JP2003005441A - Dry toner, method for manufacturing the same and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent electrophotographic characteristics, forming high-definition images, having excellent environmental stability and durability and scarcely causing contamination on a developer holding member, a photoreceptor, a fixing apparatus or the like. SOLUTION: The dry toner consists of at least one kind of binder resin, coloring agent, wax component and polyester resin and has the following features. (1) The polyester resin consists of aliphatic polyvalent carboxylic acids and aliphatic polyhydric alcohols and at least one of the polyvalent carboxylic acid units and/or polyhydric alcohol units constituting the resin has a polymerizable double bond. (2) In the equivalent circular diameter- circularity scattergram on number basis measured by a flow type particle image measuring device, the equivalent circular number average diameter D1 (μm) of the dry toner ranges from 2 μm to 10 μm. The average circularity of the toner ranges from 0.950 to 0.995 and the standard deviation of the circularity is <0.040.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry toner (hereinafter referred to as toner) used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, etc., and a method for producing the toner. And an image forming method using the toner. For more details,
The present invention relates to a toner used in an image recording apparatus that can be used in a printer, a facsimile, a plotter, etc., a method for producing the toner, and an image forming method using the toner. In particular, toner with high image density, low fog and transfer residue, excellent image quality, excellent environmental stability and durability, and low contamination to the developer holding member, photoreceptor, transfer roller, fixing device, etc. A method for producing the toner,
And an image forming method using the toner.

[0002]

2. Description of the Related Art As electrophotographic technology, US Pat.
A number of methods are known, such as those described in Japanese Patent Publication No. 97,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on a photoconductor by various means, and then the electrostatic latent image is developed with a toner,
The toner image is obtained by transferring the toner image onto a transfer material such as paper or film, if necessary, and then fixing the toner image with heat, pressure, heat and pressure, or solvent vapor.

As a method of visualizing the electrostatic latent image, a cascade developing method, a magnetic brush developing method, a pressure developing method and the like are known. Further, there is also used a method in which a magnetic toner is used and a rotating sleeve having a magnetic pole at the center is used to fly between the photosensitive member and the sleeve by an electric field.

Unlike the two-component method, the one-component developing method does not require carrier particles such as glass beads and iron powder, so that the developing apparatus itself can be made compact and lightweight. Further, in the two-component developing method, it is necessary to keep the concentration of toner in the carrier constant, so that a device for detecting the toner concentration and supplying a required amount of toner is required. Therefore, also in this case, the developing device becomes large and heavy. Since such a device is not required in the one-component developing system, it is generally possible to make it relatively small and light.

In addition, LED and LBP printers have become the mainstream of the market in recent years as the printer device, and the direction of technology is higher resolution, that is, 1200, 2400 dpi instead of 300, 600 dpi. Accordingly, the developing system is also required to have higher definition. Further, the copiers are also becoming more sophisticated, and as a result, they are moving toward digitalization. In this direction, the method of forming an electrostatic charge image by a laser is mainly used, and therefore, it is also advancing toward high resolution, and here also, similarly to a printer, a high resolution and high definition developing method is required. .

To achieve high resolution and high definition, it is required to reduce the toner particle size. However, if the toner has a small particle size, the variation in the chargeability of the toner particles tends to become large, and in order to achieve the above object, its control becomes important.

For example, in Japanese Patent No. 2632251, the average particle size produced by the polymerization method is 3 to 8 μm.
A toner in which specific carbon black is attached to the surface of the toner particles is proposed. When an image is output using the toner in which the material for controlling the charging property is arranged on the particle surface as described above, the carbon black adhering to the particle surface falls off when the number of passing sheets exceeds about 5000. As a result, the chargeability of the toner fluctuates greatly, resulting in insufficient charge stability. On the other hand, carbon black has conductivity and if present on the surface of the particles, the chargeability of the toner tends to change due to the influence of humidity,
It becomes difficult to obtain environmental stability.

Further, as a proposal for imparting charging stability from the viewpoint of materials, for example, Japanese Patent Laid-Open No. 6-242631 can be cited. However, when the image evaluation is actually performed by the method described in the above publication, the resolution is still at an insufficient level.

Similarly, the means disclosed in JP-A-53-17496 has an insufficient level of fixing property and durability.

Due to the above reasons, there is no toner that satisfies the requirements of high resolution and high definition and charge stability.

Various methods and devices have been developed for the above-mentioned final step of fixing the toner image on a sheet such as paper or film. Currently, the most general method is to use a heat roller or a heat-resistant film. It is a pressure-bonding heating method using a fixed heating heater.

The pressure-contact heating method using a heating roller fixes the toner image by allowing the surface of the heat roller having releasability to the toner and the toner image surface of the fixing sheet to come in contact with each other under pressure while passing through the fixing sheet. Is to do. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so that the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and quick fixing is required. You can

Since the surface of the heating roller and the toner image come into contact with each other in a molten state and under pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred, and this is retransferred to the next sheet to be fixed and fixed. The offset phenomenon that stains the sheet is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat given to the toner from the heating roller to fix the toner is made substantially constant regardless of the fixing speed.

Since the toner on the sheet to be fixed forms several toner layers, especially in a system where the fixing speed is high and the surface temperature of the heating roller is high, the toner layer and the toner layer contacting the heating roller are not covered. If the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer that is in contact with the fixing sheet is large, the uppermost layer of the toner easily causes an offset phenomenon (high temperature offset), and the surface of the heating roller is high. When the temperature is low, the toner in the lowermost layer is not sufficiently melted, so that a phenomenon in which the toner is not fixed on the fixing target sheet (low temperature offset) is likely to occur.

As a method of solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing to anchor the toner to the sheet to be fixed is usually used. With this method, the temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes extremely large, the fixing target sheet winds around the fixing roller, and a wrapping offset occurs, or the separation claw for separating the fixing target sheet from the fixing roller is separated. Tend to appear in fixed images. Furthermore, since the pressure is high, the image quality of the fixed image tends to be deteriorated such that the line image is crushed during the fixing and the toner is scattered.

In high-speed fixing, a toner having a lower melt viscosity than that used in low-speed fixing is generally used, and the surface temperature of the heating roller is lowered to lower the fixing pressure to prevent high-temperature offset and winding offset, The toner image is fixed. However, when such a toner having a low melt viscosity is used for low-speed fixing, an offset phenomenon easily occurs at high temperature.

By reducing the particle size of the toner, the resolution and sharpness of the image are increased, while the fixing property of the halftone portion formed by the toner having the small particle size is deteriorated. This phenomenon is remarkable especially in high-speed fixing. This is because the toner amount in the halftone portion is small, the toner transferred to the concave portion of the sheet to be fixed has a small amount of heat given from the heating roller, and the fixing pressure is also small due to the convex portion of the sheet to be fixed. This is because the pressure is suppressed and it becomes worse. The toner transferred to the convex portion of the fixing sheet in the halftone portion has a small toner layer thickness, and therefore the shearing force applied to each toner particle is larger than that in the solid black portion having a large toner layer thickness, and the offset The phenomenon is likely to occur, and a fixed image of low image quality is likely to occur.

Further, in order to cope with the recent downsizing of the apparatus, the increase of the printing speed, and the networking, the offset resistance region of the toner is widened to the low temperature side to facilitate the simplification of the fixing device and the fixing of the toner. Lowering the temperature to speed up the fixing process is an effective method.

Therefore, in JP-A-4-86828, there is disclosed a toner containing a resin obtained by polymerizing an unsaturated polyester and a vinyl monomer containing 0.01 to 5.0% by weight of a polyfunctional vinyl monomer. It is disclosed. However, with this method, the circularity of the toner is low,
The image quality is not satisfactory such that the transfer amount of toner is large and the uniformity of the halftone image is low.

On the other hand, in JP-A-8-262795, in the molecular weight distribution measured by gel permeation chromatography, a high molecular weight styrene-acrylic resin having a molecular weight peak in the region of a molecular weight of 500,000 or more, a molecular weight of 50,000. A toner comprising a styrene-acrylic resin having a molecular weight peak in the range of up to 500,000, a styrene-acrylic resin having a crosslinked structure, and a polyester resin binder resin having a molecular weight peak in the region of 50,000 or less is proposed. However, the response to high-speed fixing is still insufficient.

As described above, in the fixing process,
Although there is a demand for a toner having a wide fixing temperature range and excellent in anti-offset property, there is no one satisfying those points at present.

On the other hand, Japanese Patent Application Laid-Open No. 7-271096 proposes a toner which defines a thermoplastic elastomer and a storage elastic modulus at 200 ° C., but its effect is to improve offset resistance and prevent wrapping around a heat roller. Emphasis is placed on the image quality, which is still insufficient.

[0023]

SUMMARY OF THE INVENTION The object of the present invention is to provide excellent electrophotographic characteristics, high definition images, environmental stability and durability, and to provide a developer holding member, a photoconductor, a fixing device and the like. To provide a toner with less contamination, a method for producing the toner, and an image forming method using the toner.

Another object of the present invention is to have no adverse effect on the photoconductor or the intermediate transfer member and to reduce image deterioration such as fog.
It is an object of the present invention to provide a dry toner having a wide fixing temperature range, which is highly applicable to an electrophotographic process, a method for producing the toner, and an image forming method.

[0025]

Means and Actions for Solving the Problems The inventors of the present invention have studied the effects of the specific polyester resin and the particle size frequency distribution and the circularity frequency distribution of toner particles on the developability and transferability. I found it to be very deeply involved.

That is, the present invention relates to a dry toner comprising at least one binder resin, a colorant, a wax component, and a polyester resin. The polyester resin is composed of aliphatic polycarboxylic acids and aliphatic polyhydric alcohols,
At least one of a polyvalent carboxylic acid unit and / or a polyhydric alcohol unit constituting the resin has a polymerizable double bond, In a toner number-based circle equivalent diameter-circularity scattergram of the toner measured by a flow type particle image measuring device, the dry equivalent toner circle equivalent number average diameter D1 (μm)
Is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the standard deviation of circularity is 0.04.
It relates to a dry toner characterized by being less than 0.

Further, the present invention comprises an aliphatic polyhydric carboxylic acid and an aliphatic polyhydric alcohol, and is polymerized to at least one of the polyhydric carboxylic acid and / or the polyhydric alcohol constituting the resin. Containing a polyester resin having a polymerizable double bond as an essential component, and a mixture containing at least a polymerizable vinyl-based monomer composition, a colorant, a wax and a polymerization initiator is mixed to form a polymerizable monomer composition. The present invention relates to a method for producing a dry toner in which a polymerizable monomer composition is prepared, dispersed in an aqueous medium, granulated, and a polymerizable vinyl monomer is polymerized in the aqueous medium to produce toner particles.

Further, in the present invention, at least a charging step of applying a voltage to the charging member from the outside to charge the electrostatic latent image carrier, and an electrostatic latent image is charged on the charged electrostatic latent image carrier. A latent image forming step of forming, a developing step of developing an electrostatic charge image with toner to form a toner image on the electrostatic latent image carrier,
A first transfer step of transferring the toner image on the electrostatic latent image carrier to an intermediate transfer body, a second transfer step of transferring the toner image on the intermediate transfer body to a transfer material, and a toner on the transfer material The present invention relates to an image forming method having a fixing step of heating and fixing an image, wherein the toner having the above-mentioned configuration is used.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention comprises an aliphatic polyhydric carboxylic acid and an aliphatic polyhydric alcohol, and constitutes a resin.
Alternatively, a polyester resin having a polymerizable double bond in at least one of the polyhydric alcohol must be contained as an essential component.

The polyester resin of the present invention is composed of an aliphatic monomer and has few functional groups for stabilizing the electrons involved in the charging of the toner. On the other hand, it is considered that there are few sites that leak due to the small number of sites in the air where water is adsorbed, but the chargeability is rapid and uniform. Therefore, it becomes possible to obtain a high-definition image as a toner in the electrophotographic process. Further, since many functional groups having relatively high polarity such as ester groups are present in the molecule, the charge and the charge are appropriately transferred between particles, and as a result, the charging property becomes uniform. Is thinking.

Further, a high molecular weight component is produced due to the reaction of the polymerizable double bond in the toner manufacturing process,
Furthermore, a component such as a three-dimensionally cross-linked gel is produced, which contributes to the improvement of the durability of the toner.

Furthermore, since a large number of radical-polymerizable double bonds are contained in the polymer chain, a three-dimensional structure is easily formed. For example, due to the viscosity increasing effect and the formation of a network structure, toners such as pigments and charge control agents can be obtained. The inventors of the present invention believe that it contributes to improving the existing state of the material that is (semi) dissolved / dispersed in the particles without being significantly affected by the manufacturing method and stabilizing the chargeability. Is thinking.

