JP2010055045A - Image forming toner, developer, toner containing receptacle, image forming apparatus, image forming method and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner, having excellent low-temperature fixability, offset resistance and heat resisting preservability at the same time, and also having excellent fixing and releasing performance and durability. <P>SOLUTION: The image forming toner at least includes a coloring agent, binder resin and a mold releasing agent. As the binder resin, cyclization rubber with a cyclization rate of 50-75% is included. As the mold releasing agent, at least wax (A) having a melting point of 50-85°C and wax (B) having a melting point of 70-150°C and lower compatibility with the cyclization rubber than the wax (A) is included. An inorganic fine particle is included in the interior of toner. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used for image formation of an electrophotographic system such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, a developer using the toner, a container containing the toner, an image forming apparatus, and an image forming method. And a process cartridge.

  An electrophotographic image forming apparatus visualizes an electrically or magnetically formed latent image with toner. For example, an electrostatic charge image (latent image) is formed on a photosensitive member, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer medium (recording medium) such as paper and then fixed on the recording medium. In the fixing process of a toner image onto a recording medium, a heat fixing method such as a heating roller fixing method or a heating belt fixing method is widely used because of its energy efficiency.

In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and can provide high-quality images. However, in order to achieve low-temperature fixability of the toner, it is necessary to lower the softening point of the binder resin. When the softening point of the binder resin is low, a part of the toner image adheres to the surface of the fixing member at the time of fixing, and a so-called offset (hereinafter also referred to as hot offset) occurs on the copy sheet. Further, the heat resistance of the toner is lowered, and so-called blocking occurs in which toner particles are fused with each other particularly in a high temperature environment. In addition, in the developing device, there are problems that the toner is fused and contaminated inside the developing device and the carrier, and that the toner is liable to film on the surface of the photoreceptor.

  As techniques for achieving these problems, there are Patent Documents 1 to 4. By using a cyclized rubber as the binder resin and melting the wax, it is possible to obtain excellent heat resistant storage stability and hot offset resistance while achieving low-temperature softening of the toner. However, the cyclized rubber has a very high adhesiveness (tackiness) at the time of melting, and the toner adheres strongly to the fixing member at the time of fixing, and there is a problem that a paper jam (jam) occurs on the fixing roller or the fixing belt. It was. Further, since the wax in the toner is compatible with the cyclized rubber at the time of fixing, there is a problem that the wax does not easily move to the image surface and the release function by the wax does not act.

  Patent Document 5 proposes a toner in which cyclized rubber is used as a binder resin and inorganic fine particles are dispersed in the toner for the purpose of improving the dispersibility of the colorant. This was excellent in the fixing power to the fixing medium by utilizing the good adhesiveness of the cyclized rubber, but was not necessarily excellent in the low temperature fixing property and the heat resistant storage stability.

  As described above, the toner using the cyclized rubber can be softened at a low temperature by making the wax compatible with each other, but it has further excellent low-temperature fixability, heat-resistant storage stability, and hot-offset resistance. In order to achieve this, it is important to combine an appropriate cyclized rubber and an appropriate wax. However, these proposals do not stipulate a combination of a cyclized rubber and a wax having appropriate characteristics, and do not realize all of low-temperature fixability, heat-resistant storage stability, hot offset resistance, and fixing release properties. It was.

JP 2002-23411 A Japanese Patent No. 3750798 JP 2002-287422 A JP 2003-345064 A JP 2004-325843 A

  An object of the present invention is to solve the above conventional problems and achieve the following objects. That is, the present invention can provide excellent low-temperature fixability, offset resistance, heat-resistant storage stability, and excellent fixing releasability and durability, and a developer and toner using the toner. It is an object to provide a container, an image forming apparatus, an image forming method, and a process cartridge.

  In order to solve the above-mentioned problems, the invention according to claim 1 is an image forming toner including at least a colorant, a binder resin, and a release agent, and has a cyclization rate of 50 to 50 as the binder resin. The wax (A) containing 75% cyclized rubber and having at least a melting point of 50 to 85 ° C., and a melting point of 70 to 150 ° C. and more than the wax (A) as the release agent And a wax (B) having a low compatibility with the toner, and inorganic fine particles are contained inside the toner.

  The invention according to claim 2 is the image forming toner according to claim 1, wherein the content of the wax (A) is 20 to 65 wt% with respect to the weight of the cyclized rubber. To do. It is characterized by.

  The invention according to claim 3 is the image forming toner according to claim 1, wherein the content of the wax (B) is 4 to 40 wt% with respect to the weight of the cyclized rubber. To do.

  The invention according to claim 4 is the toner for image formation according to claim 1 or 2, wherein the wax (A) is paraffin wax, carnauba wax, synthetic ester wax, amide wax, rice wax, montanic acid wax. It is either of these.

  According to a fifth aspect of the present invention, in the image forming toner according to the first or third aspect, the wax (B) is a polyethylene wax or a polypropylene wax.

The invention according to claim 6 is the image forming toner according to any one of claims 1 to 5, wherein the weight average molecular weight Mw of the cyclized rubber is 1.0 × 10 ^{5 to} 5.0 × 10 ^5. The ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is 3.0 or less.

  The invention according to claim 7 is the image forming toner according to any one of claims 1 to 6, wherein the glass transition point (Tg) of the cyclized rubber is 55 ° C to 100 ° C. To do.

  The invention according to claim 8 is the image forming toner according to any one of claims 1 to 7, wherein the cyclized rubber is cyclized polybutadiene or cyclized polyisoprene.

  A ninth aspect of the present invention is a developer containing the image forming toner according to any one of the first to eighth aspects.

  A tenth aspect of the present invention is a toner-containing container filled with the image forming toner according to any one of the first to eighth aspects.

  According to an eleventh aspect of the present invention, there is provided at least an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the image carrier, and developing the electrostatic latent image using toner. The image forming apparatus includes a developing unit that forms a visible image, a transfer unit that transfers the visible image onto a recording medium, and a fixing unit that fixes the visible image transferred onto the recording medium. The toner is an image forming apparatus according to any one of claims 1 to 8.

  According to a twelfth aspect of the present invention, there is provided an electrostatic latent image forming step for forming at least an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image formed on the photoreceptor using toner. An image forming method comprising: a developing step for developing and forming a visible image; a transferring step for transferring the visible image onto a recording medium; and a fixing step for fixing the visible image transferred onto the recording medium. An image forming method using the toner according to claim 1 as the toner.

  According to a thirteenth aspect of the present invention, at least the electrostatic latent image carrier and the developing means for developing the electrostatic latent image formed on the image carrier using toner to form a visible image are integrated. A process cartridge that is supported and detachable from the main body of the image forming apparatus, wherein the toner is a process cartridge that is the toner according to claim 1.

  According to the present invention, it is possible to provide a toner having excellent low-temperature fixability, offset resistance, and heat-resistant storage stability, and excellent fixing releasability and durability.

Hereinafter, the present invention will be described in detail.
The present invention is an image forming toner including at least a colorant, a binder resin, and a release agent, and includes, as the binder resin, a cyclized rubber having a cyclization rate of 50 to 75%, Including a wax (A) having a melting point of 50 to 85 ° C. and a wax (B) having a melting point of 70 to 150 ° C. and having a lower compatibility with the cyclized rubber than the wax (A). By including inorganic fine particles in the toner, it is possible to obtain a toner that can have low-temperature fixability, heat-resistant storage stability, and hot-offset resistance, as well as excellent fixing releasability and durability.

  The wax used for the toner is generally used as a release agent for improving the releasability between the toner and the fixing member during fixing. The wax in the toner of the present invention is characterized by having an important function as a resin plasticizer in addition to the function as a release agent.

The cyclized rubber has higher elastomer elasticity than the polyester resin and styrene-acrylic resin conventionally used as a binder for toner, and is used for a conventional toner even in a rubbery temperature region after the glass transition point (Tg). Maintains a higher modulus of elasticity than the binder resin. On the other hand, the cyclized rubber is highly compatible with many waxes, and the cyclized rubber in which the wax is finely dispersed or / and compatible is plasticized.
That is, the present invention is to plasticize the cyclized rubber so that it softens quickly at the target fixing temperature, and to control the properties of the cyclized rubber and wax so that the elastic modulus is maintained even in a high temperature region. In addition, the wax (A) having a function of causing fine dispersion or / and compatibility with the cyclized rubber to produce a plasticizing action and exhibiting low-temperature fixability, and finely dispersed in the cyclized rubber and incompatible with the mold release The problem could be solved by using in combination with the wax (B) having the function of exerting the properties.

The cyclized rubber is composed of a cyclized part and a non-cyclized part, and the ratio of the cyclized part in the cyclized rubber is indicated by the cyclization rate. It is an important factor that determines the rate. It has also been found that there is an optimum wax melting point to plasticize the cyclized rubber to the desired degree, depending on the cyclization rate of the cyclized rubber.
Furthermore, in order to achieve both heat-resistant storage stability and low-temperature fixability, the resin must be softened from the high elastic region to the elastic region where it can be fixed quickly at the lowest temperature at which fixing is possible, that is, sharp melt properties are required. It was found that sharp melt properties were exhibited by setting the molecular weight distribution of the cyclized rubber within a specific range. That is, as a result of intensive studies, the present inventors combined the cyclization rate of the cyclized rubber and the melting point of the wax within a specific range, and by setting the molecular weight distribution of the cyclized rubber within a specific range, The inventors have invented a toner having both excellent low-temperature fixability that could not be obtained, heat resistant storage stability and hot offset resistance. Further, since the toner of the present invention has high elasticity, it is excellent in mechanical strength and does not contaminate members and carriers in the developing device. Further, since the compatibility between the binder resin and the wax is excellent, wax filming on the photoreceptor does not occur. Further, at the time of heat fixing, the wax appropriately oozes out on the toner surface and is excellent in fixing releasability.

  In addition, as one of the characteristics of the toner of the present invention, at least one endothermic peak obtained by the DSC measurement of the toner is lower than the temperature of the endothermic peak obtained by the DSC measurement of the cyclized rubber and the wax that are the binder resin. Can be mentioned. This indicates that the whole or part of the cyclized rubber is compatible with the wax, and that the cyclized rubber is plasticized. The cyclized rubber and the wax are plasticized separately from the endothermic peaks of each of them. This is because a new endothermic peak derived from the cyclized rubber appears. The problem in the present invention is to control the endothermic peak temperature and endothermic amount derived from the plasticized cyclized rubber obtained by the cyclization rate of the cyclized rubber, the melting point of the wax, and the molecular weight distribution of the cyclized rubber. Achieved.

  Further, since the toner of the present invention is used in the image forming apparatus and the image forming method of the present invention, fixing with energy saving is possible, there is no occurrence of offset or fixing release failure, and there is no defect in the carrier or the developing machine. There is no contamination or filming on the photoconductor, there is no change in color tone over a long period of use, and there are no abnormal images such as density reduction, fogging and blurring. Further, although it is expected that the toner has an appropriate elasticity at the time of fixing, the toner is not excessively crushed on the fixing paper, and a high-quality image excellent in fine line reproducibility can be obtained.

  The process cartridge of the present invention includes an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. Since it is developed using the toner of the present invention as the toner, there is no contamination in the carrier or developing machine or filming on the photosensitive member, no change in color tone over a long period of use, A high-quality image with no abnormal images such as fogging and blurring can be obtained.

Hereinafter, materials used in the toner of the present invention will be described.
The toner of the present invention is a toner comprising at least a resin containing a cyclized rubber as a binder resin and containing a wax, inorganic fine particles, and a colorant. Further, if necessary, a magnetic material, a charge control agent, an external additive, and the like. It contains an agent and, if necessary, other components.

(Cyclized rubber)
The cyclized rubber in the present invention is a resin having a cyclic structure within or / and between molecules of natural rubber and synthetic rubber composed of conjugated diene monomers, and these natural rubber and synthetic rubber are acid catalysts. It can obtain by making it react using catalysts, such as.

  Examples of natural rubber include natural polyisoprene mainly composed of cis-1,4-polyisoprene. The natural rubber may contain impurities such as non-rubber components as long as it does not affect the effects of the present invention, but it is preferable to use purified natural rubber from the viewpoint of controlling the cyclization rate.

  Synthetic rubber mainly includes polymers obtained by polymerizing conjugated diene monomers alone or in combination of two or more. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1. , 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like. Among these, 1,3-butadiene and isoprene are preferably used, and in particular, polybutadiene having a cis-1,4-butadiene structure as a main component and polyisoprene having a cis-1,4-isoprene structure as a main component are preferable. Used.

  The synthetic rubber in the present invention may be a polymer obtained by polymerizing a monomer copolymerizable with a conjugated diene monomer together with the conjugated diene monomer. Examples of the monomer copolymerizable with the conjugated diene monomer include styrene, α-methylstyrene, p-isopropylstyrene, p-phenylstyrene, p-methoxystyrene, p-methoxymethylstyrene, p-tert-butoxystyrene, And aromatic vinyl monomers such as chloromethylstyrene, 2-fluorostyrene, 3-fluorostyrene, pentafluorostyrene, vinyltoluene, vinylnaphthalene and vinylanthracene; olefin monomers such as ethylene, propylene and isobutylene; Among these, styrene and α-methylstyrene are preferably used. The content of the monomer copolymerizable with these conjugated diene monomers in the polymer is not particularly limited, but is 60 mol% or less, preferably 40% or less, particularly from the viewpoint of controlling the cyclization rate. Preferably it is 20% or less.

  The cyclized rubber used in the present invention can be obtained by reacting the above natural rubber or synthetic rubber with a cyclization catalyst. Examples of the cyclization catalyst include sulfuric acid; organic sulfonic acids such as p-toluenesulfonic acid, monofluoromethanesulfonic acid, difluoromethanesulfonic acid, xylenesulfonic acid, and alkylbenzenesulfonic acid having an alkyl group having 2 to 16 carbon atoms; Organic sulfonic acid compounds such as anhydrides or alkyl esters thereof; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, Metal halogen compounds such as iron chloride; and the like. These cyclization catalysts may be used alone or in combination of two or more. Among these, an organic sulfonic acid compound is preferable, and p-toluenesulfonic acid is preferably used.

  The cyclization rate in this invention represents the ratio of the cyclization part in cyclized rubber. The cyclization rate is measured by 1H-NMR analysis. When the peak areas of protons derived from double bonds in the polymer before and after the cyclization reaction are measured, the peak area before the cyclization reaction is (C0), and the peak area after the cyclization reaction is (C1), It can be obtained from equation (1).

