JP6826752B2 - Toner, developer, image forming apparatus, image forming method and toner accommodating unit - Google Patents

Description

The present invention relates to a toner, a developer, an image forming apparatus, an image forming method, and a toner accommodating unit used for electrophotographic, electrostatic recording, electrostatic printing, and the like.

Toners generally used in electrophotographic copiers and printers are a mixture of a binder resin as a main component and a plurality of substances such as a colorant, a mold release agent, and a charge control agent. .. In pulverized toner, usually, these raw materials are melt-kneaded, and the melt-kneaded product is pulverized and classified to obtain a toner having a desired particle size. The proportion of the binder resin in the raw materials constituting the toner usually occupies 80 to 90% by mass, and most of the components in the toner are the binder resin.

Recently, from the viewpoint of reducing power consumption and environmental load in copiers, polyester resin is generally used as the binder resin so that toner can be easily fixed even if the fixing temperature is low. In general, polyester resins for toner have a bisphenol A skeleton in the alcohol monomer constituting the resin, so that they have excellent low-temperature fixability, and because they have sharp melt properties, they also have excellent glossiness, especially for full-color toners. Suitable for. However, there is a problem that the pulverizability at the time of toner production is inferior. In addition, although polyester resin for toner has excellent low-temperature fixability, when a large amount of printing paper is piled up and deposited when continuously ejected from a copying machine, such as when used in the field of high-speed machines. So-called copy blocking, in which printed papers stick to each other, is likely to occur, and improving blocking resistance has become a major issue.

Therefore, in order to achieve both low temperature fixability and pulverizability, a resin having a reduced bisphenol A skeleton in the polyester resin has been proposed. Patent Document 1 proposes a toner resin and a toner composition made of a polyester resin obtained by polycondensing an alcohol component and a carboxylic acid component.
This polyester resin is composed of terephthalic acid, isophthalic acid, and / or lower alkyl (alkyl group carbon atoms: 1 to 4) esters having a carboxylic acid component of 80 to 100 mol%, and an alcohol component of 20. It consists of ~ 100 mol% aliphatic diol (85-100 mol% of the aliphatic diol is 1,2-propylene glycol), and 0.1 to 20 mol% of the total of alcohol component and carboxylic acid component is 3 Polyhydric alcohols above valence and / or carboxylic acids above trivalent.

In the invention of Patent Document 1, an aliphatic alcohol is used as the alcohol component in order to reduce the bisphenol A skeleton in the alcohol component. However, in this method, even if the pulverizability can be improved, the bisphenol A skeleton is reduced, so that the toner deteriorates due to the stress when the toner is agitated by a developing device or the like, and the stress resistance (durability) deteriorates. There is a risk that the filming resistance will deteriorate due to stress or contamination of members such as the photoconductor. Further, since the bisphenol A skeleton is reduced, the sharp melt property of the toner is deteriorated, and the fixing characteristics such as low temperature fixability and fixing strength are also likely to be deteriorated.
That is, in this method, it is impossible to achieve both fixing characteristics such as low temperature fixing property and fixing strength (hereinafter, simply referred to as "fixing characteristics"), stress resistance, filming resistance and blocking resistance as well as crushability. It was enough.

An object of the present invention is as follows.
-Provide toner with excellent fixing characteristics.
-To provide toner with excellent pulverizability during toner production.
-Provide toner with excellent stress resistance during development, that is, durability.
-To provide toner with excellent durability, copy blocking resistance, filming resistance, and low cost.

As a result of diligent studies to solve these problems, the present inventors have conducted an ATR method (total reflection) using at least a toner containing a binder resin and using FT-IR (Fourier transform infrared spectroscopic analysis and measurement device). The peak ratio (W /) of the maximum peak height W of the spectrum derived from the bisphenol A skeleton at 1480 to 1520 cm ^-1 and the maximum peak height R of the spectrum derived from the carbonyl group at 1700 to 1750 cm ^-1 measured by the method). The present invention was completed by finding that a toner having an R) of 0.2 to 0.70 is excellent in fixing characteristics, crushability during toner production, durability, copy blocking resistance, and filming resistance. I came to let you.

That is, the toner of the present invention is the toner as described below.
At least, the maximum peak height W of the spectrum derived from the bisphenol A skeleton at 1480 to 1520 cm ^-1 of the toner containing the binder resin and measured by the ATR method using FT-IR, and 1700 to 1750 cm ^−. The peak ratio (W / R) of the spectrum derived from the carbonyl group in ^{1 to} the maximum peak height R is 0.25 to 0.70, and the molecular weight distribution by GPC determined by the THF-soluble content in the toner is It has a main peak between 1000 and 10000, the half-value width of the molecular weight distribution is 20,000 or less, and contains 5 to 40% by mass of THF insoluble, and the volume average particle diameter (Dv) of the toner. A toner having a molecular weight of 4 to 6 μm.

By providing the above-mentioned structure, the toner of the present invention has the effects of being excellent in fixing characteristics, pulverization property during toner production, durability, copy blocking resistance, filming resistance, and low cost.

It is sectional drawing which shows the structure of the image forming apparatus which concerns on this invention. It is sectional drawing which shows the structure of the process cartridge which is one aspect of the toner accommodating unit which concerns on this invention.

In the present invention, "FT-IR" is used as a term meaning "Fourier transform infrared spectroscopic analysis and measurement device", and "ATR method" is used as a term meaning "total reflection method". The toner of the present invention is at least a toner containing a binder resin, and has the maximum peak height W of the spectrum derived from the bisphenol A skeleton at 1480 to 1520 cm ^-1 of the toner measured by the ATR method using FT-IR. The peak ratio (W / R) of the spectrum derived from the carbonyl group at 1700 to 1750 cm ^{-1 with} the maximum peak height R was 0.25 to 0.70, and it was determined by the THF-soluble content in the toner. The molecular weight distribution by GPC has a main peak between 1000 and 10000, the half-value width of the distribution is 20,000 or less in molecular weight, and contains 5 to 40% by mass of THF insoluble, and the volume average grain of the toner. It is characterized by having a diameter (Dv) of 4 to 6 μm.
In the present invention, "GPC" means "gel permeation chromatography".
Hereinafter, the toner of the present invention will be described in detail.