By controlling the amount of the polymerizable double bond contained in the polyester resin, the effect of increasing the hot offset generation temperature at the time of fixing the toner can be obtained. This effect is that, as described above, the polymerizable double bond reacts at a certain ratio during the production of the toner, thereby contributing to the formation of a high molecular weight component or a cross-linking component in the toner and improving the hot offset resistance. The present inventors believe that this is due to Further, the minimum fixing temperature can be controlled to a desired temperature by adjusting the degree of reaction at this time and the glass transition temperature of the polyester resin.

The acid value of the polyester resin (mgKO
H / g) is preferably 0.01 to 20.
When it is less than 0.01, the toner tends to be charged up under low humidity conditions when it is made into a toner, while when it exceeds 20, the charge of the toner tends to leak under high humidity conditions, which is not preferable.

The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample (JIS.
K676), and its measurement method includes, for example, titration using an indicator such as phenolphthalein, and measurement by potentiometric titration. Further, when the value is small, a heavy metal salt such as silver nitrate is reacted with the resin solution to wash excess salt, and then the amount of heavy metal salt contained is quantified by fluorescent X-ray spectrum or atomic absorption spectrum. You may ask.

The content of the polymerizable double bond is preferably 1 to 80 mol% per molecule of the polyester resin. If it is less than 1 mol%, it will be extremely difficult to obtain the effect of the present invention even if the amount of the polyester resin added is increased, and if it exceeds 80 mol%, it will be extremely difficult to control the THF insoluble matter generated during the toner production. Is not preferable.

If the content of the polyester resin contained in the toner of the present invention is less than 0.1% by mass, the above-mentioned effects cannot be obtained, and if it exceeds 30% by mass, the toner represented by development cannot be used. It becomes extremely difficult to balance the electrophotographic characteristics and the fixability. Therefore, the polyester resin used in the present invention is 0.1 to 30% by mass in the toner.
It is preferably contained. More preferably 0.1 to
15 mass% is contained.

The amount of the polymerizable double bond in the polyester resin and the content of the polyester resin are ¹ H-NMR, ¹³ C-NM directly after extracting the toner with a solvent or the like.
It may be quantified by performing various chemical analyzes such as R, or by analyzing through a purification step by GPC or liquid chromatography.

The molecular weight of the THF-soluble component of the dry toner of the present invention is not particularly limited, but in the molecular weight distribution by gel permeation chromatography (GPC) described later, the polystyrene reduced molecular weight is from 2 × 10 ³ to 1 × 10 ^5.
Those having a peak molecular weight in the range of are preferable, and more preferably in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ . If the peak molecular weight is lower than 2 × 10 ³ , charging characteristics may be adversely affected, and if it is higher than 1 × 10 ⁵ , the melt viscosity may be too high, which may cause a problem in fixability. Further, in producing the polyester resin used in the present invention, a suitable molecular weight regulator, molecular weight distribution regulator, branching agent for improving viscoelasticity, catalyst for accelerating reaction, etc. are used as necessary. be able to.

In the present invention, other resins may be used in combination with the polyester resin as a binder resin. The toner has a molecular weight of 1 × 10 ³ to 1 × 1 in combination with a high molecular weight resin or a crosslinked resin having a GPC molecular weight of more than 1 × 10 ^5.
It is generally practiced to use a low molecular weight resin of about 0 ⁴ as a binder resin to design the viscoelasticity of the toner to prevent low-temperature and high-temperature offset. Content of polyester resin is 30
When the content exceeds the mass%, it becomes difficult to produce a toner having such a design, which causes a problem. Therefore, it is preferable that the content of the polyester resin does not exceed 30% by mass in the toner. When the content of the polyester resin in the binder resin is less than 0.1% by mass, the high resolution and high definition image and the charging stability which are the effects of the present invention cannot be achieved.

The monomer constituting the polyester resin of the present invention is composed of aliphatic polyhydric carboxylic acids and aliphatic polyhydric alcohols, and the polyvalent carboxylic acid constituting the resin and / or Alternatively, it is an essential component that at least one of the polyhydric alcohols has a polymerizable double bond, but if it is satisfied, the polyester resin is not particularly limited.

Examples of the monomer of polyvalent carboxylic acid skeleton having a polymerizable double bond constituting the polyester resin include fumaric acid, maleic acid, itaconic acid, citraconic acid, cyclohexenedicarboxylic acid, dodecenylsuccinic acid, Examples thereof include dicarboxylic acids such as hexenedicarboxylic acid and dodecenedicarboxylic acid, ester compounds such as methyl ester and ethyl ester of the above dicarboxylic acid, and further anhydrides of dicarboxylic acid.

Further, examples of the monomer having a polyhydric alkanol skeleton having a polymerizable double bond constituting the polyester resin include butenediol, octenediol,
Examples thereof include cyclohexene dimethanol.

A partially modified polyester resin of the present invention is also preferably used. The polyester resin is modified with styrene, o (m
-, P-)-methylstyrene, styrene monomers such as m (p-)-ethylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-
n-propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic acid Hexyl, cyclohexyl (meth) acrylate, (meth) acrylic acid-
2-ethylhexyl, adamantyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth ) (Meth) acrylic acid ester-based monomers such as diethylaminoethyl acrylate, maleic acid ester-based monomers such as dimethyl maleate and diethyl maleate, vinyl ether-based monomers such as ethyl vinyl ether and cyclohexyl vinyl ether, (meth ) Monomers such as acrylic acid, maleic acid, fumaric acid, maleic anhydride, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used. These may be used alone or in combination of two or more.

Further, an epoxy modified product obtained by oxidizing a polymerizable double bond existing in the polyester resin with oxygen or the like is also suitably used.

Further, modification with a silicone segment is also preferable.

As the silicone segment to be introduced into the resin, among various compounds, those represented by the following formula are structurally stable and easily introduced into the polyester resin,
It is also very preferable because it greatly contributes to the improvement of image quality.

[0048]

[Chemical 2] (In the formula, R ₁ and R ₄ are any organic groups having 1 to 18 carbon atoms, R ₂ and R ₃ are any aralkyl groups having 1 to 18 carbon atoms, and X ₁ and X ₂ are , An oxygen atom or a sulfur atom, and n ₁ is an integer of 1 to 100.)

[0049]

[Chemical 3] (In the formula, R ₅ and R ₈ are any organic groups having 1 to 18 carbon atoms, R ₆ and R ₇ are any aralkyl groups having 1 to 18 carbon atoms, and X ₃ and X ₄ are , An oxygen atom or a sulfur atom, and n ₂ is an integer of 1 to 100.)

[0050]

[Chemical 4] (Wherein R ₉ and R ₁₂ are any of organic groups having 1 to 18 carbon atoms, R ₁₀ and R ₁₁ are any of aralkyl groups having 1 to 18 carbon atoms, and X ₅ is an oxygen atom. , Any of the sulfur atoms, and n ₃ is an integer of 1 to 100.)

[0051]

[Chemical 5] (In the formula, R ₁₃ and R ₁₆ are any of organic groups having 1 to 18 carbon atoms, R ₁₄ and R ₁₅ are any of aralkyl groups having 1 to 18 carbon atoms, and X ₆ is an oxygen atom. , Any of the sulfur atoms, and n ₄ is an integer of 1 to 100.)

[0052]

[Chemical 6] (Wherein R ₁₇ and R ₂₄ are any of organic groups having 1 to 18 carbon atoms, and R ₁₈ , R ₁₉ , R ₂₀ , R ₂₂ and R ₂₃ are aralkyl groups having 1 to 18 carbon atoms. In any case, R ₂₁ represents a polyoxyalkylene group, n ₅ and n ₆ are integers from 1 to 100, and n ₇ is an integer from 0 to 30.)

The polyester resin used in the present invention preferably has a peak molecular weight in the range of 1 × 10 ³ to 1 × 10 ⁵ . When the toner is less than 1 × 10 ³ , the charging property is adversely affected, and when it exceeds 1 × 10 ⁵ , the fixing temperature becomes extremely high, which is not preferable. For the same reason, the range of 2 × 10 ^{3 to} 5 × 10 ⁴ is more preferable.

Among the monomers constituting the polyester resin, an aliphatic monomer containing no polymerizable double bond, and a polyvalent carboxylic acid component include succinic acid, adipic acid,
Examples thereof include dicarboxylic acids such as sebacic acid and azelaic acid; dicarboxylic acid anhydrides such as phthalic anhydride; and lower alkyl esters of dicarboxylic acids such as dimethyl adipate. The polyester resin of the present invention may contain a small amount of tribasic carboxylic acid or its anhydride, or a lower alkyl ester thereof, to the extent that a gelled product is not formed.

These polyvalent carboxylic acids and their derivatives are
They may be used alone or in a mixed state.

Examples of the aliphatic polyhydric alcohol containing no polymerizable double bond include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol and dipropylene. Examples of diol compounds such as glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol and hydrogenated bisphenol A. You can These polyhydric alcohols may be used alone or in a mixed state.

The method for producing the polyester resin of the present invention is not particularly limited, and various conventionally known methods can be adopted.
Usually, the monomers are charged in a reaction kettle and heated to raise the temperature to carry out an esterification reaction or a transesterification reaction. The following manufacturing method can be given as an example. A polymerization tube is charged with a monomer other than a polyfunctional compound, and the mixture is heated in an inert atmosphere at 150-
At 220 ° C., an esterification reaction or a transesterification reaction is carried out to remove water or alcohol produced in the reaction. After that, decompress to 0.1 to 100 mmHg,
A prepolymer is obtained. This prepolymer was mixed with a polyfunctional compound according to a conventional method at 180 to 280 ° C.
The pressure is reduced to 01 to 100 mmHg to carry out polycondensation, and the polycondensation is taken out when a predetermined viscosity is reached. The total molar ratio of the total reaction of all acid components and all alcohol components is preferably 1: 0.7 to 1: 1.5 of total acid components: total alcohol components.

As a catalyst for promoting the reaction, sulfuric acid, dibutyltin oxide, zinc oxide, dibutyltin dilaurate, titanium butoxide, magnesium acetate, manganese acetate, tin acetate, zinc acetate, tin disulfide, antimony trioxide. , Germanium dioxide, etc., an esterification catalyst or transesterification catalyst used in a usual esterification reaction or transesterification reaction can be used. Also,
The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily set as needed.

The structure of the silicone segment used for modifying the polyester resin with silicone is as described above, but the functional groups necessary for introduction are hydroxyl group, phenol group, carboxyl group, and lower alkyl of carboxyl group. Ester, epoxy group and the like are preferable. Further, the substituent bonded to the silicon atom may be a substituent having a large carbon number if the glass transition temperature of the main chain is high, depending on the type of monomer used in the polyester part. If the temperature is low, a substituent having a small carbon number or a substituent having a cyclic structure is preferable. Further, the number of repeating units is preferably large when the glass transition temperature of the main chain portion is high, and small when the glass transition temperature of the main chain portion is low.

Further, a binder resin of which a part of the functional groups contains a polyoxyalkylene group and which can be controlled to have an appropriate polarity as a binder resin for toner is also suitably used.

The number of functional groups capable of bonding the silicone segment of the resin to the polyester portion is not particularly limited, but the average number of functional groups per molecule of the monomer constituting the resin is 2.4. It is preferable to set it so as not to exceed the value because it is easy to handle.

The number of repeating units of the silicone segment of the resin is preferably 1 or more and 100 or less. If one or more silicone segments are contained, the effect of stabilizing the chargeability of the toner is recognized, and if it exceeds 100, the compatibility with other components constituting the toner is extremely lowered, which is not preferable. Therefore, 1 or more and 100 or less is suitable for the resin of the present invention. Further, among them, 1 or more and 50 or less are more preferable.

The molecular weight of the silicone-modified polyester resin used in the present invention is not particularly limited, but the peak molecular weight measured by gel permeation chromatography (GPC) described later is from 1,000 to 50,000.
It is preferably in the range of 0, more preferably 20.
It is 00 to 100,000. The reason is that if the peak molecular weight is lower than 1000, the charging characteristics may be adversely affected, and if it is higher than 500000, the melt viscosity may be too high and the fixability may be problematic. Further, in producing the silicone-modified polyester resin used in the present invention, an appropriate molecular weight modifier, a material for improving viscoelasticity, a catalyst for accelerating the reaction and the like can be used as necessary.

