of about 2 mm and a diameter of 60φ. The impedance component HP4284A manufactured by Yokogawa-Hewlett-Packard Company was used for this, and the resistance component R measured by the AC bridge method was used as the resistivity.

69.0 parts by weight of styrene, 2-acrylic acid
Ethylhexyl 31.0 parts by weight, divinylbenzene 1.
20 parts by weight of kneaded material A and 4.5 parts by weight of 2,2′-azobisisobutyronitrile were added to 1 part by weight, and the mixture was dispersed for 1 hour using a magnetic stirrer to obtain a polymerizable composition. It was Next, 120 g of the above polymerizable composition was added to 280 g of an aqueous colloidal solution containing 4% by weight of tricalcium phosphate prepared in a glass separable flask having a capacity of 1 liter, and TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) was added. ) Was used for 3 minutes at a rotation speed of 10,000 rpm. This was covered with a 4-necked glass lid, equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stainless steel stirring rod, and placed in an electric heating mantle. This was heated to 80 ° C. with stirring under a nitrogen stream and reacted for 8 hours.

After cooling, the dispersion medium was dissolved with a 10% hydrochloric acid aqueous solution, filtered, washed with water, dried under reduced pressure at 45 ° C. and 20 mmHg for 12 hours, and classified by an air classifier to obtain an average particle size of 8 μm.
A capsule toner in which the outer shell of m is amorphous polyester was obtained. To 100 parts by weight of this capsule toner, 0.4 parts by weight of hydrophobic silica fine powder "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd.) was added and mixed to obtain a capsule toner according to the present invention. This is designated as Toner 1. The glass transition point derived from the resin in the core material was 34.5 ° C, and the softening point of Toner 1 was 128.3 ° C.

The obtained toner was uniformly dispersed in a vinyl acetate resin (Konishi Co., Ltd., bond for woodworking) and left at room temperature for one week. This toner-containing resin is steam dyed with an osmium aqueous solution, and then the ultramicrotome (LKB
A product (5000 times) obtained by observing the sample with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) is sliced into a thin piece of about several hundreds of nm using an Ultratrome NOVA manufactured by JEOL. . In the encapsulated toner obtained in the present invention, it was confirmed that the conductive substance was dispersed in the outer shell resin.

Example 2 100 parts by weight of Resin B and carbon black "Regal 99"
After thoroughly mixing 25 parts by weight of "R" (manufactured by Cabot Co.) with a Henschel mixer, they were kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product B. Here, the resistivity of each of the resin B and the kneaded material B is 5 × 10 ¹³ Ωc.
m, 6.5 × 10 ⁸ Ωcm.

69.0 parts by weight of styrene, 2-acrylic acid
Ethylhexyl 31.0 parts by weight, divinylbenzene 1.
1 part by weight of carbon black GPT-5 as a coloring agent
05P (manufactured by Ryoyu Kogyo Co., Ltd.), 15 parts by weight of the kneaded material B, and 4.5 parts by weight of 2,2′-azobisisobutyronitrile were added and dispersed for 1 hour using a magnetic stirrer. A polymerizable composition was obtained. Next, 120 g of the above polymerizable composition was added to 280 g of an aqueous colloidal solution containing 4% by weight of tricalcium phosphate prepared in a glass separable flask having a capacity of 1 liter, and the rotation speed was 10,000 rpm using a TK homomixer. And dispersed for 3 minutes. This is covered with a four-necked glass lid, a reflux condenser, a thermometer,
Attach a nitrogen inlet tube, stainless steel stirring rod,
It was installed in the electric heating mantle. This was heated to 80 ° C. with stirring under a nitrogen stream and reacted for 8 hours.

After cooling, the dispersion medium was dissolved with a 10% aqueous hydrochloric acid solution, filtered, washed with water, dried under reduced pressure at 45 ° C. and 20 mmHg for 12 hours, and classified by an air classifier to obtain an average particle size of 8 μm.
A capsule toner in which the outer shell of m is amorphous polyester was obtained. To 100 parts by weight of this capsule toner, 0.4 parts by weight of hydrophobic silica fine powder "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd.) was added and mixed to obtain a capsule toner according to the present invention. This is designated as toner 2. The glass transition point derived from the core material was 34.1 ° C, and the softening point of Toner 2 was 125.5 ° C.

