JPH0934163A - Toner for developing electrostatic charge image, device unit and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner excellent in low-temp. fixability and anti-offsetting property and stably giving a moderate gloss, to obtain a device unit with the toner and to provide an image forming method using the toner. SOLUTION: This toner contains at least 100 pts.wt. bonding resin, 1-150 pts.wt. colorant and 5-40 pts.wt. material having a low softening point. The ratio (G'60 /G'80 ) of the storage modulus (G'60 ) of elasticity of this toner at 60 deg.C to the storage modulus (G'80 ) of elasticity at 80 deg.C is >=80 and the ratio (G'155 /G'190 ) of the storage modulus (G'155 ) of elasticity at 155 deg.C to the storage modulus (G'190 ) of elasticity at 190 deg.C is 0.95-5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner suitable for heat and pressure fixing used in electrophotography and electrostatic recording, an apparatus unit having the toner, and an image formation using the toner. Regarding the method.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Numerous methods are known as described in Japanese Patent Application Laid-Open Publication No. Hei. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means, and then the electrostatic charge image is developed with a toner,
A toner image is transferred onto a transfer material such as paper by using a direct or indirect means as needed, and then fixed by heat, pressure, heat and pressure, or solvent vapor to obtain a copy or print. is there. The toner remaining on the photoconductor without being transferred is cleaned by various methods, and the above steps are repeated.

Various methods and devices have been developed for the final step of fixing the toner image to a sheet such as paper, but the most common method at present is a pressure heating method using a heating roller. In the pressure-bonding heating method using this heating roller, the toner image is fixed by passing the transfer material while bringing the surface of the heat roller having a releasability for the toner and the toner image surface on the transfer material into contact with each other under pressure. It is a thing. In this method, since the surface of the heating roller and the toner image on the transfer material come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the transfer material is extremely good, and quick fixing is required. Can be done.

Different toners are used depending on the models of copying machines and printers. This is mainly due to the difference in the fixing speed and the fixing temperature. Since the surface of the heating roller and the toner image come into contact with each other in a molten state or under pressure, the fixing property and the glossiness (gloss) of the fixed image are This is because it is greatly affected by temperature and temperature. In general, when the fixing speed is low, the heating roller surface temperature is low, and when the fixing speed is high, the heating roller surface temperature is high.
This is because, in order to fix the toner on the transfer material, the amount of heat given to the toner by the heating roller needs to be substantially constant regardless of the fixing speed.

When the amount of heat applied on the transfer material is different, a gloss difference occurs in the obtained image. For example, when the temperature of the heating roller is lowered when the transfer material is passed through the fixing device, and the amount of heat applied to the leading end and the trailing end of the transfer material is different at the start and end of fixing, the edge of the obtained image is There will be a gloss difference between the parts. Especially in the case of a full-color image, a feeling of strangeness is likely to occur. Further, when a large number of images are continuously printed, the temperature of the heating roller is lowered, and a gloss difference occurs between the image at the start and the image at the end of the printing. It may end up.

As a method of solving the above problems, there is a method of suppressing fluidization at the time of melting by using a crosslinked binder resin. However, as the degree of crosslinking of the binder resin increases, there is a problem in that the rapid melting property of the toner decreases and fixing becomes difficult unless the temperature of the heating roller is high. In fixing, a toner capable of low-temperature fixing and capable of obtaining an image having a constant gloss width in a wide temperature range is desired.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 1-128071 discloses a toner for developing an electrostatic charge image, which has a polyester resin as a binder resin and has a characteristic storage viscosity at 95 ° C. There is a demand for further improvement in gloss uniformity of a fixed image and low-temperature fixability of a toner, since the rate of decrease in storage elastic modulus at 60 to 80 ° C. is low.

In Japanese Patent Laid-Open No. 4-353866, the temperature at which the storage elastic modulus starts to fall is in the range of 100 to 110 ° C., the specific storage elastic modulus is at 150 ° C., and the peak temperature of the loss elastic modulus is A toner for developing an electrostatic charge image having a rheological property of 125 ° C. or higher is disclosed. However, this has a high start temperature of the storage elastic modulus and a high peak temperature of the loss elastic modulus, so that the low temperature fixability is improved. There is a need to.

Japanese Unexamined Patent Publication (Kokai) No. 6-59504 discloses a toner composition containing a polyester resin having a specific structure as a binder resin. The toner composition contains 70 to 1
It has a specific storage elastic modulus at 20 ° C and a specific loss elastic modulus at 130 to 180 ° C. The toner described in this publication is inferior in low-temperature fixability because it does not contain a substance having a low softening point as an essential component, and also has a large variation in storage elastic modulus in a temperature range of 155 ° C. or higher and a gloss value. There is a problem that it is easy to change.

Further, copiers or printers for forming full-color images have been used.
A full-color image is generally obtained by uniformly charging the photoconductor with a primary charger, exposing the image with laser light modulated by the magenta image signal of the original, forming an electrostatic charge image on the photoconductor, and holding a magenta toner. The electrostatic charge image is developed by a magenta developing device to form a magenta toner image. Next, the magenta toner image on the photoconductor is transferred directly or via the intermediate transfer member by the transfer charger transferred to the transfer screen.

After the development of the electrostatic image, the photoconductor is destaticized by the decharging charger, cleaned by the cleaning means, and then charged again by the primary charger to similarly form a cyan toner image and The cyan toner image is transferred to the transfer material onto which the magenta toner image has been transferred, and then the yellow color and the black color are sequentially developed to transfer the four color toner images with apologies. A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by the fixing means.

In recent years, such an image forming apparatus has begun to be used not only as a general-purpose copier for copying original documents but also as a printer as a computer output or a personal copy for individuals. It was

Such a device is being applied to a plain paper fax in addition to the field represented by a laser beam printer.

Therefore, miniaturization, weight reduction, high speed, high image quality, and high reliability have been rigorously pursued. In addition, machines are becoming simpler in many respects. As a result, the performance required of the toner has become higher, and excellent image formation cannot be realized unless the performance of the toner can be improved. In recent years, the demand for color copying has rapidly increased along with various copying needs. In order to copy the original color image more faithfully, higher image quality and higher resolution are desired.
From these viewpoints, the toner used in the color image forming method needs to be mixed with color when heat is applied.

In the case of a fixing device in a color image forming apparatus, since a plurality of toner layers such as magenta toner, cyan toner, yellow toner and black toner are formed on a transfer material, an offset occurs due to an increase in toner layer thickness. It tends to be easy.

In order to prevent the toner from adhering to the surface of the fixing roller, the roller surface is formed of a material having a good releasability for the toner (silicone rubber, fluorine resin, etc.), and the surface of the roller is prevented from offsetting and the surface of the roller is prevented. In order to prevent the fatigue of the roller, the roller surface is coated with a thin film of a liquid having a high releasability such as silicone oil or fluorine oil. However, although this method is extremely effective in preventing toner offset, it requires an apparatus for supplying an offset preventing liquid,
There is a problem that the fixing device becomes complicated. As the transfer material on which the toner image is fixed, generally, various papers,
Coated paper, plastic film, etc. are used. Above all, the need for a transparency film (OHP film) that uses an overhead projector for presentation is increasing. Especially OH
Unlike paper, the P film has a low oil absorption capacity, and therefore a large amount of oil is present on the surface of the OHP film after fixing. Silicone oil evaporates due to heat and contaminates the inside of the image forming apparatus, and there is a problem in processing the recovered oil.
A release agent such as low-molecular-weight polyethylene or low-molecular-weight polypropylene is added to the toner particles in order to supply the offset-preventing liquid from the toner particles at the time of heating and pressure fixing without using a silicone oil supply device. A method has been proposed. If such a releasing agent is added in a large amount in order to obtain a sufficient effect, filming on the photoreceptor and the surface of the toner carrier such as the carrier and the developing sleeve are easily contaminated, and the image is easily deteriorated. Currently, a small amount of releasing agent is added to toner particles so as not to cause image deterioration, a small amount of releasing oil is supplied to a fixing roller, and offset toner is used as a member such as a roll-up type web. Cleaning is performed using a device or a cleaning pad.

However, in view of recent demands for miniaturization, weight reduction and high reliability, it is preferable to remove even these auxiliary devices.

Further, in an apparatus for forming a full-color image using a non-magnetic color toner, a two-component developer having a non-magnetic color toner and a magnetic carrier is generally used, and an electrostatic charge is applied by a magnetic brush developing method. The image is being developed. In the magnetic brush developing method using the two-component developer, it is necessary to adjust the mixing ratio of the toner and the carrier to be constant, and the developing device equipped with a mechanism therefor tends to be upsized. Therefore, in order to reduce the size of the full-color image forming apparatus, for example, the developing device (apparatus unit) shown in FIG. 6 for developing the electrostatic charge image by the non-magnetic one-component developing method is preferable, but the toner applying roller 18 and the elastic blade 19 are preferable. A non-magnetic color toner having color mixing property is required, which resists pressure and rubbing due to, and has durability for a large number of sheets. is there.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image which solves the above problems.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which is excellent in low-temperature fixability and anti-offset property and has a proper gloss value.

An object of the present invention is to provide a non-magnetic color toner suitable for non-magnetic one-component development and having excellent durability on a large number of sheets.

An object of the present invention is to provide a non-magnetic color toner having an appropriate gloss value and color mixing property.

An object of the present invention is to provide a non-magnetic color toner suitable for oilless heating and pressure fixing.

An object of the present invention is to provide an apparatus unit having the above toner.

An object of the present invention is to provide an image forming method using the above toner.

An object of the present invention is to provide an image forming method for forming a multi-color or full-color image having an oilless heating and pressure fixing step.

An object of the present invention is to provide an image forming method for forming a multi-color or full-color image having a non-magnetic one-component developing process using a non-magnetic color toner.

[0028]

The present invention provides a binder resin 10
A toner for developing an electrostatic image comprising at least 0 part by weight, 1 to 150 parts by weight of a colorant and 5 to 40 parts by weight of a low softening point substance, the toner having a storage elastic modulus (G _'60 ) at a temperature of 60 ° C. Storage elastic modulus at temperature 80 ° C (G _'80 )
And the ratio (G ′ ₆₀ / G ′ ₈₀ ) is 80 or more and the temperature is 15
Ratio (G ' ₁₅₅ / G') of storage modulus at 5 ° C (G ' ₁₅₅ ) to storage modulus at temperature 190 ° C (G' ₁₉₀ )
₁₉₀ ) is 0.95 to 5 and relates to a toner for developing an electrostatic charge image.

