JP2007206097A - Toner, developer, container containing toner, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality toner that shows improved filming property, low temperature fixing property and heat-resistant storage property and achieves all of these excellent characteristics, and to provide a developer using the toner, a container containing the toner, a process cartridge, an image forming apparatus and an image forming method. <P>SOLUTION: The toner contains at least a crystalline polyester resin, an amorphous resin, a colorant and a release agent and shows properties that after the toner is stored in a temperature-controlled chamber at 45°C for 12 hours, a peak height ratio (W/R) ranges from 0.22 to 0.55, wherein W is the peak height in the characteristic spectrum of the crystalline polyester resin and R is the peak height of the characteristic spectra of the amorphous resin measured by a total reflection method using a Fourier transform IR spectroscopy analyzer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., and a developer, a container containing the toner, a process cartridge, an image forming apparatus, and an image forming method using the toner About.

In recent years, in order to save energy when fixing toner, it is required to reduce the fixing energy itself. Therefore, it is necessary to control the thermal characteristics of the resin contained in the toner. However, lowering the Tg (glass transition temperature) of the resin contained in the toner causes deterioration in heat resistant storage stability and fixing strength. In addition, a decrease in F1 _{/ 2} temperature due to the lower molecular weight of the resin contained in the toner causes problems such as occurrence of hot offset and excessively high gloss (gloss controllability). For this reason, it is difficult to obtain a toner having excellent low-temperature fixability, heat-resistant storage stability, and offset resistance by controlling the thermal characteristics of the resin contained in the toner.

  In order to cope with such low-temperature fixing of toner, it has been proposed to use a polyester resin having excellent low-temperature fixability and relatively good heat-preserving stability, instead of the styrene-acrylic resin that has been widely used conventionally. (See Patent Documents 1 to 6). In addition, for the purpose of improving the low-temperature fixability, it has been proposed to add a specific non-olefinic crystalline polymer having a sharp melt property at a glass transition temperature to the binder (see Patent Document 7). However, this proposal is not optimized for the molecular structure and molecular weight of the polymer.

  In addition, it has been proposed to use a crystalline polyester resin having sharp melt properties (see Patent Document 8 and Patent Document 9). However, in Patent Document 8, the toner containing a crystalline polyester resin has a low acid value of 5 mgKOH / g or less and a hydroxyl value of 20 mgKOH / g or less, and the affinity between paper and the crystalline polyester resin is low. Low temperature fixability cannot be obtained. Further, the molecular structure and molecular weight of the crystalline polyester resin are not optimized. In addition, even with a moderate glossiness, no fixing oil is applied to the fixing roller, or even a fixing method with a very small amount of oil applied has sufficient low-temperature fixability and sufficient offset resistance, as well as transferability. In addition, a toner excellent in durability, charge stability with respect to humidity, and pulverization has not been obtained. Also in the above-mentioned Patent Document 9, sufficient low-temperature fixability and sufficient offset prevention property even with a fixing method in which a release oil is not applied to the fixing roller or a very small amount of oil is applied while having an appropriate gloss. At the same time, a toner excellent in transferability, durability, charge stability with respect to humidity, and grindability has not been obtained.

  Patent Document 10 discloses an incompatible sea-island phase separation structure between a crystalline polyester resin and an amorphous polyester resin, or a DSC curve measured by a differential scanning calorimeter of the THF insoluble portion of the resin on the endothermic side. By defining the temperature of the maximum peak appearing in the toner, compatibility between the lower limit of fixing and storage stability is achieved, but at present, no toner having sufficiently satisfactory quality is provided.

JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 JP 2001-222138 A JP 2002-214833 A

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention relates to a high-quality toner having both excellent filming property and low-temperature fixing property and excellent heat-resistant storage stability, a developer using the toner, a container containing the toner, a process cartridge, and an image forming apparatus. And an image forming method.

  As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge has been obtained. That is, when the crystalline polyester resin on the toner surface is incompatible with the amorphous resin, that is, in the crystalline state, the crystalline polyester resin on the toner surface is selectively used during image formation by an electrophotographic image forming apparatus. There is a problem that a so-called “white spot” occurs when a film material is filled on the photosensitive member and the toner substance is filmed thereon to output a solid image. Therefore, in order to suppress the side effect of poor filming and storage stability when a crystalline polyester resin is used as a means for improving the fixing lower limit, the content of the crystalline polyester resin on the toner surface should be optimized. Is the finding that is effective.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner containing at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent,
The toner has a characteristic peak height of the crystalline polyester resin measured by a total reflection method using a Fourier transform infrared spectroscopic analyzer after storing the toner in a thermostat at 45 ° C. for 12 hours. A toner having a peak height ratio (W / R) of 0.22 to 0.55, where W is W and R is the characteristic spectral peak height of the amorphous resin. is there.
<2> The softening temperature [T (F _1/2 )] of the crystalline polyester resin is 80 to 130 ° C., and the glass transition temperature (Tg) of the crystalline polyester resin is 80 to 130 ° C. <1 >.
<3> The toner according to any one of <1> to <2>, wherein the crystalline polyester resin has an acid value of 20 to 45 mgKOH / g.
<4> The toner according to any one of <1> to <3>, wherein the crystalline polyester resin has a hydroxyl value of 5 to 50 mgKOH / g.
<5> The toner according to any one of <1> to <4>, wherein the amorphous resin is an amorphous polyester resin.
<6> Any one of <1> to <5>, wherein a mixing mass ratio (A: B) of the crystalline polyester resin (A) and the amorphous resin (B) is 1:99 to 30:70. The toner described in 1.
<7> The toner according to any one of <1> to <6>, wherein the release agent contains a wax, and the melting point of the wax is 70 to 150 ° C.
<8> The toner according to any one of <1> to <7>, wherein the wax is at least one selected from carnauba wax, polyolefin wax, and synthetic ester wax.
<9> A pulverized toner obtained by dry-mixing a toner material containing at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent, melt-kneading in a kneader, and pulverizing. The toner according to any one of <1> to <8>.
<10> A developer comprising the toner according to any one of <1> to <9>.
<11> The developer according to <10>, which is one of a one-component developer and a two-component developer.
<12> A toner-containing container filled with the toner according to any one of <1> to <9>.
<13> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <9> to be a visible image And a developing unit that forms the image forming apparatus, and is detachable from the main body of the image forming apparatus.
<14> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <9> Developing means for developing a visible image by developing using any of the toners, transfer means for transferring the visible image to a recording medium, and a transfer image transferred to the recording medium in a roller shape and a belt shape An image forming apparatus comprising at least fixing means for fixing by heating and pressing with any one of the fixing members.
<15> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and using the toner according to any one of <1> to <9> A developing process for developing and forming a visible image; a transferring process for transferring the visible image to a recording medium; and a transfer image transferred to the recording medium is heated by either a roller-shaped or belt-shaped fixing member. And an image forming method including at least a fixing step of fixing by pressing.