Example 3 100 parts by weight of Resin A and 20 parts by weight of conductive tin oxide "T-1" (manufactured by Mitsubishi Metals Co., Ltd.) were mixed well with a Henschel mixer, and then kneaded with a twin-screw extruder equipped with a barrel cooling device. Then, it was cooled and pulverized to obtain a kneaded material C. The resistivity of the obtained kneaded product C was 5.2 × 10 ⁹ Ωcm.

Capsule toners were obtained by performing the surface treatment in the same manner as in Example 2 except that the kneaded product B was changed to the kneaded product C in Example 2. This is designated as toner 3. The glass transition point derived from the core material was 35.1 ° C., and the softening point of Toner 3 was 127.5 ° C.

Comparative Example 1 In the same manner as in Example 1 except that the kneaded material A was replaced with the resin A,
By the same operation as in Example 1, surface treatment was performed to obtain a capsule toner. This is designated as comparative toner 1. The glass transition point derived from the resin in the core material is 34.5 ° C.
The softening point of Comparative Toner 1 was 130.1 ° C.

Comparative Example 2 Capsule toner 10 obtained by the same operation as in Example 1 except that Kneaded material A was changed to Resin A in Example 1.
0 parts by weight and 6 parts by weight of carbon black "Monarch 880" (manufactured by Cabot) were mixed well with a Henschel mixer. Next, carbon black was immobilized on the surface of the toner particles by hybridization. After that, 100 parts by weight of this capsule toner was charged with a hydrophobic silica fine powder "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd.).
4 parts by weight were added and mixed. This is designated as comparative toner 2.

Example 4 100 parts by weight of Resin A and negatively chargeable charge control agent "T-77"
10 parts by weight (manufactured by Hodogaya Chemical Co., Ltd.) were mixed well with a Henschel mixer, then kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product D.

Grafted carbon black "GPE-3" was added to 69.0 parts by weight of styrene, 31.0 parts by weight of 2-ethylhexyl acrylate and 6.0 parts by weight of 2,2'-azobisisobutyronitrile as a colorant. 20 parts by weight of the kneaded material D was added and dispersed for 1 hour with a magnetic stirrer to obtain a polymerizable composition. Then, 240 g of the above polymerizable composition was added to 560 g of an aqueous colloidal solution containing 4% by weight of tricalcium phosphate prepared in a 2 liter glass separable flask and emulsified and dispersed using a TK homomixer. .

Next, a four-necked glass lid was attached, a reflux cooling tube, a thermometer, a nitrogen introducing tube, and a stainless steel stirring rod were attached, and the glass was placed in an electric heating mantle heater. While continuing stirring under nitrogen, the temperature was raised to 85 ° C., a polymerization reaction was carried out for 10 hours to obtain seed particles, and the particles were cooled to room temperature to obtain precursor particles.

Then, in an aqueous suspension of the precursor particles,
13.0 parts by weight of styrene, 7.0 parts by weight of 2-ethylhexyl acrylate, and 2,2'-azobisisobutyronitrile prepared by an ultrasonic oscillator (US-150, manufactured by Nippon Seiki Seisakusho Co., Ltd.) 0 4 parts by weight, 0.22 parts by weight of divinylbenzene, 2.0 parts by weight of kneaded material D, 0.1 part by weight of sodium lauryl sulfate, and 42.7 parts by weight of a water emulsion comprising 20 parts by weight of water were added dropwise, and nitrogen was added. While continuing to stir underneath, the temperature was raised to 85 ° C. and reacted for 10 hours as the second stage polymerization. After cooling, dissolve the dispersion medium with 10% aqueous hydrochloric acid, filter, wash with water, air-dry, and then at 45 ° C. for 12 hours, 2
It was dried under reduced pressure at 0 mmHg and classified by an air classifier to obtain a capsule toner having an outer shell of amorphous polyester with an average particle diameter of 8 μm.

