JP2006011490A - Image forming apparatus - Google Patents

Abstract

A surface of a roller provided on an image carrier is formed from a highly water-repellent member having a contact angle of 90 ° or more measured using pure water, and toner used for the image carrier is made of a core and the core. A capsule structure made of a shell resin that surrounds the core, a resin having a glass transition temperature of 60 ° C. or lower and relatively easily meltable by heat in the core, and a resin having a glass transition temperature higher than that and relatively easily meltable by heat. Deploy.
[Effect] It is possible to combine a capsule structure toner having a stable electric resistance and a roller to which the toner hardly adheres.
[Selection] FIG.

Description

  The present invention relates to an electrophotographic image forming apparatus using a capsule toner for heat and pressure fixing.

  In conventional electrophotography, an electrostatic latent image is formed by uniformly charging a photoconductive insulating layer, then exposing the layer, and extinguishing the charge on the exposed portion. Further, a developing process for visualizing the latent image by attaching a fine powder (hereinafter referred to as toner) having a charge as a colorant to the latent image, and a transfer for transferring the obtained visible image to a transfer material such as transfer paper. And a fixing step for fixing by heating, pressure or other appropriate fixing method.

  In general, toner is subject to various mechanical stresses caused by rotation of a developing roller, a toner supply roller, and the like during operation of the apparatus in the developing unit, and is easily mechanically deteriorated over a long period of use. In order to prevent such toner deterioration, it is generally known that it is effective to use a resin having a large molecular weight. However, in order to sufficiently fix these resins, it is necessary to increase the temperature of the heat roller. This causes problems such as an increase in the size of the fixing device, a curling phenomenon of the paper, an increase in energy consumption, and a further deterioration of the fixing device.

  As a means for solving the above-described problems, it has been proposed to use a so-called capsule toner composed of a core and a shell provided so as to cover the surface of the core. This is intended to achieve both fixing and blocking resistance by placing a thermally soft material that is easy to fix on the core and a relatively hard material with excellent blocking resistance on the outer shell. It is.

  Various techniques such as using a low melting point wax as a core material, using a liquid material, or using a rubber-like material at room temperature have been proposed. A hard material is generally selected as the shell material. When the shell material is soft and low in strength, the fixing property is good, but it becomes difficult to exhibit the intended performance because the shell material is peeled off from the core material due to stress in the developing device or the toner itself is deformed. In addition, if the shell material is hard and has high strength, a large pressure and high temperature are required to crush the shell, and the fixability itself deteriorates.

  Therefore, when used alone as a core material for thermal pressure fixing, blocking occurs at high temperatures, but a glass with a low glass transition temperature that improves fixing strength is used, and glass is used for the purpose of providing blocking resistance as a shell material. There has been proposed a heat roller fixing capsule toner or the like in which a resin layer having a high transition temperature, that is, a shell is formed. The use of such a toner is an effective means for realizing high-speed, downsized, and low power consumption of the apparatus.

By the way, the conventional techniques as described above have the following problems to be solved.
In order to achieve a high balance between the excellent fixing performance and high-temperature storage stability of the capsule toner, the incompatibility between the shell resin and the core resin is essential. For this purpose, it is necessary to use a resin having a lower electrical resistance than the core, that is, a resin having a polar structure rather than the core resin. That is, the capsule toner having superior storage stability and low-temperature fixability needs to use a resin having a relatively polar structure as a shell material compared to the core. However, this means that charges can easily escape from the surface of the charged toner particles. For this reason, it has become a factor that makes it difficult to design the charging characteristics of the toner.

The present invention adopts the following configuration in order to solve the above points.
<Configuration 1>
In an image forming apparatus having an image carrier and a roller provided on the image carrier,
(A) The roller is a charging roller whose surface is made of a highly water-repellent member having a contact angle of 90 ° or more measured using pure water, and is in contact with the image carrier, (b) and in the image carrier The toner used is a toner having a capsule structure composed of a core and a shell resin surrounding the core, and a resin having a glass transition temperature of 60 ° C. or less and relatively easily meltable by heat is used for the shell. An image forming apparatus comprising: a resin having a high glass transition temperature and relatively easily melted by heat.

<Configuration 2>
An image forming apparatus characterized in that the glass transition temperature is a value measured by a differential scanning calorimeter.

<Configuration 3>
The image forming apparatus according to claim 1, wherein the toner further has a content of a shell resin constituting the outermost layer of 0.1 to 4 parts by weight of the resin constituting the core.
<Configuration 4>
The toner is a toner having a capsule structure using at least two kinds of polymerizable monomers having at least a thermoplastic resin and a colorant and having different glass transition temperatures, and has a volume resistivity of the shell layer constituting the outermost layer. An image forming apparatus having a volume resistivity higher than that of a material inside the shell layer.

<Specific example 1>
FIG. 1 is a schematic configuration diagram of an image forming apparatus suitable for carrying out the present invention.
The configuration of this apparatus will be described later. First, the properties of the capsule toner that is the subject of the present invention will be described.
As a result of examining the properties of these capsule toners proposed so far in various and detailed manners, the present inventor has found that the following problems exist. That is, a charging characteristic specific to a capsule toner having sufficient low-temperature fixability and having a clear advantage over conventional toners is observed. Details are described below.

The greatest advantage of using a capsule toner is that it can be fixed with less energy without sacrificing storage stability at high temperatures. It has been found that there must be some degree of incompatibility between the resin and the resin used in the shell.
This means that in order for the core and the shell to be a core and a shell, the boundary must be clear.

In capsule toner, the shell resin must be harder than the core, but in order to satisfy this requirement while maintaining incompatibility, the polarity of the shell resin is higher than that of the core (that is, the electric resistance value). It is necessary to use the one that tends to be small).
As described in a specific example, the capsule toner in the present invention uses a shell resin having a higher polarity than the core resin. That is, the capsule toner tends to have a smaller electrical resistance than the inside.

Accordingly, unless the internal resistance (volume specific electrical resistivity) is kept large, the charge is transferred from the surface of the photosensitive drum (also from the surface of the toner particles) along the toner surface, and the charge amount is attenuated. .
This is considered to be the reason why the capsule toner must keep the volume specific electrical resistivity higher than that of the single layer toner.

For comparison, when the styrene used as the core resin was used as the shell resin, the surface potential of the photosensitive drum was not lowered to a lower resistance value as in the case of the single-layer toner. However, in this system, because the interface between the core and the shell is not clear, high temperature storage stability was not satisfied with the same amount of shell.
In order to satisfy the high-temperature storage stability, almost double the amount of shell resin was required. However, the fixability at this time has no advantage over the single-layer toner, and the significance of the capsule toner can be found. There wasn't.
Therefore, in order to achieve a high balance between excellent fixing performance and high-temperature storage stability, incompatibility between the shell resin and the core resin is indispensable. It is necessary to use a resin having a polar structure.

The structural features as described above directly represent the charging characteristics of the capsule toner.
FIG. 2 is a diagram for explaining the time dependency of the blow-off charge amount of the polymerized toner having a capsule structure. FIG. 3 is an explanatory view of the time dependency of the blow-off charge amount of the polymerization toner having a single layer structure.
The toner blow-off charge amount was measured by using a powder charge amount measuring device MODELTB-2000 (referred to as a blow-off charge amount measuring device) manufactured by Toshiba Chemical, with an N2 gas pressure of 1.0 Kg / cm ^ 2 (square centimeter) and a toner concentration of 5%. Measured under conditions. The carrier was measured using TEFV-150 / 250 manufactured by Powdertech.

In the case of a toner having a capsule structure, when the amount of CCA (charge control agent) is small, the blow-off charge amount increases as the stirring time increases. When a certain amount or more of CCA is added, the charge amount does not depend on the stirring time. . On the other hand, although the tendency of the charge amount to increase with the stirring time of the polymer toner having a single layer structure decreases as the CCA addition amount increases, the dependence itself does not disappear.
The difference between the two is considered as follows.

As described above, the capsule toner having superior storage stability and low-temperature fixability needs to use a resin having a relatively polar structure as compared with the core.
This means that the charge easily escapes from the surface of the charged toner particles.
Elimination of the time dependency of the capsule toner charge amount in a system to which sufficient CCA is added is considered to indicate that the charge received by the toner and the charge that is dissipated are apparently balanced.
On the other hand, with a single layer toner, the charge amount gradually increases in all systems.
This is presumably because the surface resistance is sufficiently large so that the charge once acquired is difficult to escape.

4 and 5 are explanatory diagrams of background fog when the toner shown in FIGS. 2 and 3 is put into the image forming apparatus shown in FIG. 1 and continuous printing is performed.
Toners A, B, F, and G have a fog in the initial stage of printing worse than that in a continuous state.
The reason for this can be determined by the slow rise of the blow-off charge amount. That is, it is considered that there are a considerable amount of toner particles that are not sufficiently charged at the initial stage, and this contributes to background fogging as reversely charged particles.
On the other hand, the toners C to E and H to J have no time dependency of the blow-off charge amount and show a stable value from the initial stage. Even in actual printing, the background fog is smaller than the initial stage and stable even during continuous printing. It has changed.

6 and 7 are diagrams for explaining the charge amount on the developing roller.
From these figures, it can be seen that toner with poor background fog at the beginning of printing has a slow rise in the charge amount on the developing roller as well as the time dependency of the blow-off charge amount.
The toner charge amount q (μC / g) on the developing roller was obtained by the following equation.
q = (2Vt × ε0εt) / δP (dt) ^ 2
Vt: toner layer surface potential on developing roller (V)
ε0: dielectric constant of vacuum 8.855 × 10 ^ (− 12) C / (Vm)
εt: relative dielectric constant of toner layer 1.44
δ: true density of toner 1.175 × 10 ^ 3 (Kg / m ^ 3)
P: Toner layer filling factor 0.4
dt: toner layer thickness (m)

Here, it can be said that the difference between the blow-off charge amount and the charge amount on the developing roller represents the difference in charge amount between the two-component development method and the one-component development method.
In other words, even with the same toner, the toner charge amount varies several times due to the difference in the method of applying charge to the toner.
Compared to the two-component system, it has a number of advantages such as a simpler apparatus configuration and easy maintenance, but it is a disadvantage of the one-component system that it is difficult to charge the toner.

This is because the two-component system has a friction charging member having a very large specific surface area called a carrier, whereas the one-component system has a member with a limited surface area such as a developing roller, a toner supply roller, and a photosensitive drum. It can be considered that it is derived from the fact that it relies on triboelectric charging.
Therefore, in order to use the capsule-structure toner in the one-component development system, it is an extremely important point to increase the charge amount of the toner.

FIG. 8 shows examples of various toner structures. FIG. 9 is an explanatory diagram summarizing the presence / absence of development (background smearing) in the background in continuous image printing when the toner having these structures is employed.
Toner J was developed in the background at both 10 ° C. and 20% and 25 ° C. and 55%, and toner I was developed at 10 ° C. and 20% at low temperature and low humidity. This phenomenon is a phenomenon in which overcharged toner particles on the developing roller are developed in the background portion (the non-exposed portion of the writing exposure source) that should not be developed, and the print quality is significantly reduced. Bring.

