JP2008152212A - Electrostatic charge image developing toner, developer for electrostatic charge development, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having high gloss, which can obtain an image with less change in glossiness due to rubbing, contacting or the like, a developer for electrostatic charge development including the electrostatic image developing toner, and an image forming apparatus that uses the electrostatic image developing toner. <P>SOLUTION: The electrostatic charge image developing toner contains a crystalline resin where the ratio of a molecular weight of ≤5,000 is 15-25%, wherein the molecular weight is expressed in terms of weight; an amorphous resin; a colorant; and a releasing agent having a domain size of ≤10 μm, wherein the domain size is measured with polarization microscopy after the releasing agent is fused at 200°C and is cooled at the cooling rate of -4°C/min. The developer for electrostatic charge development contains the electrostatic charge image developing toner, and the image forming apparatus uses the electrostatic charge image developing toner. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic charge developing toner that can be used in an electrophotographic apparatus using an electrophotographic process such as a copying machine, a printer, and a facsimile machine, an electrostatic charge developing developer containing the electrostatic charge developing toner, and the electrostatic charge developing The present invention relates to an image forming apparatus using a toner for the use.

  Many methods are already known as electrophotographic methods. In general, a latent image is electrically formed on the surface of a photosensitive member (latent image holding member) using a photoconductive substance by various means, and the formed latent image is transferred to an electrostatic charge developing toner (hereinafter referred to as an electrostatic charge developing toner). The toner image on the surface of the photoconductor is transferred to the surface of a recording medium such as paper with or without an intermediate transfer body. Then, a fixed image is formed through a plurality of steps of fixing the transferred image by heating, pressing, heating and pressing, solvent vapor, or the like. The toner remaining on the surface of the photoreceptor is cleaned by various methods as necessary, and is again subjected to the plurality of steps.

  As a fixing technique for fixing the transferred image transferred to the surface of the recording material, a hot roll fixing is performed by inserting the transferred material on which the toner image is transferred between a pair of rolls including a heating roll and a pressure roll and fixing the transferred image. The law is common. In addition, as the same type of technology, one in which one or both of the rolls are replaced with a belt is also known. Compared to other fixing methods, these technologies provide a fast and robust fixed image, high energy efficiency, less environmental damage due to volatilization of solvents, etc., and a technology for fixing toner with lower energy. It is desired.

As a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of a toner resin (binder resin) is generally performed. This glass transition point is a design point of many toner resins currently on the market. Further, as a means for achieving both prevention of blocking, image storability up to 60 ° C., and low-temperature fixability, a method of using a crystalline resin as a binder resin constituting the toner has been known for a long time. Furthermore, a technique using a crystalline resin has been known for a long time for the purpose of preventing offset and fixing pressure. Furthermore, it is disclosed that a crystalline resin and an amorphous resin are mixed and used as a method expected to improve the strength.
On the other hand, the thing which prescribed | regulated the average particle diameter of the crystal grain observed with a polarizing microscope is proposed (for example, refer patent document 1).
JP 2005-25144 A

  The present invention relates to an electrostatic charge developing toner capable of obtaining an image having high gloss and little change in glossiness due to rubbing or contact, an electrostatic charge developing developer containing the electrostatic charge developing toner, and the electrostatic charge developing toner An object of the present invention is to provide an image forming apparatus using the above.

As a result of intensive studies, the present invention has found that the following present invention solves the above-described problems, and has led to the solution of the present invention.
That is, the present invention
<1> A crystalline resin having a molecular weight of 5000 or less in terms of weight of 15% or more and 25% or less, an amorphous resin, a colorant, melted at 200 ° C., and cooled at −4 ° C./min. And a release agent having a domain size of 10 μm or less as observed with a polarizing microscope when cooled at a speed.
<2> An electrostatic charge developing developer comprising the electrostatic image developing toner according to <1>.

<3> A latent image holding member, developing means for developing the electrostatic latent image formed on the latent image holding member as a toner image with a developer containing toner, and toner formed on the latent image holding member A transfer unit that transfers the image onto the transfer member; a fixing unit that fixes the toner image transferred onto the transfer member; and a cleaning unit that rubs the latent image holding member with a cleaning member to clean the transfer residual component. And the toner is an electrostatic charge developing toner according to <1>.

  The present invention relates to an electrostatic charge developing toner capable of obtaining an image having high gloss and little change in glossiness due to rubbing or contact, an electrostatic charge developing developer containing the electrostatic charge developing toner, and the electrostatic charge developing toner Can be provided.