To 100 parts by weight of this capsule toner, 0.4 parts by weight of hydrophobic silica fine powder "Aerosil R-972" was added and mixed to obtain an encapsulated toner of the present invention. This is designated as toner 4. The glass transition point derived from the resin in the core material is 27.5 ° C, and the softening point of Toner 4 is 108.0 ° C.
Met.

Example 5 100 parts by weight of Resin B and positively chargeable charge control agent "N-01"
After thoroughly mixing 10 parts by weight (manufactured by Orient Chemical Co., Ltd.) with a Henschel mixer, they were kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded material E. Example 4
In the above, except that the kneaded material D was changed to the kneaded material E, the surface treatment was performed in the same manner as in Example 4 to obtain a capsule toner. This is designated as toner 5. The glass transition point derived from the core material is 27.0 ° C., and the toner 5 has a softening point of 10
It was 7.0 ° C.

Example 6 100 parts by weight of resin C and negatively chargeable charge control agent "TRH"
After thoroughly mixing 10 parts by weight (manufactured by Hodogaya Chemical Co., Ltd.) with a Henschel mixer, the mixture was kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product F. Example 4 except that the kneaded material D is changed to the kneaded material F in Example 4.
By the same operation as above, the surface treatment was performed to obtain a capsule toner. This is designated as toner 6. The glass transition point derived from the core material is 28.0 ° C., and the softening point of Toner 6 is 10
It was 8.5 ° C.

Comparative Example 3 A surface was prepared in the same manner as in Comparative Example 2 except that 5 parts by weight of the charge control agent "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.) was used in place of carbon black in Comparative Example 2. Processing was performed to obtain a capsule toner. This is designated as comparative toner 3.

Example 7 100 parts by weight of resin A and 20 parts by weight of polyethylene wax "High Wax 200P" (manufactured by Mitsui Petrochemical Co., Ltd.) were mixed well with a Henschel mixer, and then kneaded with a twin-screw extruder equipped with a barrel cooling device. After cooling, the mixture was pulverized to obtain a kneaded material G.

A surface treatment was carried out in the same manner as in Example 2 except that the kneaded material B was changed to the kneaded material G to obtain a capsule toner. This is designated as toner 7. The glass transition point derived from the core material was 36.0 ° C, and the softening point of Toner 7 was 126.0 ° C.

Example 8 100 parts by weight of Resin A and polypropylene wax "NP-"
20 parts by weight of "055" (manufactured by Mitsui Petrochemical Co., Ltd.) were well mixed with a Henschel mixer, and then equipped with a barrel cooling device 2.
The mixture was kneaded by a shaft extruder, cooled and then pulverized to obtain a kneaded product H. In Example 2, except that the kneaded material B was changed to the kneaded material H,
The same procedure as in Example 2 was performed until surface treatment to obtain a capsule toner. This is designated as toner 8. The glass transition point derived from the core material was 36.5 ° C, and the softening point of Toner 8 was 128.0 ° C.

Comparative Example 4 The same procedure as in Comparative Example 2 was repeated except that the carbon black was replaced by 10 parts by weight of polypropylene wax "NP-055" (manufactured by Mitsui Petrochemical Co., Ltd.). Then, a capsule toner was obtained. This is designated as comparative toner 4.

Example 9 100 parts by weight of Resin B and magnetite "EPT-100"
1 part (manufactured by Toda Kogyo Co., Ltd.) was thoroughly mixed with a Henschel mixer, then kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product I. Example 2 except that the kneaded material B was changed to the kneaded material I in Example 2.
By the same operation as above, the surface treatment was performed to obtain a capsule toner. This is designated as toner 9. The glass transition point derived from the core material is 35.8 ° C., and the toner 9 has a softening point of 12
It was 7.0 ° C.