Further, the present invention is an apparatus unit having at least toner, a developing sleeve, a toner applying means installed so as to press the developing sleeve, and an outer wall for integrally holding them. The unit is attachable / detachable to / from the apparatus, and the toner has at least 100 parts by weight of a binder resin, 1 to 150 parts by weight of a colorant, and 5 to 40 parts by weight of a low softening point substance. Storage modulus at 60 ℃ (G _'60 ) and temperature 8
Ratio of storage modulus at 0 ° C (G _'80 ) (G' ₆₀ /
G _'80) is not less than 80, the storage elastic modulus at a temperature of 155 ° C. (G' ₁₅₅₎ and storage elastic modulus at a temperature of 190 ° C. ( 'ratio (G and _{190)' 155 / G '190} G) is 0. 95
5 to 5, the present invention relates to an apparatus unit.

Further, the present invention forms an electrostatic charge image on the image carrier.
And develop the electrostatic charge image with toner that has a triboelectric charge.
Toner image and the toner image through the intermediate transfer member,
Transfer the toner image on the transfer material without
An image forming method in which heat and pressure are fixed on a copying material, the toner
Is 100 parts by weight of binder resin, 1 to 150 parts by weight of colorant
And at least 5 to 40 parts by weight of the low softening point substance,
The toner has a storage elastic modulus (G ′ of 60 ° C.).₆₀)When
Storage elastic modulus at temperature 80 ° C (G '₈₀) With (G ′
₆₀/ G '₈₀) Is 80 or more and at a temperature of 155 ° C.
Storage modulus (G '₁₅₅ ) And storage at 190 ° C
Sex rate (G '₁₉₀ ) With (G ′₁₅₅ / G ' ₁₉₀ ) Is 0.
95 to 5 relates to an image forming method
You.

[0031]

Toner of the present invention DETAILED DESCRIPTION OF THE INVENTION, 60 the ratio of storage modulus at ° C. (G _'60) and a storage modulus at 80 ° C. (G' and ₈₀₎ (G _'60 / G _'80 ) is 80 or more, and the storage elastic modulus (G '
₁₅₅ ) and the storage modulus at 190 ° C. (G ′ ₁₉₀ ) (G ′ ₁₅₅ / G ′ ₁₉₀ ) of 0.95 to 5.0, the low temperature fixability and the gloss value due to the difference in the fix temperature. Has achieved the suppression of fluctuations.

[0032] In the toner of the present invention, G _'60, G'
₈₀ and the ratio _{(G '60 / G' 80} ) is synergistic in a binder resin and low-softening point substance in the process proceeding to a deformable state from the deformed-resistant glass state or glass transition state even force is applied from the outside Exhibits excellent storage elastic properties. The ratio _{(G '60 / G' 80} ) is 8
The value of 0 or more (preferably 100 to 400, more preferably 150 to 300) means that the viscoelastic property of the toner sharply decreases in the process of heating from a temperature of 60 ° C. to a temperature of 80 ° C. There is. Ratio (G _'60 / G'
_When it is ₈₀ ) or more, the low temperature fixing in the heat and pressure fixing step can be favorably performed, and the toner image can be favorably fixed to the transfer material even immediately after the power of the apparatus is turned on in the cold.
Further, the toner of the present invention contains the low softening point substance in an amount of 5 to 40 parts by weight (more preferably 12 to 35 parts by weight) per 100 parts by weight of the binder resin, which is larger than that of the usual heat and pressure fixing toner. Therefore, the low temperature fixing can be performed more favorably. In the case of a non-magnetic toner, it is preferable that the low softening point substance is contained in an amount of 11 to 30% by weight based on the toner. Further, when the low softening point substance is a compound having releasability such as wax, the high temperature offset resistance is improved, so that the offset phenomenon can be satisfactorily performed without applying an offset preventive agent such as silicone oil on the surface of the heating roller. Can be suppressed.

[0033] The toner of the present invention, preferably from G _'60 is 1 × 10 ⁸ to ^{1 × 10 10 (dyn / cm} 2) is 2 × 1
0 ⁸ to ^{9 × 10 9 (dyn / cm} 2), more preferably, withstand pressure and rubbing force of the it is in the developing device 3 × 10 ⁸ to ^{5 × 10 9 (dyn / cm} 2), It is preferable for achieving good durability of multiple sheets.

Further, in the toner of the present invention, the loss elastic modulus curve shows 1 × in the temperature range of 40 to 70 ° C.
10 ⁹ (dyn / cm ² ) or more [more preferably 1 ×
10 ⁹ to ^{1 × 10 10 (dyn / cm} 2) maximum value] (G "have a _max) preferable in order to improve blocking resistance and a large number of sheets of the toner. More preferably, G" _max The ratio (G ″ _max / G ″ ₄₀ ) of the loss elastic modulus (G ″ ₄₀ ) of the toner at a temperature of 40 ° C. is preferably 1.5 or more.

Generally, there is a correspondence between the storage elastic modulus of the toner image at the fixing temperature and the gloss value of the fixed image. For example, the larger the storage elastic modulus of the toner, the smaller the gloss value of the fixed image, and the smaller the storage elastic modulus change rate when the fixing temperature of the toner image is changed, the smaller the gloss value change rate. Therefore, the ratio (G ' ₁₅₅ / G'
The value of ₁₉₀ ) is an effective index for judging the degree of change in the gloss value of the fixed image due to the difference in the fixing temperature around 180 ° C.

In the toner for developing an electrostatic image of the present invention, the value of (G ' ₁₅₅ / G' ₁₉₀ ) is 0.95 to 5, more preferably 1 to 5 even if the fixing temperature varies. This is preferable in reducing the change in the gloss value of the image.
Further, in order to maintain color offset while maintaining anti-offset property, the toner _G'190 is 1 × 10 ^{3 to} 1 × 10 ⁴
It is preferably (dyn / cm ² ).

Further, in order to improve the offset resistance at the time of heat and pressure fixing and reduce the change in the gloss value of the fixed image, the binder resin is a component insoluble in tetrahydrofuran (T
HF insoluble matter) 0.1 to 20% by weight (more preferably,
1 to 15% by weight) is preferable.

As the binder resin of the toner, polystyrene; a homopolymer of a styrene substitution product such as poly-p-chlorostyrene and polvinyltoluene; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer , Styrene-vinylnaphthalene copolymer, styrene-
Acrylic ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Styrene-based copolymers such as polymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers; acrylic resins, methacrylic resins, polyacetic acid Examples thereof include vinyl, silicone resin, polyester resin, polyamide resin, furan resin, epoxy resin and xylene resin.

These resins are used alone or as a mixture. As a main component of the binder resin, a styrene copolymer, which is a copolymer of styrene and another vinyl monomer, is preferable in terms of developability and fixability.

Comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. Acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, monocarboxylic acid having a double bond such as acrylamide or a substitution product thereof; maleic acid,
Dicarboxylic acids having a double bond such as butyl maleate, methyl maleate and dimethyl maleate and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene such as ethylene, propylene and butylene. Examples include olefins; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

It is preferable that the styrene copolymer is crosslinked with a crosslinking agent such as divinylbenzene in order to widen the fixing temperature range of the toner and improve the offset resistance.

As the crosslinking agent, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; Divinyl ether,
Divinyl compounds such as divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

When the binder resin is mainly composed of a cross-linked styrene copolymer, the binder resin has a molecular weight distribution of 3,000 in the molecular weight distribution of the THF-soluble component of the binder resin by gel permeation chromatography (GPC). It is preferable to have a main peak in the region of 50,000 to 50,000 and a sub-peak or shoulder in the region of molecular weight of 100,000 or more.
More preferably, it has two or more sub-peaks, two or more shoulders or sub-peaks, or two or more sub-peaks and shoulders in a region having a molecular weight of 100,000 or more. Furthermore, the binder resin whose main component is styrene copolymer is TH
0.1 to 20% by weight of F insoluble matter (more preferably 1
˜15% by weight).

The THF-insoluble matter means the weight ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) which becomes insoluble in the THF solvent in the resin composition in the toner. T
The HF insoluble matter is defined as a value measured as follows.

A toner sample (0.5 to 1.0 g) was weighed (W ₁ g) and a cylindrical filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd.) was used.
R) and run through a Soxhlet extractor, where T
6 hours with 100-200 ml of HF,
After evaporating the soluble component extracted by the solvent, the resultant is dried under vacuum at 100 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W ₂ g). The weight of components other than the resin component such as the pigment and wax in the toner is defined as (W ₃ g).
The THF-insoluble content is obtained from the following equation.

[0046]

[Outside 1]

When the binder resin is a polyester resin, a binder resin having at least one peak in the molecular weight range of 3,000 to 50,000 and 60 to 100% of the components having a molecular weight of 100,000 or less is preferable. . More preferably, the molecular weight is 5
It is preferable that at least one peak exists in the region of 1,000 to 30,000.

As the binder resin, it is also preferable to use a mixture of a styrene copolymer and a polyester resin. For example, a combination of a cross-linked styrene copolymer and a non-cross-linked polyester resin, and a combination of a cross-linked styrene copolymer and a cross-linked polyester resin are preferable in terms of toner fixing properties, offset resistance, and color mixing.

The polyester resin is excellent in fixing property and transparency and is suitable for a color toner which requires good color mixing property. In particular,

[0050]

[Outside 2] (In the formula, R represents an ethylene or propylene group, x and y each represent an integer of 1 or more, and the average value of x + y is 2 to 10.), and the bisphenol derivative or a substituted product thereof is a diol component. And a carboxylic acid component consisting of a carboxylic acid having a valence of 2 or more or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid,
Non-crosslinked or crosslinked polyester resins obtained by copolycondensation with trimellitic acid and pyromellitic acid) are preferable.

Further, the polyester resin has an acid value of 1 to 3.
5 mg KOH / g (more preferably 1 to 20 mg KOH
/ G, more preferably 3 to 15 mgKOH / g), from the viewpoint of environmental stability of the charging characteristics of the toner.

Examples of the low softening point substance used in the toner for developing an electrostatic charge image of the present invention include polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer-Tropish wax, amide wax, higher fatty acid, and long fatty acid. Examples thereof include chain alcohols, ester waxes and derivatives thereof such as graft compounds and block compounds, and those having a sharp maximum endothermic peak of the DSC endothermic curve from which low molecular weight components have been removed are preferable.

The wax preferably used is a linear alkyl alcohol having 15 to 100 carbon atoms,
Examples include linear fatty acids, linear acid amides, linear esters, and montan derivatives. It is also preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

Further, the wax preferably used is
Radical polymerization of alkylene under high pressure or Ziegler contact under low pressure or polymerization using other catalysts; low molecular weight alkylene polymer; alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer; Separated and purified low molecular weight alkylene polymer by-produced; from the distillation residue of a hydrocarbon polymer obtained by the Arge process from a synthesis gas consisting of carbon monoxide and hydrogen, or synthetic carbonization obtained by hydrogenating the distillation residue A polymethylene wax obtained by extracting and fractionating a specific component from hydrogen can be mentioned. An antioxidant may be added to these waxes.