First, at least the raw materials containing the binder resin are blended and mixed in a predetermined ratio. Then, after the mixed product is melt-kneaded, the obtained melt-kneaded product is pulverized and classified to obtain a toner. The maximum peak height W of the spectrum derived from the bisphenol A skeleton at 1480 to 1520 cm ^-1 of the toner and the spectrum derived from the carbonyl group at 1700 to 1750 cm ^-1 measured by the ATR method using FT-IR of this toner. It is necessary that the peak ratio (W / R) with the maximum peak height R of is 0.20 to 0.70.
The peak ratio (W / R) of the maximum peak height W of the spectrum at 1480 to 1520 cm ^-1 and the maximum peak height R of the spectrum at 1700 to 1750 cm ^-1 of the toner is preferably 0.20 to 0.65, and further. It is preferably in the range of 0.25 to 0.60, particularly preferably 0.25 to 0.55.
If the W / R value is less than 0.20, the fixing characteristics, filming resistance, and durability deteriorate, and if the W / R value exceeds 0.70, the crushing property and blocking resistance during toner production are deteriorated. Get worse.
When the W / R value is in the range of 0.20 to 0.70, it is excellent in fixing characteristics, pulverization property during toner production, and durability, and also achieves both copy blocking resistance and filming resistance. It becomes possible.

Further, by using the FT-IR, infrared spectroscopy (KBr tablet method) spectrum of peak height W in 1480～1520Cm ^-1 of toner measured by 'peak of the spectrum in 1700～1750Cm ^-1 height R' The peak ratio (W'/ R') of is preferably 0.06 to 0.70, more preferably 0.06 to 0.60, and particularly preferably 0.06 to 0.45. When the value of W'/ R'is 0.06 or more, the filming resistance and durability are good, and when the value of W'/ R'is 0.70 or less, the crushing resistance and blocking resistance are good. It will be excellent in sex.

The maximum peak height W of the spectrum of the toner measured by infrared spectroscopy (KBr tablet method) at 1480 to 1520 cm ^-1 and the maximum peak height R of the spectrum at 1700 to 1750 cm ^-1 using FT-IR. peak ratio (W / R), by using the FT-IR infrared spectroscopy and (KBr tablet method) spectrum of peak height W in 1480～1520Cm ^-1 of toner measured by ', 1700~1750cm ^-1 It is preferable that the relationship of W'/ R'≤ W / R is established between the peak height R'of the spectrum and the peak ratio (W'/ R').
By satisfying the relationship of W'/ R'≤ W / R, stress resistance, filming resistance, and fixing characteristics are particularly excellent, and pulverization resistance and blocking resistance are also good, and these multiple characteristics are high. You can be satisfied with the level.
More preferably, the ratio (W / R) / (W'/ R') of the peak ratio (W / R) to the peak ratio (W'/ R') is 1.0 or more and 2.0 or less.
The spectral value of FT-IR is a value measured by ATR method (total reflection method) and infrared spectroscopy (KBr tablet method) using "Thermo Nicolet NEXTUS470 (manufactured by Thermo SCIENTIFIC)".

The content of the bisphenol A component contained in the alcohol component of the THF-soluble component in the toner is preferably in the range of 20 to 100 mol%, more preferably 20 to 80 mol%, and particularly preferably 20 to 50 mol%. The content of the bisphenol A component contained in the alcohol component of the THF insoluble matter in the toner is preferably in the range of 0 to 80 mol%, more preferably 0 to 50 mol%, and particularly preferably 0 to 40 mol%. Further, it is preferable that the amount of the bisphenol A component contained in the alcohol component of the THF-soluble component in the toner is larger than the amount of the bisphenol A component contained in the alcohol component of the THF-insoluble component.

By satisfying these relationships, durability, filming resistance, and fixing characteristics are particularly excellent, and crushing resistance and blocking resistance are also good, and these plurality of characteristics can be satisfied at a high level.
The content of the bisphenol A component in the THF-soluble component and the THF-insoluble component is ₁ H-NMR (JNM-ECX, manufactured by JEOL Ltd.) when dissolved in deuterated chloroform, and various alcohol monomers and acids. It can be obtained by obtaining the peak derived from the monomer and calculating the peak area ratio.

The toner of the present invention contains at least a binder resin as a component. It is most suitable to use polyester resin as the binder resin from the viewpoint of fixing characteristics, durability, etc., but resins other than polyester resin may be used alone or in combination as long as these characteristics are not impaired. it can.

The polyester resin used in the present invention is obtained by polycondensation of alcohol and carboxylic acid. Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane, and bisphenol A, and other divalent alcohols. Quantities, trihydric or higher polyhydric alcohol monomers can be mentioned. Among them, it is preferable to contain an aromatic diol such as etherified bisphenol such as bisphenol A and an aliphatic diol having an alcohol component having 2 to 6 carbon atoms. Further, the aliphatic diol preferably contains ethylene glycol or 1,2-propylene glycol as at least a part thereof.

The content of the aliphatic diol having 2 to 6 carbon atoms in the alcohol component is preferably in the range of 5 to 90 mol%, more preferably 10 to 90 mol%, and particularly preferably 15 to 85 mol%. If the content of the aliphatic diol having 2 to 6 carbon atoms in the alcohol component is less than 5 mol%, the durability and filming resistance deteriorate, and if it exceeds 90 mol%, the crushability and copy blocking resistance during toner production are deteriorated. Sex gets worse. Among the alcohol components, it is preferable that the alcohol component is composed of an aromatic diol component other than the aliphatic diol component having 2 to 6 carbon atoms.

In addition, examples of the carboxylic acid component include a divalent organic acid monomer and a trivalent or higher polyvalent carboxylic acid monomer. Examples of the divalent organic acid monomer include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, malonic acid and the like.
Examples of the trivalent or higher valent carboxylic acid monomer include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2. , 4-Naphthalene tricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid and the like.

The polyester resin of the present invention can be used alone or in combination of two or more.
Usually, the polyester resin for toner is a combination of a plurality of high molecular weight polyester resins (hereinafter, also referred to as “H”) and low molecular weight polyester resins (hereinafter, also referred to as “L”), and desired characteristics such as fixing characteristics. Is getting. The THF insoluble component is derived from the H form, and the THF soluble component is derived from the L form and a part of the H form.