The toner of the present invention contains at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent.
The toner has a characteristic peak height of the crystalline polyester resin measured by a total reflection method using a Fourier transform infrared spectroscopic analyzer after storing the toner in a thermostat at 45 ° C. for 12 hours. When the height is W and the characteristic peak height of the amorphous resin is R, the peak height ratio (W / R) is 0.22 to 0.55.
In the toner of the present invention, the peak height ratio (W / R) between the characteristic spectral peak height W of the crystalline polyester resin and the characteristic spectral peak height R of the amorphous resin. 0.22 to 0.55 and by optimizing the content of the crystalline polyester resin on the toner surface, the filming property, the low temperature fixing property, and the heat resistant storage property can be improved, and these can be achieved simultaneously. And high-quality images can be obtained.

  The developer of the present invention contains the toner of the present invention. For this reason, when image formation is performed by electrophotography using the developer, filming property and low-temperature fixability, and heat-resistant storage stability can be improved, and these can be achieved at the same time. can get.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when an image is formed by electrophotography using the toner contained in the toner-containing container, as a result, the filming property, the low-temperature fixing property, and the heat-resistant storage property are improved, and these are achieved at the same time. And high-quality images can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. As a result, the filming property and the low-temperature fixing property, and the heat-resistant storage property are improved. These can be achieved simultaneously, and a high-quality image can be obtained.

  The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops a visible image using the toner of the present invention. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium by heating and pressing the roller-type or belt-type fixing member. As a result, the filming property, the low-temperature fixability, and the heat-resistant storage stability can be improved, and these can be achieved at the same time, and a high-quality electrophotographic image can be formed.

  The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, a visible image is formed by developing with the toner of the present invention. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transfer image transferred onto the recording medium is fixed by heating and pressing with either a roller-shaped or belt-shaped fixing member. As a result, the filming property, the low-temperature fixability, and the heat-resistant storage stability can be improved, and these can be achieved at the same time, and a high-quality electrophotographic image can be formed.

  According to the present invention, high-quality toner that can solve the conventional problems, improves filming property and low-temperature fixability of the toner on the photoreceptor, and heat-resistant storage stability, and can achieve these simultaneously. In addition, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method can be provided.

(toner)
The toner of the present invention contains at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent, and further contains other components as necessary.

In the present invention, after the toner is stored in a constant temperature bath at 45 ° C. for 12 hours, the crystalline polyester is obtained by a total reflection method (ATR method) using a Fourier transform infrared spectroscopic analyzer (FT-IR). If the peak height of the characteristic spectrum of the resin is W and the peak height of the characteristic spectrum of the amorphous resin is R, the peak height ratio (W / R) is 0.22 to 0.55. It is necessary to be. This peak height ratio (W / R) represents the crystalline state of the crystalline polyester resin on the toner surface. By controlling this value within the above range, an excellent toner can be applied to the photoreceptor during image formation. The filming property, the fixing lower limit property, and the storage property can be combined.
When the peak height ratio (W / R) is less than 0.22, the toner fixing lower limit and filming properties are good, but the storage stability is inferior. Although the storage stability is good, the toner fixing lower limit property and the filming property to the photoreceptor are inferior.
The above-mentioned “storage at 45 ° C. for 12 hours” is determined by toner prescription, toner storage, and transport environment constraints.

  The peak height ratio (W / R) between the crystalline polyester resin and the amorphous resin on the toner surface represents the ratio of the crystalline state portion of the crystalline polyester resin on the toner surface. When the crystalline polyester resin and the amorphous resin on the toner surface are compatible, the value of the peak ratio is reduced, which means that the content of the crystalline polyester resin in the crystalline state is reduced. In this case, the lower limit of toner fixing and filming properties are good, but the storage stability is poor. Conversely, the toner is affected by heat and the crystalline polyester resin is recrystallized, that is, the incompatibility between the crystalline polyester resin and the amorphous resin proceeds, and the content of the crystalline state portion of the crystalline polyester resin. As the value increases, the value of the peak height ratio (W / R) increases. In that case, the lower fixing property of the toner is inferior due to a decrease in the compatible resin, and the crystalline polyester resin in the crystalline state is increased, so that it is easy to pierce the photoreceptor, so the filming property is inferior. Better heat-resistant storage stability. This is because the glass transition temperature and melting point of the crystalline polyester resin in the crystalline state are around 110 ° C., so that the storage stability is good if the ratio of the crystalline state of the crystalline polyester resin is large.

  Such control of the peak height ratio (W / R) is determined by the ratio of the compatible state between the crystalline polyester resin and the amorphous resin. However, since it is difficult to measure the degree of crystallinity, the present invention optimizes the manufacturing conditions such as the ratio of raw materials for the toner formulation, the kneading step, the pulverizing step, and the additive mixing step by using quality engineering techniques. By making the prescription and the production conditions such that the height ratio (W / R) falls within the range of 0.22 to 0.55 as the optimum conditions, it is achieved intentionally and reliably. In other words, in the present invention, the optimum conditions for the toner material formulation and the production are selected in consideration of the balance of filming property, fixing property, storage property, and productivity. For example, when the raw material ratio of the crystalline polyester resin is large, a portion compatible with the amorphous resin increases and the fixing property is good, but the filming property and the storage property are inferior. In addition, by adding a recrystallization aid into the toner material at the time of polymerization, recrystallization is promoted and good storage stability. However, if it is recrystallized too much, a problem of filming on the photosensitive member occurs and fixing. Inferior. These are balance problems, and an appropriate reference line is determined in consideration of the recrystallization state.