The low softening point substance used in the present invention is DS
In the C endothermic curve, it is preferable to have an endothermic main peak in the temperature range of 40 to 90 ° C (more preferably 45 to 85 ° C). In addition, the endothermic main peak is
A sharp-melting low softening point substance having a half width of 10 ° C. or less (more preferably 5 ° C. or less) is preferable. Especially,
An ester wax whose low softening point substance is mainly an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms is preferable.

As the black colorant used in the present invention, carbon black, a magnetic substance, and a color tone adjusted to black using the following yellow / magenta / cyan colorant are used.

As the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

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 thioindico compound, and a berylene compound are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 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 used particularly preferably.

These colorants may be used alone or in a mixture, and may be used in the state of solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, transparency on OHP film, and dispersibility in toner particles.
The amount of the colorant added is 1 to 2 per 100 parts by weight of the binder resin.
0 parts by weight Generally used.

When a magnetic substance is used as the black colorant, unlike other colorants, the amount is 40 to 100 parts by weight of the resin.
150 parts by weight Generally used.

As the charge control agent used for stabilizing the triboelectric charging property of the toner, a charge control agent which is colorless and has a high charging speed of the toner and which can stably maintain a constant charge amount is preferable. Further, when the direct polymerization method is used as the method for producing the toner particles, a charge control agent having no polymerization inhibitory property and having no solubilized product in the aqueous medium is particularly preferable. As a specific compound, salicylic acid as a negative control agent,
A metal compound of alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, sulfonic acid, a high molecular compound having a carboxylic acid as a side chain, a boron compound, a urea compound, a silicon compound, currys arene and the like can be used. As the positive control agent, a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, an imidazole compound and the like are preferably used. The charge control agent is 0.5 to 1 with respect to 100 parts by weight of the resin.
0 parts by weight is preferred. However, the addition of a charge control agent in the present invention is not essential, in the case of using the two-component developing method, utilizing the triboelectric charging with the carrier, even in the case of using the non-magnetic one-component blade coating developing method. By positively utilizing the triboelectric charging with the member or the sleeve member, the toner particles do not necessarily need to contain the charge control agent.

As one of the methods for producing the toner for developing an electrostatic image of the present invention, a binder resin, a colorant, a low softening point substance, a charge control agent and other internal additives as optional components are added. After kneading with a pressure kneader, extruder, media disperser, etc., to disperse evenly, collide with a target mechanically or under a jet stream to finely pulverize to a desired toner particle size, and further classify. Then, there is a method for producing a toner by a pulverization method in which the particle size distribution is sharpened to produce toner particles. In addition to this,
No. -10231, JP-A-59-53856,
A method of directly producing a toner using the suspension polymerization method described in JP-A-59-61842;
-106473 and JP-A-63-186253, an interface association method for obtaining at least a desired particle size by aggregating at least one kind of fine particles; soluble in a monomer The obtained polymer is a dispersion polymerization method in which an insoluble water-based organic solvent is used to directly produce a toner; and a representative example is a soap-free polymerization method in which a toner is directly polymerized in the presence of a water-soluble polymerization initiator to produce toner particles. And the production of toner particles by an emulsion polymerization method.

In the crushing method, there is a method in which a high molecular weight resin and a low molecular weight resin are blended and used as a binder resin, and if necessary, the kind and the addition amount of the low softening point substance are changed to make a correction. . In particular, it is effective when a binder resin having a hydroxyl group or a carboxyl group is used, and it is possible to add a metalorganic compound or its derivative at the time of kneading to cause metal cross-linking and produce a THF insoluble matter. . In the method for producing toner particles by the polymerization method, a suitable crosslinking agent and / or a resin component is added to a polymerizable monomer, a low softening point substance and a polymerization initiator are added and dissolved, and the mixture is granulated in an aqueous medium. Further, a polymerization reaction is further performed, and the low-softening point substance is encapsulated in the toner particles by the polymerized polymer,
It is preferable to form an island structure.

The low softening point substance is encapsulated with a binder resin,
As a method for constructing the sea-island structure, the minimum of the low softening point substance is set to be smaller than that of the main monomer in the aqueous medium, and a small amount of a resin or a monomer having a large polarity is added to the polymerizable monomer. A method of obtaining a toner particle having a core-shell structure in which a low softening point substance is coated with a binder resin by polymerizing a monomer is mentioned. This may be used as it is as toner particles, or toner particles having a sea-island structure may be generated by aggregating and associating ultrafine granular toner particles to a desired particle size. When constructing a sea-island structure using these methods, at least one of the low softening point substances preferably has a melting point (maximum endothermic peak temperature in the DSC endothermic curve) lower than the polymerization temperature.
7 and 8 show a typical example of toner particles having a sea-island structure.

By encapsulating the low softening point substance in the toner particles, even if the toner particles contain a relatively large amount of the low softening point substance, it is possible to suppress the deterioration of the blocking resistance of the toner, and The toner particles were strong against mechanical impact by using a substance having a low softening point having a sharp melt property. Toner particles having low-temperature fixability and good mixability can be produced during heat-press fixing.

A vinyl-based polymerizable monomer capable of radical polymerization is used as a polymerizable monomer used when the toner of the present invention is produced by a polymerization method. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. As the monofunctional polymerizable monomer, styrene; α-methylstyrene, β-
Methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimer styrene,
pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p Styrene derivatives such as methoxystyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, ter.
t-butyl acrylate, n-amyl acrylate, n
-Hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Acrylic polymerizable monomer such as;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-
Methacrylic polymerizable monomers such as ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl acetate, vinyl propionate, benzoe Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyryl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone. .

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis [4- (acryloxydiethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane Tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,
2'-bis [4- (methacryloxypolyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalene, divinylether and the like.

In the present invention, the above monofunctional polymerizable monomers may be used alone or in combination of two or more kinds, or
The above-mentioned monofunctional polymerizable monomer and polyfunctional polymerizable monomer are used in combination. Polyfunctional polymerizable monomers can also be used as crosslinking agents.

An oil-soluble initiator and / or a water-soluble initiator is used as a polymerization initiator used in the polymerization of the above polymerizable monomer. For example, as the oil-soluble initiator, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis-2,4-dimethylvaleronitrile, 1,
Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl baroxycarbonate, decanolyl par oxide,
Lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, Peroxide initiators such as dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide are exemplified.

Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-
Dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, sulfuric acid Ferrous or hydrogen peroxide.

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, it is possible to further add and use a chain transfer agent, a polymerization inhibitor or the like.

As the method for producing the toner of the present invention, the shape of the toner particles can be uniformly controlled, a sharp particle size distribution can be easily obtained, and toner particles having a small particle size of 3 to 8 μm can be easily obtained. The turbid polymerization method is particularly preferred.
Further, a seed polymerization method in which a monomer is further adsorbed on the obtained polymer particles and then the resultant is polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed. When suspension polymerization is used as a method for producing toner particles, toner particles can be directly produced by the following production method. A low softening point substance such as wax in a monomer, a colorant, a polymerization initiator, a cross-linking agent and other additives are added, and a homogenizer, an ultrasonic disperser or the like is used to uniformly dissolve or disperse the monomer composition. Then, it is dispersed in an aqueous medium containing a dispersion stabilizer by a usual stirrer, homomixer, homogenizer or the like. Preferably, the stirring speed and time are adjusted so that the droplets of the monomer composition have a desired toner particle size, and granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. Polymerization temperature is 4
0 ° C or higher, usually 50 to 90 ° C (preferably 55 to 85
Polymerization is carried out by setting the temperature to (° C.). The temperature may be raised in the latter half of the polymerization reaction, and may be further increased in the latter half of the reaction or after the end of the reaction to remove unreacted polymerizable monomers and by-products that cause odor at the time of fixing the toner. The partial aqueous medium may be distilled off. After the reaction, the generated 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 weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition. As the dispersant used, for example, as inorganic oxides, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide,
Examples include magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and the like. Examples of organic compounds include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose,
Ethyl cellulose, sodium salts of carboxymethyl cellulose, starch and the like are used. These dispersants are
It is preferable to use 0.2 to 2.0 parts by weight based on 100 parts by weight of the polymerizable monomer.

As these dispersants, commercially available ones may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the inorganic compound may be produced under high speed stirring in a dispersion medium. I can. For example, in the case of tricalcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring. To make these dispersants finer, 0.001 to 0.1% by weight of a surfactant may be used in combination. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate,
Sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.

The toner of the present invention has a shape factor SF-
The value of 1 is 100 to 160, more preferably 100 to 15
0, and more preferably 100 to 125 toner.

In the present invention, SF-1 indicating the shape factor
Means, for example, FE-SEM (S-800) manufactured by Hitachi, Ltd.
100 random toner images magnified at a magnification of 500 are randomly sampled, and the image information is, for example, an image analysis device (Luzex I manufactured by Nicore Co.) via an interface.
It is introduced into II) and analyzed, and the value calculated by the following formula is defined as shape factor SF-1.

[0078]

[Outside 3] [Wherein MXLNG represents the absolute maximum length of the toner particles,
AREA indicates the projected area of the toner particles. The shape factor SF-1 indicates the degree of roundness of toner particles.

A toner having a toner shape factor SF-1 of more than 160 gradually approaches a non-spherical shape from a spherical shape, and accordingly the transfer efficiency is lowered.

In the toner of the present invention, lubricant powders such as Teflon powder, zinc stearate powder, polyvinylidene fluoride powder; abrasives such as cerium oxide, silicon carbide, strontium silicate, calcium titanate and strontium titanate. External additives such as fluidity improvers such as silica, titanium oxide and aluminum oxide; anti-caking agents; conductivity imparting agents such as carbon black, zinc oxide and tin oxide;

In particular, as the inorganic fine powder, silica fine powder, titanium oxide fine powder, aluminum oxide fine powder, strontium silicate fine powder, calcium titanate fine powder,
An inorganic fine powder such as a strontium titanate fine powder is preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof. The external additive is preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the toner particles.

The toner of the present invention preferably has an aggregation degree of 1 to 30%, more preferably 4 to 20% from the viewpoint of developability.