Further, in the present invention, the above polyester resin and polystyrene, styrene-
(Meth) acrylic copolymer, general polyester, polyurethane, epoxy resin, polyolefin, polyamide, polysulfone, polycyanoaryl ether, block copolymer with polyarylene sulfide, etc., alkyl (meth) acrylate, (meth) acrylic It is also possible to use a graft-modified copolymer obtained by grafting an acid, maleic acid, styrene-based monomer or the like, and in particular, a styrene-acrylic resin can be obtained by polymerizing a monomer for forming them. . Specifically, styrene, o (m-, p-)-methylstyrene, m (p-)-
Styrene-based monomers such as ethylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, -t-butyl (meth) acrylate,
Pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, adamantyl acrylate (meth), dodecyl (meth) acrylate, (meth) acrylic acid Stearyl, behenyl (meth) acrylate,
(Meth) acrylic acid ester monomers such as isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; maleic acid ester-based monomers such as dimethyl maleate and diethyl maleate. Monomers, vinyl ether-based monomers such as ethyl vinyl ether and cyclohexyl vinyl ether, monomers such as (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride, butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide. It is preferably used. These may be used alone or in combination of two or more.

These may be used alone or generally in the publication Polymer Handbook Second Edition III-p 139-192.
(The John Wiley & Sons company make) The theoretical glass transition temperature (Tg) is 40-75 degreeC, and it mixes and uses a monomer suitably so that it may show. When the theoretical glass transition temperature is lower than 40 ° C, problems tend to occur from the viewpoint of storage stability and durability stability of the toner, while when it exceeds 75 ° C, the fixing point of the toner is increased. Particularly in the case of color toner for forming a full-color image, the color reproducibility at the time of fixing each color toner is lowered and the color reproducibility is poor,
Furthermore, the transparency of the OHP image is lowered, which is not preferable.

(Measurement of Molecular Weight Distribution by Gel Permeation Chromatography (GPC)) In the present invention, the molecular weight of the resin in the toner was determined as a polystyrene-equivalent molecular weight from the molecular weight distribution in gel permeation chromatography (GPC). The GPC measurement method is as follows.

First, as a sample preparation, the toner was dissolved in tetrahydrofuran (THF) at room temperature so that the resin component in the sample was 0.4 to 0.6 mg / ml, and the resulting solution had a pore size of Filter with a 0.2 μm solvent resistant membrane filter.

Next, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (T) was used as a solvent.
HF) is flowed at a flow rate of 1 ml / min, and about 100 μl of a THF sample solution is injected to measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, TSK standard polystyrene F-850, F-450, F-28 manufactured by Tosoh Corporation
8, F-128, F-80, F-40, F-20, F-
10, F-4, F-2, F-1, A-5000, A-2
The calibration curve was created using 500, A-1000, and A-500. The detectors are RI (refractive index) detector and UV.
The (ultraviolet) detector was used by being arranged in series. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, and in the present invention, sh manufactured by Showa Denko KK is used.
odex GPC KF-801, 802, 803, 8
The measurement was performed using a combination of 04, 805, 806, 807 and 800P.

The apparatus is a high speed GPC HPLC8120.
GPC (manufactured by Tosoh Corporation) was used.

In the present invention, the content of the THF-soluble component of the polyester resin having a GPC molecular weight of 100 to 1000 is preferably 10.0% by mass or less based on the toner. Compounds that adversely affect various performances and characteristics of the toner are also applicable to the monomers of the polyester resin, but the content thereof is proportional to the content of the compound having the GPC molecular weight of 100 to 1000,
Moreover, various studies by the present inventors have revealed that if the content of the compound having a GPC molecular weight of 100 to 1000 is set to 10.0% by mass or less based on the toner, the above-mentioned various problems do not occur. Further, in order to further improve the performance and characteristics of the toner, the GPC molecular weight of 100 to 1000 is required.
It is more preferable that the content of the compound is 5.0 mass% or less. Needless to say, it is desirable to use a polyester resin having such a small dispersion ratio that a compound having a GPC molecular weight of 100 to 1000 of the polyester resin is not detected at all even when various toner analyzes are performed.

In the present invention, G of polyester resin is used.
Qualitative and quantitative analyzes of compounds with PC molecular weights of 100 to 1000 can be carried out in various ways. For example,
Nuclear magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-
NMR), infrared absorption spectrum (IR), Raman spectrum, ultraviolet absorption spectrum (UV), mass spectrum (MS) and other spectral analysis, elemental analysis, GPC, gas chromatography (GC), liquid chromatography (HPLC), It may be analyzed by various methods such as other chemical analysis. If the toner itself is difficult to analyze, the toner may be Soxhlet extracted with a solvent such as tetrahydrofuran or toluene that dissolves the binder resin, the filtrate may be concentrated with an evaporator, and then the above analysis may be performed. Furthermore, a sample obtained by fractionating a component having a GPC molecular weight of 1000 or less by liquid chromatography or GPC, or a single sample,
Alternatively, various analysis means can be adopted, such as performing the above analysis on a sample extracted with a mixed solvent.
Further, these analysis means can be used alone or in combination as required.

In the present invention, it is desirable that the mass of the THF insoluble matter described later be 5 to 70 mass% of the total mass of the dry toner. If the THF insoluble content is less than 5% by mass, it tends to be difficult to maintain the charge stability of the toner for a long period of time, and if it exceeds 70% by mass, offset is likely to occur during fixing.

In the present invention, the THF-insoluble matter can be controlled relatively easily by the polyester type monomer. In addition to the above, the same effect can be obtained by modifying with a monomer having a polymerizable double bond.

As such a monomer, o (m-, p
-)-Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, o (m-, p-)-divinylcyclohexane, trimethylolethane tri (meth) acrylate, Examples include trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. Even if these monomers are used alone, 2
There is no problem in using a combination of two or more species.

(Measurement of THF Insoluble Content) In the present invention, the THF insoluble content of the binder resin means the mass ratio of the resin component insoluble in THF (tetrahydrofuran) of the resin composition in the toner particles, It can be used as a standard for indicating the degree of crosslinking of the resin composition containing the crosslinking component, but the THF insoluble content is 0.
Even if it is% by mass, it does not necessarily mean that it is not crosslinked. The THF-insoluble matter is defined as a value measured as follows.

That is, in the case where the developer is a non-magnetic toner, the content of the pigment and the like, and in the case of the magnetic toner, the content of the pigment and the magnetic material are measured in advance by a known method.
Next, a fixed amount of 0.5 to 1.0 g of the developer is weighed (W ₁
g), put in a cylindrical filter paper (No. 86R made by Toyo Roshi Kaisha, Ltd.), apply to a Soxhlet extractor, and use THF 100-2 as a solvent
It is extracted with 00 ml for 20 hours, and the soluble component extracted with the solvent is evaporated, followed by vacuum drying at 100 ° C. for several hours, and the amount of the THF-soluble resin component is measured (W
₂ g). Of the pigments and magnetic substances contained in the developer in a fixed amount, the mass of the component soluble in THF is W ₃ g,
When the mass of the component insoluble in THF is W ₄ g, the THF insoluble content in the resin composition is calculated according to the following formula.

[0077]

[Equation 1]

The shape of the toner of the present invention is required to have the following shape in order to improve transferability and developability in a well-balanced manner. That is, the average number of circle-equivalent numbers in the particle size frequency distribution based on the number of toner particles is 2 to 10 μm, and the average circularity in the circularity frequency distribution is 0.950 to 0.9.
95, preferably 0.970 to 0.995, more preferably 0.975 to 0.995, and the toner particle shape should be such that the standard deviation of circularity is less than 0.040, preferably less than 0.035. By controlling with precision, transferability and developability can be improved in a well-balanced manner.

By reducing the circle-equivalent number average diameter in the toner number-based particle diameter frequency distribution to 2 to 10 μm, the reproducibility of the outline portion of an image, particularly a character image or a line pattern, is improved. Will be things. However, generally, when the toner particles are made smaller, the abundance ratio of the toner having a fine particle size is inevitably increased, which makes it difficult to uniformly charge the toner and causes image fog, and also electrostatic latent image bearing. Adhesion to the body surface is increased, resulting in an increase in transfer residual toner.

However, by controlling the circularity standard deviation of the circularity frequency distribution as described above, the toner of the present invention is expected to have good stability and environmental durability of developability and transferability. Become.

The reason for this is that the present inventors, when forming a thin layer of toner on the toner carrier in the developing step,
Even if the regulation force of the toner layer thickness regulating member is stronger than usual, a sufficient toner coat amount can be maintained, so that the charge amount of the toner on the toner carrying body is set to be larger than usual without damaging the toner carrying body. I think it is possible to raise the price.

The average circularity in the circularity frequency distribution is 0.950 to 0.995, preferably 0.970 to.
By setting the ratio to 0.995, the transferability of the toner having a small particle size, which has been difficult in the past, is significantly improved, and the developing ability for a low-potential latent image is significantly improved. This is particularly effective when developing a digital type minute spot latent image.

When the average circularity is less than 0.950, not only the transfer property is deteriorated but also the developability is sometimes deteriorated.
Further, if the average circularity exceeds 0.995, the toner surface is significantly deteriorated, which causes a problem in durability and the like.

The equivalent circle diameter, the circularity and their frequency distribution of the toner in the present invention are used as a simple method for quantitatively expressing the shape of toner particles. In the present invention, the flow type particle image measurement is performed. The measurement was performed using a device FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.), and calculated using the following formula.

[0085]

[Equation 2]

Here, the "particle projection area" is the area of the binarized toner particle image, and the "perimeter of the particle projection image".
Is defined as the length of the contour line obtained by connecting the edge points of the toner particle image.

The circularity in the present invention is an index showing the degree of unevenness of the toner particles, and it is 1.000 when the toner particles are completely spherical, and the more the surface shape is complicated, the smaller the circularity is. Become.

[0088]

[0089]

[Equation 3]

[0090]

[0091]

[Equation 4]

As a specific measuring method, 10 ml of ion-exchanged water from which impure solids and the like have been removed beforehand is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant into the water. Then, 0.02 g of a measurement sample is further added and uniformly dispersed. As a means for dispersing, an ultrasonic disperser UH-50 type (manufactured by SMT) equipped with a titanium alloy chip of 5φ as a vibrator is used, and dispersion treatment for 5 minutes is performed to obtain a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion does not exceed 40 ° C.

To measure the shape of the toner particles, the flow type particle image measuring device was used, and the toner particle concentration at the time of measurement was 30.
The concentration of the dispersion liquid is readjusted so as to be 0.00 to 10,000 particles / μl, and 1000 or more toner particles are measured. After the measurement, this data is used to determine the equivalent circle diameter of the toner, the circularity frequency distribution, and the like.

In the present invention, an intermediate transfer member can be provided in order to accommodate various transfer materials. In that case, since the transfer step is performed substantially twice, the transfer efficiency is remarkably lowered, and the utilization efficiency of the toner is lowered, which is a problem. In a digital full-color copying machine or printer, a color image original is color-separated using a B (blue) filter, a G (green) filter, and an R (red) filter in advance, and then a 20 to 70 μm dot latent image is formed on the photoconductor. Formed,
It is necessary to reproduce a multicolor image faithful to the original by utilizing the subtractive color mixing action using each color toner of Y (yellow) toner, M (magenta) toner, C (cyan) toner, and B (black) toner. At this time, a large amount of Y toner, M toner, C toner, and B toner is placed on the photosensitive member or the intermediate transfer member in accordance with the color information of the original document and the CRT, so that each toner used in the present invention is used. The color toner requires extremely high transferability, and in order to realize it, the above-mentioned average circularity is 0.950 to 0.995, preferably 0.
970 to 0.995 with a circularity standard deviation of 0.04
Toner particles below 0, preferably below 0.035 are preferred.

In the present invention, for the purpose of improving the releasability at the time of heat roll fixing, waxes such as hydrocarbon compounds, higher fatty acids, higher alcohols and their derivatives which are used as a releasing agent in the toner are used. It is preferable to mix them. Specific examples of such waxes include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, alcohols, fatty acids, acid amides. Esters, ketones, hydrogenated castor oil and its derivatives, plant wax,
Examples thereof include animal wax, mineral wax, petrolactam, and the like, and derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

These releasing agents may be used alone or in combination of two or more kinds.

These wax components were contained in the DSC curve measured by a differential scanning calorimeter at 40-
It has a maximum endothermic peak in the 130 ° C region. By having the maximum endothermic peak in the above temperature range, releasability is effectively exhibited while greatly contributing to low temperature fixing. If the maximum endothermic peak is less than 40 ° C., the self-cohesive force of the wax component will be weakened, and as a result, the high temperature offset resistance will be deteriorated and the gloss will be too high. On the other hand, when the maximum endothermic peak exceeds 130 ° C., the fixing temperature becomes high, and it becomes difficult to properly smooth the surface of the fixed image. Therefore, when used for a color toner, the color mixing property deteriorates. Not preferable. Further, when granulating / polymerizing in an aqueous medium to directly obtain a toner by a polymerization method, if the maximum endothermic peak temperature is high, problems such as precipitation of a wax component mainly during granulation occur, which is not preferable.