<Toner for electrostatic charge development>
The toner for developing electrostatic charge of the present invention (hereinafter sometimes referred to as “the toner of the present invention”) includes a crystalline resin having a molecular weight of 5000 or less in terms of weight in a range of 15% or more and 25% or less. It contains a crystalline resin, a colorant, and a release agent having a domain size of 10 μm or less as observed by a polarizing microscope when melted at 200 ° C. and cooled at a cooling rate of −4 ° C./min. And
The toner of the present invention is melted at 200 ° C. with a crystalline resin (hereinafter sometimes referred to as “specific crystalline resin”) having a molecular weight in terms of weight of 5000 or less of 15% or more and 25% or less. A release agent having a domain size of 10 μm or less when observed at a cooling rate of −4 ° C./min (hereinafter sometimes referred to as “specific release agent”), In particular, the toner is an electrostatic charge developing toner that can produce an image with little change in glossiness due to rubbing or contact that occurs in a high gloss image.

  The reason why the toner of the present invention becomes a toner that can obtain an image with little change in glossiness due to rubbing or contact is considered as follows. In general, in electrophotographic image formation, a release agent oozes out from the outermost surface of a fixed image at the time of fixing, thereby exhibiting releasability from a fixing roll. However, when the crystalline resin is present immediately below the outermost release agent layer, it absorbs heat and retains heat when the crystalline resin undergoes phase transition, and therefore exists on the periphery or on the surface side of the crystalline resin. The time in the temperature zone where the release agent is crystallized becomes relatively long and selectively crystallizes. A release agent that is locally crystallized on the image surface causes diffused reflection of light and lowers the glossiness of the image. However, when the cloth is wiped with a cloth or the like, the release agent is wiped off and the glossiness of the image is increased.

  As a method for reducing the above-described change in glossiness, the surface of the fixed image, that is, the toner surface or the entire vicinity of the toner surface is controlled so that the crystalline resin is present, and the release agent is crystallized. It is conceivable to increase the number of points and further reduce the domain size itself during recrystallization of the release agent. By doing so, local growth of the release agent domain can be prevented, so that the change in glossiness due to rubbing or contact is reduced.

The toner of the present invention contains a crystalline resin having a molecular weight of 5000 or less in terms of weight of 15% or more and 25% or less, so that the crystalline resin is present on the toner surface or the entire vicinity of the toner surface. It becomes easy. This is because the low molecular weight component generally has a high acid value, and therefore, it tends to appear at the interface between the toner and the solvent, that is, the surface of the toner during wet toner production.
The toner of the present invention is further melted at 200 ° C. and contains a release agent having a domain size of 10 μm or less by observation with a polarizing microscope when cooled at a cooling rate of −4 ° C./min. Thus, an electrostatic charge developing toner can be obtained in which an image with little change in glossiness due to toner is obtained.

  The proportion of 5000 or less in terms of molecular weight in terms of weight in the specific crystalline resin must be 15% or more and 25% or less, preferably 17% or more and 23% or less, and preferably 19% or more and 21% or less. It is more preferable. When the ratio of the molecular weight in terms of weight in the specific crystalline resin is 5000 or less is less than 15%, the crystalline resin cannot be present on the entire surface of the toner or in the vicinity of the surface, the glossiness is lowered, and the gloss before and after wiping. The degree of change will not be able to withstand actual use. On the other hand, if it exceeds 25%, the resin becomes unsatisfactory due to insufficient viscoelasticity of the resin and cannot withstand actual use.

  When the specific release agent is melted at 200 ° C. and cooled at a cooling rate of −4 ° C./min, the domain size by observation with a polarizing microscope is required to be 10 μm or less, preferably 5 μm or less, preferably 3 μm. The following is more preferable. When the domain size exceeds 10 μm, the glossiness is lowered, and the glossiness change before and after wiping becomes a level that cannot withstand actual use. The measurement of the domain size of the release agent in the present invention was performed under the following conditions. First, the toner was dissolved in a solvent such as toluene heated to about 180 ° C., and then cooled to separate only the release agent. 0.2 g of the obtained release agent was placed on a slide glass and heated to 200 ° C. with a hot plate or the like to be melted. A glass slide heated to 200 ° C. was placed on the molten release agent, and then cooled at a rate of −4 ° C./min. The sample sandwiched between the slide glasses was observed with a polarizing microscope, the domain size of the obtained release agent was measured, and the average value was defined as the release agent domain size.

(Binder resin)
The toner of the present invention contains a specific crystalline resin and an amorphous resin as a binder resin. Here, “crystallinity” in the crystalline resin means that, in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a stepwise endothermic amount change. On the other hand, the resin in which a stepwise endothermic change is recognized instead of a clear endothermic peak means an amorphous resin in the present invention, which is a solid at room temperature and is thermoplasticized at a temperature equal to or higher than the glass transition temperature. .