In the present invention, various non-magnetic colorants are used to produce a non-magnetic cyan toner, a non-magnetic yellow toner, a non-magnetic magenta toner and a non-magnetic black toner which satisfy the above-mentioned physical properties, and each color The toner can be used in an image forming apparatus for multicolor image formation or full color image formation. In that case, each color toner of the present invention is not easily deteriorated even when subjected to pressure and rubbing force, and thus is preferably applied to a non-magnetic one-component developing device. Since the non-magnetic one-component developing device can be designed smaller than the two-component developing device, it is possible to downsize the image forming apparatus.
Further, since the toner of the present invention is excellent in low-temperature fixing property and anti-offset property, it is possible to simplify and downsize the heating and pressing fixing device in the image forming apparatus.

A specific example of an image forming apparatus that can use the toners of the respective colors of the present invention will be described with reference to FIG.

FIG. 5 is an image forming apparatus (copier or laser printer) capable of forming a mono-color image, a multi-color image and a full-color image using the electrophotographic process.
FIG. A medium-resistance elastic roller 5 is used as an intermediate transfer member, and a transfer belt 6 is used as secondary contact transfer means.

Reference numeral 1 denotes a rotary drum type electrophotographic photosensitive member (hereinafter referred to as a photosensitive member) which is repeatedly used as an image bearing member, and is rotationally driven in a clockwise direction indicated by an arrow at a predetermined week speed (process speed). Photoconductor 1 is a-Se, C
It may be a photosensitive drum or photosensitive belt having a photoconductive insulating material layer such as dS, ZnO ₂ , OPC or a-Si.

As the photosensitive member 1, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer.
It may be a single layer type, or may be a function-separated type photosensitive layer having a charge transport layer and a charge generation layer as components. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

Polycarbonate resin, polyester resin, and acrylic resin are particularly preferable as the binder resin of the organic photosensitive layer because of good transferability and cleaning property, poor cleaning, fusing of toner to the photoreceptor, and filming of external additives. Hard to happen.

In the charging step, there are a method in which the corona charger is not in contact with the photosensitive member 1 and a contact method in which a roller or the like is used, and either method is used. A contact type as shown in FIG. 5 is preferably used for efficient uniform charging, simplification and low ozone generation.

The charging roller 2 has a core metal bar 2b at the center and a conductive elastic layer 2a forming the outer periphery thereof as a basic structure. The charging roller 2 is pressed against the surface of the photoconductor 1 with a pressing force, and is driven to rotate as the photoconductor 1 rotates.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 5 to 500 g / c.
In m, when a DC voltage superimposed with an AC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency = 50
Hz to 5 kHz, DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to
± 1.5 kV.

As other charging means, there are a method using a charging plate and a method using a conductive brush. These contact charging means are effective in that high voltage is not required and generation of ozone is reduced.

As the material of the charging roller and the charging plate as the contact charging means, conductive rubber is preferable, and a releasing film may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

The photosensitive drum 1 is uniformly charged to a predetermined polarity and potential by the primary charging roller 2 in the course of rotation, and then image exposure means (not shown) (for example, color separation and image formation of a color original image). An exposure optical system, a scanning exposure system by a laser scanner that outputs a laser beam modulated in accordance with a time-series electric digital pixel signal of image information, and the like) is subjected to image exposure 3 to thereby obtain a first color image of a desired color image.
An electrostatic charge image corresponding to the color component image (for example, the yellow component image) is formed.

Then, the electrostatic charge image is transferred to the first developing device 4-1.
(Yellow developing device) develops with the first color yellow toner 22. The developing device 4-1 is an apparatus unit, which is detachable from the image forming apparatus main body. Developing device 4-
6 is an enlarged view of FIG.

In FIG. 6, reference numeral 22 denotes an outer wall accommodating the one-component non-magnetic yellow toner 20, and a developing sleeve 16 is disposed inside the outer wall 22 as a toner carrier so as to face the photoconductor 1 rotating in the direction of arrow a. The electrostatic charge image on the photoconductor 1 is developed with toner to form a toner image on the photoconductor 1. The developing sleeve 16 has a substantially semicircular surface on the right as viewed in FIG.
2, the left substantially half circumferential surface is exposed to the outside of the outer wall 22, and is rotatably provided laterally so as to face the photoconductor 1. A minute interval is provided between the developing sleeve 16 and the photoconductor 1. The developing sleeve 16 is driven to rotate in the direction of arrow b with respect to the rotation direction a of the photoconductor 1.

The developing sleeve 16 is not limited to the cylindrical shape, and may be in the form of an endless belt which is rotationally driven.
A conductive rubber roller may be used.

Further, in the outer wall 22, an elastic blade 19 is provided above the developing sleeve 16 as an elastic regulating member, and a toner applying roller 18 is provided at a position upstream of the elastic blade 19 in the rotational direction of the developing sleeve 16. It is provided. An elastic roller may be used as the elastic regulating member.

The elastic blade 19 is provided so as to be inclined downward toward the upstream side in the rotational direction of the developing sleeve 16, and is brought into contact with the upper outer peripheral surface of the developing sleeve 16 so as to face in the rotational direction.

The toner applying roller 18 is in contact with the developing sleeve 16 on the side opposite to the photosensitive member 1 and is rotatably supported.

In the developing device 4-1, the toner applying roller 18 is rotated in the direction of arrow c with the above construction, and the yellow toner 20 is carried by the rotation of the toner applying roller 18 and is supplied near the developing sleeve 16, Contact part (nip part) where the developing sleeve 16 and the toner applying roller 18 contact
At this time, the yellow toner 20 on the toner application roller 18 is rubbed against the developing sleeve 16 and adheres to the developing sleeve 16.

As the developing sleeve 16 rotates, the yellow toner 20 adhering to the developing sleeve 16 enters between the elastic blade 19 and the developing sleeve 16 at the abutting portion thereof, and develops when passing therethrough. Both the surface of the sleeve 16 and the elastic blade 19 are rubbed against each other to give a sufficient frictional charge.

The yellow toner 20 frictionally charged as described above passes through the contact portion between the elastic blade 19 and the developing sleeve 16, and a thin layer of the yellow toner 20 is formed on the developing sleeve 16, and The sheet is conveyed to the developing section facing the sheet No. 1. By applying an alternating voltage obtained by superimposing a direct current and an alternating current as a developing bias to the developing sleeve 16 by a bias applying unit 17, the yellow toner 20 on the developing sleeve 16 is transferred corresponding to the electrostatic image of the photoconductor 1, Attach to the electrostatic image to form a toner image.

The yellow toner 20 remaining on the developing sleeve 16 without being transferred to the photosensitive member 1 in the developing section is collected in the outer wall 22 from the lower portion of the developing sleeve 16 as the developing sleeve 16 rotates.

The collected yellow toner 20 is peeled off from the developing sleeve 16 by the toner application roller 18 at the contact portion with the developing sleeve 16. At the same time, new yellow toner 22 is supplied onto the developing sleeve 16 by the rotation of the toner applying roller 18, and the new yellow toner 22 is transported again to the contact portion between the developing sleeve 16 and the elastic blade 19.

On the other hand, most of the removed yellow toner 22 is removed from the outer wall 2 as the toner applying roller 18 rotates.
The other toner 22 in 2 mixes with the toner, and the triboelectric charge of the peeled toner is dispersed. The toner at a position distant from the toner application roller 18 is sequentially supplied to the toner application roller 18 by the stirring means 21.

The toner of the present invention has good developability and durability for many sheets in the above-mentioned non-magnetic one-component developing step.

The developing sleeve 16 is preferably a conductive cylinder formed of a metal or alloy such as aluminum or stainless steel. The conductive cylinder may be formed of a resin composition having sufficient mechanical strength and conductivity. Further, the developing sleeve 16 may have a coating layer formed of a resin composition in which conductive fine particles are dispersed on a metal or alloy cylindrical surface.

As the coating layer, a resin material containing conductive fine particles is used. Conductive particles are 120K
It is preferable that the resistance value after pressing with g / cm ² is 0.5 Ω · cm or less.

As the conductive fine particles, carbon fine particles,
A mixture of carbon fine particles and crystalline graphite, or crystalline graphite is preferred. The conductive fine particles preferably have a particle size of 0.005 to 10 μm.

The resin material is, for example, a thermoplastic resin such as a styrene resin, a vinyl resin, a polyether sulfone resin, a polycarbonate resin, a polyphenylene oxide resin, a polyamide resin, a fluororesin, a fibrin resin or an acrylic resin; an epoxy. A thermosetting resin or a photocurable resin such as a resin, a polyester resin, an alkyd resin, a phenol resin, a melamine resin, a polyurethane resin, a urea resin, a silicone resin, or a polyimide resin can be used.

Among them, those having releasability such as silicone resin and fluororesin, or polyether sulfone,
Polycarbonate, polyphenylene oxide, polyamide, phenolic resin, polyester, polyurethane,
Those having excellent mechanical properties such as styrene resins are more preferable. Particularly, a phenol resin is preferable.

The conductive fine particles are preferably used in an amount of 3 to 20 parts by weight per 10 parts by weight of the resin component.

When carbon fine particles and graphite particles are used in combination, it is preferable to use 1 to 50 parts by weight of carbon fine particles per 10 parts by weight of graphite.

The volume resistivity of the resin coating layer of the sleeve in which the conductive fine powder is dispersed is 10 ^{−6 to} 10 ⁶ Ω · cm.
Is preferred.

Magenta developing unit 4-2, cyan developing unit 4-
3 and the black developing device 4-4 also have the same structure as the yellow developing device 4-1 and are non-magnetic one-component developing methods.

Only the black developing device may be a magnetic one-component developing type developing device using an insulating magnetic toner in some cases.

The intermediate transfer member 5 is rotationally driven in the direction of the arrow at the same peripheral speed as the photosensitive drum 1.

The yellow toner image of the first color formed and carried on the photosensitive drum 1 is the photosensitive drum 1 and the intermediate transfer member 5.
In the process of passing through the nip between and, the intermediate transfer is performed on the outer peripheral surface of the intermediate transfer body 5 by the electric field and the pressure formed by the primary transfer bias 6 applied to the intermediate transfer body 5. Hereinafter, this process is called primary transfer.

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 superposed and transferred onto intermediate transfer member 5 in the same manner, and combined in accordance with the target color image. A color toner image is formed.

The transfer belt 10 is arranged in parallel with the rotation axis of the intermediate transfer member 5 so as to be in contact with the lower surface thereof. The transfer belt 10 is supported by a bias roller 11 and a tension roller 12, a desired secondary transfer bias is applied to the bias roller 11 by a secondary transfer bias source 23, and the tension roller 12 is grounded.

First to the intermediate transfer member 5 from the photosensitive drum 1
A primary transfer bias for sequentially superimposing transfer of the four color toner images is applied from a bias power supply 6 with a polarity (+) opposite to that of the toner.

The first to the intermediate transfer member 5 from the photosensitive drum 1
The transfer belt 10 and the intermediate transfer member cleaning roller 7 can be brought into contact with and separated from the intermediate transfer member 5 in the sequential transfer execution process of the fourth color toner image.