The H-form is preferably contained from the viewpoint of hot offset resistance and durability, and in the present invention, it is preferable that the alcohol component contains an aliphatic diol having 2 to 6 carbon atoms. The content of the aliphatic diol in the alcohol component of the H form is preferably in the range of 20 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 60 to 100 mol%. Further, the L-form is preferably contained from the viewpoint of fixing characteristics and pulverizability at the time of toner production, and the alcohol component of the L-form contains an aliphatic diol having 2 to 6 carbon atoms together with an aromatic diol component. May be. The content of the aliphatic diol in the alcohol component is preferably in the range of 0 to 80 mol%, more preferably in the range of 20 to 80 mol%, and particularly preferably in the range of 50 to 80 mol%.

When the H-form and the L-form are combined, it is preferable that the H-form contains a larger amount of aliphatic diol components, whereby the fixing characteristics, while maintaining durability and filming resistance, It is possible to achieve both crushability and copy blocking resistance during toner production. The reason for this is that the low molecular weight polyester resin component (L body) is easily cracked during crushing during toner production, so that it easily appears on the toner surface as an interface, and the low molecular weight polyester resin component (L body) is an aliphatic compound. It is considered that the durability, filming resistance, and fixing characteristics are maintained due to the small amount of the diol component, that is, the large amount of the aromatic diol component. On the other hand, since the high molecular weight polyester resin component (H body) contains a large amount of an aliphatic diol component, the pulverizability and blocking resistance during toner production are improved, and as a result, these plurality of characteristics are obtained. It is considered that can be satisfied at a high level. The W / R value in the present invention is a value mainly related to the content of bisphenol A contained in the L-form, and a desired W / R value can be obtained by appropriately adjusting the amount of bisphenol A contained in the L-form. The indicated toner can be obtained.

The glass transition temperature (Tg) of the polyester resin is usually in the range of 45 ° C. to 75 ° C., preferably 50 ° C. to 65 ° C., more preferably 50 ° C. to 60 ° C., and particularly 55 ° C. from the viewpoint of heat storage. It is in the range of ~ 60 ° C.

In addition, the molecular weight distribution by GPC determined by the THF-soluble content of the toner has a main peak between 1000 and 10000. It is more preferably between 2000 and 8000, particularly preferably between 3000 and 8000, and the half width of the distribution is preferably a molecular weight of 2,000 or less. When these values are within the above range, a toner having excellent fixing characteristics can be obtained. GPC (Gel Permeation Chromatography) is measured as follows.

The column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was flowed through the column at a flow rate of 1 ml per minute to prepare a sample concentration of 0.05 to 0.6% by mass of a THF sample solution of the resin. Is injected in an amount of 50 to 200 μl and measured. In measuring the molecular weight of the sample (toner), 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., Ltd. Alternatively, the molecular weights manufactured by Toyo Soda Industries Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. ^{× 10 5, 8.6 × 10 5} , 2 × 10 6, used as a 4.48 × 10 ^6, it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

The THF insoluble content of the toner is preferably 5 to 40% by mass, more preferably 5 to 35% by mass. When the value of the THF insoluble matter is in the above range, hot offset resistance can be ensured and a toner having excellent stress resistance can be obtained.

The half width of the molecular weight distribution by GPC determined by the THF-soluble content in the toner is determined as follows.
The horizontal axis is the molecular weight, the vertical axis is the concentration (mass ratio) displayed at an arbitrary height, and the width (molecular weight) of the horizontal axis of the main peak at 50% of the peak top height of the main peak is the half width. To do. If different peaks are found at the hem of the main peak, the molecular weight including the peak at the hem is calculated. If there is a peak other than the main peak on the horizontal axis at 50% of the peak top height of the main peak, the highest molecular weight and the lowest molecular weight indicated by the intersection of the horizontal axis and each peak. The difference from the molecular weight is the half width.

Further, the volume average particle size (Dv) of the toner needs to be 4 to 6 μm. When the volume average particle size exceeds 6 μm, the low temperature fixability and the fixing strength deteriorate. This is because the toner of the present invention has a reduced bisphenol A component in the binder resin, so that the sharp melt property of the toner deteriorates, and the low temperature fixability and the fixing strength tend to deteriorate. Therefore, by reducing the volume average particle size of the toner to 4 to 6 μm, the amount of toner adhered per unit area on paper (g / cm ² ) can be reduced, which is advantageous for low-temperature fixability and fixing strength. Is. Further, when the volume average particle size is less than 4 μm, the fine powder content is high, so that the members such as the photoconductor are contaminated, the cleanability is deteriorated, and an abnormal image is likely to occur.

By using the binder resin of the present invention and reducing the volume average particle size of the toner to 4 to 6 μm, it is excellent in fixing characteristics such as low temperature fixability and fixing strength, and also has excellent crushability, durability, and resistance. The filming property and blocking resistance are also good, and these plurality of characteristics can be satisfied at a high level. Further, since the toner of the present invention is excellent in pulverizability, it is possible to efficiently produce a toner having a volume average particle diameter of 4 to 6 μm, and it is possible to reduce the toner consumption, so that it is excellent in productivity and cost. It is also advantageous.

Further, the fine powder content of 5 μm or less of the toner is preferably 60 to 90%.
If the fine powder content of 5 μm or less is less than 60%, the productivity of the toner and the consumption of the toner are lowered, which is not preferable in terms of cost. When the fine powder content of 5 μm or less exceeds 90%, the members such as the photoconductor are contaminated, the cleanability is deteriorated, and an abnormal image is likely to occur.
The volume average particle size and the fine powder content can be measured with Multisizer 3 (manufactured by Beckman Coulter).

Examples of usable resins other than polyester resin include the following. Polystyrene, chloropolystyrene, polyα-methylstyrene, styrene / chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer, styrene / Styrene / maleic acid copolymer, styrene / acrylic acid ester copolymer (styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer) Combined, styrene / phenylacrylate copolymer, etc.), styrene / methacrylic acid ester copolymer (styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / Styrenic resin such as phenyl methacrylate copolymer, etc.), styrene / α-methyl chloroacrylate copolymer, styrene / acrylonitrile / acrylic acid ester copolymer, etc. (monopolymer or co-polymer containing styrene or styrene substituent) Polymer), vinyl chloride resin, styrene / vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene / ethyl acrylate Copolymers, xylene resins, polyvinyl butyral resins, etc., petroleum-based resins, hydrogenated petroleum-based resins, etc. These resins can be used alone or in combination of two or more. The method for producing these resins is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.
Further, the glass transition temperature Tg of the resin is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, in view of heat storage stability, as in the case of polyester resin.