-Measuring method of peak height ratio (W / R)-
The peak height ratio (W / R) between the characteristic peak height W of the crystalline polyester resin and the characteristic peak height R of the amorphous polyester resin is FT-IR (Fourier transform). It can be determined from the peak intensity ratio known from the ATR spectrum in the ATR method (total reflection method) using an infrared spectroscopic analysis measurement device “Avatar 370, manufactured by Thermo Electron”). Since the ATR method requires a smooth surface, the toner is pressure-molded to create a smooth surface. In this pressure molding, 0.6 g of toner was loaded with 1 ton for 30 seconds to produce a pellet having a diameter of 20 mm, which was used as a sample.
In the present invention, the peak height of the characteristic spectrum (1165 cm ⁻¹ ) in the crystalline state of the crystalline polyester resin is W (FIG. 9, the height base line is 1199 to 1137 cm ⁻¹ ), Characteristic spectrum (for example, for polyester resin, 829 cm ⁻¹ “FIG. 10, height baseline is 784-889 cm ⁻¹ ”, for styrene-acrylic resin, 699 cm ⁻¹ “FIG. 11, height base For the line, the peak height ratio (W / R) was calculated with the peak height of 714 to 670 cm ⁻¹ ”as R. In this case, the peak intensity ratio was obtained by converting the spectrum to absorbance and using the peak height. It is.

The amorphous resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include styrene, α-methylstyrene, chlorostyrene, styrene-propylene copolymer, and styrene-butadiene copolymer. Styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylonitrile-acrylic acid ester Styrenic resin such as copolymer; polyester resin, vinyl chloride resin, rosin modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, xylene resin, petroleum Resin, hydrogen added Such as petroleum resins. Among these, an amorphous polyester resin is particularly preferable.
The mixing mass ratio of the crystalline polyester resin and the amorphous polyester resin is preferably 1:99 to 30:70, and more preferably 1:99 to 15:85. If the proportion of the crystalline polyester resin is too large, the toner may be filmed on the photoreceptor, and if it is too small, the toner fixing property may be inferior.

Here, whether or not the polyester resin has crystallinity can be confirmed by whether or not there is a peak in the X-ray diffraction pattern by the powder X-ray diffractometer. The crystalline polyester resin has, in its diffraction pattern, at least one diffraction peak at a position where 2θ is 20 ° to 25 °, preferably 2θ is at least (i) 19 ° to 20 °, (ii Diffraction peaks exist at positions of 21) to 22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to 31 °. In contrast, the amorphous polyester resin has no crystal peak in the 2θ region.
The powder X-ray diffraction was measured using, for example, RINT1100 manufactured by Rigaku Corporation, using a wide-angle goniometer under the conditions of a tube with Cu and a tube voltage-current of 50 kV-30 mA. For example, FIG. 12 is a graph showing the X-ray diffraction result of the crystalline polyester resin. FIG. 13 is a graph showing the X-ray diffraction results of the toner of the present invention.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, The aliphatic containing at least 60 mol% of ester bonds represented by following General formula (1) in the molecular principal chain Polyester resins are preferred.

In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue, and is a linear unsaturated aliphatic group having 2 to 20 carbon atoms, preferably 2 to 4 carbon atoms. n is an integer of 2 to 20, preferably 2 to 6.

The presence of the structure represented by the general formula (1) can be confirmed by solid C ¹³ NMR.
Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.

In the general formula (1), (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue include linear aliphatic dihydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Can be derived from.
Since the polyester resin uses a linear unsaturated aliphatic dicarboxylic acid as its acid component, the polyester resin exhibits an effect that a crystal structure is easily formed as compared with the case where an aromatic dicarboxylic acid is used.

The polyester resin is a polyvalent carboxylic acid component comprising (i) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms, an acid halide, etc.). And (ii) a polyhydric alcohol component comprising a linear aliphatic diol can be produced by a polycondensation reaction by a conventional method.
A small amount of other polyvalent carboxylic acid can be added to the polyvalent carboxylic acid component as necessary. In this case, the polyvalent carboxylic acid includes (i) an unsaturated aliphatic divalent carboxylic acid having a branched chain, (ii) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, and the like. In addition to polyvalent carboxylic acids, (iii) aromatic polyvalent carboxylic acids such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The amount of these polyvalent carboxylic acids added is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total carboxylic acid.

  Specific examples of polyvalent carboxylic acids that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. A divalent carboxylic acid of: trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, And trivalent or higher polyvalent carboxylic acids such as 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. it can.

As the polyhydric alcohol component, a small amount of an aliphatic branched dihydric alcohol or cyclic dihydric alcohol as well as a trihydric or higher polyhydric alcohol can be added as necessary. The amount added is preferably 30 mol% or less, more preferably 10 mol% or less, and the polyester is appropriately added within the range in which the resulting polyester has crystallinity.
Examples of the polyhydric alcohol added as necessary include 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and glycerin.

In the polyester resin, the molecular weight distribution is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is preferably a relatively low molecular weight. As for the molecular weight of the polyester resin, in the molecular weight distribution by GPC of its o-dichlorobenzene-soluble component, its mass average molecular weight (Mw) is 5,500-6,500, and its number average molecular weight (Mn) is 1,300. ˜1,500 and its Mw / Mn ratio is preferably 2-5.
The molecular weight distribution of the polyester resin is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass%. In the case of the polyester resin used in the present invention, it is preferable to have a molecular weight peak in the range of 3.5 to 4.0% by mass in this molecular weight distribution diagram. Moreover, it is preferable that the half width of the molecular weight peak is 1.5 or less.

Since the crystalline polyester resin rapidly decreases in melt viscosity, the fixing lower limit temperature is controlled not only by the content thereof but also by the glass transition temperature (Tg) and the softening temperature (T (F _1/2 )). Is possible. In this invention, it is preferable that it is low in the range which does not deteriorate heat-resistant storage stability, The glass transition temperature (Tg) of crystalline polyester resin is 80-130 degreeC, T (F1 _{/ 2} ) is 80-130 degreeC. Preferably there is. When the Tg and T (F _1/2 ) are lower than the above range, it is difficult to synthesize a crystalline polyester having a sharp melt property and easily exhibiting an effect on low-temperature fixability. In addition, since the lower limit fixing temperature is increased, low temperature fixability may not be obtained.