Toner J was generated after printing 500 sheets at 25 ° C. and 55%, and after printing 100 sheets at 10 ° C. and 20%. This is considered to be caused by the fact that the triboelectric charge gradually increases due to the stirring in the developing device.
It is considered that the toner I is generated because frictional charging is actively performed at a low temperature and low humidity of 10 ° C. and 20%.

  The background development that occurs when a single-layer toner is used can be explained by the toner charge amount (toner charge amount in the mounted state) on the developing roller shown in FIG. When the toner charge amount on the developing roller exceeds approximately 20 μ / g at 25 ° C. and 55%, development to the background occurs. On the other hand, as shown in FIG. 7, when the toner with a capsule structure has a blow-off charge amount of 60 μC / g or more, the charge amount in the mounted state is constant at about 11 μC / g, and shows a stable charge amount even in continuous printing. .

  It does not behave like a toner with a single layer structure and the amount of charge gradually increases, and therefore development to the background does not occur. As far as the toner with a single layer structure is concerned, the well-known fact that an excessively high charge amount causes excessive charge and deteriorates print quality is confirmed. The actual toner design is performed while balancing the trade-off with the well-known fact that low-charged toner is easy to cover. However, as described in detail with respect to the toner of the capsule structure, since it has a relatively high blow-off charge amount with respect to the single layer structure toner, stable charging characteristics that are difficult to obtain with the single layer structure toner can be obtained. is there. This is a charged physical property that is extremely characteristic of a capsule structure toner, and is also a great advantage.

  As a result of the above considerations, the present inventor said that it was difficult to use a capsule structure toner having a blow-off charge amount of 60 μC / g or more unless the blow-off charge amount is provided within a certain range in a single-layer structure toner. It has been possible to provide an image forming apparatus capable of solving the problems and facilitating the design of the charging characteristics of the toner and providing a stable and high-quality print in continuous printing.

For convenience, reversal development using negatively charged toner will be described as an example.
Returning again to FIG. 1, the apparatus will be described.
FIG. 1 shows a configuration viewed from a cross section of the image forming apparatus.
In the drawing, a contact-type charging member 1 (hereinafter referred to as a charging roller) is driven by a conductive shaft 2 being pressed against an image carrier 5 (hereinafter referred to as a photosensitive drum) that rotates in a direction indicated by an arrow A by a dedicated spring 3. Rotate. Further, the photosensitive drum 5 is charged to a constant potential by applying a constant DC voltage from the dedicated DC power source 4.
In this specific example, −1350 V is applied from the power source 4 to the conductive shaft 2. Under this condition, the photosensitive drum surface potential Vp1 after passing through the charging roller was −800V.

Next, the charged photosensitive drum 5 is exposed by a latent image writing exposure source 6 (hereinafter referred to as an LED head) to form an electrostatic latent image on the outer peripheral surface, and that portion enters the development region.
In this specific example, the photosensitive drum surface potential Vp2 of the portion where the latent image is written by the LED head is −50V. A developer carrier 8 (hereinafter referred to as a developing roller) rotates in the direction of arrow B in the drawing and is in contact with the photosensitive drum 5 with an appropriate pressure. A voltage is supplied from a power source 15 to the metal shaft of the developing roller 8. In this specific example, a developing voltage Vd−300 V is applied from the power source 15 to the developing roller 8.

The toner supply roller 14 rotates in the direction C in the figure and contacts and rotates with the developing roller. The toner is frictionally charged at the contact portion between the developing roller 8 and the toner supply roller 14. On the other hand, a voltage is supplied from a power source 16 to the metal shaft of the toner supply roller 14. In this specific example, a developing voltage Vs−450 V is applied from the power source 16 to the toner supply roller 14.
Therefore, the charged toner is carried to the surface of the developing roller by the difference between the voltage applied to the toner supply roller 14 and the voltage applied to the developing roller 8, and the developer layer forming member 7 (hereinafter referred to as developing blade). To form a developer layer on the developing roller. The layer thickness is about 10 to 50 μm, preferably about 15 to 30 μm.

FIG. 10 shows the dependence of toner C and toner H on the developing roller on the nip between the supply roller 14 and the developing roller 8 (the difference between the roller radii and the distance between the shafts).
The charge amount is saturated at a nip of 1 mm or more. On the other hand, further increase in the nip increases the rotational load of the EP cartridge. Therefore, in this specific example, the nip is set to 1 mm.
Further, the charge amount when the supply roller 14 was removed in FIG. 1 was extremely small at 1 μC / g. Therefore, it was confirmed that substantial charging was performed at the contact portion between the supply roller and the developing roller.

  A developer (hereinafter referred to as toner) is developed on the electrostatic latent image by the developing device having the above-described configuration. The developed toner image 9 is transferred onto a sheet by a transfer member 11 (hereinafter referred to as a transfer roller). Further, in the image forming apparatus, a residual toner collecting member 12 (hereinafter referred to as a cleaning roller) that collects transfer residual toner once collects toner remaining on the photosensitive drum 5 after transfer, and during printing of paper or when warming up. When the development is not carried out, it is returned to the photosensitive drum 5 by an appropriate means (not shown) in the opposite manner to the time of collection, and is again collected into the developing device by the developing roller 8.

  In this specific example, negatively charged toner is used, and the relationship of Vp1 <Vd <Vp2 is established, so that the latent image is developed in the development area, and conversely, the transfer residual toner on the photosensitive drum is collected in the development area. Will be.

Next, an example of a method for producing the capsule structure toner used in the present invention will be described.
Examples of the resin used for the core material and the shell material of the capsule toner in the present invention include thermoplastic resins such as vinyl resin, polyamide resin, and polyester resin.

  Among the above thermoplastic resins, examples of the monomer constituting the vinyl resin include styrene, 2,4-dimethylstyrene, α-methylstyrene, p-ethylstyrene, O-methylstyrene, m-methylstyrene, Styrene or styrene derivatives such as p-methylstyrene, p-chlorostyrene, vinylnaphthalene, or 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isobutyl acrylate , T-butyl acrylate, amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, methoxyethyl acrylate, 2-hydroxyethyl acrylate, acrylic Glycidyl, phenyl acrylate, methyl α-chloroacrylate, methacrylic acid, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, Cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, decyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Ethylenic monocarboxylic acids such as phenyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and their esters, or ethylene, propylene, butylene Ethylenically unsaturated monoolefins such as ethylene and isobutylene, or vinyl esters such as vinyl chloride, vinyl bromoacetate, vinyl propionate, vinyl formate and vinyl caproate, or ethylenic such as acrylonitrile, methacrylonitrile and acrylamide Examples thereof include monocarboxylic acid substitution products, or ethylenic dicarboxylic acids such as maleic acid esters, and substitution products thereof, for example, vinyl ketones such as vinyl methyl ketone, or vinyl ethers such as vinyl methyl ether.

These resins can be used alone or in combination to form a resin for the core material and the shell material.
If necessary, a crosslinking agent can be added to the monomer composition constituting the core material resin used in the present invention. Examples include divinylbenzene, divinylnaphthalene, polyethylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxydiphenyl) propane, 2,2'-bis (4-acryloxydiethoxydiphenyl) propane, diethylene glycol di Acrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexylene glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, General crosslinking agents such as trimethylolpropane triacrylate and tetramethylolmethane tetraacrylate can be used. In addition, two or more of these crosslinking agents can be used in combination as required.

  Moreover, as a polymerization initiator used when manufacturing 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, i.e. benzoyl peroxide, Examples thereof include peroxide polymerization initiators such as methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and dicumyl peroxide.

  In the present invention, a colorant is contained in the core material of the capsule toner, and all of dyes, pigments and the like used in conventional toner colorants can be used. The colorant used in the present invention includes various carbon blacks produced by the acetylene black method, thermal black method, channel black method, lamp black method, etc., and grafted carbon black in which the surface of carbon black is coated with a resin , Brilliant first scarlet, phthalocyanine blue, nigrosine dye, pigment green B, rhodamine-B base, permanent brown FG, solvent red 49, etc., and mixtures thereof.

  In the present invention, a charge control agent can be further added to the core material, and the negative charge control agent to be added is not limited to the charge control agent described below. "Lon Black TRH" (above, manufactured by Hodogaya Chemical Co., Ltd.) Mixed metal azo dyes "Bontron S-31", "Bontron S-32", "Bontron S-34", "Vari First Black 3804" (above, Orient Chemical Co., Ltd.) Quaternary ammonium salts such as “C0PY CHARGE NX VP434” (manufactured by Hoechst), nitroimidazole derivative copper phthalocyanine dye, metal complexes of salicylic acid alkyl derivatives such as “Bontron E-81” and “Bontron E-82” ”,“ Bontron E-85 ”(manufactured by Orient Chemical Co., Ltd.), etc. That.

  The positively chargeable charge control agent is not limited to the charge control agent described below as in the case of the negatively chargeable charge control agent, but examples include “oil black BS” and “Bontron N” which are nigrosine dyes. Triphenyl containing a tertiary amine as a side chain, such as “-01”, “Bontron N-07”, “Bontron N-11”, “Nigrosine Base EX”, “Oil Black SO” (manufactured by Orient Chemical Co., Ltd.) Methane-based dyes, quaternary ammonium salt compounds such as “Bontron P-51” (manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide, “C0PY CHARGE PX VP435” (manufactured by Hoechst), and polyamine resins such as “AFP-B” (Made by Orient Chemical Co., Ltd.), imidazole derivatives and the like.

In the core material, if necessary, for example, polyolefin, fatty acid metal salt, higher fatty acid, fatty acid ester, partially saponified fatty acid ester, higher alcohol, paraffin wax, silicone oil, amide wax for the purpose of improving offset resistance. Further, any one or more offset preventive agents such as silicon varnish, polyhydric alcohol ester, and aliphatic fluorocarbon may be contained.
Examples of the polyolefin include resins such as polypropylene, polyethylene, and bolibene.

  Examples of the fatty acid metal salt include metal salts of maleic acid and zinc, magnesium, calcium and the like; metal salts of stearic acid and zinc, cadmium, barium, lead, iron, nickel, cobalt, copper, aluminum, magnesium, and the like: Dibasic lead stearate: Metal salt of oleic acid with zinc, magnesium, iron, cobalt, copper, lead, calcium, etc .: Metal salt of palmitic acid with aluminum, calcium, etc .: Caprylate; Lead caproate Metal salts of linoleic acid with zinc, cobalt, etc .: calcium ricinoleate: metal salts of ricinoleic acid with zinc, cadmium, etc., and mixtures thereof.

  Examples of the fatty acid ester include maleic acid ethyl ester, maleic acid butyl ester, stearic acid methyl ester, stearic acid butyl ester, palmitic acid cetyl ester, and montanic acid ethylene glycol ester. Examples of the partially saponified fatty acid ester include calcium partially saponified products of montanic acid esters.

  Examples of the higher fatty acids include dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, arachidic acid, behenic acid, lignoceric acid, ceracoleic acid and the like, and mixtures thereof. Can do. Examples of the higher alcohol include dodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and stearyl alcohol.