Examples of the crystalline resin and amorphous resin used in the toner of the present invention include styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene, and isoprene; vinyl acetate, vinyl propionate, vinyl benzoate, Vinyl esters such as vinyl butyrate; α such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate -Methylene aliphatic monocarboxylic esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone; It can be exemplified German polymers and copolymers.
Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. Examples thereof include a polymer, polyethylene, and polypropylene. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

The binder resin is preferably excellent in sharp melt property at the time of fixing, and from the viewpoint of obtaining low-temperature fixability and high glossiness in a fixed image, it is preferable to use an amorphous resin and a crystalline resin in combination.
As the amorphous resin, each of the exemplified resins can be used, but it is preferable to use an amorphous polyester resin from the viewpoint of chargeability.
The crystalline resin is not particularly limited as long as it is a resin having crystallinity, and specifically includes a crystalline polyester resin, a crystalline vinyl resin, and the like. A crystalline polyester resin is preferred from the viewpoint of chargeability and adjustment of the melting point within a preferred range. An aliphatic crystalline polyester resin having an appropriate melting point is preferred. Hereinafter, a typical polyester resin as the binder resin will be described.

  Other polymerizable monomers used in the polyester resin are conventional polymerizable monomer components as described in, for example, Polymer Data Handbook: Basic Edition (edited by Polymer Society: Bafukan). Known divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols may be mentioned. Specific examples of the divalent carboxylic acid include, for example, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, Dibasic acids such as naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid and mesaconic acid, and their anhydrides and lower alkyl esters thereof, maleic acid, fumaric acid, itaconic acid, citraconic acid and other fats Group unsaturated dicarboxylic acid.

Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters.
These may be used individually by 1 type and may use 2 or more types together.

  Examples of the divalent alcohol include bisphenol A, hydrogenated bisphenol A, ethylene oxide or (and) propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, Examples include propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl glycol.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together. If necessary, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can be used for the purpose of adjusting the acid value and the hydroxyl value.

  The polyester resin can be used in any combination of the polymerizable monomer components described above, for example, polycondensation (chemical doujin), polymer experimental studies (polycondensation and polyaddition: Kyoritsu Publishing) and polyester resin handbook (daily publication). Can be synthesized by using a conventionally known method as described in Kogyo Shimbun, etc., and a transesterification method or a direct polycondensation method can be used alone or in combination.

  As a means for adjusting the ratio of 5000 or less in terms of molecular weight in terms of weight to 15% or more and 25% or less, it is preferably obtained by mixing two or more crystalline resins synthesized separately.

  If the content of the specific crystalline resin in the toner of the present invention is too small, the effect of improving the low-temperature fixability cannot be sufficiently obtained, and if it is too large, the external additive is easily embedded and the life is shortened. The content is preferably 2 to 20% by mass and more preferably 3 to 10% by mass with respect to the total amount of toner particles.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent used for the toner of this invention, A well-known coloring agent is mentioned, According to the objective, it can select suitably. One colorant may be used alone, or two or more colorants of the same system may be mixed and used. Further, two or more kinds of different colorants may be mixed and used. Further, these colorants may be used after surface treatment. Specific examples of the colorant used include black, yellow, red, blue, purple, green and white colorants as shown below.

Examples of the black pigment include organic and inorganic colorants such as carbon black, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of blue pigments include organic and inorganic colorants such as bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, indanthrene blue BC, ultramarine blue, phthalocyanine blue, and phthalocyanine green. .

Yellow pigments include yellow lead, zinc yellow, yellow calcium oxide, cadmium yellow, chrome yellow, fast yellow, fast yellow 5G, fast yellow 5GX, fast yellow 10G, benzidine yellow G, benzidine yellow GR, sren yellow, quinoline yellow, Permanent yellow NCG etc. are mentioned.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like.
Examples of purple pigments include organic and inorganic colorants such as manganese purple, fast violet B, and methyl violet lake.

Examples of the green pigment include organic and inorganic colorants such as chromium oxide, chromium green, pigment green B, malachite green lake, and fanal yellow green G.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  The colorant is preferably added in a range of 4% by mass to 15% by mass with respect to the total solid content of the toner in order to ensure color developability at the time of fixing, and in the range of 4% by mass to 10% by mass. It is more preferable to add at. However, when using a magnetic substance as a black coloring agent, it is preferable to add within the range of 12 mass%-48 mass%, and it is more preferable to add within the range of 15 mass%-40 mass%. Each color toner such as yellow toner, magenta toner, cyan toner, black toner, white toner, and green toner can be obtained by appropriately selecting the type of the colorant.

[Method of dispersing colorant]
The colorant in the toner of the present invention is a granulated particle obtained by dissolving or dispersing a colorant dispersed in a resin in a polymerizable monomer in the suspension polymerization method described later. A colorant can be dispersed therein. In addition, in the case of the emulsion polymerization aggregation method described later, a colorant dispersion is prepared by dispersing a colorant in an aqueous medium by a mechanical impact together with a dispersant such as a surfactant. It can be obtained by agglomerating it together with resin particles and granulating it to a toner particle size.
Specific examples of the colorant dispersion by mechanical impact or the like include, for example, a rotary shear type homogenizer, a ball type mill, a sand mill, an attritor or other media type disperser, a high pressure opposed collision type disperser, etc. A dispersion can be prepared. Further, these colorants can be dispersed in an aqueous system by a homogenizer using a polar surfactant.