In the present invention, all known mold release agents can be used for toner, and in particular, defreed fatty acid type carnauba wax, montan wax and oxidized rice wax can be used alone or in combination. The carnauba wax is preferably microcrystalline, preferably has an acid value of 5 or less, and has a particle size of 1 μm or less when dispersed in the binder resin. The montan wax generally refers to a montan-based wax purified from minerals, and like the carnauba wax, it is preferably a microcrystal and has an acid value of 5 to 14. The oxidized rice wax is made by air-oxidizing rice bran wax, and its acid value is preferably 10 to 30. As the other release agent, any conventionally known release agent such as solid silicone varnish, higher fatty acid higher alcohol, montan ester wax, and low molecular weight polypropylene wax can be mixed and used. The amount of these release agents used is 1 to 20 parts by mass, preferably 3 to 10 parts by mass with respect to the toner resin component.

In the present invention, a colorant can be used as a toner component if necessary. Examples of colorants include carbon black, lamp black, iron black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, Rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, and triallylmethane. Any conventionally known dyeing pigment such as a dyeing pigment such as a system dye can be used alone or in combination, and can be used as a black toner or a full-color toner. The amount of these colorants used is usually 1 to 30% by mass, preferably 3 to 20% by mass, based on the toner resin component.

The toner of the present invention can also be blended with a charge control agent, a fluidity improver and the like, if necessary. As the charge control agent, any conventionally known charge control agent such as a niglosin dye, a metal complex salt type dye, and a quaternary ammonium salt can be used alone or in combination. The amount of these charge control agents used is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to the toner resin component. In particular, a salicylic acid metal complex, preferably a complex having a trivalent or higher valent metal capable of having a hexacoordinated structure, is preferable for the above reason. Here, examples of trivalent or higher valent metals include Al, Fe, Cr, Zr and the like. As the fluidity improver, any conventionally known fluidity improver such as silicon oxide, titanium oxide, silicon carbide, aluminum oxide, and barium titanate can be used alone or in combination. The amount of these fluidity improvers used is 0.1 to 5 parts by mass, preferably 0.5 to 2 parts by mass, based on the mass of the toner.

Further, the toner of the present invention can be used as a magnetic toner containing a magnetic material, and the magnetic material contained in the toner includes iron oxide such as magnetite, hematite and ferrite, metals such as iron, cobalt and nickel, or metals such as nickel. Examples thereof include alloys of these metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium and mixtures thereof. Magnetite is particularly preferable in terms of magnetic properties.
It is desirable that these magnetic materials have an average particle size of about 0.1 to 2 μm, and the amount contained in the toner is about 15 to 200 parts by mass, particularly preferably 100 parts by mass of the resin component with respect to 100 parts by mass of the resin component. It is 20 to 100 parts by mass with respect to.

The toner of the present invention can be used as a one-component developer or as a two-component developer in combination with a carrier. When the toner of the present invention is used as a two-component developer, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder, nickel powder, glass beads and the like, and these. The surface of the above is treated with resin or the like. Examples of the resin powder that can be coated on the carrier in the present invention include a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluororesin, a polyester resin, and an epoxy resin. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by mass are preferable. In this case, if the styrene content is less than 30% by mass, the developing characteristics are low, and if it exceeds 90% by mass, the coating film becomes hard and easily peeled off, and the life of the carrier is shortened. Further, the resin coating of the carrier in the present invention may contain an adhesive, a curing agent, a lubricant, a conductive material, a charge control agent and the like in addition to the above resin.

When the toner of the present invention is used as either a one-component developer or a two-component developer, the toner is filled in a container, and the container filled with the toner is distributed separately from the image forming apparatus, and the user can use the image. It is common to attach it to a forming device to form an image. The container used is not limited, and is not limited to the conventional bottle type or cartridge type. Further, the image forming apparatus is not limited as long as it is an apparatus for forming an image by an electrophotographic method, and includes, for example, a copying machine or a printer.

(Image forming device and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further has other means, if necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps if necessary.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known materials, and the material thereof is, for example, an inorganic photoconductor such as amorphous silicon or selenium. , Polysilane, organic photoconductors such as phthalopolymethine and the like. Among these, amorphous silicon is preferable from the viewpoint of long life.

<Electrostatic latent image forming means and electrostatic latent image forming process>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected depending on the intended purpose. Examples thereof include a means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for exposing the surface of the electrostatic latent image carrier in an image manner.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected depending on the intended purpose. This can be done by charging the surface of the electrostatic latent image carrier and then exposing it to an image, and it can be done by using the electrostatic latent image forming means.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a contact charging device known per se including a conductive or semi-conductive roller, brush, film, rubber blade or the like. , Corotron, non-contact charger using corona discharge such as Scorotron, and the like.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.
The shape of the charging member may be any shape such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and the shape of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use the contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed to an image to be formed, and is appropriately selected depending on the intended purpose. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. The light source used for the exposure member is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), or a semiconductor laser. (LD), electroluminescence (EL) and other light-emitting substances in general can be mentioned.
Further, in order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a bandpass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can also be used.
The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier in an image manner using the exposure member.
In the present invention, an optical back surface method may be adopted in which the back surface side of the electrostatic latent image carrier is exposed in an image-like manner.

<Development means and development process>
The developing means is not particularly limited as long as it is a developing means including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image that is a visible image. , Can be appropriately selected according to the purpose.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible toner image. , Can be appropriately selected according to the purpose, and can be performed by, for example, the developing means.
The developing means includes a stirrer that frictionally stirs and charges the toner, and a magnetic field generating means fixed inside, and a developer containing the toner is supported on the surface to carry a rotatable developer. A developing device having a body is preferable.

<< Developer >>
The developer of the present invention contains at least the toner and, if necessary, other components such as carriers which are appropriately selected.
When used in a high-speed printer or the like corresponding to an increase in information processing speed in recent years, a two-component developer composed of toner and a carrier is preferable because the life is extended.