[Formula 1]
Cyclization rate (%) = {1- (C1 / C0)} × 100

  The cyclization rate of the cyclized rubber in the present invention is preferably 50 to 75%, more preferably 55 to 70%, and particularly preferably 60 to 65%. The range is a range in which low-temperature fixability, heat-resistant storage stability, and hot-offset resistance can both be achieved when a wax having a specific melting point range described later is used. If it is lower than 50%, the melt elastic modulus of the resin in the fixing temperature range becomes too low, so that hot offset tends to occur. On the other hand, if it is higher than 75%, the melt viscosity of the toner in the fixing temperature range becomes too high, and the low-temperature fixability deteriorates. In addition, as the elastic modulus increases, the kneadability and grindability deteriorate significantly.

  The glass transition point (Tg) of the cyclized rubber in the present invention is preferably 55 to 100 ° C, more preferably 60 to 80 ° C, and particularly preferably 65 to 70 ° C. In the toner of the present invention, when the wax is finely dispersed or compatible with the cyclized rubber, the wax plasticizes a part of the cyclized rubber and exhibits excellent low-temperature fixability. The Tg of some of the cyclized rubber plasticized with wax is lower than the Tg of the cyclized rubber that has not been plasticized. Accordingly, when the Tg of the cyclized rubber is lower than the above-described range, the Tg of the plasticized cyclized rubber is too low, so that the heat resistant storage stability of the toner is deteriorated. On the other hand, when Tg is too high, the amount of wax necessary for plasticizing the cyclized rubber increases, which causes filming. Furthermore, since the Tg of the toner becomes too high, the low-temperature fixability is impaired.

In order to achieve both low-temperature fixability and heat-resistant storage stability at an extremely high level, as described above, it is preferable that the cyclized rubber is sharp-melted at a target fixing temperature. Simply specifying the cyclization rate of the cyclized rubber and the melting point of the wax within a specific range can achieve both excellent low-temperature fixability, heat-resistant storage stability, and hot-offset resistance. By imparting sharp melt properties, the effects of the present invention are maximized. The sharp melt property of the cyclized rubber can be obtained by setting the weight average molecular weight and molecular weight distribution of the cyclized rubber within a specific range. That is, the weight average molecular weight Mw of the cyclized rubber is preferably 5.0 × 10 ^{4 to} 1.0 × 10 ⁶ , more preferably 1.0 × 10 ^{5 to} 5.0 × 10 ⁵ , particularly preferably ^{1.3 × 10 5 ~3.5 × 10 5} . If it is less than 5.0 × 10 ⁴ , the width of the rubber-like flat region in the relaxation elastic modulus characteristic with respect to the temperature of the cyclized rubber is reduced, and the temperature width at which the toner can be fixed is reduced. On the other hand, when it is larger than 1.0 × 10 ⁶ , the elastic modulus of the cyclized rubber becomes too high, so that the low-temperature fixability cannot be obtained or the grindability is lowered. Furthermore, the molecular weight distribution width of the cyclized rubber greatly affects the sharp melt property of the cyclized rubber, and the ratio of the weight average molecular weight Mw and the number average molecular weight Mn (Mw / Mn) ((Mw / Mn) representing the molecular weight distribution width. ) ≧ 1.0) is preferably 10.0 or less, more preferably 3.0 or less, and particularly preferably 2.5 or less. When Mw / Mn is greater than 10.0, the sharp melt property is insufficient, and the low-temperature fixability and the heat resistant storage stability tend to deteriorate.

  The amount of the cyclized rubber used in the toner of the present invention is preferably 10 to 75% by weight, more preferably 20 to 50% by weight, and particularly preferably 30 to 40% by weight based on the weight of the toner. When the amount is less than 10% by weight, it is difficult to obtain the excellent low-temperature fixability and heat-resistant storage stability, which are the effects of the present invention. When the amount exceeds 75% by weight, the fixing releasability and grindability are deteriorated.

(Cyclic olefin resin)
In the toner of the present invention, a cyclic olefin resin can be used together with the cyclized rubber as a binder resin. Cyclic olefin resins have hard and brittle properties and are excellent in compatibility with cyclized rubber. Although the cyclized rubber has high elasticity and hardly grinds, the combined use of the cyclized rubber and the cyclic olefin resin facilitates fine pulverization of the toner. Further, since the cyclic olefin resin is a colorless and transparent resin having high light transmittance, the optical density of the fixed image can be increased.

  The cyclic olefin resin used in the present invention may be a polymer obtained by homopolymerizing one kind of cyclic olefin or a polymer obtained by copolymerizing two or more kinds of cyclic olefins. Further, it may be a copolymer of a cyclic olefin and an acyclic olefin copolymerizable with the cyclic olefin.

  The cyclic olefin-based monomer is a monomer having 3 to 17 carbon atoms, preferably 5 to 12 carbon atoms having at least one double bond. For example, a monocyclic olefin compound such as cyclobutene, cyclopentene, cyclohexene, etc .; cyclopentadiene, Cyclic conjugated diene compounds such as cyclohexadiene and cyclooctadiene; polycyclic olefin compounds such as norbornene, dicyclopentadiene, tricyclodecene and tetracyclododecene; vinyl such as vinylcyclobutane, vinylcyclopentane, vinylcyclopentene and vinylcyclohexane And the like, and the like.

  Examples of the non-cyclic olefin-based monomer copolymerizable with the cyclic olefin include α-olefins such as ethylene, propylene, 1-butylene, 1-pentene, 1-hexene and 1-octene; branched forms such as isobutene and isoprene. Olefins; and the like. Among these, preferably a lower alkene having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms is used, and specific examples include ethylene, propylene, 1-butylene and the like. These acyclic olefin monomers may be used alone or in combination of two or more.

  It is preferable that the glass transition point (Tg) of the cyclic olefin resin in this invention is 45-70 degreeC, More preferably, it is 55-65 degreeC. If the Tg is lower than this range, the heat-resistant storage stability of the toner deteriorates. Conversely, if it is high, the low-temperature fixability is inhibited.

  Moreover, when using the said cyclized rubber and the said cyclic olefin resin together, it is preferable that the composition ratio (weight ratio) of the said cyclized rubber and the said cyclic olefin resin is 15 / 85-70 / 30. More preferably, it is 30/70 to 65/35, and particularly preferably 40/60 to 60/40. If the composition ratio is within this range, the pulverization property of the toner can be improved without inhibiting the plasticizing effect of the cyclized rubber by the wax.

(Other resins that can be used in combination)
As the binder resin used in the present invention, in addition to the cyclized rubber and the cyclic olefin resin, other resins may be used in combination. The other binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, vinyl polymers such as styrene monomers, acrylic monomers, methacrylic monomers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins , Silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin, and the like.

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic. Examples include 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8) vinyl naphthalenes; (9) acrylonitrile, methacrylate. Ronitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; A monomer having a carboxyl group such as an anhydride of the α, β-unsaturated acid and a lower fatty acid, an alkenylmalonic acid, an alkenylglutaric acid, an alkenyladipic acid, an acid anhydride thereof and a monoester thereof; Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6- Examples include hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylate of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.). Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate. These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass, with respect to 100 parts by mass of the other monomers forming the vinyl polymer or copolymer. More preferred. Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one aromatic group and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

  As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component can also be used. . Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

(Release agent)
The toner of the present invention has, as a release agent, at least a wax (A) having a melting point of 50 to 85 ° C. and a melting point of 70 to 150 ° C. and is less compatible with the cyclized rubber than the wax (A). Including wax (B).
Preferably, the wax (B) has a higher melting point than the wax (A). The wax (A) has an important function as a plasticizer for the cyclized rubber, and the wax (B) has a function of improving the releasability of the toner at the time of fixing. The wax having the melting point range defined in the present invention exhibits the effects of the present invention only in combination with the cyclized rubber having the specific cyclization rate described above.

  The wax (A) has a function of finely dispersing in the cyclized rubber of the present invention and dissolving the cyclized rubber when melted, or a function of being compatible with the cyclized rubber and plasticizing the cyclized rubber. It is preferable to use what has. Due to the above-described function of the wax (A), the cyclized rubber is simultaneously dissolved or melted at the melting point of the wax (A), so that the toner has excellent low-temperature fixability having sharp melt properties at low temperatures.

In order for the wax (A) to exhibit the above function, the melting point of the wax (A) may be 50 to 85 ° C, more preferably 65 to 85 ° C, and particularly preferably 70 to 80 ° C. Examples of the type of the wax (A) include paraffin wax, carnauba wax, rice wax, montanic acid ester wax, synthetic ester wax, amide wax and the like as long as the effect is confirmed. Of the waxes mentioned above, two or more different types of waxes may be used in combination. It is a commonly used wax whose melting point is within the above range, has a function of finely dispersing well in the cyclized rubber in the present invention and dissolving the cyclized rubber at the time of melting, or compatible with the cyclized rubber. Other types of wax may be used as long as they have a function of plasticizing melted cyclized rubber.
When the melting point of the wax is less than 50 ° C., the plasticization of the cyclized rubber is excessively promoted, and the heat resistant storage stability of the toner is insufficient. On the other hand, when the temperature exceeds 85 ° C., the cyclized rubber is not sufficiently plasticized, and excellent low-temperature fixability cannot be exhibited.

  The content of the wax (A) is preferably 20 to 65 wt%, more preferably 25 to 40 wt%, and particularly preferably 30 to 35 wt% with respect to the weight of the cyclized rubber. However, the total amount of the cyclized rubber, the colorant and the wax (A) (B) should not exceed at least 100% by weight based on the total weight of the toner. When the content of the wax (A) is more than 65 wt%, the cyclized rubber is excessively plasticized, so that the heat resistant storage stability, hot offset resistance, and release properties tend to deteriorate. On the other hand, when the amount is less than 20 wt%, the cyclized rubber is not sufficiently plasticized and the low-temperature fixability is deteriorated.

  As the wax (B), those that are finely dispersed in the cyclized rubber in the present invention and are incompatible with each other and have a functional effect of improving the releasability of the toner at the time of fixing are preferable. In order to exhibit good releasability in combination with a high melting point cyclized rubber, it is sufficient that the melting point is 70 to 150 ° C., more preferably 75 to 120 ° C., particularly preferably 80 to 105 ° C. As the type of the wax (B), a wax having a high degree of crystallinity in which short-chain monomers are regularly arranged is suitable. For example, polyolefin waxes such as polyethylene and polypropylene, and modified products thereof may be used as long as the effect is confirmed. Further, two or more different types of waxes may be used in combination among the waxes listed above. If the melting point of the wax is less than 70 ° C., the crystallinity is low and the plasticization of the cyclized rubber tends to occur at the same time, which may deteriorate the heat resistant storage stability of the toner. On the other hand, when the temperature exceeds 150 ° C., the wax (B) does not melt at the time of fixing the toner, and excellent releasability cannot be exhibited.

  The content of the wax (B) is preferably 4 to 40 wt%, more preferably 4 to 30 wt%, and particularly preferably 8 to 20 wt% with respect to the weight of the cyclized rubber. However, the total amount of the cyclized rubber, the colorant, and the waxes (A) and (B) should not exceed at least 100% by weight based on the total weight of the toner. When the content of the wax (B) is more than 40 wt%, there is a tendency that the wax adheres to the member due to an increase in the amount of the wax component present on the toner surface. Moreover, when less than 4 wt%, sufficient release property cannot be given to cyclized rubber, and release property deteriorates.

(Evaluation of compatibility between cyclized rubber and wax)
The compatibility of the wax with the cyclized rubber is determined by the softening temperature [T (F1 / 2)] of the kneaded material obtained by melt-kneading 90 parts by weight of the cyclized rubber and 10 parts by weight of the wax in the melt kneading step of the toner raw material. Can be determined by measuring The higher the compatibility between the cyclized rubber and the wax, the more the cyclized rubber is plasticized by melt-kneading, so the softening temperature [T (F1 / 2)] of the cyclized rubber and wax kneaded product becomes lower.
Accordingly, for the wax (A) and the wax (B) having a lower compatibility with the cyclized rubber than the wax (A), the magnitude relationship of the softening temperature [T (F1 / 2)] of the kneaded mixture of the cyclized rubber and the wax. Is as follows.
Softening temperature of cyclized rubber and wax (A) kneaded product [T (F1 / 2)] <Softening temperature of cyclized rubber and wax (B) kneaded product [T (F1 / 2)]
Here, the softening temperature [T (F1 / 2)] is a condition using an elevated flow tester CF-500 manufactured by Shimadzu Corporation, a die diameter of 1 mm, a pressure of 10 kgf / cm ² , and a temperature rising rate of 3 ° C./min. This is the temperature at which the stroke when the sample of 1 cm ³ is melted and discharged is ½ of the stroke change amount from the outflow start point to the outflow end point.

(Measurement of melting point of wax)
In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax. The wax or toner DSC measuring device is preferably measured with a highly accurate internal heat input compensation type differential scanning calorimeter. As a measuring method, it is performed according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

(Internally added inorganic fine particles)
Specific examples of the inorganic fine particles contained in the toner include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. In addition, it is preferable to subject these surfaces to a hydrophobizing treatment because the dispersibility in the binder resin is improved.

  In the present invention, fine particles having appropriate characteristics are present in the toner, whereby fine dispersion of the binder resin, wax, and pigment, which are toner components, can be achieved. This is because, due to the presence of inorganic fine particles, these toner components have a mixing share due to the filler effect and can be uniformly mixed.

  The average primary particle size (hereinafter referred to as the average particle size) of the inorganic fine particles is 10 to 1000 nm, and particularly preferably 50 to 600 nm. When the thickness is less than 10 nm, the aggregation of fine particles is likely to occur, the toner volume resistivity decreases, and the dispersion of the toner components deteriorates. On the other hand, if it is 1000 nm or more, the dispersion effect due to the filler effect cannot be obtained.

(Coloring agent)
The colorant used in the present invention is not particularly limited, and a commonly used pigment can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow ( 10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red Antimon Zhu, Permanent Red 4R, La Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Il Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, reed Green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the colorant, various resins that can be used for the binder resin of the toner of the present invention described above can be used. Among these, particularly preferred are natural rubbers composed of conjugated diene monomers from the viewpoint of compatibility with cyclized rubbers; synthetic rubbers such as polybutadiene and polyisoprene; and these natural rubbers and synthetic rubbers. A polymer obtained by homopolymerizing one kind of cyclic olefin, a polymer obtained by copolymerizing two or more kinds of cyclic olefin, a copolymer of a cyclic olefin and a non-cyclic olefin copolymerizable with the cyclic olefin, etc. A resin having a cyclic olefin structure;

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, for example, a high shearing dispersion device such as a two-roll mill or a three-roll mill is preferably used.