  Examples of the paraffin wax include natural paraffin, micro wax, synthetic paraffin, and chlorinated hydrocarbon. Examples of the amide wax include stearic acid amide, oleic acid amide, palmitic acid amide, lauric acid amide, behenic acid amide, methylene bisstearamide, ethylene bisstearamide, N, N′-m-xylylene bis. And stearic acid amide, N, N′-m-xylylenebis-12-hydroxydistearic acid amide, N, N′-isophthalic acid bisstearylamide, N, N′-isophthalic acid bis-12-hydroxystearylamide, and the like.

  Examples of the polyhydric alcohol ester include glycerin stearate, glycerin ricinoleate, glycerin monobehenate, sorbitan monostearate, propylene glycol monostearate, sorbitan trioleate and the like. Examples of the silicon varnish include methyl silicon varnish and phenyl silicon varnish. Examples of the aliphatic fluorocarbon include low polymerization compounds of tetrafluoroethylene and propylene hexafluoride.

Among the above-mentioned substances, at least a polymerizable monomer serving as a core resin, a polymerization initiator, and a colorant are mixed, and a crosslinking agent, a wax, a charge control agent, and the like are added and mixed as necessary.
The mixture is dispersed in a dispersion medium and polymerized to form core particles.
Examples of the dispersion medium include water, methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, acetonitrile, acetone, isopropyl ether, tetrahydrofuran, dioxane and the like. These can be used alone or in combination.

  A dispersion stabilizer can also be used for the purpose of stabilizing the dispersibility of the dispersoid. Any known dispersion stabilizer can be used. Examples include polyvinyl alcohol, polystyrene sulfonic acid, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate, sodium pendadecyl sulfate, sodium octyl sulfate, allyl-alkyl. -Sodium 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-sulfonic acid sodium salt, ortho-carboxybenzene- Zo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-sodium disulfonate, tricalcium phosphate, ferric hydroxide, titanium hydroxide , Aluminum hydroxide, and the like. These dispersion stabilizers can be used alone or in combination of two or more.

The polymerization reaction proceeds or is completed by maintaining the suspension prepared as described above at 50 ° C. to 100 ° C. while stirring.
During or after the completion of the polymerization reaction, a second polymerizable monomer is added to the suspension to perform seed polymerization. That is, at least a vinyl polymerizable monomer and a vinyl polymer are added to an aqueous suspension of thermoplastic resin particles (hereinafter referred to as intermediate particles) containing a colorant during or after polymerization obtained by the first polymerization. After the initiator is added and absorbed by the intermediate particles, the monomer component in the intermediate particles is polymerized. The vinyl polymerizable monomer to be absorbed in the intermediate particles may be added alone or 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 together with a dispersion stabilizer in water, and if necessary, a crosslinking agent, an offset preventing agent, a charge control agent, etc. It can also be contained.

The vinyl polymerization initiator, crosslinking agent, and dispersion stabilizer used for seed polymerization may be the same as those used in the production of the intermediate particles, and if necessary, for example, using a water-soluble polymerization initiator. It is also possible to optimize the polymerization conditions of the shell.
The polymerizable monomer used here is preferably selected so that the glass transition temperature of the resin after polymerization is 75 ° C. or higher. That is, it is desirable that the glass transition temperature of the shell resin be 75 ° C. or higher. In the prior art, it has not been reported that a capsule toner is produced by sufficiently increasing the glass transition temperature of the shell resin in order to ensure sufficient blocking resistance.

As will be described in detail in the specific examples of the present invention, setting the glass transition temperature of the resin constituting the outermost layer to 75 ° C. or higher is extremely effective in having sufficient blocking resistance.
By the addition of the vinyl polymerizable monomer or the water emulsion, the vinyl polymerizable monomer covers the surface of the intermediate particles and the core particles swell slightly. In this state, polymerization of the polymerizable monomer component that becomes the shell resin proceeds, that is, seed polymerization is performed using the intermediate particles as core particles, thereby completing the capsule toner.

  According to the manufacturing method as described above, a core that sufficiently fixes with low energy and an excellent blocking resistance even at high temperature and high pressure have a very high balance between low temperature fixing property and offset resistance. An encapsulated toner can be obtained.

The particle size of the capsule toner in the present invention is not particularly restricted, but the average particle size is usually preferably from 3 to 30 μm.
In the capsule toner of the present invention, a fluidity improver, a cleaning property improver, and the like can be used as necessary. Examples of fluidity improvers include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide. Cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.

  The fine silica powder is a fine powder having a Si—O—Si bond, and may be any one produced by a dry method or a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used. Further, a fine powder of silica surface-treated with a silane coupling agent, a titanium coupling agent, silicon oil, silicon oil having an amine in the side chain, or the like can be used.

  Examples of cleaning improvers include metal salts of higher fatty acids represented by zinc stearate, fine powders of fluorine-based high molecular weight substances, and the like. Further, additives for adjusting developability, for example, fine particles of polymer such as methacrylic acid methyl ester and methacrylic acid butyl ester may be used.

  The heat-pressure fixing capsule toner of the present invention is used alone as a developer when it contains a magnetic fine powder, and when it does not contain a magnetic fine powder, it is a non-magnetic one-component developer. Used alone as an agent.

<Specific example 2>
Next, the invention of Example 2 will be described.
Conventionally, a method of charging (transferring) an image carrier (hereinafter referred to as a photosensitive drum) using a non-contact type charging device (transfer device) called a corotron or scorotron method has been common.
This method requires a high-voltage power supply, and generation of ozone is unavoidable in principle, and an additional device such as an ozone removal filter is required.

  The ozone-less method solves the above problems and charges (transfers) the photosensitive drum using a contact-type charging device (transfer device), which can substantially eliminate the generation of ozone. The power supply can also be used at a lower voltage value.

Examples of the ozone-less charging (transfer) device include a roller charging device that uses a solid rubber on a cylinder while rotating it in contact with a photosensitive drum, or a brush charging device that uses a cylindrical brush that rotates while contacting a photosensitive drum.
If a capsule toner capable of fixing with low energy can be applied to an ozoneless process having the above-mentioned advantages, an electrophotographic process with low power consumption and ozoneless can be completed, and image formation without adverse effects on the environment. It should be possible to provide a device.
The present inventor has been working on the development of an ozone-less process using a capsule toner for the above purpose.

However, the ozoneless system has a technical problem because it is a contact system.
In other words, if the EP cartridge is used for a long time, it is difficult to avoid the toner from adhering (or adhering) to the charging (transfer) device. Is likely to occur.
This is a phenomenon in which the surface potential of the photosensitive drum decreases due to adhesion (fixation) of toner to the surface of the charging roller (brush), and abnormal printing such as background development occurs on the printing surface.
However, this phenomenon does not occur with a small amount of adhesion (adhesion), and is not a problem in practical use.

According to the inventor's research, the surface potential was not lowered unless the toner adhesion amount on the surface of the charging device became 50 μm (1 mg / cm 2) or more. In such a state, the voltage from the power source is divided by the toner present in a layered manner on the surface of the charging device, and the effective voltage to the charging device is reduced. Such a situation usually does not occur.
However, when capsule toner is used, the surface potential of the photosensitive drum is lowered only by a very small amount on the surface of the charging device.
According to detailed observations, it showed a strong dependence on the volume specific electrical resistivity of the capsule toner.

FIG. 11 is an explanatory diagram of the volume specific electrical resistivity dependency of the capsule toner.
As shown in the figure, in the capsule toner, the amount of toner adhered to the surface of the charging device (in the present invention, a rubber roller is used as an example, hereinafter referred to as a charging roller) is only 0.05 mg / cm ^ 2 (the surface of the charging roller). Even in a state where toner particles are sparsely present), the surface potential of the photosensitive drum rapidly decreased when log ρ was 11.0 or less. As can be seen from this figure, it can be said that log ρ is more preferably 11.2 or more.
On the other hand, in the case of a toner having a single layer structure under the same conditions, this phenomenon was not observed if log ρ was 10 or more.
This difference in behavior can be explained as follows.

The greatest advantage of using a capsule toner is that it can be fixed with less energy without sacrificing storage stability at high temperatures. There must be some incompatibility between the resin and the resin used for the shell.
This means that in order for the core and the shell to be a core and a shell, the boundary must be clear.

  In capsule toner, the shell resin must be harder than the core, but in order to satisfy this requirement while maintaining incompatibility, the polarity of the shell resin is higher than that of the core (that is, the electric resistance value). It is necessary to use the one that tends to be small).

As described in a specific example, the capsule toner in the present invention uses a shell resin having a higher polarity than the core resin. That is, the capsule toner tends to have a smaller electrical resistance than the inside.
Therefore, unless the internal resistance (volume specific electrical resistivity) is kept large, the electric charge is attenuated from the surface of the photosensitive drum (also from the surface of the toner particles) through the toner surface.
This is considered to be the reason why the capsule toner must keep the volume specific electrical resistivity higher than that of the single layer toner.

  As a comparative study, when the styrene used as the core resin was used as the shell resin, the surface potential of the photosensitive drum was not lowered to a lower resistance value as in the case of the toner having a single layer structure. However, in this system, because the interface between the core and the shell is not clear, high temperature storage stability was not satisfied with the same amount of shell as the specific example.

In order to satisfy the high-temperature storage stability, almost double the amount of shell resin was required. However, the fixability at this time has no advantage over the single-layer toner, and the significance of the capsule toner can be found. There wasn't.
Therefore, in order to achieve a high balance between excellent fixing performance and high-temperature storage stability, incompatibility between the shell resin and the core resin is indispensable. It is necessary to use a resin having a polar structure.

That is, in order to use the capsule toner in the ozone-less process (particularly, the toner recycling process is performed simultaneously), it can be said that the volume specific electrical resistivity as described above needs to be satisfied.
From the experimental facts described above, it is more important to keep the volume specific electrical resistivity of the capsule toner high in a process involving toner recycling in which the transfer residual toner is finally collected by the developing roller.

In this system, it is inevitable that the transfer residual toner temporarily contacts the surface of the charging roller before being collected by the developing roller.
Therefore, the toner is always in contact with the surface of the charging roller during long running.
That is, satisfactory print quality cannot be obtained unless the volume specific electrical resistivity of the capsule toner satisfies the above-described conditions.

The above-mentioned volume specific electrical resistivity was measured by the following method.
The volume resistivity is measured under conditions of an oscillator frequency of 1 KHz using a dielectric loss measuring instrument TR-10C manufactured by Ando Electric Co., Ltd. The logarithmic value was obtained by the formula.
logρ = log [(A / t) × (1 / Gx)]
log ρ: Volume resistivity (logarithmic value)
Gx = (CONDUCTANCE Ratio) × R
R: CONDUCTANCE measured value A: Electrode area (11.34 cm ^ 2)
t: Material thickness (2mm)

  Based on the above results, the present inventor, in an ozone-less process, particularly an ozone-less process with a toner recycling system, has a volume specific electrical resistivity of 11.0 for a capsule toner that has both high fixing performance and high-temperature storage stability. The use of the above conditions has led to the completion of an electrophotographic process that is low in power consumption and ozone-free and can provide excellent print quality.