<<< Career >>
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but a carrier having a core material and a resin layer covering the core material is preferable.
The material of the core material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 50 emu / g to 90 emu / g manganese-strontium-based material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. Further, in order to secure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developing agent in the spiked state on the photoconductor can be alleviated and it is advantageous for improving the image quality, a low magnetization material such as copper-zinc of 30 emu / g to 80 emu / g should be used. Is preferable.

The volume average particle diameter of the core material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 150 μm, more preferably 40 μm to 100 μm.
If the volume average particle diameter is less than 10 μm, fine powder may increase in the carrier, the magnetization per particle may decrease and carriers may scatter, and if it exceeds 150 μm, the specific surface area decreases and the toner may be scattered. Scattering may occur, and in full color with many solid parts, the reproduction of the solid part may be particularly poor.

When the toner is used as a two-component developer, it may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 90 parts by mass to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Parts are preferable, and 93 parts by mass to 97 parts by mass are more preferable.

The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component developing method, a non-magnetic one-component developing method, and a two-component developing method. In the developing means, for example, the toner and the carrier are mixed and agitated, the toner is charged by friction at that time, and is held in a spiked state on the surface of a rotating magnet roller to form a magnetic brush. .. The magnet roller is arranged in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attraction force. As a result, the electrostatic latent image is developed by the toner, and a visible image by the toner is formed on the surface of the electrostatic latent image carrier.

<Other means and other processes>
Examples of the other means include transfer means, fixing means, cleaning means, static elimination means, recycling means, control means and the like.
Examples of the other steps include a transfer step, a fixing step, a cleaning step, a static elimination step, a recycling step, a control step, and the like.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected depending on the intended purpose. However, the visible image is transferred onto an intermediate transfer medium and composited. It is preferable to have a primary transfer means for forming a transfer image and a secondary transfer means for transferring the composite transfer image onto a recording medium.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected depending on the intended purpose. However, an intermediate transfer member can be used on the intermediate transfer member. It is preferable that the visual image is first-transferred and then the visible image is secondarily transferred onto the recording medium. The transfer step can be performed, for example, by charging the photoconductor with a transfer charger, and can be performed by the transfer means.

Here, when the image secondarily transferred onto the recording medium is a color image composed of toners of a plurality of colors, the intermediate transfer means by sequentially superimposing the toners of each color on the intermediate transfer body. An image can be formed on the body, and the image on the intermediate transfer body can be collectively secondarily transferred onto the recording medium by the intermediate transfer means. The intermediate transfer material is not particularly limited and may be appropriately selected from known transfer materials according to the purpose. For example, a transfer belt or the like is preferably used.

It is preferable that the transfer means (the primary transfer means, the secondary transfer means) has at least a transfer device that exfoliates and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose, and is used for OHP. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing means is not particularly limited as long as it is a means for fixing the transferred image transferred to the recording medium, and can be appropriately selected depending on the intended purpose, but a known heating and pressing member is preferable. Examples of the heating and pressurizing member include a combination of a heating roller and a pressurizing roller, a combination of a heating roller, a pressurizing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected depending on the intended purpose. For example, the recording medium is used for toner of each color. It may be carried out every time the transfer is made to the toner, or it may be carried out at the same time in a state where the toners of each color are laminated.

The fixing step can be performed by the fixing means. The heating in the heating and pressurizing member is usually preferably 80 ° C. to 200 ° C. In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing means, depending on the purpose. The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, it is preferably ^{10N / cm 2 ~80N / cm 2} .

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected depending on the intended purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or the like. Examples include magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected depending on the intended purpose. For example, the cleaning step can be performed.

<< Static elimination means and static elimination process >>
The static elimination means is not particularly limited as long as it is a means for applying a static elimination bias to the photoconductor to eliminate static electricity, and can be appropriately selected depending on the intended purpose. Examples thereof include a static elimination lamp.
The static elimination step is not particularly limited as long as it is a step of applying a static elimination bias to the photoconductor to eliminate static electricity, and can be appropriately selected depending on the intended purpose. For example, the static elimination step can be performed. ..

<< Recycling means and recycling process >>
The recycling means is not particularly limited as long as it is a means for recycling the toner removed by the cleaning step into the developing apparatus, and can be appropriately selected depending on the purpose. For example, a known transport means or the like can be used. Can be mentioned. The recycling step is not particularly limited as long as it is a step of recycling the toner removed by the cleaning step to the developing apparatus, and can be appropriately selected depending on the purpose. For example, the recycling step is performed. Can be done.

Next, one aspect of carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG.
The image forming apparatus 1 is a printer, but the image forming apparatus is not particularly limited as long as it is possible to form an image using toner of a copying machine, a facsimile, a multifunction device, or the like. The image forming apparatus 1 includes a paper feeding unit 210, a conveying unit 220, an image forming unit 230, a transfer unit 240, and a fixing device 250.
The paper feed unit 210 includes a paper feed cassette 211 on which the paper P to be fed is loaded, and a paper feed roller 212 for feeding the paper P loaded on the paper feed cassette 211 one by one.

The transport unit 220 sandwiches the tip of the paper P conveyed by the roller 221 and the roller 221 that conveys the paper P fed by the paper feed roller 212 in the direction of the transfer unit 240, and waits for the paper to be predetermined. It includes a pair of timing rollers 222 that are sent to the transfer unit 240 at the timing, and a paper ejection roller 223 that ejects the paper P on which the color toner image is fixed to the paper ejection tray 224.
The image forming unit 230 includes an image forming unit Y for forming an image using a developing agent having yellow toner and cyan toner in this order from left to right in the drawing at predetermined intervals. The image forming unit C using the developed agent, the image forming unit M using the developer having magenta toner, the image forming unit K using the developing agent having black toner, and the exposure device 233 are provided.