  The acid value of the crystalline polyester resin is preferably 20 to 45 mgKOH / g. From the viewpoint of the affinity between paper and resin, it is preferably 20 mgKOH / g or more in order to achieve the desired low-temperature fixability, while it is 45 mgKOH / g or less in order to improve the hot offset property. It is preferable.

  The hydroxyl value of the crystalline polyester resin is preferably 5 to 50 mgKOH / g, more preferably 5 to 25 mgKOH / g, in order to achieve a predetermined low temperature fixability and to achieve good charging characteristics. If the hydroxyl value is less than 5 mgKOH / g, an abnormal ground stain image due to poor charging may occur, and if it exceeds 50 mgKOH / g, the environmental fluctuation rate may deteriorate.

-Release agent-
As the release agent, a wax is suitable, and the melting point of the wax is preferably 70 to 150 ° C, more preferably 75 to 140 ° C. When the melting point is less than 70 ° C., the heat-resistant storage stability of the toner may be inferior, and when it exceeds 150 ° C., the releasability may be insufficient and the toner fixing property may be inferior.

The wax is not particularly limited and may be appropriately selected from conventionally known ones according to the purpose. Examples thereof include polyolefin waxes such as low molecular weight polyethylene wax and low molecular weight polypropylene wax; Fischer-Tropsch wax and the like. Synthetic hydrocarbon waxes; natural waxes such as beeswax, carnauba wax, candelilla wax, rice wax and montan wax; petroleum waxes such as paraffin wax and microcrystalline wax; stearic acid, palmitic acid, myristic acid, etc. Higher fatty acids or metal salts thereof; higher fatty acid amides; synthetic ester waxes such as pentaerythritol tetrabehenate, or various modified waxes thereof. These may be used individually by 1 type and may use 2 or more types together.
Among these, carnauba wax, polyolefin wax, and synthetic ester wax are particularly preferable.

  The content of the release agent in the toner is preferably 2 to 15% by mass. When the content is less than 2% by mass, the effect of preventing offset may be insufficient. When the content exceeds 15% by mass, toner transferability and durability may be deteriorated.

-Colorant-
As the colorant, known pigments and dyes that can obtain toner of each color of yellow, magenta, cyan, and black can be used.
Examples of yellow pigments include cadmium yellow, pigment yellow 155, benzimidazolone, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow lake, quinoline yellow lake, and permanent. Examples include yellow NCG and tartrazine lake.
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK and the like.
Examples of red pigments include bengara, quinacridone red, cadmium red, permanent red 4R, resol red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B. Etc.
Examples of purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of the blue pigment include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chlorinated product, first sky blue, and indanthrene blue BC.
Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of the black pigment include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
These may be used individually by 1 type and may use 2 or more types together.

  The content of the colorant in the toner is preferably 4 to 16% by mass, and more preferably 7 to 14% by mass. The colorant may be used as a master batch combined with a resin.

  In addition to the binder resin, the release agent, and the colorant, the toner material includes a charge control agent, inorganic fine particles, a fluidity improver, a cleaning improver, a magnetic material, a metal soap, and the like as necessary. Can be added.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferable examples include nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), and basic dyes. Specifically, C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Basic Green 4 (C.I. 42000) or lake pigments of these basic dyes; quaternary ammonium salts such as benzoylmethylhexadecyl ammonium chloride and decyltrimethyl chloride; or dialkyltin compounds such as dibutyl or dioctyl, dialkyltin Polyamine resins such as borate compounds, guanidine derivatives, vinyl polymers containing amino groups, condensation polymers containing amino groups, JP-B Nos. 41-20153, 43-27596, 44-6397 Metal complex salts of monoazo dyes described in Japanese Patent Publication No. 45-26478; salicylic acid described in Japanese Patent Publication Nos. 55-42752 and 59-7385; dialkyl salicylic acid, naphthoic acid, Z of dicarboxylic acid , Al, Co, Cr, metal complexes such as Fe; sulfonated copper phthalocyanine pigment, organic boron salts, fluorine-containing quaternary ammonium salts, and the like calixarene compounds. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (both manufactured by Orient Chemical Industries); TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (both manufactured by Hodogaya Chemical Co., Ltd.); Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (both manufactured by Nippon Carlit); quinacridone, azo pigments, Other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

  In the toner of the present invention, transferability and durability are further improved by externally adding inorganic fine particles such as silica, titanium oxide, alumina, silicon carbide, silicon nitride, boron nitride, or resin fine particles to the base toner particles. Can do. This effect can be obtained by covering the wax that lowers transferability and durability with these external additives and reducing the contact area due to the toner surface being covered with fine particles.

The surface of the inorganic fine particles is preferably hydrophobized, and metal oxide fine particles such as hydrophobized silica and hydrophobized titanium oxide are preferably used.
As the resin fine particles, polymethyl methacrylate or polystyrene fine particles having an average particle size of about 0.05 to 1 μm obtained by a soap-free emulsion polymerization method are suitably used. In addition, the hydrophobized silica and the hydrophobized titanium oxide are used in combination, and the external addition amount of the hydrophobized titanium oxide is larger than the hydrophobized silica external charge amount, thereby charging against humidity. The toner can also be excellent in stability.

In combination with the inorganic fine particles, external additives conventionally used such as silica having a specific surface area of 20 to 50 m ² / g and resin fine particles having an average particle diameter of 1/100 to 1/8 of the average particle diameter of the toner. The durability can be improved by externally adding an external additive having a particle size larger than that of the agent to the toner. This is because the metal oxide particles externally added to the toner tend to be embedded in the base toner particles in the process in which the toner is mixed with the carrier in the developing device, stirred, charged and developed. This is because it is possible to suppress embedding of the metal oxide fine particles by externally adding an external additive having a particle size larger than that of the metal oxide fine particles to the toner.

  The above inorganic fine particles and resin fine particles are contained (internally added) in the toner, but the effect is reduced as compared with the case of external addition, but the effect of improving transferability and durability is obtained and the toner pulverization property is improved. Can do. In addition, since external addition and internal addition can be used together to suppress embedding of externally added fine particles, excellent transferability can be stably obtained and durability can be improved.