As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.
The resin for the master batch has an acid value of 30 mgKOH / g or less, and is preferably used with a colorant dispersed therein, and more preferably 20 mgKOH / g or less. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070.

Further, a pigment dispersant may be used together with the masterbatch resin and the colorant, but it is preferable that the compatibility with the binder resin is high in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno), “Disperbyk-2001” (manufactured by BYK Chemie), “EFKA-4010” (manufactured by EFKA) and the like. It is done.
The pigment dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

(Magnetic material)
In the present invention, a magnetic substance can be contained together with the binder resin and the colorant.
Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.
The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.

As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be determined by measuring an enlarged photograph taken with a transmission electron microscope with a digitizer or the like.
Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively.
The magnetic material can also be used as a colorant.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge NEGVP2036 of quaternary ammonium salt, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex ( (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacrid Emissions, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the like, and is not uniquely limited. It is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded together with the masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent. Further, after the toner base particles are prepared, they may be fixed on the surface thereof.

(External additive)
The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, stearin) Metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.
Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobic titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.); IT-S (manufactured by Ishihara Sangyo Co., Ltd.) and the like.

In order to obtain the hydrophobized silica fine particles, the hydrophobized titania fine particles, and the hydrophobized alumina fine particles, the hydrophilic fine particles are made of silane cups such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with a ring agent.
Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

Further, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, and more preferably 5 to 70 nm. More preferably, the primary particles subjected to the hydrophobization treatment include at least two types of inorganic fine particles having an average particle diameter of 20 nm or less and at least one type of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by the BET method of the said inorganic fine particle is 20-500 m < ² > / g.

  The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; condensation polymerization system such as silicone, benzoguanamine, nylon; polymer particles by thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

(Other ingredients)
There is no restriction | limiting in particular as another component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, metal soap, etc. are mentioned.
The fluidity improver is capable of surface treatment to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylated Agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like.
The cleaning improver is added to the toner to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid Metal salts; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

(Toner production method)
As a method for producing the toner, conventionally known kneading and pulverization methods, polymerization methods, dissolution suspension methods, spray granulation methods, and the like can be used. A kneading / pulverizing method is used as a suitable means because of its high material selectivity.

The kneading and pulverizing method is a method of producing the toner base particles by, for example, pulverizing and classifying a melt-kneaded toner material.
In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or 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 Co., Ltd. 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 determined 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, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

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.
Next, the external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

(Weight average particle diameter of toner)
The weight average particle diameter of the toner is not particularly limited and can be appropriately selected depending on the purpose. Here, the weight average particle diameter of the toner can be obtained as follows.
[Measurement method of weight average particle diameter of toner]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion liquid: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of a measurement sample is added to 5 ml of dispersion liquid, and dispersed for 1 minute with an ultrasonic disperser. Thereafter, 25 ml of an electrolytic solution is added, and further dispersed for 1 minute by an ultrasonic disperser.
Measurement conditions: 100 ml of electrolyte solution and dispersion liquid are added to a beaker, 30,000 particles are measured at a concentration capable of measuring the particle size of 30,000 particles in 20 seconds, and the weight average particle size is obtained from the particle size distribution. .

(Developer)
The developer contains at least the toner and contains other components such as a carrier selected as appropriate. 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, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to the layer thickness regulating member such as the like, and good and stable developability and image can be obtained even when the developing means is used (stirred) for a long time. Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

(Career)
There is no restriction | limiting in particular as a 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, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material 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 (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle size (weight average particle size (D50)) 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, causing carrier scattering. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, 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 fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary, and 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, cellosolve, 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 a 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 mass. % Is preferable, and 93 to 97% by mass is more preferable.

(Image forming apparatus, image forming method)
Next, an image forming apparatus and an image forming method using the toner of the present invention will be described.
The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit, and a cleaning unit, and further if necessary. Other means appropriately selected, for example, static elimination means, recycling means, control means, etc. are provided. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit.

The image forming method of the present invention includes at least a charging step, an exposure step, a development step, a transfer step, and a fixing step, and includes a cleaning step and other steps appropriately selected as necessary, for example, It includes a static elimination process, a recycling process, a control process and the like. The charging process and the exposure process may be collectively referred to as an electrostatic latent image forming process.
The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, the fixing step can be performed by the fixing unit, and the cleaning step can be performed by the cleaning unit. The other steps can be performed by the other means.

<Electrostatic latent image carrier>
The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include a drum shape and a sheet. And endless belts. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.
For example, the amorphous silicon photosensitive member is heated to 50 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, etc. A photosensitive layer made of a-Si is formed by a film forming method. Among these, the plasma CVD method is particularly preferable, and specifically, a method in which the source gas is decomposed by direct current, high frequency, or microwave glow discharge to form a photosensitive layer made of a-Si on the support is preferable. .
The organic photoreceptor (OPC) has (1) optical characteristics such as a wide light absorption wavelength range and a large amount of light absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, (3) In general, it is widely applied because of the wide selection range of materials, (4) ease of production, (5) low cost, and (6) non-toxicity. The layer structure of such an organic photoreceptor is roughly divided into a single layer structure and a laminated structure.
The single-layered photoreceptor has a support and a single-layer type photosensitive layer provided on the support, and further includes a protective layer, an intermediate layer, and other layers as necessary.
The laminated structure of the photoreceptor comprises a support, and a laminate type photosensitive layer having at least a charge generation layer and a charge transport layer in this order on the support, and further includes a protective layer and an intermediate layer as necessary. And other layers.

<Charging step and charging means>
The charging step is a step of charging the surface of the electrostatic latent image carrier, and is performed by the charging unit.
The charging means is not particularly limited as long as it can apply a voltage to the surface of the latent electrostatic image bearing member to be uniformly charged, and can be appropriately selected according to the purpose. (1) Contact type charging means for charging in contact with the electrostatic latent image carrier and (2) Non-contact type charging means for charging in a non-contact manner with the electrostatic latent image carrier.

Examples of the contact type charging means (1) include a conductive or semiconductive charging roller, a magnetic brush, a fur brush, a film, and a rubber blade. Among these, the charging roller can significantly reduce the amount of ozone generated compared to corona discharge, and is excellent in stability during repeated use of the electrostatic latent image carrier, and effective in preventing image quality deterioration. It is.
The magnetic brush is composed of a nonmagnetic conductive sleeve that supports various ferrite particles such as Zn-Cu ferrite and a magnet roll included in the sleeve. The fur brush is formed by, for example, winding or pasting a fur treated with carbon, copper sulfide, metal, metal oxide, or the like around a metal or a treated metal core.

  Here, FIG. 1 is a sectional view showing an example of the charging roller. The charging roller 310 includes a cored bar 311 serving as a columnar conductive support, a resistance adjusting layer 312 formed on the outer peripheral surface of the cored bar 311, and a surface of the resistance adjusting layer 312. And a protective layer 313 for preventing leakage.

The resistance adjusting layer 312 is formed by extruding or injection-molding a thermoplastic resin composition containing at least a thermoplastic resin and a polymer type ionic conductive agent on the peripheral surface of the core metal 311.
The resistivity value of the resistance adjustment layer 312 is preferably 10 ⁶ to 10 ⁹ Ω · cm. When the volume resistivity value exceeds 10 ⁹ Ω · cm, the charge amount is insufficient, and the photosensitive drum may not be able to obtain a sufficient charging potential to obtain a uniform image. If the value is less than 10 ⁶ Ω · cm, there is a risk of leakage to the entire photosensitive drum.
There is no restriction | limiting in particular as a thermoplastic resin used for the said resistance adjustment layer 312, Although it can select suitably according to the objective, For example, polyethylene (PE), a polypropylene (PP), polymethyl methacrylate (PMMA), Examples thereof include polystyrene (PS) and copolymers thereof (AS, ABS, etc.).
As the polymer-type ion conductive agent, one having a resistance value of about 10 6 to 10 10 Ω · cm as a single substance and easily reducing the resistance of the resin is used. Examples thereof include a compound containing a polyether ester amide component and a quaternary ammonium base-containing polymer compound.

The protective layer 313 is formed such that its resistance value is larger than the resistance value of the resistance adjustment layer 312. As a result, leakage to the defective portion of the photosensitive drum is avoided. However, if the resistance value of the protective layer 313 is excessively increased, the charging efficiency is lowered. Therefore, the difference between the resistance value of the protective layer 313 and the resistance value of the resistance adjustment layer 312 is preferably 10 ³ Ω · cm or less. .
As the material for the protective layer 313, a resin material is preferable because of its good film formability. As the resin material, for example, a fluororesin, a polyamide resin, a polyester resin, a polyvinyl acetal resin and the like are preferable from the viewpoint of excellent non-adhesiveness and preventing toner adhesion. In addition, since the resin material generally has electrical insulation, if the protective layer 313 is formed of the resin material alone, the characteristics of the charging roller are not satisfied. Therefore, the resistance value of the protective layer 313 is adjusted by dispersing various conductive agents in the resin material. In order to improve the adhesion between the protective layer 313 and the resistance adjustment layer 312, a reactive curing agent such as isocyanate may be dispersed in the resin material.

  The charging roller 310 is connected to a power source and is applied with a predetermined voltage. The voltage may be only a direct current (DC) voltage, but is preferably a voltage obtained by superimposing an alternating current (AC) voltage on a DC voltage. By thus applying the AC voltage, the surface of the photosensitive drum can be more uniformly charged.

  Here, FIG. 2 is a schematic view showing an example in which a contact-type charging roller 310 as shown in FIG. 1 is applied to an image forming apparatus as a charging unit. In FIG. 2, around the photosensitive drum 321 as an electrostatic latent image carrier, a charging means 310 for charging the surface of the photosensitive drum, and an exposure means for forming an electrostatic latent image on the charging processing surface. 323, a developing unit 324 that forms a visible image by attaching toner to the electrostatic latent image on the surface of the photosensitive drum, and a transfer unit 325 that transfers the visible image formed on the photosensitive drum onto the recording medium 326. The fixing unit 327 for fixing the transfer image on the recording medium, the cleaning unit 330 for removing and collecting the residual toner on the photosensitive drum, and the static eliminating device 331 for removing the residual potential on the photosensitive drum are sequentially provided. It is arranged. As the charging unit 310, a contact type charging roller 310 shown in FIG. 1 is provided, and the surface of the photosensitive drum 321 is uniformly charged by the charging roller 310.

The non-contact charging means (2) includes, for example, a non-contact charger using a corona discharge, a needle electrode device, a solid discharge element; a conductive material disposed with a minute gap with respect to the electrostatic latent image carrier. Or a semiconductive charging roller.
The corona discharge is a non-contact charging method that gives positive or negative ions generated by corona discharge in the air to the surface of the electrostatic latent image carrier, and gives a constant amount of charge to the electrostatic latent image carrier. There are a coroton charger having characteristics and a scorotron charger having characteristics that give a constant potential.
The coroton charger is composed of a casing electrode that occupies a half space around the discharge wire, and a discharge wire placed almost at the center thereof.
The scorotron charger is obtained by adding a grid electrode to the corotron charger, and the grid electrode is provided at a position 1.0 to 2.0 mm away from the surface of the electrostatic latent image carrier.

Here, FIG. 3 is a schematic diagram showing an example in which a non-contact type corona charger is applied to an image forming apparatus as a charging unit. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.
As the charging means, a non-contact type corona charger 311 is provided, and the surface of the photosensitive drum 321 is uniformly charged by the corona charger 311.

As the charging roller disposed with a small gap with respect to the electrostatic latent image carrier, the charging roller is improved so as to have a minute gap with respect to the electrostatic latent image carrier. The fine gap is preferably 10 to 200 μm, more preferably 10 to 100 μm.
Here, FIG. 4 is a schematic view showing an example of a non-contact charging roller. In FIG. 4, the charging roller 310 is disposed with a minute gap H with respect to the photosensitive drum 321. The minute gap H is set by causing the spacer member surface to contact the surface of the photosensitive drum 321 by, for example, winding a spacer member having a certain thickness around the non-image forming regions at both ends of the charging roller 310. be able to. In FIG. 4, 304 is a power source.
In FIG. 4, as a method of maintaining the minute gap H, a film 302 is wound around both ends of the charging roller 310 to form a spacer member. The spacer 302 is brought into contact with the photosensitive surface of the electrostatic latent image carrier, so that a certain minute gap H in the image area of the charging roller and the electrostatic latent image carrier can be obtained. The applied bias applies an AC superposition type voltage to charge the electrostatic latent image carrier by a discharge generated in a minute gap H between the charging roller and the electrostatic latent image carrier. As shown in FIG. 4, the accuracy of maintaining the minute gap H is improved by pressing the shaft 311 of the charging roller with a spring 303.
The spacer member may be integrally formed with the charging roller. At this time, at least the surface of the gap portion is an insulator. As a result, it is possible to prevent discharge in the gap portion, deposit discharge products in the gap portion, and prevent the toner from adhering to the gap portion due to the adhesiveness of the discharge product and widening the gap.
Further, a heat shrinkable tube may be used as the spacer member. Examples of such heat-shrinkable tubes include Sumitubes for 105 ° C. (trade name: F105 ° C., manufactured by Sumitomo Chemical Co., Ltd.).

<Exposure process and exposure means>
The exposure step is a step of exposing the charged electrostatic latent image carrier surface, and is performed by the exposure means.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure unit.
The optical system in the exposure is roughly classified into an analog optical system and a digital optical system. The analog optical system is an optical system that projects an original directly onto an electrostatic latent image carrier by an optical system, and the digital optical system receives image information as an electrical signal and converts it into an optical signal. It is an optical system that exposes an electrostatic latent image carrier to form an image.
The exposure means is not particularly limited as long as the surface of the latent electrostatic image bearing member charged by the charging means can be exposed like 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, a liquid crystal shutter optical system, and an LED 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 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, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using toner or developer, for example, and can be appropriately selected from known ones. For example, the toner or developer is accommodated, and Preferable examples include those having at least developing means capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.
The developing means may be of a dry development type or a wet development type. Further, it may be a monochromatic developing unit or a multi-color developing unit. For example, a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller are provided. Preferred examples include those possessed.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. 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.
The developer accommodated in the developing unit is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

As the one-component developing means, for example, a one-component developing device having a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier is preferably used. .
FIG. 5 is a schematic diagram illustrating an example of a one-component developing device. This one-component developing device uses a one-component developer made of toner, forms a toner layer on a developing roller 402 as a developer carrying member, and uses the toner layer on the developing roller 402 as an electrostatic latent image carrying member. The photosensitive drum 1 is conveyed so as to be in contact with the photosensitive drum 1 to perform contact one-component development for developing the electrostatic latent image on the photosensitive drum 1.
In FIG. 5, the toner in the casing 401 is agitated by rotation of an agitator 411 as a stirring means, and mechanically supplied to a supply roller 412 as a toner supply member. The supply roller 412 is formed of foamed polyurethane or the like, has flexibility, and has a structure in which toner can be easily held by a cell having a diameter of 50 to 500 μm. Further, the supply roller has a relatively low JIS-A hardness of 10 to 30 °, and can be brought into contact with the developing roller 402 uniformly.
The supply roller 412 is driven to rotate in the same direction as the developing roller 402, that is, the surface of the supply roller 412 moves in the opposite direction at the opposing portion of both rollers. The linear speed ratio (supply roller / developing roller) of both rollers is preferably 0.5 to 1.5. Further, the supply roller 412 may be rotated so that the surfaces of the supply roller 412 move in the same direction as the developing roller 402, that is, at the opposite portions of the two rollers. In this embodiment, the supply roller 412 rotates in the same direction as the developing roller 402, and the linear speed ratio is set to 0.9. The biting amount of the supply roller 412 with respect to the developing roller 402 is set to 0.5 to 1.5 mm. In the present embodiment, when the unit effective width is 240 mm (A4 size vertical), the required torque is 14.7 to 24.5 N · cm.