The transfer of the composite color toner image superposedly transferred onto the intermediate transfer member 5 to the transfer material P is performed while the transfer belt 10 is brought into contact with the intermediate transfer member 5 and a registration roller from a paper feeding cassette (not shown). 13. The transfer material P is fed to the contact nip between the intermediate transfer member 5 and the transfer belt 10 at a predetermined timing after passing through the pre-transfer guide 24, and at the same time, the secondary transfer bias is supplied from the bias power supply 23 to the bias roller 11. Is applied. The composite color toner image is transferred from the intermediate transfer member 5 to the transfer material P by the secondary transfer bias. Hereinafter, this step is referred to as secondary transfer.

The transfer material P which has received the transfer of the toner image is introduced into a heating and pressure fixing device 25 having a heating roller 14 and a pressure roller 15, and is heated and fixed. The toner of the present invention can fix a toner image without causing offset even if the heating roller 14 is not coated with an offset preventive agent such as silicone oil.

The intermediate transfer member 5 is a pipe-shaped conductive core metal 5.
b and an elastic layer 5a having a medium resistance formed on the outer peripheral surface thereof. The metal core 5b may be formed by applying a conductive plating to a plastic pipe.

The elastic layer 5a of medium resistance is made of silicone rubber,
Teflon rubber, chloroprene rubber, urethane rubber, EP
An electrical resistance value (volume resistivity) of 10 is obtained by mixing and dispersing an electroconductive material such as carbon black, zinc oxide, tin oxide, or silicon carbide in an elastic material such as DM (a terpolymer of ethylene propylene diene). ^A solid or foamed layer with a medium resistance of ⁵ to 10 ¹¹ Ω · cm.

If necessary, after the toner image is transferred onto the transfer material by the detachable cleaning means, the intermediate transfer member 5 is transferred.
Is cleaned. When there is a toner image on the intermediate transfer member, the cleaning unit is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

For example, for cleaning the intermediate transfer member 5,
Simultaneously with the primary transfer from the photosensitive drum 1 to the intermediate transfer body 5, the secondary transfer residual toner is reversely transferred back to the photosensitive drum 1 and returned to the intermediate transfer body 5, and is collected by the cleaner 9 of the photosensitive drum 1. It is done by.

The mechanism will be described. Intermediate transfer member 5
The toner image formed on the toner image is sent to the transfer belt 10 by a strong electric field formed by applying a secondary transfer bias having a polarity opposite to the charging polarity (negative polarity) of the toner image to the bias roller 11. It is transferred to the transferred transfer material P.

At this time, the secondary transfer residual toner which is not transferred to the transfer material P and remains on the intermediate transfer body 5 is charged to a polarity (positive polarity) opposite to the regular charging polarity (negative polarity). There are many.

However, not all the secondary transfer residual toners are inverted to the positive polarity, and some toners are neutralized and have no charge, and some toners maintain the negative polarity.

The charging means 7 for reversing the partially neutralized toner having no electric charge and the toner maintaining the negative polarity to the opposite polarity is provided after the secondary transfer position and before the primary transfer position. Set up.

As a result, almost all of the secondary transfer residual toner can be returned to the photoconductor 1.

Reverse transfer of the secondary transfer residual toner onto the photoconductor 1 and transfer of the toner image formed on the photoconductor 1 to the intermediate transfer member 5
When the first transfer is performed simultaneously with the first transfer, the intermediate transfer member 5
The reverse-charged secondary transfer residual toner and the primary-transferred regular toner are reverse-charged in the nip portion between the photosensitive drum 1 and the intermediate transfer member 5 without substantially being electrically neutralized. The transferred toner is transferred to the photosensitive drum 1, and the normally charged toner is transferred to the intermediate transfer member 5.

This is because by lowering the primary transfer bias, the electric field applied between the photosensitive drum 1 and the intermediate transfer member 5 at the primary transfer nip is weakened to suppress the discharge at the nip portion. This is because the polarity of the toner is prevented from changing in some parts.

Further, since the triboelectrically-charged toner has an electrical insulating property, the opposite polarity toners do not cancel the charge in a short time and the polarity is not reversed or neutralized.

Therefore, the secondary transfer residual toner charged on the intermediate transfer member 5 in the positive polarity is transferred to the photosensitive drum 1, and the toner image charged in the negative polarity on the photosensitive drum 1 is transferred to the intermediate transfer member. Each of them behaves independently such as being transferred to 5.

When an image is formed on one transfer material P by one image forming start signal, the toner image is not transferred from the photosensitive drum 1 to the intermediate transfer member 5 after the secondary transfer. The secondary transfer residual toner remaining on the intermediate transfer member is transferred to the photosensitive drum 1.
Reverse transcription is performed.

In this embodiment, 2 on the intermediate transfer member 5 is used.
A contact-type charging means, specifically, an elastic roller having a plurality of layers was used as the intermediate transfer member cleaning roller 7 as a charging means for charging the next transfer residual toner.

The methods for measuring the physical properties of the toner and the low softening point substance will be described below.

Measurement of Rheological Properties of Toner Using a viscoelasticity measuring apparatus (Rheometer) RDA-II type (manufactured by Rheometrics), under the following conditions, 30 to 2
The storage elastic modulus G ′ and the intersection (Tc) between the storage elastic modulus (G ′) and the loss elastic modulus (G ″) in the temperature range of 00 ° C. are measured.

Measuring jig: A parallel plate having a diameter of 7.9 mm is used when the elastic modulus is high, and a parallel plate having a diameter of 25 mm is used when the elastic modulus is low.

Measurement sample: After heating and melting the toner, the toner is molded into a cylindrical sample having a diameter of about 8 mm and a height of 1.5 to 5 mm, or a disk-shaped sample having a diameter of about 25 mm and a height of 1.5 to 3 mm. use.

Measurement frequency: 6.28 rad / sec Measurement distortion setting: After setting the initial value to 0.1%, measurement is performed in the automatic measurement mode.

-Expansion correction of sample: Adjust in the automatic measurement mode.

Measurement temperature: 2 minutes per minute from 25 ° C to 210 ° C
Heat at a rate of ° C.

Measurement of DSC endothermic peak of low softening point substance Differential thermal analysis analyzer (DSC analyzer), DSC-7
(PerkinElmer) using ASTM D34
Measure according to 18-82. Measurement sample is 2-10m
Accurately weigh within g. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rising rate is 10 ° C / min in the measurement temperature range of 30 to 160 ° C
Then, the measurement is performed under normal temperature and normal humidity. The half-value width of the endothermic main peak refers to the temperature width of the endothermic curve at a position half the height of the endothermic main peak.

Measurement of Gloss Value of Fixed Image Gloss is measured using a handy gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition of an incident angle of light of 75 degrees.

Toner Particle Cross Section After the toner is sufficiently dispersed in an epoxy resin which is curable at room temperature, it is cured in an atmosphere at a temperature of 40 ° C. for 2 days, and the obtained cured product is ruthenium tetroxide and, if necessary, tetraoxide. After dyeing with osmium together, using a microtome equipped with diamond teeth, cut out a flaky sample,
The tomographic morphology of the toner was observed using a transmission electron microscope (TEM). It is preferable to use the ruthenium tetroxide dyeing method in order to make a contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell.

Coagulation degree measurement of toner Using a vibrating sieve of a powder tester (manufactured by Hosokawa Micron Co.), 400 mesh, 200 mesh, 1
So that the 00 mesh sieves are overlapped in the order of narrow opening, namely,
400 mesh, so that 100 mesh is the highest
The sieves of 200 mesh and 100 mesh are piled up in this order and set.

A sample was added on the set 100 mesh sieve so that the input voltage to the vibrating table became 15V,
At this time, the amplitude of the shaking table is adjusted to fall within the range of 60 to 90 μm, and vibration is applied for about 25 seconds. Thereafter, the weight of the sample remaining on each sieve is measured, and the degree of cohesion is obtained based on the following equation. .
The smaller the value of the degree of aggregation, the higher the fluidity of the toner.

[0154]

[Outside 4]

Measurement of toner particle size distribution As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter, Inc.) is used. The electrolyte is about 1 using first-grade sodium chloride.
% NcCl aqueous solution is prepared. For example,

[0156]

[Outside 5] (Manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic aqueous solution 100 to
As a dispersant, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added to 150 ml, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes.
Using a 0 μm aperture, the volume and number of toner particles are measured for each channel, and the volume distribution and number distribution of toner are calculated. Then, the weight average particle diameter (D4) of the toner based on the weight determined from the volume distribution of the toner particles.
(The median value of each channel is used as a representative value for each channel).

The channels are 2.00 to 2.52.
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μm
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08 to 12.70 μm; 12.70 to 16.
00 μm; 16.00-20.20 μm; 20.20
25.40 μm; 25.40 to 32.00 μm;
13 channels of 40.30 μm are used.

Measurement of acid value (JIS acid value) 1) 0.1-0.2 g of a sample is precisely weighed and its weight is W
(G).

2) Put the sample in a 20 cc Erlenmeyer flask,
10 cc of a mixed solution of toluene / ethanol (2: 1) is added and dissolved.

3) Add a few drops of an alcohol solution of phenolphthalein as an indicator.

4) Titrate the solution in the flask with a burette using an alcohol solution of 0.1N KOH.

The amount of KOH solution used at this time was S (ml)
And At the same time, a blank test is performed, and the amount of the KOH solution at this time is defined as B (ml).

5) The acid value is calculated by the following formula.

[0164]

[Outside 6]

Blocking resistance test Approximately 10 g of toner was placed in a 100 cc poly cup and
After leaving it at 3 ° C. for 3 days, it is visually evaluated.

A: No aggregate is observed.

B: Aggregates can be seen but are easily broken.

C: Aggregates can be seen but collapse if shaken.

D: Aggregates can be grabbed and are not easily broken.

[0170]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments.

Example 1 Styrene monomer 165 parts by weight n-Butyl acrylate monomer 35 parts by weight Phthalocyanine pigment 14 parts by weight (CI Pigment Blue 15: 3) Linear polyester resin 10 parts by weight (Polycondensation product of polyoxypropylene bisphenol A and phthalic acid, acid value 8) 2 parts by weight of aluminum compound of dialkylsalicylic acid 0.5 parts by weight of divinylbenzene C ₂₂ alkylcarboxylic acid and C ₂₂ alkyl alcohol Ester wax with 30 parts by weight (DSC main peak value 75 ° C, half-value width 3 ° C)

The above mixture was mixed with an attritor to 3
After dispersion for a time, the monomer composition to which 3 parts by weight of lauroyl peroxide as a polymerization initiator was added was added to water 120
0 parts by weight mixed with 7 parts by weight of tricalcium phosphate
After being poured into an aqueous solution at 0 ° C., 1
The mixture was stirred at 0000 rpm and granulated for 10 minutes. After that, change the stirrer from the high-speed stirrer to the propeller stirrer blade,
The polymerization was continued for 10 hours at 60 revolutions. After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, washing and drying were carried out to obtain cyan toner particles having a weight average particle diameter of 6.5 μm. When the cross section of the obtained cyan toner particles was observed, it was found that the low softening point substance was covered with the outer shell resin as shown in FIG.