The maximum endothermic peak temperature of the wax component is measured according to "ASTM D 3418-8". For the measurement, for example, Perkin Elmer DSC-7 is used. The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and measurement is performed at a temperature rising rate of 10 ° C./min.

In the present invention, the addition amount of these wax components is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the toner.

The colorant used in the present invention may be a conventionally known inorganic or organic dye or pigment,
Examples include yellow colorants, magenta colorants and cyan colorants shown below, and as black colorants, carbon black / aniline black, acetylene black, magnetic materials,
A calcined pigment or a mixture of the following yellow colorant / magenta colorant / cyan colorant and toned black is used.

The carbon black used in the present invention preferably has a particle size of 25 to 80 nm. Regarding the particle size of carbon black, if it is smaller than 25 nm, the primary particle size is so fine that it is difficult to obtain a sufficient dispersion and it is difficult to use the carbon black effectively.

When it is larger than 80 nm, even if the particles are well dispersed, the coloring power of the toner is insufficient, so that an image having a low density can be obtained, or the toner consumption increases.

With respect to the particle size of carbon black, the particle size is more preferably 35 to 70 nm, and the charging polarity and charge amount of the transfer residual toner by the charging member can be controlled more reliably and uniformly, and the toner charging can be performed. It is also more advantageous in terms of quantity stability and toner tinting strength.

Further, the toner of the present invention uses a magnetic material as a black colorant, and can also be used as a magnetic toner. Magnetic materials that can be used in this case include magnetite, hematite, iron oxides such as ferrite, iron, cobalt, metals such as nickel, or aluminum of these metals, cobalt, copper, lead, magnesium, tin, zinc, Antimony, beryllium, bismuth, cadmium,
Included are alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

The magnetic material used in the present invention is more preferably a surface-modified magnetic material, and when used in a polymerization toner, it is made hydrophobic by a surface modifier which is a substance that does not inhibit polymerization. Those that have been treated are preferred. Examples of such surface modifiers include silane coupling agents,
A titanium coupling agent etc. can be illustrated.

These magnetic materials have an average particle size of 2 μm or less,
It is preferably about 0.1 to 0.5 μm. The amount of the magnetic substance contained in the toner particles is 20 to 200 parts by mass, particularly preferably 40 to 100 parts by mass of the resin.
It is 150 parts by mass. In addition, 795.8 kA / m (10
Coercive force (Hc) when applied to
1.6-24 kA / m (20-300 Oersted),
A magnetic substance having a saturation magnetization (σs) of 50 to ²⁰⁰ Am ² / kg and a residual magnetization (σr) of ^{2 to} 20 Am ² / kg is preferable.

Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound and an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180 etc. are mentioned suitably.

As the magenta colorant, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound and a perylene compound are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 26, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5,202,206,220,221,254 are particularly preferred.

As the cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, C.I.
I. Pigment Blue 1, 7, 15, 15: 1, 15:
2, 15: 3, 15: 4, 60, 62, 66 and the like can be particularly preferably used.

These colorants may be used alone or in combination, or in the state of solid solution. The colorant is selected in terms of hue, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner particles. The amount of the colorant added is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

When a magnetic material is used as the black colorant, unlike other colorants, the amount is 40% based on 100 parts by weight of the resin.
It is preferable to use ˜150 parts by mass.

As the charge control agent used in the present invention,
Known compounds can be used, and a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is particularly preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free of a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include salicylic acid as a negative charge control agent, naphthoic acid, a metal compound of an aromatic carboxylic acid such as dicarboxylic acid, a polymeric compound having a sulfonic acid or carboxylic acid group in the side chain, a boron compound, Examples thereof include urea compounds, silicon compounds, calixarene and the like. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, and an imidazole compound. The charge control agent is preferably used in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin.

However, the addition of the charge control agent is not essential in the present invention, and when the two-component developing method is used, the triboelectric charging with the carrier is utilized and the non-magnetic one-component blade coating developing method is used. In the above, the toner particles do not necessarily need to contain the charge control agent by positively utilizing the triboelectric charging with the blade member.

In the present invention, of the above charge control agents, the compounds represented by the following general formula [I] are more preferable.

[0115]

[Chemical 7]

Typical examples of the charge control agent include the following compounds.

[0117]

[Chemical 8]

In the toner of the present invention, the charging stability,
In order to improve developability, fluidity and durability, it is preferable to use inorganic fine powder as an additive by mixing it with toner particles.

As the inorganic fine powder used in the present invention,
Examples thereof include fine silica powder, titanium oxide, and fine alumina powder. Among them, the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more (particularly 50 to 400 m ² / g)
Those in the range of give good results. The inorganic fine powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner.

The specific surface area was determined according to the BET method by using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics Co., Ltd.) to adsorb nitrogen gas on the sample surface, and calculating the specific surface area using the BET multipoint method.

The inorganic fine powder used in the present invention may contain a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oil, a silane coupling agent, and a functional group for the purpose of hydrophobizing and controlling the charging property, if necessary. It is also preferable that the silane coupling agent is treated with a treating agent such as another silane coupling agent.

As other additives, lubricants such as fluororesin, zinc stearate and polyvinylidene fluoride (polyvinylidene fluoride is preferred among them); abrasives such as cerium oxide, silicon carbide and strontium titanate (among others, strontium titanate) Preferred); anti-caking agent; carbon black, zinc oxide, antimony oxide,
Examples thereof include conductivity-imparting agents such as tin oxide; and developability improving agents such as white fine particles and black fine particles having a polarity opposite to that of the toner particles.

In the present invention, in the case of the toner produced by stirring and mixing the inorganic fine particles and other additives with the toner particles, various physical properties of the toner particles are measured by measuring the inorganic fine particles and other additives. It can be performed using the toner particles after the additives are removed. The method of removing these inorganic fine particles and other additives is not particularly limited, but it can be performed by washing the toner with water as follows, for example.

First, the toner is added to water to which a surfactant such as sodium dodecylbenzenesulfonate has been added, and the mixture is sufficiently stirred and mixed. By this operation, the inorganic fine particles having a relatively large particle diameter and other additives are released from the toner, and the toner particles and the inorganic fine particles and other additives are separately dispersed in water. The toner particles are then isolated from this mixed dispersion.
As an isolation method, for example, a filtering operation is performed using a filter paper having an appropriate opening, whereby the toner paper can be separated on the filter paper and the filtrate can be separated as an aqueous solution containing inorganic fine particles and other additives. Further, as another isolation method, a method of isolating the toner particles by wet classification of the mixed dispersion liquid can be employed.

Various methods can be used to produce the toner of the present invention. For example, when the toner is produced by a pulverization method, a binder resin containing the polyester resin, a wax component, a colorant and / or a magnetic material is used. , A charge control agent or other additives are thoroughly mixed with a mixer such as a Henschel mixer or a ball mill, melt-kneaded with a heat kneader such as a pressure kneader or an extruder, and the solid is mechanically solidified after cooling and solidification. Alternatively, the particles are made to collide with a target under a jet stream and finely pulverized to a desired toner particle size. Then, if necessary, the toner particles are smoothed and spheronized. Next, a particle size distribution is sharpened through a classification process. Furthermore, the toner of the present invention can be obtained by thoroughly mixing the classified powder with a fluidizing agent such as fine particle silica using a mixer such as a Henschel mixer. Further, as another method for producing a toner, there is also a method in which the finely divided polyester resin is added to the classified powder together with the fluidizing agent or separately and sufficiently mixed to fix the polyester resin to the toner surface. In this case, the binder resin in the classified powder may contain the polyester resin,
It need not be included at all. Further, after fixing, the toner particles may be smoothed and spheronized. Further, when the toner of the present invention is produced by a polymerization method, the polyester resin is dissolved in a monomer composition, and the mixture is prepared in Japanese Patent Publication No. 36-10231 and Japanese Patent Publication No. 59-61842.
A method for directly producing a toner using a suspension polymerization method as described in Japanese Patent Laid-Open Publication No. 2003-242242, and a dispersion polymerization method for directly producing a toner using an aqueous organic solvent in which a monomer is soluble and the obtained polymer is insoluble. Alternatively, the toner of the present invention can be obtained by an emulsion polymerization method represented by a soap-free polymerization method in which a toner is directly polymerized in the presence of a water-soluble polymerization initiator.
Further, polymer particles not containing the polyester resin are produced by a polymerization method, and then the polyester resin in the form of fine particles is attached to the surface of the polymer particles, and if necessary, the particles are smoothed and spheroidized. It is also possible to employ a method of performing the above, or a method of seed-polymerizing a monomer (composition) containing the polyester resin. Other methods include, for example, a method described in Japanese Patent Publication No. 56-13945, in which a disk or a multi-fluid nozzle is used to atomize a molten mixture containing the polyester resin into the air to obtain a spherical toner. .

Among the above-mentioned toner production methods, the melt spray method tends to widen the particle size distribution of the obtained toner. On the other hand, in the dispersion polymerization method, the obtained toner shows an extremely sharp particle size distribution, but the manufacturing equipment is complicated from the viewpoint of waste solvent treatment and solvent flammability due to narrow selection of materials to be used and utilization of organic solvent. It is easy to get complicated. Also,
The emulsion polymerization method has the advantage that the particle size distribution of the toner is relatively uniform, but generally the particle size of the particles produced is very small, and it is difficult to use it as a toner as it is.
Further, the ends of the water-soluble polymerization initiator used and the emulsifier may be present on the surface of the toner particles, which may deteriorate the environmental characteristics. On the other hand, the production method by smoothing and spheroidizing the toner particles and the production method by the polymerization method are easy to control the circularity and standard deviation of the circularity of the toner within a desired range, and are preferable production methods. I can say. Further, the method for producing the toner of the present invention by the polymerization method is particularly easy to control the shape of the toner particles, and can be used if the polyester resin is dissolved in the monomer composition.
There are many types of resins that can be used, and this is a particularly preferable manufacturing method.

The polyester resin contained in the toner of the present invention may be contained in the toner in any shape or state, and may be contained in a state compatible with other binder resins.
It may be in a phase-separated state. For example, when the polyester resin and another binder resin are melt-kneaded by the pulverization method described above, the polyester resin does not necessarily have to be melted in this melt-kneading step, and other melted binder resins may be used. It may be in a dispersed state. In such a case, the polyester resin in the toner is in a state of being dispersed in another binder resin used together. If the polyester resin and another binder resin are uniformly dissolved and mixed in advance using a solvent such as xylene, there is no problem because the polyester resin is finely dispersed in the other resin or is compatibilized in some cases. However, when the polyester resin powder and another binder resin are kneaded without performing such a homogenizing operation, and when the kneading is performed below the melting temperature of the polyester resin, the polyester resin powder Will be dispersed in the toner, so for example 1 μm or less, preferably 0.5 μm
It is preferable to use a polyester resin finely pulverized to m or less.

When the polymerization method is used as the method for producing the toner of the present invention, the particle size distribution control and the particle size control of the toner particles are controlled by the kind of the poorly water-soluble inorganic salt or the dispersant which acts as a protective colloid. Predetermined toner particles by controlling the method of changing the addition amount and mechanical device conditions (for example, the peripheral speed of the rotor, the number of passes, the stirring conditions such as the shape of the stirring blade and the shape of the container) or the solid content concentration in the aqueous solution. Can be obtained.

As the polymerizable monomer used for producing the toner, styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene, methyl (meth) acrylate, ( Ethyl (meth) acrylate, -n-propyl (meth) acrylate, isopropyl (meth) acrylate, -n-butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate,
Pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, adamantyl acrylate (meth), dodecyl (meth) acrylate, (meth) acrylic acid Stearyl, behenyl (meth) acrylate,
(Meth) acrylic acid ester monomers such as isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; maleic acid ester-based monomers such as dimethyl maleate and diethyl maleate. Polymers, vinyl ether monomers such as ethyl vinyl ether and cyclohexyl vinyl ether, and monomers such as (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used. These may be used alone or in combination of two or more.