When any image forming unit is shown among the image forming units (Y, C, M, K), it is referred to as an image forming unit.
In addition, the developer has a toner and a carrier. The four image forming units (Y, C, M, K) have substantially the same mechanical configuration except that the developing agent used for each is different. The transfer unit 240 is exposed to light by sandwiching the drive roller 241 and the driven roller 242, the intermediate transfer belt 243 that can rotate counterclockwise in the drawing as the drive roller 241 is driven, and the intermediate transfer belt 243. The primary transfer roller (244Y, 244C, 244M, 244K) provided to face the body drum 231 and the secondary opposed roller provided to face the intermediate transfer belt 243 at the transfer position of the toner image to paper. It includes 245 and a secondary transfer roller 246.
The fuser 250 is provided with a heater inside, and includes a pressurizing roller 252 that rotatably pressurizes the fixing belt 251 that heats the paper P against the fixing belt 251 to form a nip. .. As a result, heat and pressure are applied to the color toner image on the paper P, and the color toner image is fixed. The paper P on which the color toner image is fixed is discharged to the paper ejection tray 224 by the paper ejection roller 223, and a series of image forming processes is completed.

The toner accommodating unit in the present invention means a unit accommodating toner in a unit having a function of accommodating toner. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like. The toner containing container means a container containing toner. A developer has a means for accommodating and developing toner. The process cartridge is a cartridge in which at least the image carrier and the developing means are integrated, the toner is stored, and the process cartridge is removable from the image forming apparatus. The process cartridge may further include at least one selected from charging means, exposing means and cleaning means.

By mounting the toner accommodating unit of the present invention on an image forming apparatus to form an image, the durability, fixing characteristics, crushability during toner production, copy blocking resistance and filming resistance of the present invention are excellent. Since the image is formed by low-cost toner, there is an effect that a high-quality image can be obtained at low cost.

(Process cartridge)
The process cartridge according to the present invention is detachably molded into various image forming devices, and has an electrostatic latent image carrier that carries an electrostatic latent image and an electrostatic latent image that is supported on the electrostatic latent image carrier. At least has a developing means for forming a toner image by developing with the developer of the present invention. The process cartridge of the present invention may further have other means, if necessary. The developing means includes at least a developing agent accommodating portion for accommodating the developing agent of the present invention and a developing agent carrier for carrying and transporting the developing agent contained in the developing agent accommodating portion. The developing means may further include a regulating member or the like in order to regulate the thickness of the developing agent to be carried.
FIG. 2 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes a photoconductor drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Tables 1 and 2 show the resins used in each example, and Table 3 shows the characteristic evaluation methods. Further, in the following description, unless otherwise specified, parts indicate parts by mass. The method for evaluating the characteristics of the toner produced in each embodiment will be described.

[Evaluation methods]
[1] Low-temperature fixability Ricoh Co., Ltd. Copier (MF2200) using a Teflon (registered trademark) roller as the fixing roller is used to set and copy Ricoh type 6200 paper. I did a test. The cold offset temperature (lower limit temperature for fixing) was obtained by changing the fixing temperature. The lower limit temperature for fixing the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low temperature fixing are 120 to 150 mm / sec for paper feed, the surface pressure is 1.2 Kgf / cm ² , the nip width is 3 mm, and the evaluation conditions for high temperature offset are 50 mm / sec for paper feed. The surface pressure was set to 2.0 Kgf / cm ² and the nip width was set to 4.5 mm. The criteria for character evaluation are as follows.
(Evaluation criteria)
⊚: 130 ° C or higher and lower than 140 ° C ○: 140 ° C or higher and lower than 150 ° C Δ: 150 ° C or higher and lower than 160 ° C ×: 160 ° C or higher

[2] Fixing Strength Using a Ricoh copying machine (MP9001), a halftone image was output to the Ricoh type 6200 paper so that the image density was 0.75 ± 0.50.
The obtained image is used as a friction element of a smear tester (friction tester type I, JIS L0823, friction element diameter: 15φ), and a white cotton cloth (JIS L0803 cotton No. 3) of about 25 × 25 mm is applied to the friction element in the fiber direction. It was attached with double-sided tape so that it was horizontal to the movable direction. Then, the fixed image was rubbed in a continuous operation for 5 reciprocations.
Peel off the white cotton cloth, measure the image density at any three points in the friction trace where the toner is attached, using a spectrometer ("X-Rite, 938 Spectrodensitometer"", and measure the average value. It was used as a smear ID and used as an index of fixing strength.
(Evaluation criteria)
⊚: 0.15 or less ○: 0.20 or less Δ: 0.25 or less ×: 0.30 or more

[3] Crushability The volume average particle size of the coarsely pulverized product (screen mesh 1.5 mm) when pulverized with a mechanical crusher (turbo mill T250) at 9800 rpm was evaluated. The evaluation criteria are as follows.
⊚: less than 6.5 μm ○: 6.5 μm or more and less than 7.0 μm Δ: 7.0 μm or more and less than 7.5 μm ×: 7.5 μm or more

[4] Durability Using a Ricoh copying machine (MP9001), 300,000 sheets were continuously printed. The state of image scattering due to the decrease in charge during printing was evaluated. The evaluation criteria are as follows.
⊚: No charge reduction and no image scattering.
◯: 1 or more and less than 10 μC / g The charge is reduced, but image scattering does not occur.
Δ: 10 or more and less than 20 μC / g The charge is reduced, and image scattering also occurs.
X: The charge is reduced by 20 μC / g or more, and image scattering also occurs.

[5] Copy-blocking resistance Using a Ricoh copier (MP9001), five blank sheets and test charts (black solid image and white image are printed alternately) are alternately stacked and pressure is applied. After heating at 75 ° C. for 6 hours, natural cooling is performed for 1 hour. After that, the ID of the transition part to the blank sheet was measured, and it was set that the higher the ΔID, the worse the blocking property. The evaluation criteria are as follows.
⊚: less than 0.001 ○: 0.001 or more and less than 0.008 Δ: 0.008 or more and less than 0.01 ×: 0.01 or more

[6] Filming resistance Using a Ricoh copying machine (MP9001), printing of 100 sheets in succession was repeated 50 times to generate filming in the electrophotographic photosensitive member.
⊚: Does not occur ○: Slightly occurs △: Several points occur ×: Large amount occurs

[7] Cost The content of bisphenol A contained in the alcohol component of the THF-soluble component and the content of bisphenol A contained in the alcohol component of the THF-insoluble component were added, and the evaluation was performed based on the amount of bisphenol A in the entire toner.
The evaluation criteria are as follows.
⊚: 0 to less than 66 mol% ○: 66 mol% or more and less than 140 mol% Δ: 140 mol% or more and less than 171 mol% ×: 171 mol% or more and less than 200 mol%

(Manufacturing of polyester)
The raw materials shown in Tables 1 and 2 are placed in a 1 L 4-necked round-bottom flask equipped with a thermometer, a stirrer, a condenser and a nitrogen gas introduction tube, and this flask is set in a mantle heater to introduce nitrogen gas. Nitrogen gas is introduced from the tube to raise the temperature while keeping the inside of the flask under an inert atmosphere, and then 0.05 g of dibutyltin oxide is added to react while keeping the temperature at 200 ° C., and polyester resins A to polyester Resin P was obtained.