100 parts by weight of the cyan toner particles and 1.5 parts by weight of the hydrophobic silica fine powder were mixed with a Henschel mixer, and cyan toner No. 1 was obtained.

The obtained cyan toner No. A graph of storage elastic modulus G ′, loss elastic modulus G ″ and tan (δ) of No. 1 is shown in FIG.

Cyan toner No. 1 has SF-1 of 10
5 and styrene-n crosslinked with divinylbenzene
-Containing about 15 parts by weight (about 12% by weight based on toner) of the ester wax, and about 10 parts by weight of THF insoluble matter, to 100 parts by weight of the binder resin composed of the butyl acrylate copolymer and the linear polyester resin. % (Binder resin standard)
Contained. Cyan toner No. Table 1 shows the respective physical properties of 1.

Comparative Example 1 Paraffin wax (DS
The main peak value of C is 63 ° C and the full width at half maximum is 40 ° C)
Example 1 except that no divinylbenzene is used
Similarly to the cyan toner No. 2 was prepared.

Cyan toner No. 2 storage modulus G ′,
A graph of the loss elastic modulus G ″ and tan (δ) is shown in FIG.

Cyan toner No. The binder resin of No. 2 was non-crosslinked, and the binder resin contained no THF insoluble matter. Cyan toner No. In the viscoelasticity measurement, the viscosity of 2 decreased with increasing temperature, and the storage elastic modulus G ′ and loss elastic modulus at 140 ° C. or higher could not be measured. Table 1 shows the physical properties of the cyan toner.

Comparative Example 2 Instead of the ester wax, paraffin wax (DS
Cyan Toner No. 1 in the same manner as in Example 1 except that the main peak value of C is 63 ° C. and the full width at half maximum is 40 ° C.).
3 was prepared.

Cyan toner No. Storage modulus G'of 3,
A graph of loss elastic modulus G ″ and tan (δ) is shown in FIG. 3. The ratio (G ′ ₆₀ / G ′ ₈₀ ) of cyan toner No. 3 is
Cyan toner No. 10 at the time of heating from a temperature of 60 ° C. to a temperature of 80 ° C. The change rate of G'of 3 was small. Cyan toner No. The physical properties of No. 3 are shown in Table 1.

Comparative Example 3 A cyan toner was prepared in the same manner as in Example 1 except that polypropylene wax (Viscole 660P, Sanyo Kasei; DSC main peak value: 137 ° C., full width at half maximum 7 ° C.) was used instead of the ester wax. No. 4 was prepared. Cyan toner No. 4, the ratio _{(G '60 / G' 80} ) was 71.4. Cyan toner No. The physical properties of No. 4 are shown in Table 1.

Comparative Example 4 Cyan Toner No. 1 was used in the same manner as in Example 1 except that the amount of the ester wax used was 5 parts by weight. 5 was prepared. Cyan toner No. In Example 5, 2.4 parts by weight of the ester wax was contained per 100 parts by weight of the binder resin. Cyan toner No. Table 1 shows the respective physical properties of No. 5.

Comparative Example 5 Cyan Toner No. 1 was used in the same manner as in Example 1 except that the amount of the ester wax used was 100 parts by weight. 6 was prepared. Cyan toner No. 6, the binder resin 10
47 parts by weight of ester wax was contained per 0 parts by weight. Cyan toner No. The physical properties of No. 6 are shown in Table 1.

Comparative Example 6 Cyan Toner No. 1 was prepared in the same manner as in Example 1 except that the amount of divinylbenzene used was 2 parts by weight. 7 was prepared.
Cyan toner No. The binder resin of No. 7 contained 47% by weight of THF insoluble matter. Cyan toner No. The physical properties of No. 7 are shown in Table 1.

Comparative Example 7 Styrene-n-butyl acrylate-divinylbenzene copolymer (weight average molecular weight 163,000, main peak molecular weight 100 parts by weight 22,500, THF insoluble content 13.5 wt%)-Linear polyester resin 5 parts by weight (polycondensate of polyoxypropylene bisphenol a and phthalic acid, acid value 8) ester wax 3 with an alkyl alcohol an alkyl carboxylic acid and C ₂₂ of the aluminum compound 1 part by weight, C ₂₂ dialkyl salicylic acid Parts by weight (DSC main peak value 75 ° C, half-value width 3 ° C)

The above materials were sufficiently premixed with a Henschel mixer, and the temperature was about 130 ° C. with a twin-screw extrusion kneader.
Melt and knead with, cool and use a hammer mill for about 1-2 m
Coarsely pulverized to about m, and then finely pulverized by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified to obtain cyan toner particles having a weight average particle diameter of 7.5 μm.

100 parts by weight of cyan toner particles and 1.5 parts by weight of hydrophobic Syria fine powder were mixed with a Henschel mixer to obtain cyan toner No. 9 was obtained.

Comparative Example 8 Cyan toner No. 6 was prepared in the same manner as in Comparative Example 7 except that the amount of the ester wax used was changed to 15 parts by weight. 10 was obtained.

[0189]

[Table 1]

Example 2 Cyan Toner No. 1 is a developing unit which is an apparatus unit 4-
The test piece was placed in No. 3 and mounted in the image forming apparatus shown in FIG. 5, and an image output test was conducted in a mono color mode. Even in the 5000-sheet multi-sheet durability test, a good cyan fixed image with high image density and no fog was obtained. No toner fusion was observed on the toner applying roller 18, the developing sleeve 16, and the elastic blade 19 even after 5,000 sheets of durability, and good developing durability was exhibited. Furthermore, oilless fixing was performed without applying dimethyl silicone oil to the heating roller 14, but no offset was observed, and the fixing temperature was set to 1
The fixing was carried out by changing the temperature from 60 ° C. to 190 ° C., but there was little fluctuation in the gloss value of the fixed image. Table 2 shows the results.

Comparative Examples 9 to 16 Cyan Toner Nos. An imaging test was conducted in the same manner as in Example 2 except that 2 to 10 were used. Table 2 shows the results.

Image density The solid image portion is measured with a Macbeth reflection densitometer (manufactured by Macbeth Co.). At that time, a portion having a glossiness of 25 to 35 measured with a glossiness meter (PG-3D, manufactured by Nippon Coloring Industry Co., Ltd.) was measured.

Fog Measurement Method Fog is measured by REFLECTOME manufactured by Tokyo Denshoku Co., Ltd.
The measurement was performed using TER MODELTC-6DS, and the cyan toner image was calculated using the following formula using an amber filter. The smaller the value, the less fog.

Fog (reflectance) (%) = [reflectance (%) of standard paper]-[reflectance (%) of non-image part of sample]

Fixing start temperature and high temperature offset free temperature
Heating roller 14 and 100 ° C. to 200 DEG the temperature of the pressure roller 15 having a surface layer of fluorine resin in degrees heat-pressure fixing device
The temperature is adjusted every 5 ° C in the temperature range of ℃, fixing is performed at each temperature, and the obtained fixed image is rubbed twice with sillbon paper loaded with 50 g / cm ² to obtain the image density before and after rubbing. The fixing temperature at which the reduction rate is 10% or less is the fixing start temperature.

The fixing temperature is raised and the highest temperature at which the offset phenomenon does not occur visually is taken as the high temperature offset free temperature.

Evaluation of developing device during endurance of a large number of sheets When an image loss occurs due to the developing device during endurance of a large number of sheets, image output is interrupted and the surface of the toner application roller, the surface of the developing sleeve and the elastic blade are interrupted. The surface stains and the toner fusion state were visually evaluated.

When image defects did not occur during the endurance of a large number of sheets, the stains on the surface of the toner application roller, the surface of the developing sleeve and the surface of the elastic blade and the fused state of the toner were visually evaluated after the endurance of a large number of sheets.

A: Substantially no stain and no toner fusion B: Soil or toner fusion was observed, but no noticeable image loss was observed C ... Severe stain or toner fusion was observed, resulting in image loss

[0200]

[Table 2]

Example 3 Yellow toner No. 1 was used in the same manner as in Example 1 except that a yellow colorant (CI Pigment Yellow 173) was used as the colorant. 1 was prepared. Table 3 shows each physical property.

Comparative Examples 17 to 24 Yellow toner Nos. 1 to 8 were prepared in the same manner as Comparative Examples 1 to 8 except that a yellow colorant (CI Pigment Yellow 173) was used as the colorant. 2 to 9 were prepared. Table 3 shows each physical property.

Example 4 Magenta Toner No. 1 was used in the same manner as in Example 1 except that a magenta colorant (CI Pigment Red 122) was used as the colorant. 1 was prepared. Table 4 shows each physical property.

Comparative Examples 25 to 32 Magenta Toner Nos. Nos. 1 to 8 were used in the same manner as Comparative Examples 1 to 8 except that a magenta colorant (CI Pigment Red 122) was used as the colorant. 2 to 9 were prepared. Table 4 shows each physical property.

Example 5 Black No. 1 was obtained in the same manner as in Example 1 except that a black colorant (carbon black) was used as the colorant. 1 was prepared. Table 5 shows the physical properties.

Comparative Examples 33 to 40 Black Toner N was prepared in the same manner as Comparative Examples 1 to 8 except that a black colorant (carbon black) was used as the colorant.
os. 2 to 9 were prepared. Table 5 shows the physical properties.

[0207]

[Table 3]

[0208]

[Table 4]

[0209]

[Table 5]

Example 6 Yellow Toner No. 1 is put in the developing device 4-1 and the magenta toner No. 1 into the developing device 4-2, and the cyan toner No. 1 into the developing device 4-3, and the black toner No. 1
Was placed in the developing device 4-4, mounted in the image forming apparatus, and an image output test was conducted in the full color mode. Table 6 shows the results.

Comparative Examples 41 to 48 Yellow Toner Nos. 2-9, magenta toner No.
s. 2-9, cyan toner Nos. 2-9 and black toner Nos. Example 6 except using 2-9
An image output test was performed in the full color mode in the same manner as in. Table 6 shows the results.