In the present invention, other resins used in combination with the above-mentioned copolymer include styrene- (meth) acrylic resin, polyester resin, epoxy resin, polyurethane, polyolefin, polyamide, polysulfone, which are generally used. Various resins such as block copolymers with polycyanoaryl ether, polyarylene sulfide, etc., and graft modified copolymers grafted with alkyl (meth) acrylate, (meth) acrylic acid, maleic acid, styrene-based monomers, etc. , Especially styrene-
Acrylic resins can be obtained by polymerizing monomers for forming them. Specifically, styrene, o (m-, p-)-methylstyrene, m (p-)
-Styrenic monomers such as ethylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
-N-propyl acrylate, isopropyl (meth) acrylate, -n-butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, adamantyl acrylate (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, (Meth) acrylic acid ester monomers such as isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; maleic acid ester-based monomers such as dimethyl maleate and diethyl maleate. Polymer, ethyl vinyl ether,
Vinyl ether monomers such as cyclohexyl vinyl ether, (meth) acrylic acid, maleic acid, fumaric acid,
Monomers such as maleic anhydride, butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used. These may be used alone or in combination of two or more.

Further, as a polymerization initiator used for producing a toner, for example, 2,2'-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvalero Azo- or diazo-type polymerization initiators such as nitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, etc. The peroxide-based polymerization initiator is used. The amount of the polymerization initiator used varies depending on the desired degree of polymerization, but is generally 0.5 to 20% by mass based on the polymerizable monomer.
The type of the polymerization initiator varies slightly depending on the polymerization method, but it may be used alone or in combination with reference to the 10-hour half-life temperature.

To control the degree of polymerization, known crosslinking agents, chain transfer agents, polymerization inhibitors and the like may be further added and used.

When the suspension polymerization method using a dispersion stabilizer is used as the toner production method, the dispersion stabilizer to be used is
As inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite , Silica, alumina and the like. As an organic compound,
Polyvinyl alcohol, gelatin, methyl cellulose,
Methyl hydroxypropyl cellulose, ethyl cellulose, hydroxyethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like can be mentioned. It can be used by dispersing it in these aqueous phases. These dispersion stabilizers include 100 polymerizable monomers.
It is preferable to use 0.2 to 20 parts by mass with respect to parts by mass.

When an inorganic compound is used as the dispersion stabilizer, a commercially available product may be used as it is, but fine particles of the inorganic compound may be produced in a dispersion medium in order to obtain fine particles. For example, in the case of tricalcium phosphate, it is advisable to mix the sodium phosphate aqueous solution and the calcium chloride aqueous solution under high speed stirring.

For fine dispersion of these dispersion stabilizers,
You may use together 0.001-0.1 mass part surfactant. This is for promoting the intended action of the above dispersion stabilizer, and for example, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and lauric acid. Anionic surfactants such as sodium, potassium stearate and potassium oleate; nonionic surfactants such as ethylene oxide and / or propylene oxide adducts of alkylphenols; cationic surfactants of alkylonium salt type; betaine type and Examples thereof include amino acid type amphoteric surfactants.

When the direct polymerization method is used as the method for producing the toner of the present invention, the following production method is suitable.

A releasing agent, a colorant, a charge control agent, a polymerization initiator, and other additives made of a low softening point substance are added to the polymerizable monomer and uniformly dissolved by a homogenizer, an ultrasonic disperser or the like. Alternatively, the dispersed monomer composition is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, a homomixer, a homogenizer or the like. Preferably, the stirring speed and stirring time are adjusted so that the droplets of the monomer composition have a desired toner particle size, and granulation is performed. After that, stirring may be performed to the extent that the particle state is maintained and the particles are prevented from settling due to the action of the dispersion stabilizer. The polymerization temperature may be set to 40 ° C. or higher, generally 50 to 90 ° C. to carry out the polymerization. The temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc., a part of the aqueous medium is distilled off from the reaction system in the latter half of the reaction or after completion of the reaction. May be. After the reaction is completed, the produced toner particles are collected by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer composition.

If the reaction time is less than 2 hours, the desired conversion of the polymerizable monomer is not obtained, and the amount of unreacted polymerizable monomer is large, and the removal process becomes complicated, and if it exceeds 24 hours. 2 to 24 because the reaction time is too long and the productivity becomes low.
Time is preferred.

The particle size distribution can be measured by various methods, but in the present invention, the particle size distribution can also be measured using a Coulter counter multisizer.

That is, a Coulter counter Multisizer II type (manufactured by Coulter) was used as a measuring device, an interface (manufactured by Nikkaki) for outputting number distribution and volume distribution, and a personal computer were connected, and the electrolyte was of a special grade or 1 using primary sodium chloride
% NaCl aqueous solution is prepared. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, as a dispersant is added to 100 to 150 ml of the electrolytic aqueous solution in an amount of 0.1
Add ~ 5 ml, and then add 2 to 20 mg of the measurement sample.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and a 100 μm aperture is used as an aperture when measuring the toner particle size with the Multisizer II type Coulter Counter. taking measurement. The volume and number of toner were measured, and the volume distribution and number distribution were calculated. Then, the weight-based weight average diameter according to the present invention is determined from the volume distribution.

Next, an image forming method to which the toner of the present invention is applied will be described below with reference to the accompanying drawings.

A schematic view of an example of an image forming apparatus using an intermediate transfer belt is shown in FIG.

FIG. 5 shows a color image forming apparatus (copier or laser beam printer) using an electrophotographic process.

Reference numeral 101 denotes a drum-shaped electrophotographic photosensitive member (hereinafter referred to as photosensitive drum) as a first image bearing member,
It is rotationally driven in the direction of the arrow at a predetermined peripheral speed (process speed).

In the course of rotation, the photosensitive drum 101 is uniformly charged to a predetermined polarity and potential by the primary charger 102, and then exposed 103 by the image exposure means 103 (not shown).
Receive. In this way, an electrostatic latent image corresponding to the first color component image (for example, yellow color component image) of the target color image is formed.

Then, the electrostatic latent image is developed into a yellow component image of the first color by the first developing device (yellow color developing device 141). At this time, the second to fourth developing devices, that is, the magenta developing device 142, the cyan developing device 143, and the black developing device 144 are not operating and do not act on the photosensitive drum 101. The color yellow component image is not affected by the second to fourth developing devices.

At the time of development, the moving speed of the surface of the toner carrying member in the developing area is relative to the moving speed of the surface of the electrostatic latent image carrying member.
The speed is preferably 1.05 to 3.0 times. By setting the moving speed to be 1.05 to 3.0 times, the toner layer on the toner carrying member is subjected to an appropriate stirring effect, so that the faithful reproduction of the electrostatic latent image is further improved. Will be things.

Further, in the present invention, the surface roughness Ra (μm) of the toner carrier is preferably 1.5 or less.
By setting the surface roughness Ra to 1.5 or less, the toner carrying ability of the toner carrier is suppressed, the toner layer on the toner carrier is thinned, and the number of times of contact between the toner carrier and toner is large. Therefore, the chargeability of the toner is also improved and the image quality is synergistically improved.

The toner layer thickness on the toner carrier is regulated by the regulation member.

The toner layer-thinning regulating member is a doctor blade such as a metal blade or a magnetic blade which is arranged at a constant distance from the toner carrier. Alternatively, instead of the doctor blade, a rigid roller or sleeve made of metal, resin, ceramic or the like may be used, and a magnetism generating means may be provided inside them.

Further, an elastic body such as an elastic blade or an elastic roller for applying the toner under pressure may be used as a toner thin layer regulating member. For example, the base of the upper side of the elastic blade is fixed to the developer container, the variable side is flexed in the forward or reverse direction of the toner carrier against the elasticity of the blade, and the inner surface of the blade (reverse side) is reversed. In the case of the direction, the outer surface side) is brought into contact with the surface of the toner carrier with an appropriate elastic pressure. According to such a device, a dense toner layer is obtained which is stable against environmental changes. The reason is not necessarily clear, but it is presumed that the elastic member is forcibly rubbed against the surface of the toner carrying member, so that the charging is always performed in the same state regardless of the change in behavior due to the environmental change of the toner. .

For the elastic body, it is preferable to select a triboelectrification series material suitable for charging the toner to a desired polarity. A rubber elastic body such as silicone rubber, urethane rubber or NBR; a synthetic material such as polyethylene terephthalate. Resin elastic body: Metal elastic body such as stainless steel, steel and phosphor bronze can be used. Further, it may be a complex thereof.

Further, when durability is required for the elastic body and the toner carrier, it is preferable that the elastic metal and the resin are adhered to each other so that the sleeve abutting portion is abutted with the resin or rubber, or coated. Furthermore, an organic substance or an inorganic substance may be added to the elastic body, and may be melt-mixed or dispersed. For example, the chargeability of the toner can be controlled by adding metal oxides, metal powders, ceramics, carbon allotropes, whiskers, inorganic fibers, dyes, pigments, surfactants and the like. In particular, when the elastic body is a molded body such as rubber or resin, silica, alumina, titania,
It is also preferable to contain fine powder of metal oxide such as tin oxide, zirconia, and zinc oxide, carbon black, and a charge control agent generally used for toner.

Furthermore, by applying a DC electric field and / or an AC electric field to the developing blade which is the regulating member, the supply roller which is the supplying member, and the brush member,
Due to the effect of loosening the toner, uniform thin layer coating property and uniform charging property are further improved at the regulation site on the toner carrier, and the toner is smoothly supplied / peeled off at the supply site, resulting in a sufficient image quality. Achievement of density and good quality image can be obtained.

The intermediate transfer belt 120 is rotationally driven in the direction of the arrow at the same peripheral speed as the photosensitive drum 101. In the process in which the yellow component image of the first color formed on the photosensitive drum 101 passes through the nip portion between the photosensitive drum 1 and the intermediate transfer belt 120, the bias power source 129 passes the intermediate transfer belt via the primary transfer roller 162. The electric field formed by the primary transfer bias applied to 120 causes transfer (primary transfer) to the outer peripheral surface of the intermediate transfer belt 120.

The surface of the photosensitive drum 101, which has transferred the yellow toner image of the first color corresponding to the intermediate transfer belt 120, is cleaned by the cleaning device 113.

Similarly, the magenta toner image of the second color, the cyan toner image of the third color, and the black toner image of the fourth color are sequentially transferred onto the intermediate transfer belt 120 in an overlapping manner to correspond to the intended color image. The combined color toner image is formed.

Reference numeral 163 denotes a secondary transfer roller, which corresponds to the secondary transfer counter roller 164 and bears in parallel to the lower surface of the intermediate transfer belt 120 so as to be separated therefrom.

The primary transfer bias for transferring the toner image from the photosensitive drum 101 to the intermediate transfer belt 120 is
It is applied from a bias power source 129 with a polarity opposite to that of the toner. The applied voltage is, for example, in the range of + 100V to + 2kV.

From the photosensitive drum 101 to the intermediate transfer belt 12
In the primary transfer process of the first to third color toner images to 0, the secondary transfer roller 163 and the transfer residual toner charging member 152 can be separated from the intermediate transfer belt 120.

For the full-color image transferred on the intermediate transfer belt 120, the secondary transfer roller 163 is brought into contact with the intermediate transfer belt 120, and the paper feed roller 111 is brought into contact with the intermediate transfer belt 120 and the secondary transfer roller 163. The transfer material P, which is the second image carrier, is fed to the portion at a predetermined timing, and the secondary transfer bias is applied from the bias power source 128 to the secondary transfer roller 163 to be secondarily transferred to the transfer material P. It The transfer material P on which the toner image has been transferred is introduced into the fixing device 115 and heated and fixed.

After the image transfer to the transfer material P is completed, the transfer residual toner cleaning device 150 is brought into contact with the intermediate transfer belt 120, and the surface of the intermediate transfer belt 120 is cleaned.

Then, the toner image on the transfer material is fixed by the heating and pressing fixing means. As the heating and pressure fixing means, a heating roller system having a heating roller having a heating element such as a halogen heater and an elastic pressure roller pressed against the heating roller with a pressing force, or a heater through a film is used. A method of fixing by heating (FIGS. 2 and 3) can be mentioned, but the toner of the present invention shows good matching with the above heating and pressure fixing means. Furthermore, the toner of the present invention can preferably heat-fix a toner image on a recording material even in a heat-fixing device that does not supply an offset preventing liquid or does not have a fixing device cleaner.

Although the image forming method using the image forming apparatus having the intermediate transfer belt has been described above, the toner of the present invention is preferably used in the image forming apparatus having no intermediate transfer member. You can Also,
The untransferred residual toner on the electrostatic latent image bearing member after transfer is cleaned and collected, and the collected toner is supplied to the developing unit and held again in the developing unit, and the electrostatic latent image carrier It can also be suitably used in an image forming apparatus having a toner reuse mechanism for developing a latent image.