The developing roller 402 has a surface layer made of a rubber material on a conductive substrate, has a diameter of 10 to 30 mm, and appropriately roughens the surface to have a surface roughness Rz of 1 to 4 μm. The value of the surface roughness Rz is preferably 13 to 80% with respect to the average particle diameter of the toner. As a result, the toner is conveyed without being buried in the surface of the developing roller 402. In particular, the surface roughness Rz of the developing roller 402 is preferably in the range of 20 to 30% of the average particle diameter of the toner so as not to retain the toner with extremely low charge.
Examples of the rubber material include silicone rubber, butadiene rubber, NBR rubber, hydrin rubber, EPDM rubber, and the like. Further, it is preferable to coat the surface of the developing roller 402 with a coating layer in order to stabilize the quality with time. Examples of the material for the coating layer include silicone materials and Teflon (registered trademark) materials. The silicone material is excellent in toner chargeability, and the Teflon (registered trademark) material is excellent in releasability. In order to obtain conductivity, a conductive material such as carbon black can be appropriately contained. The thickness of the coat layer is preferably 5 to 50 μm. If it is out of this range, problems such as easy cracking may occur.
Toner having a predetermined polarity (negative polarity in the case of the present embodiment) existing on or inside the supply roller 412 is pinched by the developing roller 402 that rotates in the opposite direction at the contact point by rotation, thereby causing friction. A negatively charged charge is obtained by the charging effect and is held on the developing roller 402 by an electrostatic force and by a conveying effect by the surface roughness of the developing roller 402. However, the toner layer on the developing roller 402 at this time is not uniform and is considerably excessively attached (1 to 3 mg / cm ² ). Accordingly, a toner thin layer having a uniform layer thickness is formed on the developing roller 402 by bringing a regulating blade 413 as a layer thickness regulating member into contact with the developing roller 402. The restriction blade 413 is a so-called belly contact where the tip is directed downstream with respect to the rotation direction of the developing roller 402 and the central portion of the restriction blade 413 contacts, but it can be set in the reverse direction. It is also possible to realize edge contact.

As the material of the regulating blade, a metal such as SUS304 is preferable, and the thickness is 0.1 to 0.15 mm. In addition to the metal, a rubber material such as polyurethane rubber having a thickness of 1 to 2 mm or a resin material having a relatively high hardness such as a silicone resin can be used. Note that since resistance can be reduced by mixing carbon black or the like other than metal, an electric field can be formed between the developing roller 402 and a bias power source.
The regulating blade 413 as the layer thickness regulating member is preferably 10 to 15 mm as a free end length from the holder. If the free end length exceeds 15 mm, the developing means becomes large and cannot be stored compactly in the image forming apparatus. If it is less than 10 mm, vibration occurs when the regulating blade comes into contact with the surface of the developing roller 402. In some cases, an abnormal image such as unevenness in the horizontal direction is likely to occur on the image.
The contact pressure of the regulating blade 413 is preferably in the range of 0.049 to 2.45 N / cm. When the contact pressure exceeds 2.45 N / cm, the toner adhesion amount on the developing roller 402 decreases and the toner charge amount increases excessively, so the development amount may decrease and the image density may decrease. If it is less than 0.049 N / cm, the thin layer may not be formed uniformly, and the toner mass may pass through the regulating blade, and the image quality may be significantly lowered. In this embodiment, the developing roller 402 has a JIS-A hardness of 30 °, the regulating blade 413 is a SUS plate having a thickness of 0.1 mm, and the contact pressure is set to 60 gf / cm. At this time, the target toner adhesion amount on the developing roller could be obtained.
Further, the contact angle of the regulating blade 413 as the layer thickness regulating member is preferably 10 to 45 ° with respect to the tangent line of the developing roller 402 in the direction in which the tip faces the downstream side of the developing roller 402. A portion unnecessary for forming a thin layer of toner sandwiched between the regulating blade 413 and the developing roller 402 is peeled off from the developing roller 402 and is 0.4 to 0.8 mg / cm ² per unit area which is a target range. A thin layer having a uniform thickness is formed. The toner charge at this time is finally in the range of −10 to −30 μC / g in this embodiment, and is developed to face the electrostatic latent image on the photosensitive drum 1.
Therefore, according to the one-component developing device of this embodiment, the distance between the surface of the photosensitive drum 1 and the surface of the developing roller 402 is further narrower than in the case of the conventional two-component developing unit, the developing ability is increased, and the further low potential is achieved. But development is possible.

<Two-component developing means>
The two-component developing means has a magnetic field generating means fixed inside, and a two-component development having a rotatable developer carrying member carrying a two-component developer comprising a magnetic carrier and a toner on the surface. A device is preferred.
Here, FIG. 6 is a schematic view showing an example of a two-component developing device using a two-component developer composed of toner and a magnetic carrier. In the two-component developing device of FIG. 6, the two-component developer is stirred and conveyed by a screw 441 and supplied to a developing sleeve 442 as a developer carrying member. The two-component developer supplied to the developing sleeve 442 is regulated by a doctor blade 443 as a layer thickness regulating member, and the amount of developer supplied is controlled by a doctor gap which is a distance between the doctor blade 443 and the developing sleeve 442. The If the doctor gap is too small, the developer amount is too small and the image density is insufficient. Conversely, if the doctor gap is too large, the developer amount is excessively supplied and the photosensitive drum as an electrostatic latent image carrier. There arises a problem that carrier adhesion occurs on 1. Therefore, the developing sleeve 442 is provided with a magnet as a magnetic field generating means for generating a magnetic field so as to make the developer stand up on the peripheral surface thereof, so as to follow a normal magnetic field line generated from the magnet. Then, the developer is spiked in a chain shape on the developing sleeve 442 to form a magnetic brush.

  The developing sleeve 442 and the photosensitive drum 1 are disposed so as to be close to each other with a certain gap (developing gap) therebetween, and a developing region is formed in a portion facing both. The developing sleeve 442 is formed of a non-magnetic material such as aluminum, brass, stainless steel, or conductive resin in a cylindrical shape, and is rotated by a rotation drive mechanism (not shown). The magnetic brush is transferred to the developing area by the rotation of the developing sleeve 442. A developing voltage is applied to the developing sleeve 442 from a developing power source (not shown), and the toner on the magnetic brush is separated from the carrier by the developing electric field formed between the developing sleeve 442 and the photosensitive drum 1, and the photosensitive drum 1. It is developed on the upper electrostatic latent image. An alternating current may be superimposed on the development voltage.

The development gap is preferably about 5 to 30 times the particle size of the developer, and is preferably set to 0.5 to 1.5 mm if the developer particle size is 50 μm. If the development gap is wider than this, the desired image density may be difficult to achieve.
The doctor gap is preferably the same as or slightly larger than the development gap. The drum diameter and drum linear speed of the photosensitive drum 1 and the sleeve diameter and sleeve linear speed of the developing sleeve 442 are determined by restrictions such as the copying speed and the size of the apparatus. The ratio of the sleeve linear velocity to the drum linear velocity is preferably 1.1 or more in order to obtain a necessary image density. It is also possible to control the process conditions by installing a sensor at a position after development and detecting the toner adhesion amount from the optical reflectance.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image to a recording medium, and is performed using a transfer unit. As the transfer means. Using a transfer unit that directly transfers a visible image on the electrostatic latent image bearing member to a recording medium, or an intermediate transfer member, after the primary transfer of the visible image onto the intermediate transfer member, the visible image is It is roughly divided into secondary transfer means for secondary transfer onto a recording medium.
The transfer can be performed, for example, by charging the electrostatic latent image carrier using a transfer charger, and can be performed by the transfer unit. The transfer unit preferably includes a primary transfer unit that forms a composite transfer image by transferring a visible image onto an intermediate transfer member, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. .

There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably from well-known transfer bodies, For example, a transfer belt, a transfer roller, etc. are mentioned suitably.
The intermediate transfer member preferably has a static friction coefficient of 0.1 to 0.6, more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably several Ωcm or more and 10 ³ Ωcm or less. Thus, by setting the volume resistance of the intermediate transfer member 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 hardly remains on the intermediate transfer member. Therefore, transfer unevenness during secondary transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

There is no restriction | limiting in particular as a material of the said intermediate transfer body, Although it can select suitably according to the objective from well-known materials, the following are suitable.
(1) A material having a high Young's modulus (tensile modulus) is used as a single layer belt. For example, PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) and PAT (Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) and PC blend material, ETFE and PAT blend material, PC and PAT blend material, thermosetting of carbon black dispersion Examples thereof include polyimide. 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 rib displacement is unlikely 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 (1) is used as a base layer and a surface layer or an intermediate layer is formed on the outer periphery thereof. It has a performance capable of preventing the line image from being lost due to the hardness of the single layer belt.
(3) An elastic belt having a relatively low Young's modulus using resin, rubber, or elastomer, and such an elastic belt has an advantage that almost no void in a line image occurs due to its softness. In addition, the elastic belt is wider than the drive roll and tension roll, and the elasticity of the belt ears protruding from the roll can be used to prevent meandering, thus reducing costs without requiring ribs or meandering prevention devices. it can.
Among these, the elastic belt (3) is particularly preferable.
The elastic belt is deformed corresponding to the toner layer and the recording medium having poor smoothness in the transfer portion. In other words, since the elastic belt deforms following the local unevenness, good adhesion can be obtained without excessively increasing the transfer pressure with respect to the toner layer, there is no void in characters, and flatness is poor. A transfer image with excellent uniformity can be obtained even on a recording medium.

  There is no restriction | limiting in particular as resin used for the said elastic belt, Although it can select suitably according to the objective, For example, polycarbonate resin, fluororesin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-alpha -Methylstyrene resin, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-acrylic) Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer Polymer (eg, styrene-methyl methacrylate copolymer) Styrene resins such as styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate copolymer, etc. Or a styrene-substituted monopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, 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, polyethylene resin, polypropylene Resin, polybutadiene Emissions, polyvinylidene chloride resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as rubber | gum used for the said elastic belt, According to the objective, it can select suitably, For example, natural rubber, butyl rubber, fluorine-type rubber, acrylic rubber, EPDM rubber, NBR rubber, acrylonitrile-butadiene-styrene 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, epichlorohydride Examples thereof include phosphorus rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as an elastomer used for the said elastic belt, According to the objective, it can select suitably, For example, a polystyrene-type thermoplastic elastomer, a polyolefin-type thermoplastic elastomer, a polyvinyl chloride-type thermoplastic elastomer, a polyurethane-type thermoplasticity Examples thereof include elastomers, polyamide-based thermoplastic elastomers, polyurea thermoplastic elastomers, polyester-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers. These may be used individually by 1 type and may use 2 or more types together.

  The conductive agent for adjusting the resistance value used in the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal powder such as carbon black, graphite, aluminum, nickel; tin oxide, titanium oxide And conductive metal oxides such as antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), and indium oxide-tin oxide composite oxide (ITO). The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  In addition, the surface layer of the elastic belt prevents contamination of the electrostatic latent image carrier by the elastic material, reduces the frictional resistance of the belt surface, reduces the adhesion of the toner, and improves the cleaning property and the secondary transfer property. What can do is preferable. The surface layer is made of, for example, a binder resin such as a polyurethane resin, a polyester resin, or an epoxy resin, and a material capable of increasing the lubricity by reducing the surface energy, such as a fluororesin, a fluorine compound, a fluorocarbon, titanium dioxide, a silicon car It is preferable to contain powder or particles such as bites. Further, it is possible to use a material having a reduced surface energy by forming a fluorine-rich surface layer by heat treatment, such as a fluorine-based rubber material.

  There is no restriction | limiting in particular as a manufacturing method of the said elastic belt, Although it can select suitably according to the objective, For example, (1) Centrifugal molding method which pours material into a rotating cylindrical type | mold and forms a belt, ( 2) Spray coating method to form a film by spraying a liquid paint, (3) Dipping method in which a cylindrical mold is dipped in a solution of the material, and (4) Casting to be injected into an inner mold or an outer mold And (5) a method in which a compound is wound around a cylindrical mold and vulcanized and polished.

  The method for preventing the elastic belt from stretching is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a method of adding a material for preventing elongation to the core layer, 2) A method of forming a rubber layer on a core layer with little elongation, and the like.

  There is no restriction | limiting in particular as a material which prevents the said elongation, Although it can select suitably according to the objective, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol Synthetic fibers such as fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers; inorganic fibers such as carbon fibers, glass fibers, boron fibers; iron fibers, copper fibers, etc. A metal fiber etc. are mentioned, What made these materials into the shape of a woven fabric or a thread form is used suitably.

The method for forming the core layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a woven fabric woven in a cylindrical shape is covered with a mold or the like and coated thereon (2) A method of providing a covering layer on one or both sides of a core layer by immersing a woven fabric woven in a cylindrical shape in liquid rubber or the like, and (3) a thread at an arbitrary pitch on a die For example, a method of winding in a spiral shape and providing a coating layer thereon may be used.
The thickness of the coating layer depends on the hardness of the coating layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Further, since the amount of expansion / contraction increases and the expansion and contraction of the image increase, it is not preferable that the thickness is too thick (about 1 mm or more).

The transfer unit (the primary transfer unit and the secondary transfer unit) includes at least a transfer unit that peels and charges the visible image formed on the electrostatic latent image carrier to the recording medium side. Is preferred. There may be one transfer unit or two or more transfer units. 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 an unfixed image after development can be transferred, and can be appropriately selected according to the purpose. Etc. can also be used.