[0212]

[Table 6]

Examples 7 to 12 Type of polyester resin, amount of divinylbenzene used,
A cyan toner Nos 2 was prepared in the same manner as in Example 1 except that the type of wax was changed. Table 7 shows each physical property.
Shown in

Examples 13 to 18 Cyan toner Nos. Example 2 using 10 to 15
An image-drawing test was performed in the same manner as described above. Table 8 shows the results.

[0215]

[Table 7]

[0216]

[Table 8]

[0219]

By using the toner for developing an electrostatic image of the present invention, the low-temperature fixing property is further improved, an image having a certain gloss is obtained in a wide temperature range, and immediately after the power is turned on even in cold weather. It is possible to obtain a high-quality image showing good fixing property.

[Brief description of drawings]

FIG. 1 shows an example of a storage elastic modulus curve, a loss elastic modulus curve, and a tan (δ) curve of the toner of the present invention.

FIG. 2 shows a storage elastic modulus curve, a loss elastic modulus curve, and a tan (δ) curve of a comparative toner.

FIG. 3 shows a storage elastic modulus curve, a loss elastic modulus curve, and a tan (δ) curve of another comparative toner.

FIG. 4 is an explanatory diagram of a DSC endothermic curve of a low softening point substance.

FIG. 5 is an explanatory diagram showing an example of an image forming apparatus for carrying out the image forming method of the present invention.

FIG. 6 is a schematic sectional view showing an example of an apparatus unit of the present invention.

FIG. 7 is a schematic illustration of a cross section of toner particles.

FIG. 8 is a schematic illustration of a cross section of another form of toner particle.

[Explanation of symbols]

 1 image carrier (photoreceptor) 2 charging roller 5 intermediate transfer member 8 cleaning blade 16 developing sleeve 18 toner applying roller

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03G 9/08 361 365

Claims (93)