The reuse mechanism will be described with reference to FIG. After the transfer step, the transfer residual toner remaining on the photosensitive drum 70 is brought into contact with the elastic blade 72 which is in contact with the photosensitive drum.
Scraped off and collected in the cleaner 71. The collected transfer residual toner is conveyed through a cleaner screw 73, a supply pipe 74 provided with a conveying screw, and returned to a developing device 76 via a hopper 75. The returned transfer residual toner is subjected to development again.

[0166]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Production Example 1 of Polyester Resin A polyvalent carboxylic acid component and a polyhydric alcohol component were prepared so as to have the compositions shown in Table 1, and as a catalyst, 0.1% of the total monomer mass was used.
Along with 05% by mass of dibutyltin oxide, it was placed in a glass-made 2 liter separable flask, a thermometer, a stainless stir bar, a downflow condenser and a nitrogen inlet tube were attached, and the esterification reaction was carried out under a nitrogen stream in a mantle heater. It was carried out at 200 ° C.

Further, the reaction temperature was raised to 230 ° C., and 200 Pascal (1.5 mmH.
The polyester resin (1) according to the present invention (1) is depressurized to a high vacuum degree of less than g), the internal temperature is maintained, and the polycondensation reaction is continuously performed.
Got

The characteristic values are shown in Table 2.

Production Examples 2 to 5 of Polyester Resin A polyester resin was prepared in the same manner as in Production Example 1 of polyester resin except that the polyvalent carboxylic acid component and the polyhydric alcohol component used were changed as shown in Table 1. (2) ~
(5) was obtained. The characteristic values are summarized in Table 2.

Production Example 6 of Polyester Resin Polyester resin except that the polycarboxylic acid component and polyhydric alcohol component used were changed as shown in Table 1 and a reactive siloxane derivative was added immediately before the depressurizing step. Polyester resin (6) in the same manner as in Production Example 1 of
Got The characteristic values are summarized in Table 2.

Comparative Production Example 1 of Polyester Resin A polyester resin (polyester resin) was prepared in the same manner as in Production Example 1 of polyester resin except that the polyvalent carboxylic acid component and the polyhydric alcohol component used were changed as shown in Table 1. 7) was obtained. The characteristic values are summarized in Table 2.

[0173]

[Table 1]

[0174]

[Chemical 9]

[0175]

[Table 2]

Binder Resin Production Example 1 200 parts by mass of xylene was placed in a glass separable flask equipped with a thermometer, a stainless stir bar, a falling condenser and a nitrogen introducing tube, and the temperature was raised to the reflux temperature. After adding a mixed solution of 80 parts by mass of styrene, 20 parts by mass of n-butyl acrylate, and 2.3 parts by mass of di-tert-butyl peroxide, solution polymerization was completed in 7 hours under reflux of xylene. A low molecular weight resin solution was obtained.

On the other hand, 65 parts by mass of styrene, 25 parts by mass of butyl acrylate, 10 parts by mass of monobutyl maleate, 0.2 parts by mass of polyvinyl alcohol, 200 parts by mass of degassed water, and 0.5 parts by mass of benzoyl peroxide were mixed and suspended. It was turbidly dispersed. The suspension-dispersed solution was heated and kept at 85 ° C. for 24 hours in a nitrogen atmosphere to complete the polymerization, thus obtaining a high molecular weight resin.

30 parts by mass of the high molecular weight resin was added to a solution containing 70 parts by mass of the low molecular weight resin at the end of the solution polymerization, completely dissolved in the solvent and mixed, and then the solvent was distilled off. Then, the binder resin (I) was obtained.

When the binder resin was analyzed, the low molecular weight side peak molecular weight was 10,000 and the high molecular weight side peak molecular weight was 55.
The weight average molecular weight (Mw) was 300,000 and the number average molecular weight (Mn) was 55,000. The glass transition temperature was 55 ° C.

Production Example 2 of Binder Resin 200 parts by mass of xylene was placed in a glass separable flask equipped with a thermometer, a stainless stir bar, a falling condenser and a nitrogen introducing tube, and the temperature was raised to the reflux temperature. After adding a mixed solution of 80 parts by mass of styrene, 20 parts by mass of n-butyl acrylate, and 2.3 parts by mass of di-tert-butyl peroxide, solution polymerization was completed in 7 hours under reflux of xylene. A low molecular weight resin solution was obtained.

On the other hand, 75 parts by mass of styrene, 25 parts by mass of butyl acrylate, 0.2 parts by mass of polyvinyl alcohol,
200 parts by mass of degassed water and 0.5 parts by mass of benzoyl peroxide were mixed, suspended and dispersed. The suspension-dispersed solution was heated and kept at 85 ° C. for 24 hours in a nitrogen atmosphere to complete the polymerization, thus obtaining a high molecular weight resin.

30 parts by mass of the high molecular weight resin was put into a solution containing 70 parts by mass of the low molecular weight resin at the end of the solution polymerization, and completely dissolved in the solvent to perform mixing, and then the solvent was distilled off. Then, a binder resin (II) was obtained.

When the binder resin was analyzed, the peak molecular weight on the low molecular weight side was 12,000 and the peak molecular weight on the high molecular weight side was 5.
80,000, the weight average molecular weight (Mw) was 300,000, and the number average molecular weight (Mn) was 55,000. The glass transition temperature was 55 ° C.

Toner Production Example 1 100 parts by mass of binder resin (I) 25 parts by mass of polyester resin (1) (peak molecular weight = 4500) 10 parts by mass of carbon black (BET specific surface area = 62 m ² / g) Negative charge control agent (compound [I] -1) 1 part by mass / low molecular weight polyethylene having maximum endothermic peak 115 ° C. 3 parts by mass The above materials were mixed in a blender and melted in a biaxial extruder heated to 160 ° C. The kneaded and cooled kneaded product was roughly pulverized with a hammer mill, and then the coarsely pulverized product was finely pulverized with a jet mill.

Next, a surface modification treatment was carried out by using a device for rotating the rotor to give a mechanical impact amount, and the obtained particles were classified to obtain classified powder (A). The classified powder (A) 1
00 parts by mass and hydrophobic silica fine powder (BET: 250 m ²
/ G) 1.5 parts by mass was dry-mixed with a Henschel mixer to obtain a toner (A) of the present invention.

The average circularity of the toner (A) is 0.965,
The circularity standard deviation was 0.039, the circle-equivalent number average diameter D1 was 5.1 μm, the high molecular weight side peak molecular weight was 560,000, and the low molecular weight side peak molecular weight was 11,000.

Further, a component having a GPC molecular weight of 1000 or less in the toner is separated by GPC, and this is collected by GPC / IR,
^When analyzed by ¹ H-NMR, ¹³ C-NMR, and GC / MS, the content of components having a GPC molecular weight of 1000 or less having a repeating unit of polyester resin in the structure is 8.9 based on the toner. It was mass%.

Toner Production Examples 2 and 3 Toners (B) and (C) were obtained in the same manner as in Toner Production Example 1 except that the type of binder resin, the type of polyester resin and the addition amount were changed. Table 3 shows the types and amounts of materials used together with Toner (A), and Table 5 shows the results of toner analysis.

Comparative Toner Production Example 1 Toner (D) was obtained in the same manner as in Toner Production Example 1 except that the raw materials were the same in kind and addition amount and the surface modification treatment was not performed. Table 3 shows the types and amounts of materials used
Table 5 shows the toner analysis results.

Comparative Toner Production Example 2 Toner (E) was obtained in the same manner as Toner Production Example 1 except that the type of binder resin, the type of polyester resin and the addition amount were changed. Table 3 shows the types and amounts of materials used together with Toner (D), and Table 5 shows the results of toner analysis.

Toner Production Example 4 High Speed Stirrer TK Homomixer (made by Tokushu Kika Kogyo Co., Ltd.)
In a 2 liter four-necked flask equipped with a reactor, 650 parts by mass of ion-exchanged water and 0.1 mol / liter-Na ₃ PO _{4 were} added.
Charge 500 parts by mass of aqueous solution and rotate at 12,000 rp
It was adjusted to m and heated to 70 ° C. 1.0mo here
80 parts by mass of 1 / liter-CaCl ₂ aqueous solution was added,
An aqueous dispersion medium containing a minute sparingly water-soluble dispersion stabilizer (calcium phosphate salt) was prepared.

On the other hand, as the dispersoid: styrene 82 parts by mass, 2-ethylhexyl acrylate 18 parts by mass, carbon black (BET specific surface area = 62 m ² / g) 10 parts by mass, polyester resin (peak molecular weight = 4500) 5 parts by mass 6 parts by mass of wax (ester wax, mp = 72 ° C.) 1 part by mass of negative charge control agent (compound [I] -1) After dispersing the above mixture for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.) , 2′-azobis (2,4-dimethylvaleronitrile), 3 parts by mass was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was charged into the aqueous dispersion medium, and while maintaining the rotation speed of the high-speed stirrer at 12000 rpm in a nitrogen atmosphere at an internal temperature of 70 ° C., 10
After stirring for a minute, the polymerizable monomer composition was granulated. Then, the stirrer was replaced with a propeller stirring blade, and the mixture was stirred at 50 rpm and maintained at the same temperature for 10 hours to complete the polymerization. After completion of the polymerization, the suspension was cooled, and then diluted hydrochloric acid was added to remove the dispersion stabilizer. Further, washing with water was repeated several times and then dried to obtain polymer particles (F).

100 parts by mass of the above polymer particles (F) and hydrophobic
Fine silica powder (BET; 250m ²/ G) 1.5 mass
Part of the toner of the present invention by dry mixing with a Henschel mixer
(F).

The toner (F) has an average circularity of 0.992,
The circularity standard deviation was 0.024, the circle-equivalent number average diameter D1 was 6.1 μm, the peak molecular weight was 29,000, and the THF-insoluble matter was 32%.

Further, a component having a GPC molecular weight of 1000 or less in the toner is separated by GPC, and this is collected by GPC / IR,
^When analyzed by ¹ H-NMR, ¹³ C-NMR, and GC / MS, the content of GPC molecules of 10,000 or less having a repeating unit of polyester resin in the structure was 0.8 based on the toner. It was mass%.

Toner Production Examples 5 to 12 Toners (G) to (N) were obtained in the same manner as Toner Production Example 4 except that the type of binder resin, the type of polyester resin, and the addition amount were changed. Table 4 shows the types and amounts of the materials used together with the toner (F), and Table 5 shows the toner analysis results.

Toner Comparative Production Examples 3 and 4 Toners (O) and (P) were obtained in the same manner as in Toner Production Example 6 except that the type of binder resin, the type of polyester resin and the addition amount were changed. Table 4 shows the types and amounts of materials used, and Table 5 shows the results of toner analysis.

[0199]

[Table 3]

[0200]

[Table 4]

[0201]

[Table 5]

<Examples 1 to 12, Comparative Examples 1 to 4> Hereinafter,
The evaluation of the toner manufactured according to the above-described manufacturing example will be described.

The image forming apparatus used in this embodiment will be described. In this example, a commercially available laser beam printer LBP-PX (manufactured by Canon Inc.) was used after being modified for non-magnetic one-component development.

A preferred specific example of the image forming apparatus will be described with reference to FIG.

In this embodiment, a reversal developing device for developing a negative (negative polarity) latent image on a photosensitive member using a negative (negative polarity) toner will be described as an example.

FIG. 1 is a schematic explanatory view of a cross section of a laser beam printer applied to the present invention. 2 and 3 are schematic views of the heat fixing device in the printer of FIG.

OPC photosensitive drum 10 (diameter 24 mm)
Rotates in the direction of the arrow and is uniformly charged by the charging roll 11 so that the dark portion potential (Vd) becomes −600V. Next, the image unit is exposed by the exposure device 14,
An electrostatic latent image having a bright portion potential (Vl) of −150 V is formed.

A non-contact gap (300 μm) is set between the photosensitive drum 10 and the developer layer on the toner carrier 17 having the toner applying roller 16, and an AC bias (f: 1) is set.
While applying 800 Hz, Vpp = 1400 V) and DC bias (Vdc = -400 V) to the toner carrier 17 by the bias applying means V, the image portion was developed with the negative toner T to form a toner image on the photosensitive drum. The obtained toner image is transferred onto the recording material by the transfer roll 19, and the toner remaining on the surface of the photoconductor is cleaned by the cleaner 13. On the other hand, the photosensitive drum 10
The recording material P separated from is heated and fixed by the heating and fixing device H to fix the toner image on the recording material P. The above steps are repeated to form an image. At this time, the temperature detecting element 21d of the heating body 21 of the heat fixing device H
Has a surface temperature of 190 ° C., the heating body 21 and the pressure roller 23.
The total pressure between them is 58.8 N (6 kg), and the nip between the pressure roller 23 and the film 22 is 3 mm.
A heat-resistant polyimide film having a thickness of 50 μm having a low-resistance release layer in which a conductive material is dispersed in PTFE is used on the contact surface with the recording material.