  The hydrophobizing agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane , 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, Nyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyl-trichlorosilane, decyl-trichlorosilane, nonyl-trichlorosilane, (4-t-propylphenyl) -trichlorosilane, (4-t-butylphenyl) -Trichlorosilane, dipentyl-dichlorosilane, dihexyl-dichlorosilane, dioctyl-dichlorosilane, dinonyl-dichlorosilane, didecyl-dichlorosilane, didodecyl-dichlorosilane, dihexadecyl-dichlorosilane, (4-t-butylphenyl) -octyl-dichlorosilane, dioctyl-dichlorosilane -Dichlorosilane, dinonenyl-dichlorosilane, di-2-ethylhexyl-dichlorosilane, di-3,3-dimethylpentyl-dichloro Lan, trihexyl-chlorosilane, trioctyl-chlorosilane, tridecyl-chlorosilane, dioctyl-methyl-chlorosilane, octyl-dimethyl-chlorosilane, (4-t-propylphenyl) -diethyl-chlorosilane, octyltrimethoxysilane, hexamethyldisilazane, hexa Examples thereof include ethyl disilazane, diethyl tetramethyl disilazane, hexaphenyl disilazane, hexatolyl disilazane, titanate coupling agent, and aluminum coupling agent.

  As other components, a lubricant such as an aliphatic metal salt or polyvinylidene fluoride fine particles can be used in combination as an external additive for the purpose of improving cleaning properties.

  The method for producing the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a melt-kneading and pulverizing method, a specific crystalline polymer and a polymerizable monomer. A polymerization method (suspension polymerization method, emulsion polymerization method) for directly polymerizing a monomer composition in an aqueous phase, a composition containing a specific crystalline polymer and an isocyanate group-containing prepolymer in an aqueous phase Examples include a polyaddition reaction method in which the amines are directly extended / crosslinked, a polyaddition reaction method using an isocyanate group-containing prepolymer, a method of dissolving in a solvent, removing the solvent, and pulverizing, and a melt spray method. Among these, the melt-kneading pulverization method is particularly preferable.

In the present invention, it has been found that the control of toner characteristics is greatly related not only to the selection and formulation of raw materials but also the production conditions in the production process. In particular, precisely controlling manufacturing conditions and storage conditions in processes related to the thermal history of toner greatly affects toner characteristics.
For example, when a toner is produced by a kneading method, by changing the kneading temperature, feed, rolling thickness, cooling rate, time, etc., the toner has a maximum peak temperature change characteristic in the range of 40 to 75 ° C. by DSC. It is possible to control. For example, if the kneading temperature is too high, the previously melted polyester resin having crystallinity may act as a flux for the counterpart resin, but may separate and precipitate after cooling, and the cooling rate will be slow after kneading. If the amount is too large, the counterpart resin may separate and precipitate. The same applies when the feed amount is too large or the rolling thickness is too thick.

In the melt-kneading and pulverization method, a toner material containing at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent is dry-mixed, melt-kneaded in a kneader, and pulverized to obtain a pulverized toner. Is the method.
First, toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay, PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. Preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed by removing the fine particle portion by, for example, a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

  Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above. For mixing such additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

The volume average particle diameter of the toner is preferably 4 to 10 μm, and more preferably 5 to 10 μm. The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.00 to 1.40, more preferably 1.10 to 1.25. preferable.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using, for example, a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics. Can be measured.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm.
When the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
The mixing ratio of the toner and the carrier of the two-component developer is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

The developer of the present invention can maintain good transferability and cleanability for a long period of time, there is no fluctuation in image unevenness, and there is no burying of external additives by stirring the developer during use, fluidity, In addition, since the toner of the present invention, which has excellent stability with little change in chargeability over a long period of time, is contained, an excellent, clear and high-quality image can be stably formed.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, a polyester resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polychlorinated resin is preferable. Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge according to the present invention forms a visible image by developing an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using toner. And at least a developing unit for selecting the charging unit, an exposing unit, a developing unit, a transferring unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other members as necessary. It has. In FIG. 1, reference numeral 103 denotes exposure by an exposure unit, and a light source capable of writing with high resolution is used. Reference numeral 105 denotes a recording medium.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 102.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The photoconductor 101 is charged on the surface by charging by the charging means 102 and exposure 103 by the exposure means (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the exposure image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention is constructed by integrally combining the electrostatic latent image carrier and the components such as a developing device and a cleaning device as a process cartridge, and this unit can be attached to and detached from the apparatus main body. It may be configured. In addition, a process cartridge is formed by integrally supporting at least one of a charging device, a developing device, a transfer device, and a cleaning device together with an electrostatic latent image carrier to form a single unit that is detachable from the device body. It is good also as a structure which can be attached or detached using guide means, such as this rail.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention comprises at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, It includes a cleaning process, a recycling process, a control process, and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image bearing member (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. . Among these, amorphous silicon and the like are preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used by a film forming method such as the above. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. When using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn-Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. The Or, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound or attached to a metal or other conductive core. To make a charger.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. Is preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the latent electrostatic image bearing member charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. By setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, (1) a material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery of the belt. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

For the intermediate transfer belt, fluorine resin, polycarbonate resin, polyimide resin and the like have been conventionally used. However, in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. . The transfer of a color image using a resin belt has the following problems. A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.
The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.

  Examples of the resin in the elastic belt include polycarbonate resin, fluorine resin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-α-methylstyrene resin, styrene-butadiene copolymer, and styrene-vinyl chloride copolymer. Styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic) Acid butyl copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-methacrylic acid) Ethyl copolymer, styrene-me Styrene-based resins (styrene or styrene-substituted monopolymers or copolymers) such as phenyl crylate copolymer), styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate ester copolymer, etc. Coalesced), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (eg, silicone-modified acrylic resin, vinyl chloride resin-modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride Resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, io Mer resin, a polyurethane resin, a silicone resin, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinylbutyral resin, polyamide resin and modified polyphenylene oxide resins.

  Examples of the elastic rubber or elastomer include butyl rubber, fluorine-based rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, Ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, ricone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, Hydrogenated nitrile rubber, thermoplastic elastomer (eg, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) And the like.