For convenience, reversal development using negatively charged toner will be described as an example.
FIG. 12 is a schematic configuration diagram of an image forming apparatus showing an example in which a specific example of the present invention is used.
In FIG. 12, a contact-type charging member 1 (hereinafter referred to as a charging roller) rotates in the direction of arrow B in the drawing, and an image carrier 5 (hereinafter referred to as “hereinafter referred to as charging roller”) rotates a conductive shaft 2 in the direction of arrow A in the drawing by a dedicated spring 3. (Referred to as a photosensitive drum). The photosensitive drum 5 is charged to a constant potential by applying a constant DC voltage to the contact charging member 1 by a dedicated DC power source 4.
In this specific example, −1350 V is applied from the power source 4 to the conductive shaft 2. Under this condition, the photosensitive drum surface potential Vp1 after passing through the charging roller was −800V.

  Next, the charged photosensitive drum 5 is exposed by a latent image writing exposure source 6 (hereinafter referred to as an LED head), an electrostatic latent image is formed on the photosensitive drum 5 and enters a developing region. In this specific example, the photosensitive drum surface potential Vp2 of the portion where the latent image is written by the LED head is −50V. The developer carrying member 8 (hereinafter referred to as a developing roller) rotates in the direction of arrow C in the drawing and is in contact with the photosensitive drum with an appropriate pressure. A voltage is supplied from a power source 15 to the metal shaft of the developing roller 8. In this specific example, a developing voltage Vd−300 V is applied from the power source 15 to the developing roller 8.

Further, a developer layer forming member 7 (hereinafter referred to as a developing blade) that forms a developer layer on the developing roller is in contact with the developing roller at an appropriate pressure to develop a toner layer of about 10 to 50 μm, preferably about 15 to 30 μm. Form on the roller.
A developer (hereinafter referred to as toner) is developed on the electrostatic latent image by the developing device having the above-described configuration. The developed toner image 9 is transferred onto a sheet by a transfer member 11 (hereinafter referred to as a transfer roller). Further, in the image forming apparatus, a residual toner collecting member 12 (hereinafter referred to as a cleaning roller) that collects transfer residual toner once collects toner remaining on the photosensitive drum 5 after transfer, and during printing of paper or when warming up. When the development is not carried out, it is returned to the photosensitive drum 5 by an appropriate means (not shown) in the opposite manner to the time of collection, and is again collected into the developing device by the developing roller 8.

In this specific example, negatively charged toner is used, and the relationship of Vp1 <Vd <Vp2 is established, so that the latent image is developed in the development area, and conversely, the transfer residual toner on the photosensitive drum is collected in the development area. Will be.
FIG. 13 shows an image forming apparatus provided with a cleaning blade 18 instead of the cleaning roller 12 of the apparatus of FIG.
In this example, the transfer residual toner is mechanically collected by the cleaning blade 18 and collected in the collection box 19.

FIG. 11 shows Vp1 when the image forming apparatus shown in FIG. 1 is printed using toner having different volume resistivity.
Although a detailed method for producing the toner of the present invention will be described later, the volume specific electrical resistivity was adjusted by varying the amount of carbon black as a colorant.

The photosensitive drum surface potential Vp1 was a measured value after printing 5 sheets with a printing DYUTY of 10%. Further, the toner adhesion amount on the charging roller at this time was 0.05 mg / cm 2.
In the present invention, by using a toner having a capsule structure shown below, the problems of the contact development method can be solved, and the simple structure as an advantage can be fully utilized.

  The heat-pressure fixing capsule toner of the present invention is used alone as a developer when it contains a magnetic fine powder, and when it does not contain a magnetic fine powder, it is a non-magnetic one-component developer. A two-component developer can be prepared by mixing with an agent or carrier. The carrier is not particularly limited, and iron powder, ferrite, glass beads, or the like, or those coated with a resin, and further, a magnetite fine powder, a resin carrier in which fine ferrite powder is kneaded in a resin, and the like are used. The mixing ratio is 0.5 to 20 parts by weight. The carrier particle diameter is 15 to 500 μm.

<Specific example 3>
Next, specific example 3 will be described.
In general, toners use resin as a main component, carbon, etc., as an internal additive, charge control agents that control charging characteristics, wax to prevent offset, etc. Design is made.

Among the characteristics required for the toner, the charging characteristics that directly influence the print quality are particularly important. If the charge amount is low, background fogging tends to occur, and the reproducibility of dots and lines tends to decrease.
On the other hand, if it is too high, the development efficiency is deteriorated, or excessive energy is required for transfer, which makes it difficult to design an electrophotographic process.

Therefore, it is necessary to control the charge amount of the toner within a desired narrow range, but it is a matter of course that the charge amount is required to be stable under a different environment and after a long running printing.
However, it is not easy to satisfy these requirements. Since materials such as CCA and carbon are dispersoids, both theoretically and actually obtained toners are dispersed with a certain distribution in the main resin. If this distribution is extremely narrow, there is no problem, but in reality it is difficult.

  In general, since particles having a specific charge are preferentially consumed during running, if the toner has a wide charge amount distribution, the toner with a wider charge amount distribution remains in the developer. It increases fogging during running, lowers the reproducibility of dots and lines, and lowers print quality. In addition, since CCA and carbon are polar substances, they easily adsorb and dissociate water molecules, and easily change due to the environment.

As a result, the electrical resistance of the toner particles is likely to change, which affects the transfer of charges and easily changes the environment.
Since these polar substances are difficult to mix with the resin due to their characteristics, they are likely to be localized on the surface of the toner particles or unevenly distributed on specific particles.
Such properties are inevitable as long as CCA and carbon are used.

  Therefore, in this specific example, the toner charging characteristic is not changed even after the environmental change or running printing as well as the initial characteristic, and the toner having a sharp charge distribution is provided, and the print quality is not deteriorated. Can be printed stably.

  As a result of diligent research, the present inventors have found that the volume resistivity of the shell layer constituting the outermost layer is more inward of the outermost shell in the heat and pressure fixing toner comprising at least a thermoplastic resin and a colorant. It has been found that a toner having a capsule structure characterized by being larger than the component having the lowest volume electric resistivity constituting a shell layer or core is extremely effective.

  More specifically, these polar substances are directly charged by covering the outside of core particles containing a charge control agent (hereinafter abbreviated as CCA) and a polar substance called carbon as a dispersoid with a shell composed only of a resin. It has been found that a toner having excellent characteristics can be obtained by avoiding contact with a part such as a developing roller, reducing variation in charge amount for each particle, and reducing influence on the environment.

In this case, since CCA particles which are considered to transfer charges to the shell do not exist on the surface, the triboelectric charge of this toner is caused by the CCA existing in the core particles through the surface of the charge imparting agent such as the developing roller and the shell layer. It is thought that it is performed by charge exchange between and.
Therefore, if the shell is too thick, the barrier for charge transfer is increased, resulting in a toner having a poor charge start-up or a low charge amount.

The present inventor has also considered and experimented on the thickness of the shell and concluded that 0.4 to 4 parts by weight is appropriate for the core resin.
The toner of the present invention comprises a core material containing at least a thermoplastic resin and a colorant, and a shell material provided so as to cover the surface of the core material.

To summarize the main points of Example 3 again,
1. A toner having a capsule structure using at least two kinds of polymerizable monomers which are composed of at least a thermoplastic resin and a colorant and become a thermoplastic resin by polymerization.
2. The shell layer constituting the outermost layer does not contain a polar substance such as CCA or carbon, and is synthesized using only a series of substances such as a polymerizable monomer and a polymerization initiator or a crosslinking agent that makes this resin a resin. Therefore, the outermost shell layer is larger than the component having the lowest volume resistivity constituting the inner shell layer or core.
3. The content of the resin constituting the outermost layer is 0.1 to 4 parts by weight of the resin constituting the core. A core having a particle diameter of 1 to 30 μm is suitable.

  The heat-pressure fixing capsule toner of the present invention is used alone as a developer when it contains a magnetic fine powder, and when it does not contain a magnetic fine powder, it is a non-magnetic one-component developer. A two-component developer can be prepared by mixing with an agent or carrier. The carrier is not particularly limited, and iron powder, ferrite, glass beads, or the like, or those coated with a resin, and further, a magnetite fine powder, a resin carrier in which fine ferrite powder is kneaded in a resin, and the like are used. The mixing ratio is 0.5 to 20 parts by weight. The carrier particle diameter is 15 to 500 μm.

<Specific Example 4>
Next, specific example 4 will be described.
In recent years, so-called ozone-less electrophotographic methods have been proposed and put into practical use from the viewpoint of environmental problems. This is a method in which an image carrier (hereinafter referred to as a photosensitive drum) is charged by contact of a charging member, and the transfer process enables ozone-less by a similar method.
This makes it possible to perform an electrophotographic process substantially free of ozone as compared with the conventional corona charging and transfer method.

  However, this method also has problems. Since the charging member is used in contact with the photosensitive drum, the toner existing on the photosensitive drum is likely to adhere due to poor cleaning or the like, and the once adhered toner melts due to stress between the photosensitive drum and the surface of the charging member. If such a phenomenon occurs, the photosensitive drum cannot obtain a normal charged potential and printing failure occurs.

Such a phenomenon is particularly likely to occur in an image forming apparatus using a so-called low-temperature fixing toner.
The low-temperature fixing toner is a toner intended to obtain high fixing performance while minimizing energy consumption in the fixing process. This toner has a capsule structure composed of a core and a shell resin surrounding the outer periphery thereof. The main feature of the toner having a capsule structure is that a resin that is easily soluble in the core (core) is arranged with a resin that is hardly soluble in the shell.

This makes it possible in principle to achieve both low-temperature fixability and storage stability.
However, according to the inventor's research, such toners have the above-mentioned excellent characteristics, but also have technical difficulties.
Toners that are easy to fix are generally vulnerable to mechanical stress and generally deform easily after prolonged use. For this reason, sticking to the charging member is more likely to occur than conventional toner.

This is considered as follows.
Capsule toner satisfies storage stability under conditions where no large pressure is applied to the toner, such as when transported or stored as a single toner cartridge, but deforms under conditions where relatively high pressure is applied as in actual use. It's easy to do. In actual use, a constant pressure is applied between the photosensitive drum and the charging member. At this time, it is considered that some of the individual particles are at a high temperature due to the received pressure. In the first place, the material of the capsule toner is designed so as to be softened at a low temperature. Therefore, the capsule toner is easily deformed when both the temperature and the pressure are high, and as a result, the capsule toner is easily fixed to the surface of the charging member or the like.

There is also an electrophotographic apparatus that combines a so-called toner recycling system with a contact charging system. This is an epoch-making method that is ozone-free and does not produce waste toner. However, advanced technology and reliability are also required.
In this method, the transfer residual toner returned from the cleaning member to the photosensitive drum passes through the charging process, that is, the contact point between the charging member and the photosensitive drum in the process of being collected by the developing device, so that the toner adheres to the charging member. More opportunities to do.
Therefore, in this method, it is necessary to pay more attention to the toner adhesion to the charging member than in the method that does not involve toner recycling.