<Transfer means of tandem type image forming apparatus>
These transfer units are also preferably used in a tandem type image forming apparatus. The tandem image forming apparatus has a plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit. In this tandem type image forming apparatus, four image forming elements for yellow, magenta, cyan, and black are mounted, and each visible image is created in parallel with the four image forming elements, and is recorded on a recording medium or an intermediate transfer member. Therefore, a full color image can be formed at a higher speed.

  As the tandem type image forming apparatus, (1) as shown in FIG. 7, the surface moves so as to pass through a transfer position which is a region facing each electrostatic latent image carrier 1 of a plurality of image forming elements. A direct transfer system in which the visible image formed on each electrostatic latent image carrier 1 is sequentially transferred to the recording medium S by the transfer means 2, and (2) a plurality of images as shown in FIG. The visible image on each electrostatic latent image carrier 1 of the forming element is once transferred sequentially to the intermediate transfer body 4 by the transfer means (primary transfer means) 2, and then the image on the intermediate transfer body 4 is transferred to the secondary transfer means 5. There is an indirect transfer method in which the image is transferred to the recording medium S at once. In FIG. 8, a transfer conveyance belt is used as the secondary transfer unit, but a roller shape may be used.

Comparing the direct transfer method (1) and the indirect transfer method (2), the direct transfer method (1) is a tandem type image forming unit T in which the electrostatic latent image carriers 1 are arranged. The sheet feeding device 6 must be disposed on the upstream side, and the fixing device 7 serving as a fixing unit must be disposed on the downstream side, which increases the size of the recording medium in the conveying direction. On the other hand, in the indirect transfer method (2), the secondary transfer position can be set relatively freely, and the paper feeding device 6 and the fixing device 7 are arranged so as to overlap the tandem type image forming unit T. There is an advantage that downsizing is possible.
In the direct transfer method (1), the fixing device 7 is disposed close to the tandem image forming unit T in order not to increase the size in the recording medium conveyance direction. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the recording medium S can bend, and an impact when the leading end of the recording medium S enters the fixing device 7 (particularly with a thick recording medium). In addition, the fixing device 7 tends to affect upstream image formation due to the speed difference between the recording medium conveyance speed when passing through the fixing device 7 and the recording medium conveyance speed by the transfer conveyance belt. On the other hand, in the indirect transfer method (2), the fixing device 7 can be disposed with a sufficient margin that the recording medium S can bend, so that the fixing device 7 hardly affects image formation.

  In view of the above, in recent years, indirect transfer methods have attracted attention. In such a color image forming apparatus, as shown in FIG. 8, the transfer residual toner remaining on the electrostatic latent image carrier 1 after the primary transfer is removed by a cleaning device 8 as a cleaning unit, and the electrostatic latent image is thus removed. The surface of the carrier 1 is cleaned to prepare for the image formation again. 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.

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit.
The fixing unit is not particularly limited and may be appropriately selected according to the purpose. A fixing device having a fixing member and a heat source for heating the fixing member is preferably used.
The fixing member is not particularly limited as long as it can abut against each other to form a nip portion, and can be appropriately selected according to the purpose. For example, a combination of an endless belt and a roller, a roller and a roller, The heating method from the surface of the fixing member by a combination of an endless belt and a roller or induction heating can be used in order to reduce the warm-up time and realize energy saving. It is preferable to use it.

  Examples of the fixing member include known heating and pressing means (combination of heating means and pressing means). In the case of a combination of the endless belt and the roller, for example, a combination of a heating roller, a pressure roller, and an endless belt may be used as the heating and pressing unit, and the combination of the roller and the roller may be used. In this case, for example, a combination of a heating roller and a pressure roller can be used.

  When the fixing member is an endless belt, the endless belt is preferably formed of a material having a small heat capacity. For example, an embodiment in which an offset prevention layer is provided on a substrate may be used. Examples of the material for forming the base include nickel and polyimide, and examples of the material for forming the offset prevention layer include silicone rubber and fluorine-based resin.

  When the fixing member is a roller, the cored bar of the roller is preferably formed of an inelastic member to prevent deformation (deflection) due to high pressure. There is no restriction | limiting in particular as this inelastic member, Although it can select suitably according to the objective, For example, high thermal conductivity bodies, such as aluminum, iron, stainless steel, brass, are mentioned suitably. Moreover, it is preferable that the surface of the roller is covered with an offset prevention layer. The material for forming the offset prevention layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include RTV silicone rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA), and polytetrafluoroethylene. (PTFE).

In the fixing step, the image by the toner may be transferred to the recording medium, and the recording medium on which the image has been transferred may be passed through the nip portion to fix the image on the recording medium. The image may be simultaneously transferred and fixed to the recording medium at the nip portion.
Further, the fixing step may be performed each time the toner of each color is transferred to the recording medium, or may be performed at the same time in a state where the toner of each color is laminated.

The nip portion is formed by bringing at least two fixing members into contact with each other.
The surface pressure of the nipping section is not particularly limited, it may be appropriately selected depending on the intended purpose, 5N / cm ² or more, more preferably ^{7~100N / cm 2, 10~60N / cm} 2 Is more preferable. If the surface pressure of the nip portion is too high, the durability of the roller may decrease. On the other hand, when the surface pressure of the nip portion is less than 5 N / cm ² , the offset prevention property may be insufficient.

  The temperature for fixing the image on the recording medium with the toner (that is, the surface temperature of the fixing member by the heating unit) is not particularly limited and may be appropriately selected depending on the intended purpose. ° C is preferred, and 120 to 160 ° C is more preferred. If the fixing temperature is less than 100 ° C., the fixability may be insufficient, and if it exceeds 170 ° C., it is not preferable in terms of realizing energy saving.

As the fixing means, (1) an aspect in which the fixing means has at least one of a roller and a belt, is heated from a surface not in contact with the toner, and the transferred image transferred onto the recording medium is fixed by heating and pressing. (Internal heating system) and (2) A fixing unit has at least one of a roller and a belt, and heats and presses a transfer image transferred onto a recording medium by heating from the surface in contact with the toner. (External heating method). It is also possible to use a combination of both.
As the internal heating type fixing means (1), for example, the fixing member itself has a heating means inside. Examples of such heating means include a heat source such as a heater and a halogen lamp.
As the (2) external heating type fixing means, for example, at least a part of the surface of at least one of the fixing members is preferably heated by the heating means. There is no restriction | limiting in particular as such a heating means, According to the objective, it can select suitably, For example, an electromagnetic induction heating means etc. are mentioned.

There is no restriction | limiting in particular as said electromagnetic induction heating means, Although it can select suitably according to the objective, What has a means to generate | occur | produce a magnetic field and a means to generate | occur | produce heat | fever by electromagnetic induction, etc. are suitable.
The electromagnetic induction heating means includes, for example, an induction coil disposed so as to be close to the fixing member (for example, a heating roller), a shielding layer provided with the induction coil, and an induction coil of the shielding layer. What consists of an insulating layer provided in the other side of the provided surface is preferable. In this case, it is preferable that the heating roller is formed of a magnetic material or a heat pipe.
The induction coil is arranged in a state of wrapping at least a semi-cylindrical portion on the opposite side of the contact portion between the heating roller and the fixing member (for example, a pressure roller, an endless belt, etc.) of the heating roller. Is preferred.

<Internal heating fixing method>
FIG. 9 is a belt-type fixing device showing an example of an internal heating type fixing means. The belt-type fixing device 510 in FIG. 9 includes a heating roller 511, a fixing roller 512, a fixing belt 513, and a pressure roller 514.

  The fixing belt 513 is stretched by a heating roller 511 and a fixing roller 512 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 511. The heating roller 511 has a built-in heating source 515 and is designed so that the temperature can be adjusted by a temperature sensor 517 attached in the vicinity of the heating roller 511. The fixing roller 512 is rotatably disposed inside the fixing belt 513 and in contact with the inner surface of the fixing belt 513. The pressure roller 514 is in contact with the outer side of the fixing belt 513 and the outer surface of the fixing belt 513 so as to press the fixing roller 512 and is rotatably arranged. Further, the surface hardness of the fixing belt 513 is lower than the surface hardness of the pressure roller 514, and the nip portion N formed between the fixing roller 512 and the pressure roller 514 has an introduction side end and a discharge side of the recording medium S. An intermediate region located between the ends is located closer to the fixing roller 512 than the introduction side end and the discharge side end.

In the belt-type fixing device 510 shown in FIG. 9, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the heating roller 511. The toner image T on the recording medium S is heated and melted by the heating roller 511 and the fixing belt 513 heated to a predetermined temperature by the action of the built-in heating source 515. In this state, the recording medium S is inserted into a nip portion N formed between the fixing roller 512 and the pressure roller 514. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 513 that rotates in conjunction with the rotation of the fixing roller 512 and the pressure roller 514 and is pressed when passing through the nip N. The toner image T is fixed on the recording medium S.
Next, the recording medium S on which the toner image T is fixed passes between the fixing roller 512 and the pressure roller 514, is peeled off from the fixing belt 513, and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 514, and the recording medium S is prevented from being wound around the fixing belt 513. The fixing belt 513 is cleaned by the cleaning roller 516.

Further, the heat roll type fixing device 515 shown in FIG. 10 includes a heating roller 520 as the fixing member, and a pressure roller 530 disposed in contact therewith.
The heating roller 520 has a hollow metal cylinder 521, the surface of which is covered with an offset prevention layer 522, and a heating lamp 523 is disposed therein. The pressure roller 530 includes a metal cylinder 531 and the surface thereof is covered with an offset prevention layer 532. In the pressure roller 530, the metal cylinder 531 may have a hollow shape, and a heating lamp 533 may be disposed therein.
The heating roller 520 and the pressure roller 530 are urged by a spring (not shown), and are rotatably provided in a pressure-contacted state to form a nip portion N. Further, the surface hardness of the offset prevention layer 522 in the heating roller 520 is lower than the surface hardness of the offset prevention layer 532 in the pressure roller 530, and in the nip portion N formed between the heating roller 520 and the pressure roller 530, An intermediate region located between the introduction side end and the discharge side end of the recording medium S is located closer to the heating roller 520 than the introduction side end and the discharge side end.

In the heat roll type fixing device 515 shown in FIG. 10, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the nip portion N between the heating roller 520 and the pressure roller 530. The toner T on the recording medium S is heated and melted by the heating roller 520 heated to a predetermined temperature by the action of the built-in heating lamp 523, and at the same time, when passing through the nip portion N, the toner T is heated. The toner image T is fixed on the recording medium S by being pressed by the pressing force of the pressure roller 530.
Next, the recording medium S on which the toner image T is fixed passes between the heating roller 520 and the pressure roller 530 and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 530, and the recording medium S is prevented from being wound around the pressure roller 530. The heating roller 520 is cleaned by a cleaning roller (not shown).

<External heat fixing method>
FIG. 11 shows an electromagnetic induction heating type fixing device 570 showing an example of an external heating type fixing unit. The electromagnetic induction heating type fixing device 570 includes a heating roller 566, a fixing roller 580, a fixing belt 567, a pressure roller 590, and an electromagnetic induction heating unit 560.
The fixing belt 567 is stretched by a heating roller 566 and a fixing roller 580 that are rotatably disposed therein, and is heated to a predetermined temperature by the heating roller 566.
The heating roller 566 has, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals. For example, the outer diameter is 20 to 40 mm and the wall thickness is 0.3 to 1.0 mm. It has a low heat capacity and quick temperature rise.
The fixing roller 580 has, for example, a metal core 581 made of stainless steel or the like, and the surface thereof is formed by coating a heat-resistant silicone rubber with a solid or foamed elastic layer 582. The fixing belt 567 is disposed so as to be rotatable inside the fixing belt 567 and in contact with the inner surface of the fixing belt 567. The fixing roller 580 is provided with an outer diameter of about 20 to 40 mm in order to form a nip portion N having a predetermined width between the pressure roller 590 and the fixing roller 580 by the pressing force from the pressure roller 590, and is heated. It is larger than the roller 566. The elastic layer 582 has a thickness of about 4 to 6 mm, and is formed so that the heat capacity of the heating roller 566 is smaller than the heat capacity of the fixing roller 580, thereby shortening the warm-up time of the heating roller 566.
The pressure roller 590 has a metal core 591 made of a cylindrical member made of a metal having high thermal conductivity such as copper or aluminum, and the surface thereof is covered with an elastic layer 592 having high heat resistance and toner releasability. The fixing roller 580 is in contact with the outer surface of the fixing belt 567 and the outer surface of the fixing belt 567 so as to be in pressure contact therewith, and is rotatably disposed. In addition to the above metal, SUS may be used for the metal core 591.
The electromagnetic induction heating unit 560 is disposed in the vicinity of the heating roller 566 and in the axial direction of the heating roller 566. The electromagnetic induction heating unit 560 includes an excitation coil 561 that is a magnetic field generation unit, and a coil guide plate 562 around which the excitation coil 561 is wound. The coil guide plate 562 has a semi-cylindrical shape that is disposed close to the outer peripheral surface of the heating roller 566, and the excitation coil 561 includes a single long excitation coil wire along the coil guide plate 562 in the axial direction of the heating roller 566. It is one that is wound alternately. The exciting coil 561 is connected to a driving power source (not shown) whose frequency is variable. On the outside of the excitation coil 561, a semi-cylindrical excitation coil core 563 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 564 and is disposed close to the excitation coil 561.

In the electromagnetic induction heating type fixing device 570 shown in FIG. 11, when the excitation coil 561 of the electromagnetic induction heating unit 560 is energized, an alternating magnetic field is formed around the electromagnetic induction heating unit 560, close to the excitation coil 561, and The heating roller 566 surrounded by the excitation coil 561 is preheated uniformly and efficiently by excitation of overcurrent. The recording medium S on which the toner image T to be fixed is formed is conveyed to the nip N between the fixing roller 580 and the pressure roller 590. The toner image T on the recording medium S is then heated by the fixing belt 567 heated at the contact portion W1 with the heating roller 566 by the heating roller 566 heated to a predetermined temperature by the action of the electromagnetic induction heating unit 560. It is heated and becomes a molten state. In this state, the recording medium S is inserted into a nip portion N formed between the fixing roller 580 and the pressure roller 590. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 567 that rotates in conjunction with the rotation of the fixing roller 580 and the pressure roller 590, and is pressed when passing through the nip N. The toner image T is fixed on the recording medium S.
Next, the recording medium S on which the toner image T is fixed passes between the fixing roller 580 and the pressure roller 590, is peeled off from the fixing belt 567, and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 590 and the winding of the recording medium S around the fixing belt 567 is prevented. The fixing belt 567 is cleaned by a cleaning roller (not shown).