The conductive material for adjusting the resistance value is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, oxidation Conductive metal oxides such as indium, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO), and the conductive metal oxides are barium sulfate and magnesium silicate. Further, it may be coated with insulating fine particles such as calcium carbonate.
The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one type or a combination of two or more types such as polyurethane, polyester, and epoxy resin to reduce surface energy and increase lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide Such powders and particles can be used by dispersing one type, two or more types, or a combination of particles having different particle sizes. Further, it is also possible to use a material having a reduced surface energy by forming a fluorine-rich layer on the surface by performing a heat treatment like a fluorine-based rubber material.
The manufacturing method of the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid paint is sprayed to form a film, a cylindrical mold is used. Examples include, but are not limited to, a dipping method in which the material is dipped in a solution of the material, a casting method in which it is injected into the inner mold and the outer mold, a method in which a compound is wound around a cylindrical mold and vulcanized and polished. In general, a belt is manufactured by combining a plurality of manufacturing methods.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation in a core layer, and the like, but the method is limited to a specific manufacturing method is not.
The material constituting the core layer for preventing elongation includes, for example, natural fibers such as cotton and silk; polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, Synthetic fibers such as polyurethane fiber, polyacetal fiber, polyfluoroethylene fiber, and phenol fiber; inorganic fibers such as carbon fiber, glass fiber, and boron fiber; one or two kinds selected from metal fibers such as iron fiber and copper fiber By using the above combination, a woven fabric or a yarn may be used.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, one-twisted yarn, various twisted yarns, double yarn, or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment. On the other hand, as the woven fabric, any woven fabric such as knitted fabric can be used. Interwoven woven fabric can also be used and naturally conductive treatment can be performed.
The production method for providing the core layer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a woven fabric woven in a cylindrical shape is covered with a mold or the like, and a coating layer is formed thereon. A method of providing, a method of providing a coating layer on one or both sides of a core layer by immersing a woven fabric woven in a cylindrical shape in a liquid rubber, etc. Examples thereof include a method of providing a coating layer.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur on the surface layer. Also, it is not preferable that the thickness is too large (approximately 1 mm or more) because the amount of expansion and contraction becomes large and the image is stretched.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing process is a process in which a transfer image transferred to a recording medium is fixed by heating and pressing with either a roller-shaped or belt-shaped fixing member, and each time the toner of each color is transferred to the recording medium. Alternatively, it may be carried out at the same time in a state in which the toner of each color is laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a recording medium 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the recording medium 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the recording medium 95. As a result, a transfer image is formed on the recording medium 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

In the tandem type electrophotographic apparatus in which the image forming method of the present invention is performed by the image forming apparatus of the present invention, an image on each photoconductor 1 is transferred by a transfer device 2 by a sheet conveying belt 3 as shown in FIG. As shown in FIG. 5, the image on each photosensitive member 1 is sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2 and then the intermediate transfer member. There is an indirect transfer type in which an image on the transfer body 4 is collectively transferred to a sheet s by a secondary transfer device 5. The transfer device 5 is a transfer conveyance belt, but there are also roller shapes and methods.
Comparing the direct transfer type and the indirect transfer type, the former arranges the paper feeding device 6 on the upstream side of the tandem type image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveyance direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. There is a drawback that the fixing device 7 tends to affect image formation on the upstream side due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that allows the sheet s to bend, so that the fixing device 7 hardly affects the image formation.
In view of the above, in recent years, indirect transfer type among tandem type electrophotographic apparatuses has been attracting attention.
In this type of color electrophotographic apparatus, as shown in FIG. 5, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

A tandem image forming apparatus 100 shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 6. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the recording medium in order to form an image on both sides of the recording medium is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. An exposure device that exposes the photoconductor for each color image corresponding image (L in FIG. 7) and forms an electrostatic latent image corresponding to each color image on the photoconductor; Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, since the filming property, the low-temperature fixing property, and the heat-resistant storage stability are improved, and the toner of the present invention that can achieve these simultaneously is used, high image quality is achieved. Efficient image formation.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

(Synthesis Example 1)
-Crystalline polyester resin no. Synthesis of 1
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 25 mol of 1,4-butanediol, 23.75 mol of fumaric acid, 1.65 mol of trimellitic anhydride And hydroquinone 5.3 g, reacted at 160 ° C. for 5 hours, then heated to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour. 1 was synthesized.
The obtained crystalline polyester resin No. In the molecular weight distribution by GPC of 1 o-dichlorobenzene-soluble component, the mass average molecular weight (Mw) was 48,000.

(Synthesis Example 2)
-Crystalline polyester resin no. Synthesis of 2
In the same manner as in Synthesis Example 1 except that the raw materials were changed to the following in Synthesis Example 1, crystalline polyester resin No. 2 was synthesized.
〔material〕
・ 1,4-Butanediol ・ ・ ・ 22.5 mol ・ Ethylene glycol… 5 mol ・ Fumaric acid… 23.75 mol ・ Trimellitic anhydride ... 5 mol ・ Hydroquinone… 5.8 g
The obtained crystalline polyester resin No. In the molecular weight distribution by GPC of the o-dichlorobenzene soluble matter of No. 2, the mass average molecular weight (Mw) was 32,000.

(Synthesis Example 3)
-Crystalline polyester resin no. Synthesis of 3
In the same manner as in Synthesis Example 1 except that the raw materials were changed to the following in Synthesis Example 1, crystalline polyester resin No. 3 was synthesized.
〔material〕
・ 1,4-Butanediol ・ ・ ・ 23.75 mol ・ Ethylene glycol ... 1.25 mol ・ Fumaric acid ... 22.75 mol ・ Trimellitic anhydride ... 1.65 mol ・ Hydroquinone・ 4.8g
The obtained crystalline polyester resin No. In the molecular weight distribution by GPC of 1 o-dichlorobenzene-soluble component, the mass average molecular weight (Mw) was 15,000.

(Synthesis Example 4)
-Amorphous polyester resin no. Synthesis of 4
In a four-necked flask made of glass, 390 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 120 g of isophthalic acid, 38 g of 1,2,5-benzenetricarboxylic acid, and oxidation 1 g of dibutyltin was added, a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen introduction tube were attached, and the reaction was performed in a mantle heater under a nitrogen stream at 220 ° C. until the desired softening point was reached. Amorphous polyester resin No. 4 was synthesized.
The obtained amorphous polyester resin No. In the molecular weight distribution by GPC of o-dichlorobenzene-soluble matter of No. 4, the mass average molecular weight (Mw) was 420,000.

  Next, the physical properties of each synthesized resin were measured as follows. The results are shown in Table 1.