Under the above conditions, normal temperature and normal humidity (25 ° C, 60%
RH), high temperature and high humidity (30 ° C, 80% RH), and low temperature and low humidity (15 ° C, 10% RH) environment, 6 sheets (A4 size)
A printout test was conducted continuously on 5,000 sheets while replenishing the toner according to the present invention and the comparative toner at a printout speed of / minute, and the obtained images were evaluated for the following items.

The toner carrier used here has a surface roughness Ra of 1.5, and the toner regulating blade is made of stainless steel.

[Evaluation of Printout Image] (1) Image Density The image density was evaluated by maintaining the image density at the end of the printing of 5000 sheets on a normal copying machine plain paper (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to a printout image of a white background portion having a document density of 0.00. A (excellent): 1.40 or more B (good): 1.35 or more and less than 1.40 C (possible): 1.00 or more and less than 1.35 D (impossible): less than 1.00

(2) Dot reproducibility The pattern shown in FIG. 4 was printed out and its dot reproducibility was evaluated. A: Very good (2 defects or less / 100 defects) B: Good (3-5 defects / 100 defects) C: Practical (6-10 defects / 100 defects) D: Not practical (11 defects or more) / 100 pieces)

(3) Image fog The fog density (%) was calculated from the difference between the whiteness of the white part of the printout image and the whiteness of the transfer paper measured by the "reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.), Image fog was evaluated. A: Very good (less than 1.5%) B: Good (1.5% or more and less than 2.5%) C: Practical (2.5% or more and less than 4.0%) D: Not practical (4% that's all)

[Matching Evaluation of Image Forming Apparatus] <1> Matching with Developing Sleeve After completion of the printout test, the state of fixation of residual toner on the surface of the developing sleeve was visually evaluated. A: Not generated B: Almost not generated C: Some sticking D: Many sticking

<2> Matching with Photosensitive Drum After the completion of the printout test, the state of occurrence of scratches on the surface of the photosensitive drum and fixation of residual toner was visually evaluated. A: Not generated B: Slight scratches were observed C: There was sticking or scratches D: Many sticking

<3> Matching with Fixing Device After the completion of the printout test, the scratches on the fixing film surface and the fixing condition of residual toner were visually evaluated. A: Not generated B: Slightly adhered C: Adhered or scratched D: Adhered often

The evaluation results are summarized in Tables 6 and 7.

[0218]

[Table 6]

[0219]

[Table 7]

<Examples 13 to 24, Comparative Examples 5 to 8> FIG. 5 is a schematic view of an example of an image forming apparatus using an intermediate transfer belt.
Shown in.

FIG. 5 shows a color image forming apparatus (copier or laser beam printer) using an electrophotographic process.

Reference numeral 101 denotes a drum-shaped electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) as a first image bearing member, which is rotationally driven in the direction of an arrow at a predetermined peripheral speed (process speed).

The photosensitive drum 101 is uniformly charged to a predetermined polarity and potential by the primary charger 102 in the course of rotation, and then exposed 103 by the image exposure means 103 (not shown).
Receive. In this way, an electrostatic latent image corresponding to the first color component image (for example, yellow color component image) of the target color image is formed.

Next, the electrostatic latent image is developed into a yellow component image of the first color by the first developing device (yellow color developing device 141). At this time, the second to fourth developing devices, that is, the magenta developing device 142, the cyan developing device 143, and the black developing device 144 are not operating, and the photosensitive drum 1
No. 01 does not act, so the yellow component image of the first color is not affected by the second to fourth developing devices.

The intermediate transfer belt 120 is rotationally driven in the direction of the arrow at the same peripheral speed as the photosensitive drum 1.

[0226] The above-mentioned first formed on the photosensitive drum 101.
A color yellow component image is formed by a primary transfer bias applied from the bias power source 129 to the intermediate transfer belt 120 via the primary transfer roller 162 while passing through the nip portion between the photosensitive drum 101 and the intermediate transfer belt 120. By the electric field generated, the image is sequentially transferred (primary transfer) to the outer peripheral surface of the intermediate transfer belt 120.

The surface of the photosensitive drum 101 on which the transfer of the yellow toner image of the first color corresponding to the intermediate transfer belt 120 has been completed is cleaned by the cleaning device 113.

Similarly, the magenta toner image of the second color, the cyan toner image of the third color, and the black toner image of the fourth color are successively superimposed and transferred onto intermediate transfer belt 120 to correspond to the intended color image. The combined color toner image is formed.

Reference numeral 163 denotes a secondary transfer roller, which is arranged in a separable state on the lower surface of the intermediate transfer belt 120 by bearing in parallel with the secondary transfer opposing roller 164.

The primary transfer bias for transferring the toner image from the photosensitive drum 101 to the intermediate transfer belt 120 is
It is applied from a bias power source 129 with a polarity opposite to that of the toner. The applied voltage is, for example, in the range of + 100V to + 2kV.

From the photosensitive drum 101 to the intermediate transfer belt 12
In the primary transfer process of the first to third color toner images to 0, the secondary transfer roller 163 can be separated from the intermediate transfer belt 120.

For the full-color image transferred on the intermediate transfer belt 120, the secondary transfer roller 163 is brought into contact with the intermediate transfer belt 120, and the paper feed roller 111 is brought into contact with the intermediate transfer belt 120 and the secondary transfer roller 163. The transfer material P, which is the second image carrier, is fed to the portion at a predetermined timing, and the secondary transfer bias is applied from the bias power source 128 to the secondary transfer roller 163 to be secondarily transferred to the transfer material P. It The transfer material P on which the toner image has been transferred is introduced into the fixing device 115 and heated and fixed.

After the image transfer onto the transfer material P is completed, the transfer residual toner cleaning device 150 is brought into contact with the intermediate transfer belt 120 to clean the surface of the intermediate transfer belt 120.

Using the above-mentioned image forming apparatus, the moving speed of the surface of the toner carrying member is different from that of the surface of the electrostatic latent image carrying member.
It was set to be 150%.

Next, each of the toners (A) to (P) is filled in the developing device, and the peripheral speed of the toner carrier surface of this developing device is 23.
It is mounted on the driving device of the developing device, which is set to 5 mm / sec and is not provided with the electrostatic latent image carrier, and is rotated at room temperature and normal humidity for 30 minutes without passing the paper. After printing, the image was printed out.

In this embodiment, the apparatus shown in FIG. 5 is used as the image forming apparatus, and the temperature and humidity (25 ° C., 60% R) are used.
H), high temperature and high humidity (30 ° C., 80% RH), and low temperature and low humidity (15 ° C., 10% RH) at a printout speed of 20 sheets / minute (A4 size) toner (A) to (P). Was subjected to a printout test of 5,000 sheets in a continuous mode in a single color (that is, a mode in which toner consumption is promoted without stopping the developing device). Then, the obtained printout image was evaluated for the items described below.

In the fixing device, the heater set temperature of the fixing device 115 was 180 ° C., and the nip between the rollers was 8 mm.

Further, the matching between the image forming apparatus used and the toner was evaluated after the printout test.

The surface roughness Ra of the toner carrier used here is 1.5, and the material of the toner regulating blade is stainless steel.

[Evaluation of Printout Image] (1) Image Density Evaluation was carried out by maintaining the image density at the end of printing out 5000 sheets on a normal copying machine plain paper (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to a printout image of a white background portion having a document density of 0.00. A (excellent): 1.40 or more B (good): 1.35 or more and less than 1.40 C (possible): 1.00 or more and less than 1.35 D (impossible): less than 1.00

(2) Fog density (%) was calculated from the difference between the whiteness of the white background of the printout image and the whiteness of the transfer paper measured with the image fog "Reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.), Image fog was evaluated. A: Very good (less than 1.5%) B: Good (1.5% or more and less than 2.5%) C: Practical (2.5% or more and less than 4.0%) D: Not practical (4% that's all)

(3) Uniformity of halftone image The image quality judgment criteria are as follows. A: Very good. B: A good image although slightly shaky. C: Although it is rough, it is a level with no practical problems. D: Practically impractical due to severe roughness.

[Matching Evaluation of Image Forming Apparatus] <1> Matching with Developing Sleeve After completion of the printout test, the state of sticking of residual toner on the surface of the developing sleeve was visually evaluated. A: Not generated B: Almost not generated C: Some sticking D: Many sticking

<2> Matching with Photosensitive Drum After the printout test was completed, the state of occurrence of scratches on the surface of the photosensitive drum and sticking of residual toner was visually evaluated. A: Not generated B: Slight scratches were observed C: There was sticking or scratches D: Many sticking

<3> Matching with Intermediate Transfer Belt After the completion of the printout test, the scratches on the surface of the intermediate transfer member and the adhered state of the residual toner were visually evaluated. A: Not generated B: Presence of residual toner on the surface C: There is sticking or scratches D: Many sticking

<4> Matching with Fixing Device After the completion of the printout test, the scratches on the surface of the fixing film and the fixing state of residual toner were visually evaluated. A: Not generated B: Slightly adhered C: Adhered or scratched D: Adhered often

The evaluation results are summarized in Tables 8 and 9.

[0248]

[Table 8]

[0249]

[Table 9]

Example 25 In this example, a reuse mechanism was attached to a commercially available laser beam printer LBP-EX (manufactured by Canon Inc.) for modification and resetting, and used. That is, in FIG. 6, after the untransferred toner on the photoconductor drum 70 is scraped off by the elastic blade 72 of the cleaner 71 which is in contact with the photoconductor drum, it is sent to the inside of the cleaner by the cleaner roller and further passed through the cleaner screw 73. , Is returned to the developing device 76 via the hopper 75 by the supply pipe 74 provided with the conveying screw, and the system for utilizing the collected toner is attached again,
A rubber roller (diameter 12 m) in which conductive carbon coated with nylon resin is dispersed as the primary charging roller 77.
m, contact pressure 49 N / m), and the dark potential Vd = -7 by laser exposure (600 dpi) on the electrostatic latent image carrier.
00V and bright part potential Vl = -200V were formed. A developing sleeve 78 having a surface roughness Ra of 1.1 coated with a resin in which carbon black is dispersed as a toner carrier is set to be 1.1 times the moving speed of the photosensitive drum surface. The gap between the photosensitive drum and the developing sleeve (between S and D) was set to 290 μm, and a urethane rubber blade was used as a toner regulating member in contact therewith. Further, an AC bias component was superimposed on the DC bias component and used as a developing bias. Further, in the heat fixing device H,
Using the fixing device shown in FIGS. 2 and 3, the surface temperature of the temperature measuring element 21d of the heating body 21 is 190 ° C., and the heating body 21-sponge pressure roller 2 having a foam of silicone rubber as the lower layer.
The total pressure between 3 is 88.2 N, the nip between the pressure roller and the film is 8 mm, and the fixing film 22 has a low resistance in which the conductive material is dispersed in PTFE (high molecular weight type) on the contact surface with the transfer material. A heat-resistant polyimide film having a release layer of 60 μm in thickness was used.

Next, the developing device was filled with toner (J), and the developing device was set in the image forming apparatus. High temperature and high humidity (30 ℃,
Under 80% RH environment, 20 sheets / minute (A4 size) printout speed, intermittent mode (that is, every time one printout, the developing device is paused for 10 seconds, and the preparatory operation of the developing device at restarting is performed. Then, a printout test of 5,000 sheets was performed in a mode in which the deterioration of the toner is accelerated.

As a result, the image density, dot reproducibility and fog were all A ranks according to the above ranks.

[0253]

INDUSTRIAL APPLICABILITY As described above, the toner of the present invention has excellent electrophotographic characteristics, gives a high-definition image, is excellent in environmental stability and durability, and can be applied to a developer holding member, a photoconductor, a fixing device, etc. There is little pollution.

[Brief description of drawings]

FIG. 1 is a schematic explanatory diagram of an image forming apparatus used in an embodiment of the present invention.

FIG. 2 is an exploded perspective view of a main part of a fixing device used in an embodiment of the present invention.

FIG. 3 is an enlarged cross-sectional view of a main part showing a film state of the fixing device used in the embodiment of the present invention when the fixing device is not driven.

FIG. 4 is an explanatory diagram of a checkered pattern for checking the developing characteristics of toner.

FIG. 5 is a schematic view of a color image output device using the intermediate transfer belt used in the examples of the present invention.