[Example 1]
Polyester resin A 60 parts Polyester resin G 40 parts Carnauba wax 5 parts Carbon black (# 44: manufactured by Mitsubishi Kasei Corp.) 10 parts Zr (IV) salicylate compound 1 part After thoroughly stirring and mixing the mixture of the above composition in a Henschel mixer. After heating and melting at a temperature of 130 to 140 ° C. for about 30 minutes in a roll mill and cooling to room temperature, the obtained kneaded product is pulverized and classified by a jet mill, a mechanical crusher, or a wind classifier, and the volume average particle size is 4.9 μm. A toner matrix having a fine powder content of 5 μm or less and a fine powder content of 80% was obtained. 0.5% by mass of hydrophobic silica was added and mixed with the obtained toner matrix to prepare a final toner.

[Example 2]
Toners were obtained in the same manner as in Example 1 except that the polyester resin A of Example 1 was changed to the polyester resin C and the polyester resin G was changed to the polyester resin I.

[Example 3]
Toners were obtained in the same manner as in Example 1 except that the polyester resin A of Example 1 was changed to the polyester resin D and the polyester resin G was changed to the polyester resin H.

[Example 4]
Toners were obtained in the same manner as in Example 1 except that the polyester resin A of Example 1 was changed to the polyester resin E and the polyester resin G was changed to the polyester resin J.

[Example 5]
Toner was obtained in the same manner as in Example 1 except that the fine powder content of 5 μm or less in Example 1 was changed from 80% to 60%.

[Comparative Example 1]
Polyester resin B 60 parts Polyester resin K 40 parts Carnauba wax 5 parts Carbon black (# 44: manufactured by Mitsubishi Kasei Corp.) 10 parts Zr (IV) salicylate compound 1 part After thoroughly stirring and mixing the mixture of the above composition in a Henschel mixer. After heating and melting at a temperature of 130 to 140 ° C. for about 30 minutes in a roll mill and cooling to room temperature, the obtained kneaded product is pulverized and classified by a jet mill, a mechanical crusher, or a wind classifier, and the volume average particle size is 4.9 μm. A toner matrix having a fine powder content of 5 μm or less and a fine powder content of 80% was obtained. 0.5% by mass of hydrophobic silica was added and mixed with the obtained toner matrix to prepare a final toner.

[Comparative Example 2]
Toners were obtained in the same manner as in Comparative Example 1 except that the polyester resin B of Comparative Example 1 was changed to the polyester resin F and the polyester resin K was changed to the polyester resin J.

[Comparative Example 3]
Except for changing the polyester resin B of Comparative Example 1 to the polyester resin D, the polyester resin K to the polyester resin H, the volume average particle size of 4.9 μm to 7.0 μm, and the fine powder content of 5 μm or less to 70%. , Toner was obtained in the same manner as in Comparative Example 1.

[Comparative Example 4]
Except for changing the polyester resin B of Comparative Example 1 to the polyester resin D, the polyester resin K to the polyester resin H, the volume average particle size of 4.9 μm to 9.0 μm, and the fine powder content of 5 μm or less to 15%. , Toner was obtained in the same manner as in Comparative Example 1.

The combinations of polyester resins in Examples and Comparative Examples are shown in Table 3.

(Example 1)
In Example 1, as a resin, a resin having a content of bisphenol A contained in the L-form alcohol component, which is a soluble component when dissolved in THF, is 50 mol%, and an insoluble resin when dissolved in THF. As a result of combining the bisphenol A content contained in the H-form alcohol component to be a component with a 90 mol% resin, the constitution of the present invention was satisfied. The value of W'/ R'was 0.70 or more, and since the toner contained a large amount of bisphenol A, the pulverizability became Δ.
(Example 2)
In Example 2, the content of bisphenol A contained in the L-form alcohol component, which is a soluble component when dissolved in THF as a resin, is 60 mol%, and the insoluble component when dissolved in THF. As a result of combining the content of bisphenol A contained in the alcohol component of the H-form to be 55 mol% with the resin, the constitution of the present invention was satisfied, and all the evaluations gave good results.
(Example 3)
In Example 3, the content of bisphenol A contained in the L-form alcohol component, which is a soluble component when dissolved in THF as a resin, is 30 mol%, and the insoluble component when dissolved in THF. As a result of combining the resin containing 20 mol% of bisphenol A and 35% by weight of THF insoluble in the alcohol component of the H form, the constitution of the present invention was satisfied. It satisfies all the characteristics in a well-balanced manner, and has good pulverizability due to the large amount of aliphatic diol contained in the THF insoluble matter, but it is durable because it contains 35% by mass of the THF insoluble matter. Was also a good result. Further, although the content of bisphenol A is small, the toner particle size is 4.9 μm, so that the toner adhesion amount can be reduced, and the low temperature fixability and fixing strength are good.
(Example 4)
In Example 4, the content of bisphenol A contained in the L-form alcohol component, which is a soluble component when dissolved in THF as a resin, is 100 mol%, and the insoluble component when dissolved in THF. As a result of combining the resin containing 35 mol% of bisphenol A and 5% by mass of THF insoluble in the alcohol component of the H form, the constitution of the present invention was satisfied. Since a large amount of aromatic diol components are contained in the THF-soluble component, which is an L-form that easily appears on the toner surface, low-temperature fixability, filming resistance, and durability are good.
Further, since the THF insoluble content was as small as 5% by mass, the pulverizability was also good.
(Example 5)
In Example 5, as a resin, a resin having a content of bisphenol A contained in the L-form alcohol component, which is a soluble component when dissolved in THF, is 50 mol%, and an insoluble resin when dissolved in THF. As a result of combining the bisphenol A content contained in the H-form alcohol component to be a component with a 90 mol% resin, the constitution of the present invention was satisfied. However, since the fine powder content was set to 60%, the proportion of the small particle size toner decreased, and the low temperature fixability and the fixing strength deteriorated.