Comparative Example 5 In Comparative Example 2, the surface treatment was performed in the same manner as in Comparative Example 2 except that 10 parts by weight of magnetite "EPT-1001" (manufactured by Toda Kogyo Co., Ltd.) was used instead of carbon black. Capsule toner was obtained. This is designated as comparative toner 5.

Example 10 100 parts by weight of Resin B and the yellow pigment "Seikafast Yellow"
Twenty-five parts by weight of "2400" (manufactured by Dainichiseika Kogyo Co., Ltd.) were well mixed with a Henschel mixer, then kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product J.

69.0 parts by weight of styrene, 2-acrylic acid
Ethylhexyl 31.0 parts by weight, divinylbenzene 1.
15 parts by weight of Kneaded product J and 4.5 parts by weight of 2,2′-azobisisobutyronitrile were added to 1 part by weight, and the mixture was dispersed for 1 hour using a magnetic stirrer to obtain a polymerizable composition. It was Next, 120 g of the above polymerizable composition was added to 280 g of an aqueous colloidal solution containing 4% by weight of tricalcium phosphate prepared in a glass separable flask having a capacity of 1 liter, and the rotation number was 10,000 using a TK homomixer.
Disperse at rpm for 3 minutes. This was covered with a 4-necked glass lid, equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stainless steel stirring rod, and placed in an electric heating mantle. This was heated to 80 ° C. with stirring under a nitrogen stream and reacted for 8 hours.

After cooling, the dispersion medium was dissolved with a 10% hydrochloric acid aqueous solution, filtered, washed with water, dried under reduced pressure at 45 ° C. and 20 mmHg for 12 hours, and classified by an air classifier to obtain an average particle size of 8 μm.
A capsule toner in which the outer shell of m is amorphous polyester was obtained.

To 100 parts by weight of this capsule toner, 0.4 parts by weight of hydrophobic silica fine powder "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd.) was added and mixed to obtain a capsule toner according to the present invention. This is designated as toner 10. The glass transition point derived from the core material was 34.5 ° C., and the softening point of Toner 10 was 126.0 ° C.

Example 11 100 parts by weight of Resin B and magenta pigment "Hostaperm Pink E
After thoroughly mixing 25 parts by weight of "B" (manufactured by Hoechst) with a Henschel mixer, they were kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product K.

In Example 10, kneaded material J was mixed with kneaded material K
A surface treatment was carried out in the same manner as in Example 10 except that the above procedure was repeated to obtain a capsule toner. Toner 11
And The glass transition point derived from the core material is 35.0 ° C,
The softening point of Toner 11 was 126.5 ° C.

Example 12 100 parts by weight of resin C and magenta pigment "Hostaperm Pink E
Twenty-five parts by weight of "B" (manufactured by Hoechst) was well mixed by a Henschel mixer, then kneaded by a twin-screw extruder equipped with a barrel cooling device, cooled and ground to obtain a kneaded product L.

In Example 10, kneaded material J was mixed with kneaded material L
A surface treatment was carried out in the same manner as in Example 10 except that the above procedure was repeated to obtain a capsule toner. Toner 12
And The glass transition point derived from the core material is 34.3 ° C,
The softening point of Toner 12 was 125.8 ° C.

Example 13 100 parts by weight of Resin B and 25 parts by weight of a cyan pigment "KET Blue 104" (manufactured by Dainippon Ink and Chemicals, Inc.) were mixed well with a Henschel mixer, and then with a twin-screw extruder equipped with a barrel cooling device. The mixture was kneaded, cooled, and then ground to obtain a kneaded material M.

In Example 10, kneaded material J was mixed with kneaded material M
A surface treatment was carried out in the same manner as in Example 10 except that the above procedure was repeated to obtain a capsule toner. Toner 13
And The glass transition point derived from the core material is 34.0 ° C,
The softening point of Toner 13 was 125.5 ° C.

Example 14 100 parts by weight of Resin C and 25 parts by weight of cyan pigment "KET Blue 104" (manufactured by Dainippon Ink and Chemicals, Inc.) were mixed well with a Henschel mixer, and then with a twin-screw extruder equipped with a barrel cooling device. After kneading, cooling and pulverizing, a kneaded material N was obtained.