12 includes a fixing roller 520 serving as the fixing member, a pressure roller 530 disposed in contact with the fixing roller 520, a fixing roller 520, and a pressure roller. The fixing unit includes an electromagnetic induction heating source 540 that heats from the outside.
The fixing roller 520 includes a cored bar 521, and the surface thereof is formed by covering a heat insulating elastic layer 522, a heat generating layer 523, and a release layer 524 in this order. The pressure roller 530 has a metal core 531, and the surface thereof is formed by covering a heat insulating elastic layer 532, a heat generating layer 533, and a release layer 534 in this order. Note that the release layer 524 and the release layer 534 are formed of tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA).
The fixing roller 520 and the pressure roller 530 are urged by a spring (not shown), and are rotatably provided in a pressure-contacted state to form a nip portion N.
The electromagnetic induction heating source 540 is disposed in the vicinity of the fixing roller 520 and the pressure roller 530, respectively, and heats the heat generation layer 523 and the heat generation layer 533 by electromagnetic induction.
In the fixing device shown in FIG. 12, the fixing roller 520 and the pressure roller 530 are uniformly and efficiently preheated by the electromagnetic induction heating source 540. In addition, since the combination of the roller and the roller, a high surface pressure of the nip portion N can be easily realized.

<Cleaning process and cleaning means>
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
Further, the developing means has a developer carrier that abuts on the surface of the electrostatic latent image carrier, and develops the electrostatic latent image formed on the electrostatic latent image carrier and By collecting the residual toner on the latent image carrier, cleaning can be performed without providing a cleaning means (cleaning-less method).
The cleaning means is not particularly limited, and may be selected from known cleaners as long as it can remove the toner remaining on the electrostatic latent image carrier. For example, a magnetic brush cleaner, Examples thereof include an electrostatic brush cleaner, a magnetic roller cleaner, a cleaning blade, a brush cleaner, and a web cleaner. Among these, a cleaning blade having a high toner removing ability, a small size and an inexpensive price is particularly preferable.
Examples of the material of the rubber blade used for the cleaning blade include urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, and butadiene rubber. Among these, urethane rubber is particularly preferable.

Here, FIG. 13 is an explanatory view showing, in an enlarged manner, the vicinity of the contact portion 615 of the cleaning blade 613 with the electrostatic latent image carrier. The cleaning blade 613 is provided with a toner blocking surface 617 that forms a space S that expands from the contact portion 615 toward the upstream side in the rotation direction of the electrostatic latent image carrier with the surface of the photosensitive drum 1. Yes. In the present embodiment, the toner blocking surface 617 extends from the contact portion 615 to the upstream side in the rotation direction of the photosensitive drum 1 so that the space S has an acute angle.
As shown in FIG. 13, the toner blocking surface 617 is provided with a coating portion 618 as a high friction portion having a higher friction coefficient than the cleaning blade 613. The coating portion 618 is formed of a material (high friction material) having a higher friction coefficient than the material forming the cleaning blade 613. Examples of such a high friction material include DLC (diamond-like carbon). The high friction material is not limited to DLC. The coating portion 618 is provided in a range where the toner blocking surface 617 does not contact the surface of the photosensitive drum 1.
Although not shown, the cleaning unit includes a toner collection blade that collects the residual toner scraped by the cleaning blade, a toner collection coil that conveys the residual toner collected by the toner collection blade to the collection unit, and the like. ing.

FIG. 14 is a schematic diagram illustrating an example of a cleaningless type image forming apparatus in which the developing unit also serves as the cleaning unit.
In FIG. 14, 1 is a photosensitive drum as an electrostatic latent image carrier, 620 is a brush charging device as contact charging means, 603 is an exposure device as exposure means, 604 is a developing device as development means, and 640 is a supply. A paper cassette, 650 is a roller transfer means, and P is a recording medium.
In this cleaningless type image forming apparatus, the untransferred toner on the surface of the photosensitive drum 1 reaches the position of the contact charging device 620 that is in contact with the photosensitive drum 1 by the subsequent rotation of the photosensitive drum 1, and the photosensitive drum. 1 is temporarily collected by a magnetic brush portion (not shown) of the brush charging member 621 that is in contact with the toner 1, and the collected toner is again discharged onto the surface of the photosensitive drum 1 and finally into the developing device 604. The developer is collected together with the developer by the developer carrier 631, and the photosensitive drum 1 is repeatedly used for image formation.
Here, the developing means 604 also serves as a cleaning means that the toner slightly remaining on the photosensitive drum 1 after the transfer is developed bias (between the DC voltage applied to the developer carrier 631 and the surface potential of the photosensitive drum 1). It means a method of collecting by (potential difference).
In such a cleaningless type image forming apparatus in which the developing unit also serves as a cleaning unit, the transfer residual toner is collected by the developing unit 604 and is used after the next step, so that waste toner is eliminated, maintenance-free, and cleaner-less. Since it becomes a system, the advantage in terms of space is remarkably large, and the image forming apparatus can be greatly downsized.

<Other processes and other means>
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 recycling step is a step of recycling the electrophotographic toner removed in the cleaning step to the developing unit, and can be suitably performed by a 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.

<Image Forming Apparatus and Image Forming Method>
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. 15 includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, exposure 30 by an exposure unit as an exposure unit, and a developing unit as a developing unit. 40, an intermediate transfer member 50, a cleaning blade 60 as a cleaning means, and a static elimination lamp 70 as a static elimination means.
The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. 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. An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.
The developing device 40 includes a developing belt 41 as a 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. Yes. The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.
In the image forming apparatus 100 shown in FIG. 15, first, the charging roller 20 uniformly charges the photosensitive drum 10. An exposure device (not shown) performs image-wise exposure 30 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 visible image. The visible 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 electrostatic latent image carrier 10 is removed by the cleaning blade 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination lamp 70.

  Next, 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. 16 does not include the developing belt 41 as the developer carrying member in the image forming apparatus 100 shown in FIG. 15, and the black developing unit 45 </ b> K is disposed around the electrostatic latent image carrying member 10. The yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are configured in the same manner as the image forming apparatus 100 shown in FIG. Show. In FIG. 16, the same components as those in FIG. 15 are denoted by the same reference numerals.

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 tandem type image forming apparatus shown in FIG. 17 is a tandem type color image forming apparatus. The tandem color image forming apparatus 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. 17. In the vicinity of the support roller 15, an intermediate transfer member cleaning unit 17 for removing residual toner on the intermediate transfer member 50 is disposed. A tandem in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched by the support roller 14 and the support roller 15 along the conveyance direction. A mold developing means 120 is arranged. An exposure device 21 is disposed in the vicinity of the tandem developing unit 120. On the opposite side of the intermediate transfer member 50 from the side on which the tandem developing unit 120 is disposed, the secondary transfer unit 22 is disposed. In the secondary transfer unit 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 unit 22.
A 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 unit 22 and the fixing device 25.

Next, formation of a full-color image (color copy) using the tandem developing unit 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 a 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.

The image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing unit 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. 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 developing means 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (an electrostatic latent image carrier 10K for black, an electrostatic latent image carrier 10Y for yellow, an electrostatic latent image carrier 10M for magenta, and an electrostatic latent image carrier 10C for cyan); The electrostatic latent image carrier 10 is uniformly charged, and the electrostatic latent image carrier is exposed like an image corresponding to each color image based on each color image information (L in FIG. 18). An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Using The image forming apparatus includes a developing device 61 configured to form a toner image using each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this manner are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15 and 16. The black image formed on the surface, the yellow image formed on the yellow electrostatic latent image carrier 10Y, the magenta image formed on the magenta electrostatic latent image carrier 10M, and the cyan electrostatic latent image carrier. The cyan image formed on 10C is sequentially transferred (primary transfer). 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 the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper 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 to stop. Alternatively, the recording roller 142 is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 145, 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 recording medium. 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 the recording medium is sent between the intermediate transfer member 50 and the secondary transfer means 22. Then, by transferring (secondary transfer) the composite color image (color transfer image) onto the recording medium by the secondary transfer means 22, a color image is transferred and formed on the recording medium. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.
The recording medium on which the color image has been transferred is conveyed by the secondary transfer means 22 and sent to the fixing device 25, where the combined color image (color transfer image) is generated by heat and pressure. ) Is fixed on the recording medium. Thereafter, the recording medium is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57. Alternatively, the recording medium is switched by the switching claw 55 and reversed by the reversing device 28, and again led to the transfer position. After the image is also recorded on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

<Toner container>
The toner-containing container of the present invention contains the toner or the developer of the present invention 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 irregularity 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, and among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The container containing toner is easy to store, transport, etc., has excellent handleability, and can be detachably attached to the process cartridge, the image forming apparatus, etc. of the present invention and can be suitably used for replenishing toner.

<Process cartridge>
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to produce a visible image. The image forming apparatus includes at least a developing unit to be formed, and further includes other units such as a charging unit, an exposure unit, a transfer unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary.
The toner of the present invention is used as the toner.
The developing means includes at least a developer container that contains the toner or the developer, and a developer carrier that carries and transports the toner or developer contained in the developer container. In addition, a layer thickness regulating member for regulating the thickness of the toner layer carried on the developer carrying member may be provided. Specifically, any one of the one-component developing unit and the two-component developing unit described in the image forming apparatus and the image forming method can be preferably used.
Further, as the charging unit, the exposure unit, the transfer unit, the cleaning unit, and the charge eliminating unit, the same ones as those of the above-described image forming apparatus can be appropriately selected and used.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, facsimile machines, and printers, and it is particularly preferable that the process cartridge is detachably provided in the image forming apparatus of the present invention.
Here, as shown in FIG. 19, for example, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further, if necessary. And other means. In FIG. 19, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 19 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, “cyclization rate of cyclized rubber”, “glass transition temperature (Tg) of resin”, “weight average molecular weight Mw of resin, number average molecular weight Mn”, and “melting point of wax” are The measurement was performed as follows.

(Cyclization rate of cyclized rubber)
The cyclization rate of the cyclized rubber was measured using 1H-NMR (manufactured by JEOL Ltd., JOEL JNM400 FT NMR SYSTEM). Put each 1wt% deuterated chloroform solution of the polymer before and after the cyclization reaction into a sample tube (manufactured by WILMAD, high-precision NMR sample tube). It was measured. The peak area before the cyclization reaction was (C0), the peak area after the cyclization reaction was (C1), and the cyclization rate was determined from the formula (1).

[Formula 1]
Cyclization rate (%) = {1- (C1 / C0)} × 100

(Glass transition temperature (Tg) of resin)
The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). 10 mg of a sample was weighed into an aluminum sample pan, and while performing a nitrogen flow (flow rate 50 mL / min), the temperature was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. After the temperature was lowered at min, the DSC curve was measured when the temperature was raised from 20 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min. From the obtained DSC curve, the temperature of the intersection of the extended line of the base line below the endothermic peak temperature and the tangent showing the maximum inclination from the peak rising portion to the peak apex was determined and used as the glass transition temperature (Tg).

(Weight average molecular weight Mw, number average molecular weight Mn of resin)
The molecular weight distribution of the resin was measured with a GPC (gel permeation chromatography) measuring device (manufactured by Tosoh Corporation, HLC-8220 GPC). A TSK-GEL H type (manufactured by Tosoh Corporation) was used for the column. The column was stabilized in a heat chamber at 40 ° C., and HFIP (hexafluoro-2-propanol) or THF (tetrahydrofuran) as a solvent was allowed to flow through the column at this temperature at a flow rate of 1 ml / min. Measurement was performed by injecting 50 to 200 μl of a resin sample solution prepared to ˜0.6% by weight. Here, HFIP was used as the solvent for the cyclized rubber, and THF was used as the solvent for the other resins. In measuring the weight average molecular weight Mw and the number average molecular weight Mn, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or a molecular weight of 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , manufactured by Toyo Soda Kogyo Co., Ltd. 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ were used. An RI (refractive index) detector was used as the detector.

(Melting point of wax)
The melting point of the wax was measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). 10 mg of a sample was weighed into an aluminum sample pan, and while performing a nitrogen flow (flow rate 50 mL / min), the temperature was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. After the temperature was lowered at min, the temperature at the peak top of the endothermic peak of the wax measured when the temperature was raised from 20 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min was taken as the melting point of the wax.

<Production example of cyclized rubber>
(Production example 1 of cyclized rubber)
To a four-necked flask equipped with a nitrogen inlet tube, a reflux condenser, a stirrer, and a thermometer, polyisoprene (weight average molecular weight Mw 3.0 × 10 ⁵ , Mw / Mn 2.1, cis-1,4 structure 86% , Trans-1,4 structure 7%, 3,4 structure 7%) 120 parts by weight and 1000 parts by weight of toluene were charged and dissolved, and then 6 parts by weight of p-toluenesulfonic acid was added, and 85 ° C. under a nitrogen atmosphere. The cyclization reaction was carried out for 2 hours. Thereafter, 40 parts of a 10% sodium carbonate solution was added and stirred for 1 hour to stop the cyclization reaction. The reaction solution was poured into a large amount of methanol solution, and the precipitate was collected and dried under reduced pressure to obtain cyclized polyisoprene A. Table 1 shows the physical properties of cyclized polyisoprene A.

(Production example 2 of cyclized rubber)
A cyclized polyisoprene B was obtained in the same manner as in the cyclized rubber production example 1 except that in the cyclized rubber production example 1, the cyclization reaction time was changed to 4 hours. Table 1 shows the physical properties of cyclized polyisoprene B.

(Production example 3 of cyclized rubber)
A cyclized polyisoprene C was obtained in the same manner as in the cyclized rubber production example 1 except that the cyclization reaction time was changed to 6 hours in the cyclized rubber production example 1. Table 1 shows the physical properties of cyclized polyisoprene C.

(Production example 4 of cyclized rubber)
In the manufacture example 1 of cyclized rubber, cyclized polyisoprene D was obtained in the same manner as in manufacture example 1 of cyclized rubber except that the cyclization reaction temperature was changed to 75 ° C. and the reaction time was changed to 1 hour. Table 1 shows the physical properties of cyclized polyisoprene D.

(Production Example 5 of cyclized rubber)
In the manufacture example 1 of cyclized rubber, cyclized polyisoprene E was obtained in the same manner as in manufacture example 1 of cyclized rubber except that the cyclization reaction time was changed to 8 hours. Table 1 shows the physical properties of cyclized polyisoprene E.