[Claims] 1. A binder resin 100 parts by weight, and colorants 1 to 1
A toner for developing an electrostatic charge image, which comprises at least 50 parts by weight and 5 to 40 parts by weight of a low softening point substance, the toner having a storage elastic modulus (G _'60 ) at a temperature of 60 ° C.
And the storage modulus (G _'80 ) at a temperature of 80 ° C (G' ₆₀ / G _'80 ) is 80 or more, and the storage modulus (G' ₁₅₅ ) at a temperature of 155 ° C and the temperature 1
Ratio (G ′) to storage elastic modulus (G ′ ₁₉₀ ) at 90 ° C.
₁₅₅ / G ′ ₁₉₀ ) is 0.95 to 5 for developing electrostatic image. 2. The toner has a ratio (G ′ ₆₀ / G ′ ₈₀ ) of 10
The toner according to claim 1, which is 0 to 400. 3. The toner has a ratio (G ′ ₆₀ / G ′ ₈₀ ) of 15
The toner according to claim 1, which is 0 to 300. 4. The toner according to claim 1, wherein the toner has a ratio (G ′ ₁₅₅ / G ′ ₁₉₀ ) of 1 to 5. 5. The toner has a storage elastic modulus (G ′ ₁₉₀ ) at a temperature of 190 ° C. of 1 × 10 ^{3 to} 1 × 10 ⁴ (dyn).
/ Cm ² ). The toner according to any one of claims 1 to 4. 6. The toner has a maximum value (G ″ _max ) in the temperature range of 40 to 65 ° C. in the loss modulus curve, and the maximum value (G ″ _max ) is 1 × 10 ⁹ (dyn / cm ² ). The toner according to any one of claims 1 to 5, which is as described above. 7. The toner has a ratio (G ″ _max / g / _max ) of a loss elastic modulus (G ″ ₄₀ ) at a temperature of 40 ° C. to a maximum value (G ″ _max ) of a loss elastic modulus curve in a temperature range of 40 to 65 ° C.
7. The toner according to claim 1, wherein G ″ ₄₀ ) is 1.5 or more. 8. The binder resin has a THF insoluble content of 0.1 to 2
The toner according to claim 1, having 0% by weight. 9. The toner according to claim 1, wherein the binder resin has a THF insoluble content of 1 to 15% by weight. 10. The binder resin has a cross-linked styrene copolymer, and the low softening point substance has an endothermic main peak in a temperature range of 40 to 90 ° C. in a DSC endothermic curve. The toner according to Crab. 11. The binder resin comprises a crosslinked styrene copolymer and a non-crosslinked polyester resin, and the low softening point substance has an endothermic main peak in a temperature range of 40 to 90 ° C. in a DSC endothermic curve. 10. The toner according to any one of 1 to 9. 12. The binder resin comprises a crosslinked styrene copolymer and a crosslinked polyester resin, and the low softening point substance has an endothermic main peak in a temperature range of 40 to 90 ° C. on a DSC endothermic curve. 10. The toner according to any one of 1 to 9. 13. The low softening point substance has an endothermic main peak in a region of a temperature of 45 to 85 ° C. in a DSC endothermic curve, and a half width of the endothermic main peak is within 10 ° C. The toner according to. 14. The toner according to claim 13, wherein the low softening point substance has a half-value width of an endothermic main peak within 5 ° C. 15. The toner according to claim 1, wherein the low softening point substance is a solid wax. 16. The toner according to claim 14, wherein the low softening point substance is a solid ester wax. 17. The low-softening-point substance is a solid ester wax having a main endothermic peak in the temperature range of 45 to 85 ° C. in the DSC endothermic curve and having a full width at half maximum of the main endothermic peak within 10 ° C. 16. The toner according to any one of 16. 18. The toner according to claim 17, wherein the solid ester wax has a half-value width of an endothermic main peak within 5 ° C. 19. The low-softening substance is a solid polymethylene wax having an endothermic main peak in a temperature range of 40 to 90 ° C. in a DSC endothermic curve and having a half-value width of the endothermic main peak within 10 ° C. 17. The toner according to any one of 1 to 16. 20. The low-softening substance is a solid polyolefin wax having an endothermic main peak in a temperature range of 40 to 90 ° C. in a DSC endothermic curve and having a half-value width of the endothermic main peak within 10 ° C. 17. The toner according to any one of 1 to 16. 21. The low softening point substance has an endothermic main peak in a region of a temperature of 40 to 90 ° C. in a DSC endothermic curve, and the half-value width of the endothermic main peak is 1 ° C. or less.
The toner according to any one of claims 1 to 16, which is 5 to 100 long chain alkyl alcohols. 22. The low softening point substance is 11 based on toner particles.
22. The toner according to claim 1, wherein the toner is contained in an amount of 30 to 30% by weight. 23. The toner according to claim 22, wherein the low softening point substance is contained in an amount of 12 to 35 parts by weight per 100 parts by weight of the binder resin. 24. The toner according to claim 1, wherein the toner is a non-magnetic cyan toner. 25. The toner according to claim 1, wherein the toner is a non-magnetic magenta toner. 26. The toner according to claim 1, wherein the toner is a non-magnetic yellow toner. 27. The toner according to claim 1, wherein the toner is a non-magnetic black toner. 28. An apparatus unit having at least a toner, a developing sleeve, a toner applying unit installed so as to press the developing sleeve, and an outer wall for integrally holding them, the apparatus unit being an apparatus. The toner is removable, and the toner is 100 parts by weight of the binder resin and the coloring agents 1 to 15
The toner has a storage elastic modulus (G ′ ₆₀ ) at a temperature of 60 ° C.
And the storage modulus (G _'80 ) at a temperature of 80 ° C (G' ₆₀ / G _'80 ) is 80 or more, and the storage modulus (G' ₁₅₅ ) at a temperature of 155 ° C and the temperature 1
Ratio (G ′) to storage elastic modulus (G ′ ₁₉₀ ) at 90 ° C.
₁₅₅ / G ' ₁₉₀ ) is 0.95 to 5. 29. The apparatus unit according to claim 29, wherein the developing sleeve is a cylinder formed of a conductive metal or alloy, and a toner applying roller and an elastic blade are provided as toner applying means. 30. The apparatus unit according to claim 28, wherein the developing sleeve is a cylinder formed of a conductive metal or alloy and has a plurality of toner applying rollers as toner applying means. 31. The developing sleeve has a surface layer formed of a resin composition in which conductive fine powder is dispersed.
The apparatus unit according to any one of 8 to 30. 32. The toner has a ratio (G ′ ₆₀ / G ′ ₈₀ ) of 1
32. Apparatus unit according to any of claims 28 to 31, which is 00 to 400. 33. The toner has a ratio (G ′ ₆₀ / G ′ ₈₀ ) of 1
32. Apparatus unit according to any of claims 28 to 31, which is 50 to 300. 34. The toner has a ratio (G ′ ₁₅₅ / G ′ ₁₉₀ )
34. The device unit according to claim 28, wherein is 1 to 5. 35. The toner has a storage elastic modulus (G ′ ₁₉₀ ) at a temperature of 190 ° C. of 1 × 10 ^{3 to} 1 × 10 ⁴ (dy).
n / cm ² ) 35. The device unit according to any one of claims 28 to 34. 36. The toner has a maximum value (G ″ _max ) in a temperature range of 40 to 65 ° C. in a loss elastic modulus curve,
36. The apparatus unit according to claim 28, wherein the maximum value (G ″ _max ) is 1 × 10 ⁹ (dyn / cm ² ) or more. 37. The toner has a ratio (G ″ _max ) of a loss elastic modulus (G ″ ₄₀ ) at a temperature of 40 ° C. and a maximum value (G ″ _max ) of a loss elastic modulus curve in a region of a temperature of 40 to 65 ° C.
37. The apparatus unit according to claim 28, wherein / G ″ ₄₀ ) is 1.5 or more. 38. The binder resin has a THF insoluble content of 0.1 to 0.1%.
38. Apparatus unit according to any of claims 28 to 37 having 20% by weight. 39. The binder resin has a THF insoluble content of 1 to 15
39. The device unit of claim 38 having a weight percent. 40. The binder resin has a cross-linked styrene copolymer, and the low softening point substance has an endothermic main peak in a region of a temperature of 40 to 90 ° C. on a DSC endothermic curve. The device unit according to claim 1. 41. The binder resin comprises a crosslinked styrene copolymer and a non-crosslinked polyester resin, and the low softening point substance has an endothermic main peak in a region of a temperature of 40 to 90 ° C. in a DSC endothermic curve. The apparatus unit according to any one of 28 to 39. 42. The binder resin comprises a cross-linked styrene copolymer and a cross-linked polyester resin, and the low softening point substance has an endothermic main peak in a temperature range of 40 to 90 ° C. on a DSC endothermic curve. The apparatus unit according to any one of 28 to 39. 43. The low softening point substance has an endothermic main peak in a region of a temperature of 45 to 85 ° C. in a DSC endothermic curve, and a half value width of the endothermic main peak is within 10 ° C. The device unit according to any of the above. 44. The apparatus unit according to claim 43, wherein the low softening point substance has a half-value width of an endothermic main peak within 5 ° C. 45. The device unit according to claim 28, wherein the low softening point substance is a solid wax. 46. The device unit according to claim 28, wherein the low softening point substance is a solid ester wax. 47. The low softening point substance is a solid ester wax having an endothermic main peak in the temperature range of 45 to 85 ° C. in the DSC endothermic curve, and the full width at half maximum of the endothermic main peak is within 10 ° C. The apparatus unit according to any one of 46. 48. The apparatus unit according to claim 47, wherein the solid ester wax has a half-value width of the endothermic main peak within 5 ° C. 49. The low softening point substance is a solid polymethylene wax having an endothermic main peak in the temperature range of 40 to 90 ° C. in the DSC endothermic curve and having a half-value width of the endothermic main peak within 10 ° C. The apparatus unit according to any one of 28 to 46. 50. The low-softening substance is a solid polyolefin wax having an endothermic main peak in the temperature range of 40 to 90 ° C. on the DSC endothermic curve and having a full width at half maximum of the endothermic main peak within 10 ° C. 47. The apparatus unit according to any one of 46 to 46. 51. The low softening point substance has an endothermic main peak in the temperature range of 40 to 90 ° C. on the DSC endothermic curve, and the half-value width of the endothermic main peak is 1 ° C. or less.
47. Apparatus unit according to any of claims 28 to 46, which is 5 to 100 long chain alkyl alcohols. 52. The low softening point substance is 1 based on toner particles.
52. The apparatus unit according to any one of claims 28 to 51, which contains 1 to 30% by weight. 53. The apparatus unit according to claim 52, wherein the low softening point substance is contained in an amount of 12 to 35 parts by weight per 100 parts by weight of the binder resin. 54. The apparatus unit according to claim 28, wherein the toner is a non-magnetic cyan toner. 55. The apparatus unit according to claim 28, wherein the toner is a non-magnetic magenta toner. 56. The apparatus unit according to claim 28, wherein the toner is a non-magnetic yellow toner. 57. The apparatus unit according to claim 28, wherein the toner is a non-magnetic black toner. 58. An electrostatic charge image is formed on an image carrier, the electrostatic charge image is developed with a toner having a triboelectric charge to form a toner image, and the toner image is transferred with or without an intermediate transfer member. An image forming method in which a toner image on a transfer material is transferred and the toner image on the transfer material is heated and pressed and fixed on the transfer material. The toner is 100 parts by weight of a binder resin and 1 to 15 of colorants.
0% by weight and at least 5 to 40 parts by weight of the low softening point substance, the toner has a storage elastic modulus (G ′ ₆₀ ) at a temperature of 60 ° C.
And the storage modulus (G _'80 ) at a temperature of 80 ° C (G' ₆₀ / G _'80 ) is 80 or more, and the storage modulus (G' ₁₅₅ ) at a temperature of 155 ° C and the temperature 1
Ratio (G ′) to storage elastic modulus (G ′ ₁₉₀ ) at 90 ° C.
₁₅₅ / G ′ ₁₉₀ ) is 0.95 to 5; 59. An electrostatic charge image is formed on a photoconductor, the electrostatic charge image is developed with toner to which a triboelectric charge is applied by a toner application roller to form a toner image, and the toner image is transferred to an intermediate transfer member. 59. The image forming method according to claim 58, wherein the toner image on the intermediate transfer member is transferred to a transfer material, and the toner image on the transfer material is heated and pressed and fixed. 60. The photoconductor is charged by contact charging means, and the charged photoconductor is exposed to form an electrostatic image.
9. The image forming method according to item 9. 61. The image forming apparatus according to claim 59 or 60, wherein the intermediate transfer member is a drum-shaped member to which a voltage is applied, and the surface of the intermediate transfer member is cleaned by a cleaning unit. 62. A transfer belt, wherein the intermediate transfer member is a drum-shaped object to which a voltage is applied, and a toner image on the intermediate transfer member is applied with a bias that presses the intermediate transfer member through the transfer material. The image forming apparatus according to claim 59 or 61, wherein the image is transferred onto a transfer material. 63. The intermediate transfer member is an endless belt to which a voltage is applied, and the toner image on the intermediate transfer material is transferred to the transfer material by a transfer roller to which a voltage is applied.
63. The image forming method according to any one of 62 to 62. 64. (a) A first electrostatic charge image is formed on a photoconductor, and the first electrostatic charge image is a first toner selected from the group consisting of yellow toner, cyan toner, magenta toner and black toner. And then the first toner image is formed on the photosensitive member, the first toner image is transferred from the photosensitive member to the intermediate transfer member, and (b) the second electrostatic charge image is formed on the photosensitive member. The electrostatic image is developed with a second toner having a color tone different from that of the first toner to form a second toner image on the photoconductor, and the second toner image is transferred from the photoconductor to the intermediate transfer body. (C) A third electrostatic charge image is formed on the photoconductor, the third electrostatic charge image is developed with a third toner having a color tone different from that of the first and second toners, and the third toner image is formed on the photoconductor. And the third toner image is transferred from the photoconductor to the intermediate transfer body. A fourth electrostatic charge image is formed on the body, and the fourth electrostatic charge image has a color tone different from that of the first, second, and third toners.
Is developed with the toner of No. 1 to form a fourth toner image on the photoconductor, and the fourth toner image is transferred from the photoconductor to the intermediate transfer member. (E) First to fourth toners on the intermediate transfer member 64. The image is transferred to a transfer material, and (f) the first to fourth toner images on the transfer material are heated and pressure-fixed to form a multi-color image or a full-color image on the transfer material. The image forming method described in 1 .. 65. The image forming method according to claim 58, wherein the toner image on the transfer material is heated and pressure-fixed by a heating roller not coated with the offset prevention liquid. 66. The image forming method according to claim 58, wherein the surface of the heating roller is made of a fluororesin. 67. The image forming method according to claim 64, wherein each of the yellow toner, the cyan toner, and the magenta toner satisfies the physical properties of the toner according to claim 58. 68. The toner has a ratio (G ′ ₆₀ / G ′ ₈₀ ) of 1
68. The image forming method according to claim 58, wherein the image forming method is 00 to 400. 69. The toner has a ratio (G ′ ₆₀ / G ′ ₈₀ ) of 1
The image forming method according to claim 68, wherein the image forming method is 50 to 300. 70. The toner has a ratio (G ′ ₁₅₅ / G ′ ₁₉₀ )
70. The image forming method according to claim 58, wherein is 1 to 5. 71. The toner has a storage elastic modulus (G ′ ₁₉₀ ) at 190 ° C. of 1 × 10 ^{3 to} 1 × 10 ⁴ (dy).
71. The image forming method according to claim 58, wherein the image forming method is n / cm ² ). 72. The toner has a maximum value (G ″ _max ) in the temperature range of 40 to 65 ° C. in the loss elastic modulus curve,
72. The image forming method according to claim 58, wherein the maximum value (G ″ _max ) is 1 × 10 ⁹ (dyn / cm ² ) or more. 73. The toner has a ratio (G ″ _max ) of a loss elastic modulus (G ″ ₄₀ ) at a temperature of 40 ° C. and a maximum value (G ″ _max ) of a loss elastic modulus curve in a region of a temperature of 40 to 65 ° C.
73. The image forming method according to claim 58, wherein / G ″ ₄₀ ) is 1.5 or more. 74. The binder resin contains THF-insoluble matter in an amount of 0.1 to 0.1.
The image forming method according to any one of claims 58 to 73, having 20% by weight. 75. The binder resin has a THF insoluble content of 1 to 15
75. The image forming method according to claim 74, wherein the image forming method has a weight percentage. 76. The binder resin has a cross-linked styrene copolymer, and the low softening point substance has an endothermic main peak in a region of a temperature of 40 to 90 ° C. on a DSC endothermic curve. An image forming method according to claim 1. 77. The binder resin comprises a cross-linked styrene copolymer and a non-cross-linked polyester resin, and the low softening point substance has an endothermic main peak in the temperature range of 40 to 90 ° C. on the DSC endothermic curve. The image forming method according to any one of 58 to 75. 78. The binder resin has a cross-linked styrene copolymer and a cross-linked polyester resin, and the low softening point substance has an endothermic main peak in a region of a temperature of 40 to 90 ° C. in a DSC endothermic curve. The image forming method according to any one of 58 to 75. 79. The low softening point substance has an endothermic main peak in a region of a temperature of 45 to 85 ° C. in a DSC endothermic curve, and a half width of the endothermic main peak is within 10 ° C. The image forming method described in 1 .. 80. The image forming method according to claim 79, wherein the low softening point substance has a half-value width of the endothermic main peak within 5 ° C. 81. The image forming method according to claim 58, wherein the low softening point substance is a solid wax. 82. The image forming method according to claim 58, wherein the low softening point substance is a solid ester wax. 83. The low-softening-point substance is a solid ester wax having an endothermic main peak in the temperature range of 45 to 85 ° C. in the DSC endothermic curve, and the full width at half maximum of the endothermic main peak is within 10 ° C. 82. The image forming method according to any one of 82. 84. The image forming method according to claim 83, wherein the solid ester wax has a half-value width of an endothermic main peak within 5 ° C. 85. The low softening point substance is a solid polymethylene wax having an endothermic main peak in a temperature range of 40 to 90 ° C. in a DSC endothermic curve and having a half width of the endothermic main peak within 10 ° C. The image forming method according to any one of 58 to 82. 86. The low softening point substance is a solid polyolefin wax having an endothermic main peak in a temperature range of 40 to 90 ° C. in a DSC endothermic curve and having a half width of the endothermic main peak within 10 ° C. 82. The image forming method according to any one of 82 to 82. 87. The low softening point substance has an endothermic main peak in the temperature range of 40 to 90 ° C. on the DSC endothermic curve, and the half-value width of the endothermic main peak is 1 ° C. or less.
The image forming method according to any one of claims 58 to 82, which is 5 to 100 long-chain alkyl alcohols. 88. The low softening point substance is 11 based on toner particles.
88. The image forming method according to claim 58, wherein the image forming method further comprises 30 to 30% by weight. 89. The image forming method according to claim 88, wherein the low softening point substance is contained in an amount of 12 to 35 parts by weight per 100 parts by weight of the binder resin. 90. The image forming method according to claim 58, wherein the toner is a non-magnetic cyan toner. 91. The image forming method according to claim 58, wherein the toner is a non-magnetic magenta toner. 92. The image forming method according to claim 58, wherein the toner is a non-magnetic yellow toner. 93. The image forming method according to claim 58, wherein the toner is a non-magnetic black toner.