  In this specific example, a low-temperature fixing toner, more specifically, a toner having a resin with the lowest glass transition temperature among constituent resins having a value of 60 ° C. or less is used. In an electrophotographic image forming apparatus, which is a contact charging method performed by contacting a carrier, toner adhesion to a charging member is prevented, and the surface potential of the image carrier is stabilized even during long-term use, and excellent print quality is achieved. An image forming apparatus is provided. This is effective when applied not only to the charging member but also to all members such as a transfer roller cleaning roller that contacts the image carrier.

  As a result of diligent research, the present inventors have used pure water as a charging member in an electrophotographic image forming apparatus using a toner having a resin having the lowest glass transition temperature of 60 ° C. or less among constituent resins. It was concluded that the above problem can be solved by designing the contact angle measured in this way to be 90 ° or more. The use of a charging member having a surface characteristic with a large contact angle is considered to have an effect of preventing adhesion and adhesion of toner, paper powder, etc. to the surface of the charging member. Using a contact charging member having such a surface characteristic The present invention is found to be indispensable for an electrophotographic process using a low-temperature fixing toner, and further more important for a contact charging type electrophotographic process using a low-temperature fixing toner and a toner recycling system. It came to.

The apparatus used in this specific example can be the image forming apparatus of FIG. 12 used in the description of specific example 2.
In the apparatus of FIG. 12, there is an opportunity for the toner returned to the photosensitive drum 5 by the cleaning roller 12 to adhere to the surface of the charging roller 1 while the printing operation is repeated.

  The apparatus shown in FIG. 13 is provided with a blade-type transfer residual toner collecting member 18 instead of the cleaning roller. In the image forming apparatus shown in FIG. 13, the transfer residual toner collected by the cleaning blade 18 is accumulated in the collected toner BOX 19 and is not collected by the developing roller through the photosensitive drum as in the apparatus of FIG.

Therefore, structurally, toner does not adhere to the charging roller.
However, in practice, the ability of the cleaning blade is reduced due to running (due to wear of a portion that is in pressure contact with the photosensitive drum), and the risk of defective cleaning cannot be wiped out.

FIG. 22 is a schematic sectional view of a charging roller showing a specific example of the present invention.
The charging roller shown in the figure has the following configuration.
(A) A conductive adhesive 22 is applied around the conductive shaft 21.
(A) An elastic layer 23 made of epichlorohydrin rubber adjusted to be semiconductive by ionic conduction is provided around the conductive adhesive 22.
(C) The surface of the elastic layer 23 was impregnated with an isocyanate solution adjusted to a constant concentration with a solvent, and a heat curing treatment (isocyanate treatment) portion 24 was provided at a constant temperature.

FIG. 23 is a schematic sectional view showing the charging roller used in the comparative example. In FIG. 23, the charging roller has the following configuration.
(A) A conductive adhesive 32 is applied around the conductive shaft 31.
(A) An elastic layer 23 made of urethane rubber adjusted to be semiconductive by ionic conduction is provided around the conductive adhesive 32 in a cylindrical shape.
(C) The surface layer 24 made of urethane resin adjusted to be semiconductive with conductive carbon is coated around the elastic layer 23 so as to be thin on the non-gear side.

FIG. 24 is a schematic explanatory diagram showing the application process of the isocyanate or urethane resin using the dipping method.
In this figure, a rubber roller 41 comprising only a rubber elastic layer 42 is connected to a coating device 47 with a lifting chuck 45 attached to a shaft 43 at one end so that it can move up and down. Further, the rubber roller 41 is provided with a protective cover 46 at the portion of the shaft 43 that enters the coating liquid 44.

The coating device 47 puts the rubber roller 41 into the coating solution 44 in the tank 48 with the chuck 45 side up. Then, the coating device 47 raises the rubber roller 41 at a constant speed and applies the coating liquid 44.
At this time, the charging roller used in the comparative example of the present invention is manufactured by using the rubber roller 41 as urethane rubber and the coating liquid 44 as a nylon resin liquid or a urethane resin liquid adjusted to a constant viscosity with a solvent.

  On the other hand, in the specific example of the present invention, the rubber roller 41 is made of epichlorohydrin rubber, and the coating solution 44 is produced as an isocyanate solution adjusted to a constant concentration with a solvent. At this time, the isocyanate solution has a sufficiently lower viscosity than the nylon resin solution or the urethane resin solution. This is because when the isocyanate solution is laminated on the surface of the rubber roller 41, the insulating layer of the insulating isocyanate causes a charging failure. Therefore, dripping does not occur in the isocyanate solution, and a small amount adheres to the rubber roller surface almost uniformly regardless of the pulling direction.

Moreover, the isocyanate solution adhering to the surface is almost taken into the rubber molecules of epichlorohydrin rubber by being heated after this coating step, and becomes isocyanate.
In other words, the specific example of the present invention is characterized by having an appropriate electrical insulation and water repellency by curing isocyanate in epichlorohydrin rubber molecules without having a conventional surface layer.
In the present invention, the surface water repellency is variously changed by changing the impregnation time in the isocyanate solution.

The contact angle measurement of the charging roller produced by the above method was measured using a contact angle measuring device FACE CA-S roll type manufactured by Kyowa Interface Science Co., Ltd.
Pure water was used as the measurement liquid. The size of the droplet before dropping was 2 mm, and the value 10 seconds after dropping on the object to be measured was taken as the measured value.

FIG. 25 shows the relationship between the impregnation time in the isocyanate solution and the contact angle of the charging roller.
It can be seen that increasing the impregnation time increases the contact angle (improves water repellency).
Next, a method for producing the toner used in the present invention will be described.
67.5 parts by weight of styrene, 32.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, charge control agent “Eisenspiron Black TRH” (manufactured by Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours while stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, 9.5 parts by weight of methyl methacrylate, 0.5 parts by weight of acrylic acid-n-butyl, 0.5 parts by weight of 2,2'-azobisisobutyronitrile, 0.1 parts by weight of sodium lauryl sulfate, 80 parts by weight of water A water emulsion A consisting of parts was prepared. 4 parts by weight of this water emulsion A was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.
The glass transition temperature derived from the core of the capsule toner obtained in the present invention was 35 ° C.

Moreover, the glass transition temperature of the thermoplastic resin obtained when polymerizing only the water emulsion A alone was 95 ° C. That is, it can be considered that the glass transition temperature of the resin derived from the shell is 95 ° C.
Further, in the present invention, it is possible to produce a toner having a different glass transition temperature of the core by changing the composition ratio of styrene and acrylate-n-butyl.

In the present invention, samples in which the core glass transition temperature was changed to 35 to 85 ° C. were prepared.
Further, in the present invention, a toner having a single layer structure without a shell was also produced.
A method for producing a toner having a single layer structure without a shell will be described below.
67.5 parts by weight of styrene, 32.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, charge control agent “Eisenspiron Black TRH” (manufactured by Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes.

  Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. After cooling, dissolve the dispersion medium in 0.5N aqueous hydrochloric acid, filter, wash with water, air dry, 20 ° C. for 20 hours, vacuum dry at 10 mmHg, classify with an air classifier, and toner with an average particle size of 7 μm. Got.

Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) (0.35 parts by weight) was added to and mixed with 50 parts by weight of this toner to obtain the toner of the present invention. This toner had a glass transition temperature of 35 ° C.
Similarly to the toner having a capsule structure, a toner having a different core glass transition temperature can be prepared by changing the composition ratio of styrene and acrylic acid-n-butyl.
In the present invention, a toner having a single layer structure was prepared by changing the glass transition temperature from 35 to 85 ° C.

  Hereinafter, 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 and the like. The invention is illustrated by the following examples.

<< Example of Example 1 and Comparative Example >>
<Specific Example 1 Example 1>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 2 parts by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, in an aqueous suspension of the intermediate particles, 9.25 parts by weight of methyl methacrylate and 0.75 parts of acrylic acid-n-butyl were obtained using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). A water emulsion A comprising 0.5 parts by weight of 2,2′-azobisisobutyronitrile, 0.1 parts by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 9 parts by weight of this water emulsion A was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

The glass transition temperature of the resin particles obtained in the stage before seed polymerization was 55 ° C. That is, it can be considered that the glass transition temperature derived from the core of the capsule toner obtained in this example is 55 ° C.
Moreover, the glass transition temperature of the thermoplastic resin obtained when only the water emulsion A was polymerized alone was 85 ° C. That is, it can be considered that the glass transition temperature of the resin derived from the shell is 85 ° C.
To 50 parts by weight of this capsule toner, 0.35 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 of the present invention (Toner E).

  This toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 1 and continuous printing was performed using A4 paper. The printing DYUTY was 10%. As shown in FIG. 4, the background fog was at a very good level from the beginning, and high-quality printing was obtained. Further, as shown in FIG. 6, the charge amount on the developing roller was stable at a negative charge of 11 μC / g, and development to the background did not occur.

<Specific Example 1 Example 2>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, in an aqueous suspension of the intermediate particles, 9.25 parts by weight of methyl methacrylate and 0.75 parts of acrylic acid-n-butyl were obtained using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). A water emulsion A comprising 0.5 parts by weight of 2,2′-azobisisobutyronitrile, 0.1 parts by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 9 parts by weight of this water emulsion A was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

The glass transition temperature of the resin particles obtained in the stage before seed polymerization was 55 ° C. That is, it can be considered that the glass transition temperature derived from the core of the capsule toner obtained in this example is 55 ° C.
Moreover, the glass transition temperature of the thermoplastic resin obtained when only the water emulsion A was polymerized alone was 85 ° C. That is, it can be considered that the glass transition temperature of the resin derived from the shell is 85 ° C.
To 50 parts by weight of this capsule toner, 0.35 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 of the present invention (Toner C).

  This toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 1 and continuous printing was performed using A4 paper. The printing DYUTY was 10%. As shown in FIG. 4, the background fog was at a very good level from the beginning, and high-quality printing was obtained. Further, as shown in FIG. 6, the charge amount on the developing roller was stable at a negative charge of 11 μC / g, and development to the background did not occur.

<Specific Example 1 Comparative Example 1>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, charge control agent “Eisenspiron Black TRH” (manufactured by Hodogaya Chemical Co., Ltd.) 2 parts by weight, 7 parts by weight of carbon black (manufactured by Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile were added, and attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.) And dispersed at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours while stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, in an aqueous suspension of the intermediate particles, 9.25 parts by weight of methyl methacrylate and 0.75 parts of acrylic acid-n-butyl were obtained using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). A water emulsion A comprising 0.5 parts by weight of 2,2′-azobisisobutyronitrile, 0.1 parts by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 9 parts by weight of this water emulsion A was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

The glass transition temperature of the resin particles obtained in the stage before seed polymerization was 55 ° C. That is, it can be considered that the glass transition temperature derived from the core of the capsule toner obtained in this example is 55 ° C.
Moreover, the glass transition temperature of the thermoplastic resin obtained when only the water emulsion A was polymerized alone was 85 ° C. That is, it can be considered that the glass transition temperature of the resin derived from the shell is 85 ° C.
To 50 parts by weight of this capsule toner, 0.35 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 of the present invention (Toner A).

This toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 1 and continuous printing was performed using A4 paper. The printing DYUTY was 10%. As shown in FIG. 4, the initial background fog was as bad as 15% and improved as continuous printing was performed, but more than 500 sheets were required.
Further, to cope with this, the charge amount on the developing roller was initially low at 4 μC / g.

<Specific Example 1 Comparative Example 2>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 2 parts by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours while stirring at 100 rpm in a nitrogen stream.

After cooling, dissolve the dispersion medium in 0.5N aqueous hydrochloric acid, filter, wash with water, air dry, then dry at 40 ° C. for 10 hours under reduced pressure at 10 mmHg, classify with an air classifier, and have an average particle size of 7 μm. A polymer toner having a layer structure was obtained.
To 50 parts by weight of this capsule toner, 0.35 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 of the present invention (Toner J).

  This toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 1 and continuous printing was performed using A4 paper. The printing DYUTY was 10%. As shown in FIG. 4, although the background fog was very good, there was a phenomenon that the toner developed in the background (non-printing portion) as continuous printing was performed. This phenomenon was confirmed after printing 500 sheets in an environment of 25 ° C. and 55%, and the charging amount on the developing roller at this time was as high as 20 μC / g.

  Further, the charging amount on the developing roller when continuous printing was performed up to 1000 sheets was further increased to 21 μC / g.

<< Example and Comparative Example of Specific Example 2 >>
<Specific Example 2 Example 1>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, in an aqueous suspension of the intermediate particles, 9.25 parts by weight of methyl methacrylate and 0.75 parts of acrylic acid-n-butyl were obtained using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). A water emulsion A comprising 0.5 parts by weight of 2,2′-azobisisobutyronitrile, 0.1 parts by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 9 parts by weight of this water emulsion A was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

The glass transition temperature of the resin particles obtained in the stage before seed polymerization was 55 ° C. That is, it can be considered that the glass transition temperature derived from the core of the capsule toner obtained in this example is 55 ° C.
Moreover, the glass transition temperature of the thermoplastic resin obtained when only the water emulsion A was polymerized alone was 85 ° C. That is, it can be considered that the glass transition temperature of the resin derived from the shell is 85 ° C.
Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.

The toner had a volume specific electrical resistivity log ρ = 11.5.
When this toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 12 and the surface potential Vp1 of the photosensitive drum was measured, it was −800 V, and a high-quality printed matter was obtained.

Further, the surface potential Vp1 did not change at all after running 30,000 sheets of A4 paper, and the same high quality printed matter was obtained.
Next, this toner was put into LED printer OKI MICROLINE16n to perform printing, and the fixing rate was measured. The set temperature of the fixing device heat roller was 130 ° C.
The fixing rate was defined by the following equation.

Fixing rate (%) = (density after peeling / density before peeling) × 100
The density before peeling is a value obtained by measuring a solid black portion of a printed material with a Macbeth density measuring device. The density after peeling is 3 cm / sec after a 3M scotch tape is applied to the solid black part of the printed material and a load of 50 g / cm ^ 2 is applied on the black portion and the sheet is reciprocated once. The density of the image remaining on the printed material when the scotch tape is peeled off at a speed of 2 mm.
The capsule toner of this example showed a very good fixing property of 99% or more.

  Further, the anti-blocking property of this toner was measured by the following method. First, 20 g of the toner sample was put in a cylindrical container having a bottom area of 20 cm 2 and a weight was applied so that the pressure was 500 g / cm 2. In this state, it was left in a 50 ° C. atmosphere for 1 month. Next, 20 g of the sample toner was placed on a 45 μm mesh sieve and subjected to vibration at 1 KHz for 30 seconds, and then the remaining amount of toner remaining on the sieve was measured. The blocking property was defined by the following formula.

Blocking rate (%) = remaining toner remaining on the sieve (g) / sample toner weight (g) × 100
The capsule toner of this example had a blocking rate of zero and showed very good storage stability. From the above results, by using the capsule toner of volume specific electrical resistivity obtained in this embodiment for the contact charging type image forming apparatus (with toner recycling system), no ozone is generated (and waste toner is also produced). In an electrophotographic process, an epoch-making image forming apparatus capable of obtaining an extremely high quality printed matter from the beginning through running printing, showing a good fixing performance even at a low fixing device temperature, and having a very good high temperature storage property. It can be provided.

<Specific Example 2 Example 2>
90 parts by weight of methyl methacrylate, 10 parts by weight of acrylic acid-n-butyl and 3 parts by weight of 2,2′-azobisisobutyronitrile are put into a glass 2-liter 4-neck flask, a thermometer and a stainless steel stirring rod Then, a flow-down condenser and a nitrogen introduction tube were attached, and the reaction was carried out at 100 ° C. under a nitrogen stream in a mantle heater. Further, the polymerization product was sampled at any time during the reaction, and its glass transition point was measured. The reaction was stopped when the glass transition point of the polymerization product reached 60 ° C. The glass transition point was measured with a differential scanning calorimeter (“DSC220 type”, manufactured by Seiko Denshi Kogyo Co., Ltd.). This is designated as resin B. It was confirmed that the glass transition temperature of the polymerization product obtained when the reaction time of the main polymerization was sufficiently extended was 90 ° C.

  77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 0.25 parts by weight of the above-mentioned resin B, 1.5 parts by weight of low molecular weight polyethylene as an offset preventing agent, charge control agent “Eisenspiron Black TRH” 1 part by weight (manufactured by Hodogaya Chemical Co., Ltd.), 7 parts by weight of carbon black (manufactured by Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile were added, and attritor (“MA-01SC”, (Mitsui Miike Chemical Co., Ltd.) and dispersed at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. The resulting dispersion was then transferred into a 1 liter separable flask and 100 r.p. The mixture was reacted at 85 ° C. for 12 hours with stirring at m. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

Next, the same amount of the water emulsion A used in Example 2 and Example 1 was added to the aqueous suspension of the intermediate particles, and the following treatment was also exactly the same as Example 1.
This toner had a volume specific electrical resistivity log ρ = 11.3.
When this toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 12 and the surface potential Vp1 of the photosensitive drum was measured, it was −800 V, and a high-quality printed matter was obtained.

Further, the surface potential Vp1 did not change at all after running 30,000 sheets of A4 paper, and the same high quality printed matter was obtained.
Next, this toner was put into an LED printer OKI MICROLINE 16n to perform printing, and the fixing rate was measured under the same conditions as in Example 1.

The capsule toner of this example showed a very good fixing property of 99% or more.
The blocking rate was zero as in Example 1. From the above results, by using the capsule toner of volume specific electrical resistivity obtained in this embodiment for the contact charging type image forming apparatus (with toner recycling system), no ozone is generated (and waste toner is also produced). In an electrophotographic process, an epoch-making image forming apparatus capable of obtaining an extremely high quality printed matter from the beginning through running printing, showing a good fixing performance even at a low fixing device temperature, and having a very good high temperature storage property. It can be provided.

<Specific Example 2 Example 3>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 0.25 parts by weight of resin B used in Example 2, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, charge control agent “Eisen 1 part by weight of spiron black TRH (manufactured by Hodogaya Chemical Co., Ltd.), 8 parts by weight of carbon black (manufactured by Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile were added. -01SC "(manufactured by Mitsui Miike Chemical Co., Ltd.) and dispersed at 15 ° C for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion solution was transferred into a 1 liter separable flask and 100 r. p. m. The mixture was reacted at 85 ° C. for 12 hours with stirring. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

Next, the same amount of the water emulsion A used in Examples 1 and 2 was added to the aqueous suspension of the intermediate particles, and the following treatment was also the same as in Examples 1 and 2.
The toner had a volume specific electrical resistivity log ρ = 11.0.
When this toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 12 and the surface potential Vp1 of the photosensitive drum was measured, it was −800 V, and a high-quality printed matter was obtained.

Further, the surface potential Vp1 did not change at all after running 30,000 sheets of A4 paper, and the same high quality printed matter was obtained.
Next, this toner was put into an LED printer OKI MICROLINE 16n to perform printing, and the fixing rate was measured under the same conditions as in Example 1.

The capsule toner of this example showed a very good fixing property of 99% or more.
The blocking rate was zero as in Example 1. From the above results, by using the capsule toner of volume specific electrical resistivity obtained in this embodiment for the contact charging type image forming apparatus (with toner recycling system), no ozone is generated (and waste toner is also produced). In an electrophotographic process, an epoch-making image forming apparatus capable of obtaining an extremely high quality printed matter from the beginning through running printing, showing a good fixing performance even at a low fixing device temperature, and having a very good high temperature storage property. It can be provided.

<Specific Example 2 Example 4>
The toner used in Examples 1 to 3 was placed in the image forming apparatus shown in FIG. 13, and running was performed up to 50,000 printed sheets in A4.
Immediately before the 50,000 sheets, toner adhesion on the streaks was partially observed on the charging roller, and the adhesion amount was 0.5 mg / cm ^ 2. At this time, the edge of the corresponding cleaning blade (1102) (in contact with the photosensitive drum) was rounded, and it was confirmed that a cleaning failure occurred. However, there was no problem in print quality and there was no decrease in the surface potential of the photosensitive drum.

<Specific Example 2 Comparative Example 1>
A capsule toner was prepared in the same manner as in Example 3 except that the amount of carbon black was 9 parts by weight in the toner synthesis in Example 3.

The volume specific electrical resistivity of this toner was log ρ = 10.0.
When this toner was put in an image forming apparatus (EP cartridge) having the structure shown in FIG. 12 and the surface potential Vp1 of the photosensitive drum was measured, it was −650V.
At this time, the toner developed on a part of the background of the printed matter, and satisfactory print quality could not be obtained.

Further, Vp1 gradually decreased while continuing printing, and decreased to −500 V after about 100 sheets. At this time, the development to the background was remarkably impossible to continue further running.
At this time, it is considered that 2 mg / cm ^ 2 of toner adhered to the charging roller, which accelerated the decrease in charging voltage.

<Specific Example 2 Comparative Example 2>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) 9.5 parts by weight of carbon black (printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile were added, and attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.) And dispersed at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, 10 parts by weight of styrene, 0.5 parts of 2,2′-azobisisobutyronitrile was added to the aqueous suspension of the intermediate particles using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho). A water emulsion C consisting of parts by weight, 0.1 part by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 9 parts by weight of this water emulsion C was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

The glass transition temperature of the resin particles obtained in the stage before seed polymerization was 55 ° C. That is, it can be considered that the glass transition temperature derived from the core of the capsule toner obtained in this example is 55 ° C.
Moreover, the glass transition temperature of the thermoplastic resin obtained when only water emulsion C was polymerized alone was 100 ° C. That is, it can be considered that the glass transition temperature of the resin derived from the shell is 100 ° C.
Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.