(Production Example 6 of cyclized rubber)
In Production Example 2 of the cyclized rubber, as polyisoprene, the weight average molecular weight Mw 1.3 × 10 ⁵ , Mw / Mn 1.8, cis-1,4 structure 85%, trans-1,4 structure 9%, 3,4 A cyclized polyisoprene F was obtained in the same manner as in Production Example 2 of cyclized rubber, except that one having a structure of 6% was used. Table 1 shows the physical properties of cyclized polyisoprene F.

(Manufacture example 7 of cyclized rubber)
In Production Example 2 of the cyclized rubber, as polyisoprene, the weight average molecular weight Mw 5.0 × 10 ⁵ , Mw / Mn 2.2, cis-1,4 structure 83%, trans-1,4 structure 10%, 3,4 A cyclized polyisoprene G was obtained in the same manner as in the cyclized rubber production example 2 except that one having a structure of 7% was used. Table 1 shows the physical properties of cyclized polyisoprene G.

(Manufacture example 8 of cyclized rubber)
In Production Example 2 of the cyclized rubber, instead of polyisoprene, polybutadiene (weight average molecular weight Mw 3.2 × 10 ⁵ , Mw / Mn 1.8, cis-1,4 structure 93%, trans-1,4 structure 2% The cyclized polybutadiene A was obtained in the same manner as in Production Example 2 of the cyclized rubber except that 1 and 2 structures 5%) were used. Table 1 shows the physical properties of cyclized polybutadiene A.

<Production example of subresin>
(Production example of polyester resin)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermometer, 150 parts by weight of terephthalic acid, 207 parts by weight of bisphenol A (2,2) propylene oxide, and bisphenol A (2,2) ethylene oxide 127 parts by weight and 2.5 parts by weight of dibutyltin oxide as an esterification catalyst were charged and subjected to a condensation polymerization reaction at 230 ° C. for 15 hours in a nitrogen atmosphere, and then reacted at 230 ° C. and 8.0 kPa for 1 hour. . After cooling to 180 ° C., 115 parts by weight of trimellitic anhydride was added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was carried out at normal pressure (101.3 kPa) for 10 hours, followed by 210 ° C. and 20 kPa. and reacted for 3 hours at, polyester resin ^{a (Mw1.5 × 10 4, Mw} / Mn4.6, Tg60 ℃) was synthesized.

(Examples of vinyl resin production)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermometer, 440 parts by weight of styrene, 105 parts by weight of methacrylic acid, 68 parts by weight of butyl methacrylate, and t-butyl hydroperoxide as a polymerization initiator 40 parts by weight were charged, under a nitrogen atmosphere for 6 hours while stirring at 135 ° C., a vinyl resin a (styrene - methacrylic acid - butyl methacrylate copolymer, Mw5.2 × ¹⁰ 4, Mw / Mn 7.3, Tg 65 ° C.).

<Example of master batch production>
(Manufacture example 1 of a master batch)
A pigment having the following composition, cyclized rubber, and pure water were mixed at a ratio of 1: 1: 0.5 (weight ratio) and kneaded by two rolls. The kneading is performed at 80 ° C., and then the roll temperature is increased to 130 ° C. to evaporate water, and cyan master batch 1 (MB-C1), magenta master batch 1 (MB-M1), yellow master batch 1 (MB -Y1) and master batch 1 (MB-1) consisting of black master batch 1 (MB-K1) were produced.

[Cyan toner masterbatch 1 (MB-C1) formulation]
Cyclized polyisoprene A: 100 parts by weight Cyan pigment (CI Pigment blue 15: 3): 100 parts by weight Pure water: 50 parts by weight

[Magenta Toner Masterbatch 1 (MB-M1) prescription]
Cyclized polyisoprene A: 100 parts by weight Magenta pigment (CI Pigment red 122): 100 parts by weight Pure water: 50 parts by weight

[Yellow toner masterbatch 1 (MB-Y1) formulation]
Cyclized polyisoprene A: 100 parts by weight Yellow pigment (CI Pigment yellow 180): 100 parts by weight Pure water: 50 parts by weight

[Black Toner Masterbatch 1 (MB-K1) prescription]
Cyclized polyisoprene A: 100 parts by weight Black pigment (carbon black): 100 parts by weight Pure water: 50 parts by weight

(Manufacture example 2 of master batch)
Cyan masterbatch 2 (MB-C2) and magenta masterbatch 2 were the same as masterbatch production example 1 except that cyclized polyisoprene A was changed to cyclized polyisoprene B in master batch production example 1. Master batch 2 (MB-2) consisting of (MB-M2), yellow master batch 2 (MB-Y2), and black master batch 2 (MB-K2) was produced.

(Manufacture example 3 of a master batch)
In master batch production example 1, cyan master batch 3 (MB-C3), magenta master batch 3 were the same as in master batch production example 1 except that cyclized polyisoprene A was changed to cyclized polyisoprene C. Master batch 3 (MB-3) consisting of (MB-M3), yellow master batch 3 (MB-Y3), and black master batch 3 (MB-K3) was produced.

(Manufacture example 4 of a master batch)
Cyan masterbatch 4 (MB-C4) and magenta masterbatch 4 were the same as in Masterbatch Production Example 1 except that cyclized polyisoprene A was changed to cyclized polyisoprene D in Masterbatch Production Example 1. Master batch 4 (MB-4) consisting of (MB-M4), yellow master batch 4 (MB-Y4), and black master batch 4 (MB-K4) was produced.

(Manufacture example 5 of a master batch)
Cyan masterbatch 5 (MB-C5) and magenta masterbatch 5 were the same as in Masterbatch Production Example 1 except that cyclized polyisoprene A was changed to cyclized polyisoprene E in Masterbatch Production Example 1. Master batch 5 (MB-5) consisting of (MB-M5), yellow master batch 5 (MB-Y5), and black master batch 5 (MB-K5) was produced.

(Master batch production example 6)
Cyan masterbatch 6 (MB-C6), magenta masterbatch 6 were the same as masterbatch production example 1 except that cyclized polyisoprene A was changed to cyclized polyisoprene F in master batch production example 1. Master batch 6 (MB-6) consisting of (MB-M6), yellow master batch 6 (MB-Y6), and black master batch 6 (MB-K6) was produced.

(Manufacture example 7 of a master batch)
Cyan masterbatch 7 (MB-C7) and magenta masterbatch 7 were the same as masterbatch production example 1 except that cyclized polyisoprene A was changed to cyclized polyisoprene G in master batch production example 1. Master batch 7 (MB-7) consisting of (MB-M7), yellow master batch 7 (MB-Y7), and black master batch 7 (MB-K7) was produced.

(Master batch production example 8)
In the master batch production example 1, except that the cyclized polyisoprene A was changed to cyclized polybutadiene A, a cyan master batch 8 (MB-C8), a magenta master batch 8 ( A master batch 8 (MB-8) consisting of MB-M8), yellow master batch 8 (MB-Y8), and black master batch 8 (MB-K8) was produced.

<Example of toner production>
(Toner Production Example 1)
In the following manner, toner 1 composed of cyan toner 1, magenta toner 1, yellow toner 1 and black toner 1 was produced.

[Production of Cyan Toner 1]
The Henschel mixer (Mitsui Mitsui) is a raw material for toner 1 shown in Table 2 below. After preliminary mixing using FM10B, manufactured by Kakoki Co., Ltd., it was melted and kneaded at a temperature of 100 to 130 ° C. with a biaxial kneader (Ikegai, PCM-30). The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labojet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the weight average particle size becomes 6.2 ± 0.3 μm. The louver opening is adjusted so that the weight average particle size is 7.0 ± 0.2 μm and the amount of fine powder of 4 μm or less is 10% by number or less with an air classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was carried out with appropriate adjustment to obtain toner base particles. The inorganic fine particles were internally added using calcium carbonate (particle size: 500 to 1000 nm).

  Next, 1.0 part by weight of an additive (HDK-2000, manufactured by Clariant Co., Ltd.) was stirred and mixed with a Henschel mixer with respect to 100 parts by weight of toner base particles to produce cyan toner 1.

In addition, the cyclic olefin A described in Tables 2 to 6 is a norbornene-ethylene copolymer (TOPAS COC, manufactured by Ticona Japan, Mw1.8 × 10 ⁴ , Mw / Mn2.0, Tg62 ° C. ). Wax A1 is a paraffin wax having a melting point of 78 ° C. (manufactured by Nippon Seiwa Co., Ltd.), wax A2 is a paraffin wax having a melting point of 53 ° C. (manufactured by Nippon Seiwa Co., Ltd.), and wax A3 is a paraffin wax having a melting point of 85 ° C. Nippon Seiwa Co., Ltd.), wax A4 is a paraffin wax (Fischer Tropsch wax) having a melting point of 47 ° C. (manufactured by Nippon Seiwa Co., Ltd.), and wax A5 is a paraffin wax having a melting point of 93 ° C. (Fischer Tropsch wax) (Nippon Seiki) Wax B1 is a polyethylene wax having a melting point of 95 ° C, Wax B2 is a polyethylene wax having a melting point of 70 ° C, Wax B3 is a polypropylene wax having a melting point of 145 ° C, Wax B4 is a polyethylene wax having a melting point of 68 ° C, and Wax B5 is Polypropylene wax having a melting point of 153 ° C.

(Evaluation of compatibility between cyclized rubber and wax)
The compatibility of the wax with the cyclized rubber was evaluated according to the toner production method described in <Toner Production Example 1> above, 90 parts by weight of cyclized rubber and 10 parts by weight of wax (A), or 90 parts of cyclized rubber. Part by weight and 10 parts by weight of wax (B) were premixed using a Henschel mixer (Mitsui Miike Chemical Co., Ltd., FM10B), and then mixed with a biaxial kneader (Ikegai Co., Ltd., PCM-30). After melting and kneading at a temperature of ˜130 ° C., the obtained kneaded product is cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill to measure the softening temperature [T (F1 / 2)]. evaluated.
Here, the softening temperature [T (F1 / 2)] is a condition using an elevated flow tester CF-500 manufactured by Shimadzu Corporation, a die diameter of 1 mm, a pressure of 10 kgf / cm ² , and a temperature rising rate of 3 ° C./min. This is the temperature at which the stroke when the sample of 1 cm ³ is melted and discharged is ½ of the stroke change amount from the outflow start point to the outflow end point.

[Manufacture of magenta toner 1]
In the method for producing cyan toner 1, cyan toner is used except that a magenta master batch is used in a prescribed amount shown in Table 2 instead of the cyan master batch of the master batch which is the raw material used for toner 1 shown in Table 2. Magenta toner 1 was produced in the same manner as in Production Method 1.

[Production of Yellow Toner 1]
In the cyan toner 1 manufacturing method, cyan toner is used except that a yellow master batch is used in a prescribed amount shown in Table 2 instead of the cyan master batch among the master batches that are used raw materials of toner 1 shown in Table 2. The yellow toner 1 was produced in the same manner as in Production Method 1.

[Production of Black Toner 1]
In the method for producing cyan toner 1, cyan toner was used except that a black master batch was used in a prescribed amount shown in Table 2 instead of the cyan master batch of the master batch as the raw material of toner 1 shown in Table 2. The black toner 1 was produced in the same manner as in the production method 1.

(Toner Production Examples 2 to 29)
Tables 2 to 6 show toners 2 to 29 composed of cyan toners 2 to 29, magenta toners 2 to 29, yellow toners 2 to 29, and black toners 2 to 29 in the same manner as in the toner 1 production example. Each was manufactured with a combination of raw materials and prescribed amounts.

  In Tables 2 to 6, bold letters indicate prescriptions serving as comparative examples in the next performance evaluation. Moreover, the numerical value in parenthesis shows a prescription amount (part by weight).

(Toner performance evaluation method)
Next, the obtained toners 1 to 29 were evaluated for heat resistant storage stability and grindability (dispersed state in the toner) as follows. The results are shown in Table 7.

(Heat resistant storage stability of toner)
The heat-resistant storage stability was measured using a penetration tester (manufactured by Nikka Engineering Co., Ltd.). Specifically, 10 g of each toner was weighed and placed in a 30 ml glass container (screw vial) in an environment of 20 to 25 ° C. and 40 to 60% RH, and the lid was closed. After tapping the glass container containing the toner 100 times, leaving it in a thermostatic bath set at 50 ° C. for 24 hours, measuring the penetration with a penetration tester and heat-resistant storage stability according to the following evaluation criteria Evaluated. The greater the penetration value, the better the heat resistant storage stability. Of the measurement results for the four colors of each toner, the worst result was taken as the evaluation value for that toner.
〔Evaluation criteria〕
◎: Needle penetration is 30 mm or more ○: Needle penetration is 20 mm to 29 mm
Δ: penetration is 15 mm to 19 mm
X: The penetration is 8 mm to 14 mm
XX: Needle penetration is 7mm or less

(Dispersed state in toner)
The toner particles were cut into ultra-thin sections of about 100 nm, dyed with ruthenium tetroxide, and then observed with a transmission electron microscope (TEM) at a magnification of 20,000 to photograph and rank and evaluate the dispersion state.
Distributed state:
◎: No incompatible domain in the toner ○: No incompatible domain exceeding 0.5 μm Δ: No incompatible domain exceeding 1.5 μm ×: Incompatible domain exceeding 2 μm There is no

(Evaluation of toner using image forming apparatus A)
The toners 1 to 29 produced as described above are mixed with the following carrier, loaded into the image forming apparatus A shown in FIG. 20, and image formation is performed. As described below, low temperature fixability, hot offset resistance, fixing release , Carrier contamination, and photoconductor filming were evaluated. The results are shown in Table 7.
An image forming apparatus A shown in FIG. 20 is an indirect transfer type tandem type image forming apparatus that employs a non-contact charging method, a two-component development method, a secondary transfer method, a blade cleaning method, and an external heating roller fixing method. .
In the image forming apparatus A shown in FIG. 20, a non-contact corona charger as shown in FIG. As the developing unit 324, a two-component developing device as shown in FIG. As the cleaning means 330, a cleaning blade as shown in FIG. As the fixing means 327, an electromagnetic induction heating type roller fixing device as shown in FIG. 12 is adopted.
An image forming element 351 in the image forming apparatus A shown in FIG. 20 includes a charging unit 311, an exposing unit 323, a developing unit 324, a primary transfer unit 325, and a cleaning unit 330 around the photosensitive drum 321. As the photosensitive drum 321 in the image forming element 351 rotates, charging by the charging unit 310 and exposure by the exposure unit 323 form an electrostatic latent image corresponding to the exposure image on the surface. This electrostatic latent image is developed with yellow toner by the developing means 324, and a visible image with yellow toner is formed on the photosensitive drum 321. The visible image is transferred onto the intermediate transfer belt 355 by the primary transfer unit 325, and the yellow toner remaining on the photosensitive drum 321 is removed by the cleaning unit 330. Similarly, visible images of magenta toner, cyan toner, and black toner are formed on the intermediate transfer belt 355 by the image forming elements 352, 353, and 354. The color image on the intermediate transfer belt 355 is transferred onto the recording medium 326 by the transfer device 356, and the toner remaining on the intermediate transfer belt 355 is removed by the intermediate transfer belt cleaning unit 358. The color image formed on the recording medium 326 is fixed by the fixing unit 327.