In Example 10, kneaded material J was mixed with kneaded material N
A surface treatment was carried out in the same manner as in Example 10 except that the above procedure was repeated to obtain a capsule toner. Toner 14
And The glass transition point derived from the core material is 33.5 ° C,
The softening point of Toner 14 was 125.0 ° C.

Comparative Example 6 The same procedure as in Comparative Example 2 was repeated except that the carbon black was replaced by 10 parts by weight of the yellow pigment "Seikafast Yellow 2400" (manufactured by Dainichiseika Kogyo Co., Ltd.). Then, a capsule toner was obtained. This is designated as comparative toner 6.

Example 15 100 parts by weight of Resin A and negatively chargeable charge control agent "T-77"
10 parts by weight, polypropylene wax "NP-055"
After 20 parts by weight were mixed well with a Henschel mixer, they were kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product O.

In the same manner as in Example 4, except that the kneaded material D was changed to the kneaded material O, the surface treatment was performed in the same manner as in Example 4 to obtain a capsule toner. This is designated as toner 15. The glass transition point derived from the core material was 28.0 ° C., and the softening point of Toner 15 was 109.0 ° C.

Example 16 100 parts by weight of resin A and positively chargeable charge control agent "N-01"
10 parts by weight and carbon black "Monarch 880" 25
After thoroughly mixing parts by weight with a Henschel mixer, they were kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and pulverized to obtain a kneaded product P.

In the same manner as in Example 4, except that the kneaded material D was changed to the kneaded material P, the surface treatment was performed in the same manner as in Example 4 to obtain a capsule toner. This is designated as toner 16. The glass transition point derived from the core material was 27.7 ° C, and the softening point of Toner 16 was 108.8 ° C.

Test Example 6 parts by weight of each of the toners obtained in the above Examples and Comparative Examples and styrene / particles having a particle size of 250 to 400 mesh were used.
94 parts by weight of spherical ferrite powder coated with methylmethacrylate resin was put in a plastic container, and the rotation speed was 150 rpm.
The mixture was tumbled on a roller together with the container for 20 minutes to prepare a developer. The obtained developer was evaluated for charge amount, fixing property, blocking resistance, cleaning property, and in-machine contamination.

(1) The charge amount was measured by a blow-off type charge amount measuring device described below. That is,
Using a specific charge measuring device equipped with a Faraday gauge, condenser, and electrometer, first, 500 mesh
W (g) (0.15 to 0.20 g) of the prepared developer was put in a brass measuring cell equipped with a stainless mesh (which can be appropriately changed to a size in which carrier particles do not pass). Next, after suctioning for 5 seconds from the suction port, the atmospheric pressure regulator
Blow was performed for 5 seconds at a pressure of kgf / cm ² to remove only the toner from the cell.

At this time, the voltage of the electrometer 2 seconds after the start of blowing was set to V (volt). Here, if the electric capacity of the condenser is C (μF), the specific charge Q / m of this toner is obtained by the following equation. Q / m (μC / g) = C × V / m Here, m is the weight of the toner contained in the developer in W (g), and the weight of the toner in the developer is T (g). When the weight of the developer is D (g), the toner concentration of the sample is expressed as T / D × 100 (%), and m is calculated by the following formula. m (g) = W * (T / D) Tables 1 to 6 show the results of measurement of the charge amount of the developers prepared under the normal environment.

[0145]

[Table 1]

[0146]

[Table 2]

[0147]

[Table 3]

[0148]

[Table 4]

[0149]

[Table 5]

[0150]

[Table 6]

(2) The fixability was evaluated by the method described below. That is, the prepared developer described above is used as a commercially available electrophotographic copying machine (rotation speeds of the photoconductor and the fixing roller are as shown in Tables 1 to 6, the thermal pressure temperature in the fixing device is variable, and the oil coating device is removed. Image) was used. The fixing temperature was controlled at 100 ° C to 240 ° C, and the fixing property and offset property of the image were evaluated. The results are also shown in Tables 1 to 6.