The volume specific electrical resistivity of this toner was log ρ = 10.1.
When this toner was put into an image forming apparatus (EP cartridge) having the configuration shown in FIG. 12 and the surface potential Vp1 of the photosensitive drum was measured, it was −800 V, and a high-quality printed matter was obtained.

Further, the surface potential Vp1 did not change at all after running 30,000 sheets of A4 paper, and the same high-quality printed matter as that in the initial stage was obtained, and the fixing rate was 95% or more.
However, the blocking rate was extremely poor at 55%.
In addition, in order to make a blocking rate into zero, it confirmed that it was necessary to make the addition amount of the water emulsion C into 20 weight part.

However, the fixing rate at this time was 45%, and it was found that when the water emulsion C was used, both the fixing performance and the high-temperature storage performance could not be satisfied.
Further, the following toner was synthesized.
87.5 parts by weight of styrene, 12.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. After cooling, the dispersion medium is dissolved in 0.5N aqueous hydrochloric acid, filtered, washed with water, air dried, dried at 40 ° C. for 10 hours under reduced pressure at 10 mmHg, classified with an air classifier, and toner having an average particle diameter of 7 μm. Got. This toner had a glass transition temperature of 75 ° C.

Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) (0.35 parts by weight) was added to and mixed with 50 parts by weight of this toner to obtain the toner of the present invention.
The fixing rate of this toner without capsules was 45%, while the blocking resistance was zero. In addition, it was confirmed that the glass transition temperature must be 75 ° C. or higher in order to make the anti-blocking rate zero with the toner synthesized by this method.

  From the above facts, it is said that the fixing property and the high temperature storage property of the capsule toner added with 20 parts by weight of the water emulsion C and ensuring sufficient high temperature storage property and the toner having no capsule having a glass transition temperature of 75 ° C. are the same. be able to.

  Therefore, it can be said that the capsule toner using the water emulsion C does not have the advantage of having a capsule structure.

<< Example and Comparative Example of Specific Example 3 >>
<Specific Example 3 Example 1>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, 8.5 parts by weight of methyl methacrylate and 1.5 parts of acrylic acid-n-butyl were mixed into the aqueous suspension of the intermediate particles using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). As a polymerization initiator, an aqueous emulsion A comprising 0.5 part by weight of 2,2′-azobisisobutyronitrile, 0.1 part by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 4 parts by weight of this water emulsion A was dropped to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

  Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.

Next, the electrical resistance value (volume resistivity) of each substance used for toner synthesis was determined.
The volume resistivity is measured by using a dielectric loss measuring instrument TR-10C manufactured by Ando Electric Co., Ltd. under a condition of an oscillator frequency of 1 KHz after preparing a sample to be measured with a 3 g weighing tablet forming device. As a logarithmic value.
logρ = log [(A / t) × (1 / Gx)]
log ρ: Volume resistivity (logarithmic value)
Gx = (CONDUCTANCE Ratio) × R
R: CONDUCTANCE measured value A: Electrode area (11.34 cm ^ 2)
t: Material thickness (2mm)
The carbon black used in this example had log ρ = 6.2, and the charge control agent had log ρ = 9.5.
The resin obtained by polymerizing water emulsion A alone was log ρ = 12.8.

That is, the component having the lowest electrical resistance for toner synthesis used in this embodiment is arranged in the core.
This toner was put into LED printer OKI MICROLINE16n and running printing was performed. The background fog and blow-off charge amount on the photosensitive drum were measured at high temperature and high humidity (28 ° C., 80 RH%) and low temperature and low humidity (10 ° C., 20 RH%).

A spectrocolorimeter CM-1000 manufactured by Minolta Co., Ltd. was used for background fog measurement on the photosensitive drum. Then, the difference between the light reflectance of the 3M Scotch tape as a reference and the light reflectance of the sample obtained by transferring the fog toner on the photosensitive drum to this tape was defined and measured as fog.
The charge amount was measured by using a blow-off charge amount measuring device manufactured by Toshiba Chemical Co., Ltd. 57 g of commercially available iron powder carrier and 3 g of toner under each condition were sampled, mixed and stirred for 10 minutes with a ball mill, and then air pressure of 1 kg / Toner was blown and measured at cm ^ 2.
14 to 17 show measurement results according to Example 1. FIG.

The toner produced in this example showed a stable blow-off charge amount during running and under different environments, and the background fog was small and stable.
18 to 21 show the initial background fog on the photosensitive drum and the blow-off charge amount when only the addition amount of the water emulsion A to the intermediate particles is changed under the synthesis conditions in this embodiment.

When the amount of water emulsion A added is 0.1 parts by weight or less and 5 parts by weight or more, the fogging under high temperature and high humidity is large and the charge amount is low.
As described above, if there is no shell layer or if it is thin, the polar substance carbon and charge control agent are exposed on the particle surface and cause charge leakage. If it is too thick, the charge control agent in the core is effective. This is thought to be due to the fact that it no longer works.

<Specific Example 3 Example 2>
Put 100 parts by weight of methyl methacrylate and 3 parts by weight of 2,2'-azobisisobutyronitrile into a glass 2-liter 4-neck flask, and put a thermometer, a stainless steel stirring bar, a falling condenser, and a nitrogen inlet tube. The reaction was carried out at 100 ° C. under a nitrogen stream in a mounting mantle heater. Further, the polymerization product was sampled at any time during the reaction, and its glass transition temperature was measured. The reaction was stopped when the glass transition point of the polymerization product reached 60 ° C. The glass transition point was measured with a differential scanning calorimeter (“DSC220 type”, manufactured by Seiko Denshi Kogyo Co., Ltd.). This is designated as resin B.

  Next, 0.25 parts by weight of the above-mentioned resin B, 77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an offset preventive agent, charge control agent “Eisenspiron” 1 part by weight of “Black TRH” (manufactured by Hodogaya Chemical Co., Ltd.), 7 parts by weight of carbon black (manufactured by Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile were added, and attritor (“MA-01SC And then dispersed at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, 8.5 parts by weight of methyl methacrylate and 1.5 parts of acrylic acid-n-butyl were mixed into the aqueous suspension of the intermediate particles using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). As a polymerization initiator, an aqueous emulsion A comprising 0.5 part by weight of 2,2′-azobisisobutyronitrile, 0.1 part by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 4 parts by weight of this water emulsion A was dropped to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.
The volume specific resistance of the carbon black used in this example is log ρ = 6.2, the charge control agent is log ρ = 9.5, and the log ρ = 12.8 of the resin obtained by polymerizing the water emulsion A alone. This is the same as in the first embodiment.

That is, also in this embodiment, the component having the lowest electrical resistance used for toner synthesis is arranged in the core.
The toner produced in this example showed a stable blow-off charge amount in running and under different environments as in the toner produced in Example 1, and the background fog was small and stable.

<Specific Example 3 Comparative Example 1>
After synthesizing the intermediate particles in the same manner as in Example 1, cooling, dissolving the dispersion medium in 0.5N hydrochloric acid aqueous solution, filtering, washing with water, air drying, and drying under reduced pressure at 10 mmHg for 10 hours at 40 ° C., The toner was classified by an air classifier to obtain a toner having an average particle size of 7 μm.
Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain the toner of the present invention.

  This toner was put into LED printer OKI MICROLINE16n and running printing was performed. The background fog and blow-off charge amount on the photosensitive drum were measured at high temperature and high humidity (28 ° C., 80 RH%) and low temperature and low humidity (10 ° C., 20 RH%).

  As a result, as shown in FIGS. 14 to 17, charging characteristics under high temperature and high humidity and low temperature and low humidity are remarkably different, fogging is large under high temperature and high humidity, and conversely, the charge amount is too large under low temperature and low humidity. The toner developed a phenomenon.

<Specific Example 3 Comparative Example 2>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to an attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, 8.5 parts by weight of methyl methacrylate and 1.5 parts of acrylic acid-n-butyl were mixed into the aqueous suspension of the intermediate particles using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). As a polymerization initiator, an aqueous emulsion A comprising 0.5 part by weight of 2,2′-azobisisobutyronitrile, 0.1 part by weight of sodium lauryl sulfate, and 80 parts by weight of water was prepared. 0.01 part by weight of this water emulsion A was added dropwise to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.
This toner was put into LED printer OKI MICROLINE16n for running printing. The toner produced in this example showed almost the same behavior as the toner of Comparative Example 1. In other words, the fog was large under high temperature and high humidity, and conversely, the charge amount was too large under low temperature and low humidity, so that a phenomenon that the toner developed in the background was observed.

<Specific Example 3 Comparative Example 3>
A toner was obtained by synthesis under the same conditions as in Comparative Example 2 except that the amount of water emulsion A used in Comparative Example 2 was changed to 10 parts by weight.

This toner was put into LED printer OKI MICROLINE16n for running printing.
The toner produced in this example had a large time dependency of the blow-off charge amount, and the rise of charge was extremely slow. The blow-off values of the toners of Examples 1 and 2 and Comparative Examples 1 and 2 are substantially equal to those after 10 minutes of mixing and stirring and those after 30 while the toner of this example has a value of 30 minutes and a value of 30 minutes. %, Indicating a slow rise in charging. In order to cope with this, the fog at the initial stage of printing was particularly large, and although it improved with running, it was not acceptable in practice.

<Specific Example 3 Comparative Example 4>
77.5 parts by weight of styrene, 22.5 parts by weight of acrylic acid-n-butyl, 1.5 parts by weight of low molecular weight polyethylene as an anti-offset agent, 1 part by weight of charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.) Part, 7 parts by weight of carbon black (Printex L Degussa) and 1 part by weight of 2,2′-azobisisobutyronitrile are added to the attritor (“MA-01SC”, manufactured by Mitsui Miike Chemical Co., Ltd.). And dispersion at 15 ° C. for 10 hours to obtain a polymerizable composition.

  Further, 180 parts by weight of ethanol in which 8 parts by weight of polyacrylic acid and 0.35 parts by weight of divinylbenzene were dissolved were prepared, and 600 parts by weight of distilled water was added thereto to prepare a dispersion medium for polymerization. The polymerizable composition was added to this dispersion medium, and dispersed with a TK homomixer (“M type”, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 15 ° C. and 8000 rpm for 10 minutes. Next, the obtained dispersion was transferred into a 1 liter separable flask and reacted at 85 ° C. for 12 hours with stirring at 100 rpm in a nitrogen stream. The dispersoid obtained by the polymerization reaction of the polymerizable composition in the steps so far will be referred to as intermediate particles.

  Next, 8.5 parts by weight of methyl methacrylate and 1.5 parts of acrylic acid-n-butyl were mixed into the aqueous suspension of the intermediate particles using an ultrasonic oscillator (US-150, Nippon Seiki Seisakusho Co., Ltd.). , 0.05 part by weight of a charge control agent “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.), 0.5 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator, 0.1% of sodium lauryl sulfate A water emulsion A consisting of parts by weight and 80 parts by weight of water was prepared. 4 parts by weight of this water emulsion A was dropped to swell the intermediate particles. Observation with an optical microscope immediately after the dropping showed that no emulsion droplets were observed, and it was confirmed that the swelling was completed in a very short time.