(Carrier production)
A coating material having the following formulation is dispersed with a stirrer for 10 minutes to prepare a coating solution, and 5,000 parts by weight of this coating solution and a core material (Cu—Zn ferrite particles, weight average diameter = 35 μm) are rotated in a fluidized bed. The coating liquid was applied to the core material by applying it to a coating apparatus for coating while forming a swirling flow provided with a type bottom plate disk and stirring blades. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to prepare a carrier.
[Coating material prescription]
Toluene: 450 parts by weight Silicone resin (SR2400, manufactured by Toray Dow Corning Silicone Co., Ltd., nonvolatile content: 50% by weight): 450 parts by weight Aminosilane (SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.)・ 10 parts by weight Carbon black ... 10 parts by weight

(Preparation of two-component developer)
A two-component developer composed of 5% by weight of each of the prepared toners 1 to 29 and 95% by weight of the prepared carrier was prepared by a conventional method.

(Fixability)
<Low temperature fixability>
Using the evaluation machine, the toner adhesion amount 0.85 ± 0.1 mg / cm ² for each of black, cyan, magenta and yellow on a thick transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <135>). A single color solid image is prepared, fixing is performed by changing the temperature of the fixing roller or belt, and the surface of the obtained fixed image is drawn on a ruby needle (tip radius) using a drawing tester (AD-401, manufactured by Ueshima Seisakusho). 260 ° to 320 μm R, tip angle 60 °), 50 g of load, fiber (Hanicot # 440, manufactured by Hanilon Co., Ltd.) is strongly rubbed with the drawing surface 5 times, and the fixing belt temperature at which image shaving is almost eliminated is set as the minimum fixing temperature. The low temperature fixability was evaluated according to the following criteria. The solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. Further, the worst result among the measurement results of the four colors of each toner was used as the evaluation value of the toner.
〔Evaluation criteria〕
A: Fixing lower limit temperature is 110 ° C. or less ○: Fixing lower limit temperature is 111 ° C. or more and 120 ° C. or less Δ: Fixing lower limit temperature is 121 ° C. or more and 135 ° C. or less ×: Fixing lower limit temperature is 136 ° C. or more and 140 ° C. or less XX: Fixing lower limit temperature Temperature is 141 ℃ or more

<Hot offset resistance>
Using the evaluation machine, a solid solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² in black, cyan, magenta, and yellow on plain paper transfer paper (type 6200, manufactured by Ricoh Co., Ltd.). A fixing test is performed by changing the temperature of the fixing roller or belt, and the presence or absence of hot offset is visually evaluated. The upper limit temperature at which hot offset does not occur is set as the upper limit fixing temperature, and the hot offset resistance is evaluated according to the following criteria. did. The solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. Of the measurement results for the four colors of each toner, the worst result was taken as the evaluation value for that toner.
〔Evaluation criteria〕
A: Fixing upper limit temperature is 220 ° C. or more. ○: Fixing upper limit temperature is 210 ° C. or more and less than 220 ° C. Δ: Fixing upper limit temperature is 190 ° C. or more and less than 210 ° C. ×: Fixing upper limit temperature is 180 ° C. or more and less than 190 ° C. Temperature is less than 180 ° C

(Fixing releasability)
Using the evaluation machine, a solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was prepared on a thin transfer paper (manufactured by Ricoh Co., Ltd., copy printing paper <55>), and the temperature of the fixing roller or belt A fixed image generated by a fixed image ejected in the A4 lateral direction contacting a separation claw arranged to separate the fixing paper and the fixing belt near the fixing nip exit. The extent of the upper scar was visually evaluated. The extent of the scar was evaluated in five stages using a rank sample, and an upper limit temperature at which no scar or jam was generated was used as an index for fixing releasability. The solid image was created on the transfer paper at a position 0.5 cm from the front end in the paper passing direction.
〔Evaluation criteria〕
◎: Upper limit temperature is 200 ° C or higher ○: Upper limit temperature is 190 ° C or higher and lower than 200 ° C △: Upper limit temperature is 170 ° C or higher and lower than 190 ° C ×: Upper limit temperature is 160 ° C or higher and lower than 170 ° C XX: Upper limit temperature is lower than 160 ° C

(Carrier contamination)
The carrier contamination property is a characteristic that serves as an index of toner carrier contamination. The higher the mechanical strength of the toner, the less the carrier contamination. Specifically, as the evaluation method, using the above-described evaluation machine, the developer after 100 sheets running output of 50% image area image output in monochrome mode and after 30,000 sheets running output are extracted, and the developer is checked. An appropriate amount was placed in a gauge with a mesh having an opening of 32 μm, and air blowing was performed to separate the toner and the carrier. 1.0 g of the obtained carrier was put in a 50 ml glass bottle, 10 ml of chloroform was added, and the mixture was shaken 50 times and allowed to stand for 10 minutes. Thereafter, the supernatant chloroform solution was placed in a glass cell, and the transmittance of the chloroform solution was measured using a turbidimeter, and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Transmittance is 95% or more ○: Transmittance is 90% or more and 94% or less △: Transmittance is 80% or more and 89% or less ×: Transmittance is 70% or more and 79% or less XX: Transmittance is 69% or less

(Photoreceptor filming property)
Using the evaluation machine, the toner filming state on the photosensitive member was visually evaluated after running and outputting 100 sheets of an image chart having a 50% image area in a monochrome mode. Considering the presence or absence of abnormality in the output image, the determination was made in the following five stages.
〔Evaluation criteria〕
A: No image abnormality and no toner filming on the photoreceptor.
◯: There is no image abnormality at all, but a slight toner filming is seen on the photoreceptor.
Δ: Some image abnormality is observed, and clear toner filming is also observed on the photoreceptor.
X: Clear image abnormality was observed, toner filming on the photosensitive member was severe, and there was a problem level.
XX: Clear image abnormality is observed, toner filming on the photoconductor is severe, and a normal image cannot be obtained.

(Evaluation of toner using image forming apparatus B)
(Example 17 and Comparative Example 13)
The toners 1 and 27 are loaded into the image forming apparatus B shown in FIG. 21, and image formation is performed. The low-temperature fixability, the hot offset resistance, the fixing release property, the photoreceptor filming property, Initial image quality and temporal image quality were evaluated. The results are shown in Table 7.
An image forming apparatus B shown in FIG. 21 is a tandem type image forming apparatus of a direct transfer method adopting a contact charging method, a one-component developing method, a direct transfer method, a cleanerless method, and an internally heated belt fixing method.
In the image forming apparatus B shown in FIG. 21, a contact-type charging roller as shown in FIG. 1 is used as the charging unit 310. As the developing means 324, a one-component developing device as shown in FIG. 5 is used, and this developing device adopts a cleaner-less system capable of collecting residual toner. A belt-type fixing device as shown in FIG. 9 is adopted as the fixing means 327, and this fixing device uses a halogen lamp as a heat source of the heating roller. In FIG. 21, reference numeral 330 denotes a conveyor belt.
The image forming element 341 in the image forming apparatus B shown in FIG. 21 is provided with a charging unit 310, an exposure unit 323, a developing unit 324, and a transfer unit 325 around the photosensitive drum 321. As the photosensitive drum 321 in the image forming element 341 rotates, an electrostatic latent image corresponding to the exposure image is formed on the surface by charging by the charging unit 310 and exposure by the exposure unit 323. This electrostatic latent image is developed with yellow toner by the developing means 324, and a visible image with yellow toner is formed on the photosensitive drum 321. This visible image is transferred onto the recording medium 326 by the transfer unit 325, and then the toner remaining on the photosensitive drum 321 is collected by the developing unit 324. Similarly, the image forming elements 342, 343, and 344 superimpose visible images of magenta toner, cyan toner, and black toner on the recording medium 326, and the color image formed on the recording medium 326 is fixed by the fixing unit. 327 is fixed.
Evaluation of low-temperature fixability, hot offset resistance, fixing releasability, and photoconductor filming was performed in the same manner as described above except that the image forming apparatus B was used instead of the image forming apparatus A.

  From Tables 1 to 7, the cyclization rate of the cyclized rubber used in the toner, the melting points of the waxes A and B, the compatibility of the waxes A and B with the cyclized rubber, and the contents of the waxes A and B However, it is apparent that it acts as an important factor on low-temperature fixability, heat-resistant storage stability, hot offset resistance, fixing releasability, and photoconductor filming properties. It is also important to appropriately select the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the cyclized rubber.

FIG. 3 is a schematic cross-sectional view illustrating an example of a charging roller in the image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example in which a contact-type charging roller in an image forming apparatus of the present invention is applied to an image forming apparatus. 1 is a schematic diagram illustrating an example in which a non-contact type corona charger in an image forming apparatus of the present invention is applied to an image forming apparatus. FIG. 2 is a schematic diagram illustrating an example of a non-contact charging roller in the image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating an example of a one-component developing unit in the image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating an example of a two-component developing unit in the image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example of a direct transfer method of a tandem type image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of an indirect transfer method of the tandem type image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of a belt-type fixing unit in the image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of a heat roller type fixing unit in the image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of an electromagnetic induction heating type fixing unit in the image forming apparatus of the present invention. FIG. 5 is a schematic diagram illustrating another example of an electromagnetic induction heating type fixing unit in the image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of a cleaning blade in the image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example of a cleaningless type image forming apparatus in an image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. It is the schematic which shows another example of the image forming apparatus of this invention. 1 is a schematic diagram illustrating an example of a tandem type image forming apparatus of the present invention. FIG. 18 is an enlarged view of each image forming element in FIG. 17. It is the schematic which shows an example of the process cartridge of this invention. It is the schematic which shows the image forming apparatus (evaluation machine A) used in the Example. It is the schematic which shows the image forming apparatus (evaluation machine B) used in the Example.

Explanation of symbols

1 Electrostatic latent image carrier (photosensitive drum)
2 Transfer means (primary transfer means)
DESCRIPTION OF SYMBOLS 3 Conveying belt 4 Intermediate transfer body 5 Secondary transfer means 6 Paper feeding device 7 Fixing device 8 Cleaning device 9 Intermediate transfer body cleaning device 10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning means DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer means 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Reversing apparatus 30 Exposure apparatus 32 Contact glass 33 First traveling body 34 Second traveling Body 35 Imaging lens 36 Reading sensor 40 Developing device 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 Development roller 4 4Y developing roller 44M developing roller 44C developing roller 45K black developing unit 45Y yellow developing unit 45M magenta developing unit 45C cyan developing unit 49 registration roller 50 intermediate transfer member 51 roller 52 separation roller 53 manual feed path 54 manual tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 60 Cleaning means 61 Developing device 62 Transfer charger 63 Cleaning device 64 Discharge device 70 Discharge lamp 80 Transfer roller 90 Cleaning device 95 Recording medium 100 Image forming device 101 Electrostatic latent image carrier Body 102 Charging means 103 Exposure means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developing means 130 Document table 142 Feed roller 143 Paper Link 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed table 220 Heating roller 230 Pressure roller 300 Scanner 302 Film 303 Spring 310 Charging roller 311 Core ( Charging roller shaft)
312 Resistance adjustment layer 313 Protective layer 310 Charging roller 321 Electrostatic latent image carrier 323 Exposure unit 324 Development unit 325 Transfer unit 326 Recording medium 327 Fixing unit 330 Cleaning unit 331 Static elimination device 400 Automatic document feeder (ADF)
401 casing 402 developing roller 411 agitator 412 supply roller 413 regulating blade 510 belt type fixing device 511 heating roller 512 fixing roller 513 fixing belt 514 pressure roller 515 heat roll type fixing device 525 roll type fixing device 570 electromagnetic induction heating type fixing device 613 Cleaning blade S Recording medium P Recording medium

Claims (13)

An image forming toner including at least a colorant, a binder resin, and a release agent, wherein the binder resin includes a cyclized rubber having a cyclization rate of 50 to 75%, and the release agent has at least a melting point. Inorganic fine particles contained in the toner, comprising a wax (A) having a temperature of 50 to 85 ° C. and a wax (B) having a melting point of 70 to 150 ° C. and a lower compatibility with the cyclized rubber than the wax (A) An image forming toner comprising: 2. The image forming toner according to claim 1, wherein the content of the wax (A) is 20 to 65 wt% with respect to the weight of the cyclized rubber. 2. The image forming toner according to claim 1, wherein the content of the wax (B) is 4 to 40 wt% with respect to the weight of the cyclized rubber. The image forming toner according to claim 1, wherein the wax (A) is any one of paraffin wax, carnauba wax, synthetic ester wax, amide wax, rice wax, and montanic acid wax. The image forming toner according to claim 1, wherein the wax (B) is polyethylene wax or polypropylene wax. The weight average molecular weight Mw of the cyclized rubber is 1.0 × 10 ^{5 to} 5.0 × 10 ⁵ , and the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 3.0 or less. The image forming toner according to claim 1, wherein the toner is image forming toner. The image forming toner according to claim 1, wherein the cyclized rubber has a glass transition point (Tg) of 55 ° C. to 100 ° C. 7. The image forming toner according to claim 1, wherein the cyclized rubber is cyclized polybutadiene or cyclized polyisoprene. A developer comprising the image forming toner according to claim 1. A toner-containing container filled with the image forming toner according to claim 1. At least an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the image carrier, and a developing unit that develops the electrostatic latent image with toner to form a visible image An image forming apparatus comprising: a transfer unit that transfers the visible image onto a recording medium; and a fixing unit that fixes the visible image transferred onto the recording medium. An image forming apparatus comprising the toner according to claim 8. An electrostatic latent image forming step for forming at least an electrostatic latent image on the electrostatic latent image carrier, and development for forming a visible image by developing the electrostatic latent image formed on the photosensitive member with toner. 2. An image forming method comprising: a transfer step of transferring the visible image onto a recording medium; and a fixing step of fixing the visible image transferred onto the recording medium, wherein the toner is used as the toner. An image forming method using the toner according to any one of Items 8 to 8. At least an electrostatic latent image carrier and a developing unit that develops the electrostatic latent image formed on the image carrier using toner to form a visible image are integrally supported and attached to and detached from the image forming apparatus main body. A process cartridge which is free, wherein the toner is the toner according to claim 1.

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