The minimum fixing temperature here means that the bottom surface is 15 m.
Place a load of 500g on an mx 7.5 mm sand eraser,
Rubbing the image fixed through the fixing machine 5 times back and forth, and measuring the optical reflection density with a reflection densitometer of Macbeth company before and after rubbing, and the temperature of the fixing roller when the fixing rate exceeds 70% according to the definition below. Say. Fixing rate = (image density after rubbing / image density before rubbing) ×
100

(3) Regarding blocking resistance, the degree of aggregation was evaluated when each toner was left for 24 hours under the conditions of 50 ° C. and 40% relative humidity. The results are also shown in Tables 1 to 6.

(4) Further, continuous copying of 10,000 sheets was carried out using the electrophotographic copying machine (blade cleaning method for cleaning the photoconductor), and black streaks appeared on the paper as the transfer material due to poor cleaning. I checked the number to do. In addition, the number of sheets in which contamination inside the machine occurred was also examined in the same manner. The results are also shown in Tables 1 to 6.

As is clear from Tables 1 to 6, in the toners 1 to 16 of the present invention, good effects of the various additives shown in Tables 1 to 6 were observed, and in-machine contamination and the like occurred. It did not occur, and the low temperature fixability and blocking resistance were also good. On the other hand, in Comparative Toner 1 containing no conductive substance, black streaks due to poor cleaning occurred and the image quality deteriorated. Further, in the comparative toners 2, 3, 5, and 6 in which the conductive substance, the charge control agent, the magnetic powder, and the coloring material pigment are adhered on the surface of the toner, in-machine contamination due to the additive such as the conductive substance occurred. Further, in Comparative Toner 4 in which the wax component was attached on the surface of the toner, the photoreceptor was contaminated by the wax component.

[0156]

The capsule toner for heat and pressure fixing obtained in the present invention contains various additives dispersed in the outer shell resin and does not exist on the outer shell surface of the toner. Therefore, there is no problem that various additives are peeled off to cause contamination in the machine. In addition, the functions of various additives can be appropriately exhibited. Further, in a heat pressure fixing method such as a heat roller, the offset resistance is excellent, fixing can be performed at a low fixing temperature, the blocking resistance is excellent, and a clear image free from fog can be stably formed many times. .

[Brief description of drawings]

FIG. 1 is a photograph showing a particle structure of a toner obtained by observing a cross section of a heat and pressure fixing capsule toner of the present invention obtained in Example 1 with a transmission electron microscope.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03G 9/08 384

Claims (6)

[Claims] 1. A method for producing a heat-pressure fixing capsule toner comprising a heat-fusible core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material. , Charge control agent, wax component,
By conducting in situ polymerization using a resin in which one or more additives selected from the group consisting of coloring material pigments and magnetic powders are previously dispersed, the surface of the core material is coated with the resin to disperse the additives. A method for producing a capsule toner for heat and pressure fixing, which comprises forming an outer shell. 2. The manufacturing method according to claim 1, wherein the main component of the resin forming the outer shell is amorphous polyester. 3. The amorphous polyester comprises, as constituent monomers, at least one divalent alcohol monomer, at least one divalent carboxylic acid monomer, and at least a trivalent or more polyhydric alcohol monomer. And / or a polyvalent carboxylic acid monomer having a valence of 3 or more and a glass transition point of 50 to 80 ° C. and an acid value of 3 to 50 (KO
Hmg / g). 4. A capsule toner for heat and pressure fixing comprising a heat-fusible core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material. A capsule toner for heat and pressure fixing, comprising at least a conductive substance dispersed therein. 5. A heat-and-pressure fixing capsule toner comprising a heat-fusible core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material. A capsule toner for heat and pressure fixing, comprising at least a color material pigment dispersed therein. 6. A capsule toner for heat and pressure fixing comprising a heat-fusible core material containing at least a thermoplastic resin and an outer shell provided so as to cover the surface of the core material. A capsule toner for heat and pressure fixing, comprising at least magnetic powder dispersed.