FIG. 6 is a schematic explanatory diagram of an image forming apparatus that reuses untransferred toner.

[Explanation of symbols]

10 Electrostatic latent image carrier (photosensitive drum) 11 Charging means (charging roll) 12 cartridges 13 Cleaning means 14 Exposure means 15 Developer storage container 16 charging roller 17 Toner carrier (developing sleeve) 18 Elastic layer thickness control member 19 Transfer means (transfer roll) 20 stay 21 heating body 21a heater substrate 21b heating element 21c Surface protection layer 21d Temperature measuring element 22 Fixing film 23 Pressure roller 24 coil spring 25 Film edge control flange 26 power supply connector 27 disconnection member 28 Entrance guide 29 Exit guide 101 photosensitive drum 102 primary charger 103 image exposure means 110 Transfer material guide 111 Paper feed roller 113 Cleaning Device for Photosensitive Drum 115 Fixer 120 Intermediate transfer belt 128 bias power supply 129 Bias power supply 141 yellow color developing device 142 Magenta color developing device 143 Cyan color developing device 144 Black color developing device 150 Intermediate transfer member cleaning device 162 primary transfer roller 163 secondary transfer roller 164 Secondary transfer counter roller 165 Intermediate transfer belt support roller 166 Intermediate transfer belt support roller

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/06 101 G03G 15/08 504B 2H200 15/08 501 506A 504 15/16 506 103 507 15/20 101 15/16 9/08 331 103 346 15/20 101 15/08 507D 21/10 21/00 326 9/08 325 384 (72) Inventor Takehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. In-house (72) Inventor Motoki Hisaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA01 AA06 AA15 CA08 CA14 CA22 DA02 EA06 EA10 2H033 AA01 AA23 BA25 BA26 BA58 BB18 BB21 BB28 BE03 2H073 AA01 BA03 BA13 BA43 CA02 CA22 2H077 AA37 AC16 AD02 AD06 AD13 AD18 AD36 BA03 BA07 EA11 FA01 FA19 FA21 GA13 2H134 GA 01 HD01 JA01 JA11 JA14 KA15 KA20 KA24 KB08 KB11 KB12 KB14 KC00 KG03 KG07 KG08 KH01 KH04 KH11 KJ02 2H200 FA01 FA14 FA20 GA23 GA42 GA44 GA47 GA49 GA50 GA51 GA57 GB12 GB22 GB26 HA02 HA28 HB12 JA01 J13 J12 JC03 J12 JB10 JC03 J12

Claims (37)

[Claims] 1. A dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin, wherein: The polyester resin is composed of aliphatic polycarboxylic acids and aliphatic polyhydric alcohols,
At least one of a polyvalent carboxylic acid unit and / or a polyhydric alcohol unit constituting the resin has a polymerizable double bond, In a toner number-based circle equivalent diameter-circularity scattergram of the toner measured by a flow type particle image measuring device, the dry equivalent toner circle equivalent number average diameter D1 (μm)
Is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the standard deviation of circularity is 0.04.
A dry toner characterized by being less than 0. 2. Tetrahydrofuran (TH) of the toner
F) In the molecular weight distribution of the soluble component by gel permeation chromatography (GPC), the peak molecular weight is in the range of 2 × 10 ³ to 1 × 10 ⁵ , and THF
The dry toner according to claim 1, wherein the mass of the insoluble component is 5 to 70 mass% of the total mass of the dry toner. 3. The monomer constituting the polyester-based resin has a dicarboxylic acid such as fumaric acid, maleic acid, itaconic acid, citraconic acid, cyclohexene dicarboxylic acid, dodecenyl succinic acid, its ester and / or dicarboxylic acid anhydride skeleton. The dry toner according to claim 1, further comprising at least one dicarboxylic acid unit selected from the above and / or at least one diol unit selected from butenediol, octenediol, and cyclohexene dimethanol. 4. The acid value of the polyester resin (mgK
OH / g) is 0.01 to 20, and the content of the polymerizable double bond is 1 to 8 per molecule of the polyester resin.
The dry toner according to claim 1, wherein the dry toner is 0 mol%. 5. The dry toner according to claim 1, wherein the content of the polyester resin is 0.1 to 30 mass% with respect to the total mass of the toner. 6. The polyester resin has a peak molecular weight of 1 × 10 ³ to 1 in the molecular weight distribution by GPC.
The dry toner according to claim 1, wherein the dry toner is in the range of × 10 ⁵ . 7. The polyester resin has a peak molecular weight of 2 × 10 ^{3 to} 5 in the molecular weight distribution by GPC.
The dry toner according to claim 1, wherein the dry toner is in the range of × 10 ⁴ . 8. The toner is tetrahydrofuran (TH
F) In the molecular weight distribution of the soluble component by gel permeation chromatography (GPC), the molecular weight 1 having the repeating unit of the polyester resin in the structure
8. The toner according to claim 1, which contains 10.0% or less of a component in an amount of 10.0% by mass or less based on the toner.
The dry toner according to any one of 1. 9. The dry toner according to claim 1, wherein the polyester resin is modified with a silicone segment containing or not containing an aromatic ring. 10. The dry toner according to claim 1, further comprising at least one charge control agent represented by the following general formula (I). [Chemical 1] 11. The average circularity of the toner is 0.970 to.
11. The dry toner according to claim 1, which has a circularity standard deviation of less than 0.035 at 0.995. 12. A toner number-based toner particle having a circularity of less than 0.950 is 15% by number or less in a circle equivalent diameter-circularity scattergram based on the number of toner measured by the flow type particle image measuring device. The dry toner according to any one of claims 1 to 11, characterized in that. 13. A polymerizable double bond comprising at least one of a polyvalent carboxylic acid and / or a polyhydric alcohol which comprises an aliphatic polyhydric carboxylic acid and an aliphatic polyhydric alcohol and which constitutes the resin. A polymerizable vinyl-based monomer composition containing a polyester resin having
A mixture containing at least a colorant, a wax and a polymerization initiator is mixed to prepare a polymerizable monomer composition, and the polymerizable monomer composition is dispersed in an aqueous medium and granulated. A method for producing a dry toner, in which a polymerizable vinyl monomer is polymerized to produce toner particles. 14. At least a charging step of externally applying a voltage to a charging member to charge an electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier. A forming step, a developing step of developing an electrostatic charge image with toner to form a toner image on an electrostatic latent image carrier, a transfer step of transferring the toner image on the electrostatic latent image carrier to a transfer material, An image forming method including a fixing step of heating and fixing a toner image on a transfer material, wherein the toner is a dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin, The polyester resin is composed of aliphatic polycarboxylic acids and aliphatic polyhydric alcohols,
At least one of a polyvalent carboxylic acid unit and / or a polyhydric alcohol unit constituting the resin has a polymerizable double bond, In a toner number-based circle equivalent diameter-circularity scattergram of the toner measured by a flow type particle image measuring device, the dry equivalent toner circle equivalent number average diameter D1 (μm)
Is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the standard deviation of circularity is 0.04.
An image forming method characterized by being less than 0. 15. An average circularity of the toner is 0.970 to.
The image forming method according to claim 14, wherein the circularity standard deviation is 0.995 and is less than 0.035. 16. In a toner equivalent number-based circle equivalent diameter-circularity scattergram measured by the flow-type particle image measuring device, the toner has 15% by number or less of toner particles having a circularity of less than 0.950. The image forming method according to claim 14 or 15, wherein 17. In the developing step, the moving speed of the surface of the toner carrying member in the developing area is 1.05 to 3.0 times the moving speed of the electrostatic latent image carrying member. The image forming method according to claim 14, wherein the surface roughness Ra (μm) is 1.5 or less. 18. The image forming method according to claim 14, wherein a ferromagnetic metal blade is arranged facing the toner carrier at a minute interval. 19. The image forming method according to claim 16, wherein a blade made of an elastic body is brought into contact with the toner carrier so as to face the toner carrier. 20. The image according to claim 14, wherein the latent electrostatic image bearing member and the toner bearing member have a certain interval and are developed while applying an alternating electric field. Forming method. 21. In the charging step, the charging member is brought into contact with the electrostatic latent image carrier, and a voltage is applied to the charging member from the outside,
15. The electrostatic latent image carrier is electrically charged.
21. The image forming method according to any one of 20 to 20. 22. In the transfer step of electrostatically transferring a toner image on an electrostatic latent image carrier to a transfer material using a transfer device, the electrostatic latent image carrier and the transfer device interpose the transfer material. The image forming method according to any one of claims 14 to 21, wherein the image forming method is performed by abutting against each other. 23. The heat-fixing step heat-fixes the toner image on the recording material by a heat-fixing device that does not supply an offset preventing liquid or does not have a fixing device cleaner. 23. The image forming method according to any one of 22 to 22. 24. A toner image is recorded on a recording material by a heating member fixedly supported in the heating and fixing step, and a pressing member that is in pressure contact with the heating member and is in close contact with the heating member through a film. The image forming method according to any one of claims 14 to 23, wherein the image is fixed by heating. 25. An untransferred residual toner on the electrostatic latent image bearing member after transfer is cleaned and collected, and the collected toner is supplied to a developing unit to be retained again in the developing unit. 25. The image forming method according to claim 14, further comprising a toner reuse mechanism for developing the electrostatic latent image on the carrier. 26. At least a charging step of externally applying a voltage to a charging member to charge the electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier. A forming step, a developing step of developing an electrostatic charge image with toner to form a toner image on an electrostatic latent image carrier, and a first step of transferring the toner image on the electrostatic latent image carrier to an intermediate transfer body. A transfer step and a second step of transferring the toner image on the intermediate transfer member to a transfer material
And a fixing step of heating and fixing the toner image on the transfer material, the toner is a dry toner containing at least a binder resin, a colorant, a wax component, and a polyester resin. ,. The polyester resin is composed of aliphatic polycarboxylic acids and aliphatic polyhydric alcohols,
At least one of a polyvalent carboxylic acid unit and / or a polyhydric alcohol unit constituting the resin has a polymerizable double bond, In a toner number-based circle equivalent diameter-circularity scattergram of the toner measured by a flow type particle image measuring device, the dry equivalent toner circle equivalent number average diameter D1 (μm)
Is 2 to 10 μm, the average circularity of the toner is 0.950 to 0.995, and the standard deviation of circularity is 0.04.
An image forming method characterized by being less than 0. 27. The toner has an average circularity of 0.970 to.
27. The image forming method according to claim 26, wherein the circularity standard deviation is 0.995 and is less than 0.035. 28. In a toner number-based circle equivalent diameter-circularity scattergram measured by the flow type particle image measuring device, the toner has 15% by number or less of toner particles having a circularity of less than 0.950. 28. The image forming method according to claim 26, wherein: 29. In the developing step, the moving speed of the surface of the toner carrying member in the developing area is 1.05 to 3.0 times the moving speed of the electrostatic latent image carrying member. 29. The image forming method according to claim 26, wherein the surface roughness Ra (μm) is 1.5 or less. 30. The image forming method according to claim 26, wherein a ferromagnetic metal blade is arranged facing the toner carrier at a minute interval. 31. The image forming method according to claim 26, wherein a blade made of an elastic body is brought into contact with the toner carrier so as to face the toner carrier. 32. The image according to claim 26, wherein the latent electrostatic image bearing member and the toner bearing member have a certain distance and are developed while applying an alternating electric field. Forming method. 33. In the charging step, the charging member is brought into contact with the electrostatic latent image carrier, and a voltage is applied to the charging member from the outside,
27. The electrostatic latent image carrier is charged.
33. The image forming method according to any one of 32 to 32. 34. In a transfer step of electrostatically transferring a toner image on an electrostatic latent image carrier onto a transfer material using a transfer device, the electrostatic latent image carrier and the transfer device interpose the transfer material. The image forming method according to any one of claims 26 to 33, characterized in that the image forming method is performed by abutting. 35. The heat-fixing step heat-fixes the toner image on the recording material by a heat-fixing device having no supply of an offset preventing liquid or having no fixing device cleaner. 35. The image forming method according to any one of 34 to 34. 36. In the heating and fixing step, a toner image is recorded on a recording material by a fixedly supported heating member and a pressing member that is in pressure contact with the heating member and is in close contact with the heating member via a film. The image forming method according to claim 26, wherein the image is fixed by heating. 37. The untransferred residual toner on the electrostatic latent image carrier after the transfer is cleaned and collected, and the collected toner is supplied to the developing means to be retained again in the developing means. 37. The image forming method according to claim 26, further comprising a toner reuse mechanism for developing the electrostatic latent image on the carrier.