<Measurement of peak height ratio (W / R)>
The peak height ratio (W / R) between the characteristic peak height W of the crystalline polyester resin and the characteristic peak height R of the amorphous polyester resin is FT-IR (Fourier transform). Using an infrared spectroscopic analyzer (Avatar 370, manufactured by Thermo Electron), the peak intensity ratio determined from the ATR spectrum in the ATR method (total reflection method) is obtained. Since the ATR method requires a smooth surface, the toner is pressure-molded to produce a smooth surface. In this pressure molding, 1 ton was applied to 0.6 g of toner for 30 seconds to form pellets having a diameter of 20 mm.
The peak height of the characteristic spectrum (1165 cm ⁻¹ ) when the crystalline polyester resin is in a crystalline state is W (see FIG. 9, the height base line is 1199 to 1137 cm ⁻¹ ), and the characteristic height of the amorphous resin is Spectrum (for example, 829 cm ⁻¹ for polyester resin, “FIG. 10, height baseline is 784-889 cm ⁻¹ ”, for styrene-acrylic resin, 699 cm ⁻¹ “FIG. 11, height baseline is 714 The peak height of ˜670 cm ⁻¹ ”) was calculated as R, and W / R was calculated as the peak intensity ratio. In the present invention, the peak intensity ratio is obtained by converting the spectrum to absorbance and using the peak height.

<Measurement of acid value and hydroxyl value of resin>
The acid value and hydroxyl value of the resin are measured according to the method specified in JIS K0070. However, when the sample did not dissolve, a solvent such as dioxane, tetrahydrofuran (THF) or o-dichlorobenzene was used as the solvent.

<Measurement of softening point of resin>
An elevated flow tester CFT-100 manufactured by Shimadzu Corporation was used. The flow curve of this flow tester becomes the data shown in FIGS. 8A and 8B, from which each temperature can be read. In FIG. 8A, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the T _1/2 method in FIG. 8B is the F _1/2 temperature.
〔Measurement condition〕
・ Load: 10 kg / cm ²
・ Raising rate: 3.0 ° C / min
・ Die diameter: 0.50mm
・ Die length: 10.0mm

<Measurement of wax melting point>
A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Heat from room temperature to 180 ° C. at a heating rate of 10 ° C./min. The melting point was calculated from the contact point between the tangent line of the endothermic curve near the melting point and the base line using the analysis system in the TAS-100 system.

Example 1
-Toner production by kneading and grinding method-
The toner material having the following composition was sufficiently mixed with a blender and then melt-kneaded (kneading temperature: 140 ° C., extrusion speed: 10 kg / hour, rolling gap: 2 mm, standing time until pulverization: 48 hours) with a twin screw extruder. Thereafter, this was pulverized and classified to obtain a base toner having a volume average particle diameter of 7.6 μm.
To 100 parts of the obtained base toner, 0.4 part of hydrophobic silica (surface-treated product with hexamethyldisilazane, average particle diameter of primary particles: 0.02 μm) as an external additive is mixed with a Henschel mixer. Thus, a cyan toner was produced.
[Toner material]
-Crystalline polyester resin No. 1 ... 25 parts Amorphous polyester resin No. 1 4 ... 75 parts Polypropylene wax (melting point: 148 ° C.) 5 parts Charge control agent (metal salt of salicylic acid derivative) 2 parts Colorant (copper phthalocyanine blue pigment) 6 parts

(Example 2)
In Example 1, a toner was prepared in the same manner as in Example 1 except that the toner material and the melt-kneading conditions were changed as follows.
[Toner material and melt-kneading conditions]
-Crystalline polyester resin No. 1 ... 10 parts Amorphous polyester resin No. 1 4 ... 90 parts ・ Rolling gap: 3 mm
・ Pushing speed: 8kg / hour

(Comparative Example 1)
A toner was produced in the same manner as in Example 1 except that the melt-kneading conditions in Example 1 were changed as follows.
[Melting and kneading conditions]
Extruding speed: 12kg / hour Rolling gap: 1mm
・ Left time until crushing: 72 hours

(Comparative Example 2)
In Example 2, a toner was prepared in the same manner as in Example 2 except that the melt-kneading conditions were changed as follows.
[Melting and kneading conditions]
Extruding speed: 6kg / hour Rolling gap: 4mm
・ Leaving time until crushing: 12 hours

(Example 3)
In Example 2, the crystalline polyester resin no. 1 is a crystalline polyester resin no. A toner was prepared in the same manner as in Example 2 except that the toner was changed to 2.

Example 4
In Example 3, crystalline polyester resin no. 2 is a crystalline polyester resin no. A toner was prepared in the same manner as in Example 3 except that the toner was changed to 3.

(Example 5)
A toner was prepared in the same manner as in Example 4, except that the polypropylene wax (melting point: 148 ° C.) was changed to the polypropylene wax (melting point: 73 ° C.).

-Carrier manufacturing-
・ Silicone resin solution 132.2 parts [Solid content 23%, SR2410, Toray Dow Corning Silicone Co., Ltd.]
・ Aminosilane 0.66 parts [Solid content 100%, SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.]
Conductive particles 1 ... 31 parts [Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = indium oxide containing tin dioxide, particle size: 0.35 μm, particle powder specific resistance: 3.5 Ω · cm ]
-Toluene: 300 parts The above composition was dispersed with a homomixer for 10 minutes to obtain a silicone resin coating film forming solution. A sintered ferrite powder having a volume average particle size of 70 μm is used as the core material, and the temperature inside the coater is 40 ° C. by a Spira coater (Okada Seiko Co., Ltd.) so that the coating film forming solution has a film thickness of 0.15 μm on the core material surface. And then dried. The obtained carrier was baked in an electric furnace at 300 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an opening of 125 μm to prepare a carrier.

-Preparation of developer-
8% by mass of the produced toner and 92% by mass of the carrier were mixed to prepare the two-component developers of Examples 1 to 5 and Comparative Examples 1 and 2.

  Next, using the obtained toners and developers, various characteristics were evaluated as follows. The results are shown in Table 2.