  Therefore, the reaction was carried out at 85 ° C. for 10 hours as the second stage polymerization while continuing stirring under nitrogen. After cooling, dissolve the dispersion medium in 0.5N hydrochloric acid aqueous solution, filter, wash with water, air dry, 40 ° C for 10 hours, dry under reduced pressure at 10 mmHg, classify with an air classifier, capsules with an average particle size of 7 μm A toner was obtained.

Hydrophobic silica fine powder “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) 0.35 parts by weight was added to 50 parts by weight of the capsule toner and mixed to obtain a capsule toner of the present invention.
When this toner was put into LED printer OKI MICROLINE16n and running printing was performed, the blow-off charge amount was as low as -30 μC / g under high temperature and high humidity, and the background fog was large.

On the contrary, under low temperature and low humidity, the blow-off charge amount was as extremely large as −120 μC / g, and development on the background portion occurred.
It has been found that the presence of a charge control agent on the toner surface results in a toner that is very susceptible to environmental changes and lacks practical utility.

<< Example and Comparative Example of Specific Example 4 >>
<Specific Example 4 Example 1>
A capsule toner having a core glass transition temperature of 35 ° C. and an isocyanate-treated charging roller prepared with an impregnation time of 10 minutes were prepared. As can be seen from FIG. 25, the contact angle of the charging roller used in this example is 120 °.
The EP cartridge having the configuration shown in FIGS. 1 and 2 equipped with the toner and the charging roller was placed in the LED printer OKI MICROLINE 16n for running printing.
The printing conditions were A4 size printing DYUTY 15%.

FIG. 26 shows the transition of the photosensitive drum surface potential with respect to the number of printed sheets.
In this example, the photosensitive drum potential was extremely stable from the beginning, and no change was observed even during long running. Further, as shown in FIG. 27, the surface of the charging roller was a clean surface that did not show any toner sticking or the like and was completely different from the initial one.

Next, similar running printing was performed using a capsule toner having a core glass transition temperature of 85 ° C. FIG. 26 shows the surface potential of the photosensitive drum after printing 20,000 sheets, and FIG. 27 shows the presence or absence of toner adhesion on the surface of the charging roller. Also in this case, as in the case of the toner having a core glass transition temperature of 35 ° C., no toner sticking or the like was observed, and the surface of the charging roller was a clean surface that was not different from the initial one.
Further, in this example, toner having a single layer structure having no shell was prepared with a glass transition temperature of 35 to 85 ° C., and the same test was performed.
The result is shown in FIG.

FIG. 27 is an explanatory diagram showing the relationship between the glass transition temperature and the contact angle.
As in the case of the capsule toner, toner of all glass transition temperatures did not adhere to the charging roller, the surface potential of the photosensitive drum did not change before and after running, and the printing quality was very good.

<Specific Example 4 Example 2>
The charging roller was produced in the same manner as in Example 1 with an isocyanate impregnation time of 2 minutes.
The contact angle was 90 °. The same test as in Example 1 was performed using this charging roller, capsule toner of each glass transition temperature, and toner having a single layer structure. The result is shown in FIG.
In all the tests, toner adhesion to the charging roller was not observed, the surface potential of the photosensitive drum after running was stable, and the print quality was extremely good.

  Further, a charging roller having an isocyanate impregnation time of 3 minutes and a contact angle of 100 ° was also produced and evaluated in the same manner. As in the case of the contact angle of 100 °, all toners were charged into the charging roller in all tests. No toner adhesion was observed, the surface potential of the photosensitive drum after running was stable, and the printing quality was extremely good.

<Specific Example 4 Comparative Example 1>
A similar charging roller was produced by setting the impregnation time in the isocyanate solution shown in Example 1 to 1 minute.
The contact angle of the charging roller produced in this example was 80 °.
Using this charging roller, the same tests as in Example 1 were performed using capsule toners having various glass transition temperatures and single layer structure toners produced in Example 1. The result is shown in FIG.

In the case of this example, in the test using the toner recycling type EP cartridge shown in FIG. 12, there was no difference between the capsule toner and the toner having a single layer structure, but the glass transition of the toner to the state of fixing the toner to the charging roller. Dependence on temperature was observed.
That is, in the system using a toner having a glass transition temperature of less than 60 ° C., the background development due to the toner fixing to the charging roller and the accompanying decrease in the photosensitive drum surface potential was confirmed as a result of running. The surface potential of the photosensitive drum decreased from the initial setting value of −850 V to −650 V after printing 20,000 sheets.

  In the test using the EP cartridge shown in FIG. 13, a cleaning failure of about 0.5 mm in width occurred after printing 20,000 sheets. However, in the system using toner having a glass transition temperature of less than 60 ° C., the printed surface On the other hand, toner having the same width was observed on the surface of the charging roller in the corresponding part in the longitudinal direction.

<Specific Example 4 Comparative Example 2>
A charging roller of epichlorohydrin rubber single layer not subjected to isocyanate treatment was produced.
The contact angle of the charging roller produced in this example was 70 °.
Using this charging roller, the same tests as in Example 1 were performed using capsule toners having various glass transition temperatures and single layer structure toners produced in Example 1.
The results are shown in FIG.

  In the case of this example, in the test using the toner recycling type EP cartridge shown in FIG. 12, there was no difference between the capsule toner and the toner having a single layer structure, but the glass transition of the toner to the state where the toner is fixed to the charging roller. Dependence on temperature was observed.

  That is, in the system using the toner having a glass transition temperature of less than 65 ° C., the background development due to the toner fixing to the charging roller and the accompanying decrease in the photosensitive drum surface potential was confirmed as a result of running. The surface potential of the photosensitive drum decreased from the initial setting value of −850 V to −650 V after printing 20,000 sheets.

  In the test using the EP cartridge shown in FIG. 13, a cleaning failure of about 0.5 mm in width occurred after printing 20,000 sheets. However, in the system using a toner having a glass transition temperature of less than 65 ° C., On the other hand, toner having the same width was observed on the surface of the charging roller in the corresponding part in the longitudinal direction.

<Specific Example 4 Comparative Example 3>
Using the dipping apparatus shown in FIG. 24, a charging roller having an elastic layer made of urethane rubber having the configuration shown in FIG. 23 and adjusted to be semiconductive by ionic conduction was produced.
The contact angle of this charging roller was 75 °.
Using this charging roller, the same tests as in Example 1 were performed using capsule toners having various glass transition temperatures and single layer structure toners produced in Example 1. The result is shown in FIG.

  In the case of this example, in the test using the toner recycling type EP cartridge shown in FIG. 12, there was no difference between the capsule toner and the toner having a single layer structure, but the glass transition of the toner to the state where the toner is fixed to the charging roller. Dependence on temperature was observed.

  That is, in the system using the toner having a glass transition temperature of less than 65 ° C., the background development due to the toner fixing to the charging roller and the accompanying decrease in the photosensitive drum surface potential was confirmed as a result of running. The surface potential of the photosensitive drum decreased from the initial setting value of −850 V to −600 V after printing 20,000 sheets.

  In the test using the EP cartridge shown in FIG. 13, a cleaning failure of about 0.5 mm in width occurred after printing 20,000 sheets. However, in the system using a toner having a glass transition temperature of less than 65 ° C., On the other hand, toner having the same width was observed on the surface of the charging roller in the corresponding part in the longitudinal direction.

1 is a schematic configuration diagram of an image forming apparatus suitable for implementing the present invention. FIG. 6 is an explanatory view of blow-off charge amount time dependency of a polymer toner having a capsule structure. FIG. 6 is an explanatory diagram of blow-off charge amount time dependency of a polymer toner having a single layer structure. It is explanatory drawing (the 1) of background fogging. It is explanatory drawing (the 2) of background fogging. FIG. 6 is a first diagram illustrating the amount of charge on the developing roller. FIG. 10 is a second diagram illustrating the amount of charge on the developing roller. It is an example explanatory view of various toner structures. FIG. 5 is an explanatory diagram summarizing the presence or absence of development to the background in continuous image printing when the toner of each structure is employed. It is explanatory drawing which shows the nip dependence of the charging amount on a developing roller. It is explanatory drawing of the volume intrinsic electrical resistivity dependence of surface potential. It is a schematic block diagram of the image forming apparatus in which the specific example 2 is used. FIG. 3 is a schematic configuration diagram of an image forming apparatus provided with a blade-type transfer residual toner collecting member instead of a cleaning roller. It is a measurement result by Example 1 of the specific example 3. FIG. It is a measurement result by Example 1 of the specific example 3. FIG. It is a measurement result by Example 1 of the specific example 3. FIG. It is a measurement result by Example 1 of the specific example 3. FIG. It is explanatory drawing which shows the background fog and shell addition amount on an initial stage photoconductor drum. It is explanatory drawing which shows a blow-off charge amount and a shell addition amount. It is explanatory drawing which shows the background fog and shell addition amount on an initial stage photoconductor drum. It is explanatory drawing which shows a blow-off charge amount and a shell addition amount. 10 is a schematic cross-sectional view of a charging roller described in a specific example 4. FIG. It is a schematic sectional view of the charging roller used in the comparative example. It is a schematic explanatory drawing showing the application process of the isocyanate and urethane resin which used the dipping method. It is explanatory drawing which shows the relationship between the impregnation time to an isocyanate solution, and a charging roller contact angle. It is explanatory drawing which shows transition of the photoreceptor drum surface potential with respect to the number of printed sheets. It is explanatory drawing which shows the relationship between a glass transition temperature and a contact angle.

Explanation of symbols

4 DC power supply 5 Image carrier (photosensitive drum)
6 Exposure source (LED head)
7 Developer layer forming member (developing blade)
8 Developer carrier (developing roller)
9 Toner image 11 Transfer member (transfer roller)
12 Residual toner recovery member (cleaning roller)
13 Paper 14 Toner supply roller 15, 16 Power supply

Claims (4)

In an image forming apparatus having an image carrier and a roller provided on the image carrier,
(A) The roller is a charging roller whose surface is made of a highly water-repellent member having a contact angle of 90 ° or more measured using pure water, and is in contact with the image carrier.
(B) The toner used in the image carrier is a toner having a capsule structure comprising a core and a shell resin surrounding the core, and has a glass transition temperature of 60 ° C. or less in the core and is relatively heated by heat. An image forming apparatus comprising: a resin that is easily meltable; and a resin that has a glass transition temperature higher than that and is relatively easily melted by heat. The image forming apparatus according to claim 1.
An image forming apparatus characterized in that the glass transition temperature is a value measured by a differential scanning calorimeter. The image forming apparatus according to claim 1 or 2,
In the image forming apparatus, the content of the shell resin constituting the outermost layer is 0.1 to 4 parts by weight of the resin constituting the core. The image forming apparatus according to claim 1 or 2,
The toner is a toner having a capsule structure using at least two types of polymerizable monomers having at least a thermoplastic resin and a colorant and having different glass transition temperatures, and has a volume resistivity of a shell layer constituting the outermost layer. Is larger than the volume resistivity of the material inside the shell layer.

Images