(Comparative Example 1)
In Comparative Example 1, both the L-form, which is a soluble component when dissolved in THF, and the H-form, which is an insoluble component when dissolved in THF, are combined with a resin containing no bisphenol A in the alcohol component. Therefore, good results were obtained in pulverization property and image blocking resistance. However, since bisphenol A is not contained, the low temperature fixability, fixing strength, durability, chargeability, and filming resistance are inferior.
(Comparative Example 2)
Comparative Example 2 is a resin in which 100 mol% of bisphenol A is contained in the alcohol component of both the L-form, which is a soluble component when dissolved in THF, and the H-form, which is an insoluble component when dissolved in THF. As a result of the combination of the above, low temperature fixability, fixing strength, filming resistance, and durability were good. However, the crushability and image blocking resistance were inferior, and the cost was high.
(Comparative Example 3)
Comparative Example 3 shows a resin in which the content of bisphenol A contained in the L-form alcohol component, which is a soluble component when dissolved in THF as a resin, is 30 mol%, and an insoluble component when dissolved in THF. As a result of combining the resin containing 20 mol% of bisphenol A and 35% by weight of THF insoluble in the H-form alcohol component, the content of bisphenol A is reduced, and the content of bisphenol A is reduced. Since the particle size of the toner is 7.0 μm, the amount of the toner adhering to the toner increases, and the low temperature fixability and the fixing strength deteriorate.
(Comparative Example 4)
In Comparative Example 4, a resin having a bisphenol A content of 30 mol% contained in the L-form alcohol component, which is a soluble component when dissolved in THF as a resin, and an insoluble component when dissolved in THF As a result of combining the resin containing 20 mol% of bisphenol A and 35% by weight of THF insoluble in the H-form alcohol component, the content of bisphenol A is reduced, and the content of bisphenol A is reduced. Since the particle size of the toner is 9.0 μm, the amount of adhered to the toner is increased, and the low temperature fixability and the fixing strength are further deteriorated.

As shown above, the toner of the example is a toner which is excellent in fixing characteristics such as low temperature fixability and fixing strength, crushability at the time of toner production, and also excellent in durability, copy blocking resistance and filming resistance. It turned out to be.

1 Image forming device 10 Photoreceptor drum 40 Developer 58 Corona charger 80 Transfer roller 90 Cleaning device 110 Process cartridge 210 Feeding unit 211 Feeding cassette 212 Feeding roller 220 Transporting unit 221 Roller 222 Timing roller 223 Paper ejection roller 224 Discharge Paper tray 230 Image forming unit 231 Photoreceptor drum 232 Charger 233 Exposed device 240 Transfer unit 241 Drive roller 242 Driven roller 243 Intermediate transfer belt 244Y, 244C, 244M, 244K Primary transfer roller 245 Secondary opposed roller 246 Secondary transfer roller 250 Fixer 251 Fixer Belt 252 Pressurized Roller P Paper

Japanese Patent No. 5138630

Claims (9)

At least a toner containing a binder resin,
The binding resin is a polyester resin, and the alcohol component constituting the polyester resin contains a bisphenol A component.
The polyester resin contains a high molecular weight polyester resin (H body) and a low molecular weight polyester resin (L body).
The high molecular weight polyester resin (H form) contains 20 to 100 mol% of an aliphatic diol and 0 to 80 mol% of a bisphenol A component in the alcohol component.
The low molecular weight polyester resin (L-form) contains 0 to 80 mol% of an aliphatic diol and 20 to 100 mol% of a bisphenol A component in the alcohol component.
Moreover, the amount of the aliphatic diol contained in the alcohol component of the high molecular weight polyester resin (H body) is larger than that of the aliphatic diol contained in the alcohol component of the low molecular weight polyester resin (L body).
Maximum peak height W of the spectrum derived from the bisphenol A skeleton at 1480 to 1520 cm ^-1 of the toner measured by the ATR method using FT-IR, and the maximum peak height of the spectrum derived from the carbonyl group at 1700 to 1750 cm ^-1 . The peak ratio (W / R) to R is 0.25 to 0.70, and the molecular weight distribution by GPC determined by the THF-soluble content in the toner has a main peak between 1000 and 10000. The half-value width of the molecular weight distribution is 20,000 or less, the THF insoluble content is 5 to 40% by mass, and the volume average particle diameter (Dv) of the toner is 4 to 6 μm. Toner to do. Using FT-IR, infrared spectroscopy spectrum peaks 'and the spectrum peak height in 1700~1750cm ^-1 R' height W of the toner 1480～1520Cm ^-1 measured by (KBr tablet method) and The toner according to claim 1, wherein the peak ratio (W'/ R') of is 0.06 to 0.70. The toner according to claim 2, wherein the peak ratio (W / R) and the peak ratio (W'/ R') satisfy the following relationship.
W'/ R'≤ W / R The feature is that the ratio (W / R) / (W'/ R') of the peak ratio (W / R) to the peak ratio (W'/ R') is 1.0 or more and 2.0 or less. The toner according to claim 2 or 3 . The toner according to any one of claims 1 to 4 , wherein the toner has a THF insoluble content of 10 to 35% by mass. The toner according to any one of claims 1 to 5 , wherein the toner has a fine powder content of 5 μm or less of 60 to 90%. A toner storage unit containing the toner according to any one of claims 1 to 6 . An electrostatic latent image carrier, a charging means for charging the electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the charged electrostatic latent image carrier, and the static image carrier. A developing means for developing a toner image by developing an electrostatic latent image formed on the electrostatic latent image carrier with toner, and transferring the toner image formed on the electrostatic latent image carrier to a recording medium. An image forming feature comprising a transfer means and a fixing means for fixing a toner image transferred to the recording medium, wherein the toner is the toner according to any one of claims 1 to 6. apparatus. An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier are developed with toner and toner is used. It includes a developing step of forming an image, a transfer step of transferring the toner image formed on the electrostatic latent image carrier to a recording medium, and a fixing step of fixing the toner image transferred to the recording medium. The image forming method, wherein the toner is the toner according to any one of claims 1 to 6 .

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