<Filming properties>
Using each developer obtained, development was performed with a remodeling machine of a copying machine (Imagio NEO C600, manufactured by Ricoh Co., Ltd.), and evaluation images were obtained at 50,000 sheets / day, initial and 100,000 sheets, respectively. put out. Three black solid images (A3 size) were output, and the number of white spots due to photoconductor filming was measured.
The modified contents of the copier (Imagio NEO C600 manufactured by Ricoh Co., Ltd.) include a development gap of 1.26 mm, a doctor blade gap of 1.6 mm, a Vs / Vp linear velocity ratio of 2.6, and a reflection type. The photosensor function was turned off.
Toner drop evaluation standard for black solid images (average of three images counting the number of white spots in A3 size images) The larger the number of white spots, the worse the image quality. If it is 20 or less per 100,000 sheets, it is determined that the normal image has no sense of incongruity to human eyes and is at a level that is not a problem. The evaluation results were evaluated according to the following criteria in terms of the number of white spots.
〔Evaluation criteria〕
◎: Less than 20 ○: 20 or more and less than 40 △: 40 or more and less than 60 ×: 60 or more

<Evaluation of heat-resistant storage stability>
Each toner was stored in a constant temperature bath at 50 ° C. for 24 hours, and then 2 g of toner was sieved for 2 minutes with a 42 μm mesh sieve. In addition, the residual ratio is smaller as the toner has better heat-resistant storage stability.
〔Evaluation criteria〕
◎: Remaining amount is very small and heat-resistant storage stability is excellent. ○: Remaining amount is small and heat-resistant storage property is relatively excellent. △: Remaining amount is relatively large and heat-resistant storage property is relatively poor. Quite a lot, poor heat resistance

<Low temperature fixability>
Replace the fixing roller with a PFA tube-coated roller and use a modified color copier (Ricoh Co., Ltd., Pretail 650) with the silicone oil applicator removed. The possible temperature was measured. The fixing roller was evaluated under the condition that no oil was applied, and a full color PPC paper type 6200 manufactured by Ricoh Co., Ltd. was used as the recording paper.
By changing the fixing temperature of the fixing unit alone, a copy image was obtained in which the image density by the Macbeth densitometer was 1.2. The copy image at each temperature was rubbed 10 times with a clock meter equipped with a sand eraser, and the image density before and after that was measured.
<Formula 1>
Fixing rate (%) = [(image density after 10 times of sand eraser) / (previous image density)] × 100
A temperature at which a fixing rate of 70% or more was achieved was defined as a minimum fixing temperature. Evaluation criteria for low-temperature fixability are as follows.
〔Evaluation criteria〕
◎: Fixing starts at a very low temperature, the fixing minimum temperature is low, and the fixing property is very low. ○: Excellent fixing property at a low temperature. △: Lower fixing temperature equivalent to that of a conventional toner. This is the minimum fixing temperature above, and is inferior in low-temperature fixability.

The toner of the present invention has a peak height ratio (W / R) where W is the characteristic peak height of the crystalline polyester resin and R is the characteristic peak height of the amorphous resin. 0.22 to 0.55, and by optimizing the content of the crystalline polyester resin on the toner surface, the filming property and the low-temperature fixability and the heat-resistant storage stability are improved, and these excellent properties are simultaneously achieved. Since it can be achieved, it is suitably used for high-quality electrophotographic image formation.
The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic configuration diagram showing an example of a process cartridge of the present invention. FIG. 2 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 4 is a partial schematic view showing an example of the tandem type image forming apparatus of the present invention. FIG. 5 is a partial schematic view showing another example of the tandem type image forming apparatus of the present invention. FIG. 6 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 7 is a partially enlarged view of FIG. FIG. 8A is a diagram showing a flow curve by a flow tester when obtaining a softening temperature and an outflow start temperature. FIG. 8B is a diagram showing a flow curve by a flow tester when obtaining the F1 / 2 temperature. FIG. 9 is a spectrum diagram showing characteristic peaks in the crystalline state of the crystalline polyester resin. FIG. 10 is a spectrum diagram showing characteristic peaks of the amorphous polyester resin. FIG. 11 is a spectrum diagram showing a characteristic peak of a styrene-acrylic resin. FIG. 12 is a graph showing the X-ray diffraction results of the crystalline polyester resin. FIG. 13 is a graph showing the X-ray diffraction results of the toner of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer body cleaning device 10 Photoconductor (photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Recording medium 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure Means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Belt-type image fixing device 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed Cassette 145 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 400 Automatic document feeder (ADF)

Claims (15)

A toner containing at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent,
The toner has a characteristic peak height of the crystalline polyester resin measured by a total reflection method using a Fourier transform infrared spectroscopic analyzer after storing the toner in a thermostat at 45 ° C. for 12 hours. A toner having a peak height ratio (W / R) of 0.22 to 0.55, where W is W and R is a characteristic spectral peak height of the amorphous resin. The softening temperature [T (F _1/2 )] of the crystalline polyester resin is 80 to 130 ° C, and the glass transition temperature (Tg) of the crystalline polyester resin is 80 to 130 ° C. toner.   The toner according to claim 1, wherein the acid value of the crystalline polyester resin is 20 to 45 mg KOH / g.   The toner according to claim 1, wherein the hydroxyl value of the crystalline polyester resin is 5 to 50 mg KOH / g.   The toner according to claim 1, wherein the amorphous resin is an amorphous polyester resin.   The toner according to claim 1, wherein a mixing mass ratio (A: B) of the crystalline polyester resin (A) and the amorphous resin (B) is 1:99 to 30:70.   The toner according to claim 1, wherein the release agent contains a wax, and the melting point of the wax is 70 to 150 ° C.   The toner according to claim 1, wherein the wax is at least one selected from carnauba wax, polyolefin wax, and synthetic ester wax.   The toner is a pulverized toner obtained by dry-mixing a toner material containing at least a crystalline polyester resin, an amorphous resin, a colorant, and a release agent, melt-kneading in a kneader, and pulverizing. The toner according to any one of 1 to 8.   A developer comprising the toner according to claim 1.   The developer according to claim 10, which is either a one-component developer or a two-component developer.   A toner-containing container filled with the toner according to claim 1.   An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. And a process cartridge that is detachable from the main body of the image forming apparatus.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 9 Developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and a fixing member of either a roller shape or a belt shape for transferring the transferred image transferred to the recording medium And an image forming apparatus having at least fixing means for fixing by heating and pressing. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 9 to form a visible image A developing process for forming the visible image, a transferring process for transferring the visible image to a recording medium, and a fixing for fixing the transferred image transferred to the recording medium by heating and pressing with a fixing member of either a roller shape or a belt shape. And an image forming method.