(Release agent)
The release agent is generally used for the purpose of improving the releasability, and the specific release agent used in the toner of the present invention is particularly limited as long as it satisfies the requirement that the domain size is 10 μm or less. Specific examples include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide; carnauba Plant waxes such as wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; mineral and petroleum systems such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax Wax; fatty acid Ester, montanic acid ester, and ester waxes such as carboxylic acid esters. In this invention, these mold release agents may be used individually by 1 type, and may use 2 or more types together.

  The addition amount of the specific release agent is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass with respect to the total amount of toner particles. If the amount is less than 0.5% by mass, the effect of adding a release agent may not be obtained. If the amount exceeds 20% by mass, not only the copper compound is hardly dispersed uniformly in the toner but also inside the developing machine. In some cases, the toner particles are easily destroyed, the release agent is spent on the carrier, and the charge is likely to be lowered.

[Method of dispersing release agent]
As a specific example of the release agent dispersion by mechanical impact or the like, a dispersion of release agent particles can be prepared using, for example, a high-pressure opposed collision type disperser. Further, these release agents can be dispersed in an aqueous system by a homogenizer using a polar surfactant.

(Toner production method)
Examples of the method for producing the toner of the present invention include an emulsion polymerization aggregation method, a suspension polymerization method, and the like, and the emulsion polymerization aggregation method is particularly preferable from the viewpoint of simplicity of structure control.
The emulsion polymerization aggregation method will be described.
A method for producing a toner by an emulsion polymerization aggregation method includes a step of aggregating dispersed specific crystalline resin particles, amorphous resin particles, a colorant, and a specific release agent into a toner particle size (hereinafter referred to as “aggregation step”). The agglomerated particles that have been agglomerated in some cases and heated through the agglomeration step are heated to a temperature equal to or higher than the glass transition point of the resin particles to fuse the agglomerates to form toner particles (hereinafter referred to as “fusion step”). The manufacturing method may include:

  In the aggregating step, resin particle dispersions mixed with each other (a specific crystalline resin particle dispersion and an amorphous resin particle dispersion are collectively referred to as “resin particle dispersion”), a colorant dispersion, And if necessary, the particles in the release agent dispersion liquid aggregate to form aggregated particles. The agglomerated particles are formed by heteroaggregation or the like. For the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the agglomerated particles, or a monovalent or more monovalent metal salt or the like is used. A charged compound is added.

  In the fusing step, the resin particles in the aggregated particles are melted under a temperature condition equal to or higher than the glass transition point, and the aggregated particles change from an irregular shape to a more spherical shape. Thereafter, the aggregate is separated from the aqueous medium, and washed and dried as necessary to form toner particles.

The volume average particle size of the toner of the present invention is preferably 2 to 10 μm, more preferably 3 to 8 μm, and further preferably 4 to 6 μm. Further, it is preferable that the toner particle size distribution is narrow, and more specifically, the ratio of the 16% diameter (abbreviated as D16v) and the 84% diameter (abbreviated as D84v) in terms of the smaller volume particle diameter of the toner is used as the square root. What is shown (GSDv), ie GSDv = {(D84v) / (D16v)} ^0.5
It is preferable that GSDv represented by is 1.23 or less. More preferably, it is 1.21 or less.

  When the emulsion polymerization aggregation method is used for the production of the toner in the present invention, the aggregation can be generated by the pH change in the aggregation process to prepare particles. At the same time, an aggregating agent may be added to stably and rapidly aggregate the particles, or to obtain aggregated particles having a narrower particle size distribution. As the flocculant, a compound having a monovalent or higher charge is preferable. Specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, oxalic acid Aliphatic acids such as sodium, sodium phthalate and potassium salicylate, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride and aniline hydrochloride And inorganic acid salts of aromatic amines.

In consideration of the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable as the aggregating agent in terms of performance and use. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate.
The amount of these flocculants to be added varies depending on the valence of the charge, but they are all small, in the case of monovalent, about 3% by mass or less, in the case of divalent, about 1% by mass, in the case of trivalent Is about 0.5 mass% or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

In the production of the toner of the present invention, for example, for the purpose of stabilizing the dispersion in the suspension polymerization method, and stabilizing the dispersion of the resin particle dispersion, the colorant dispersion, and the release agent dispersion in the emulsion polymerization aggregation method. A surfactant can be used.
Examples of the surfactant include sulfate surfactants, sulfonates, phosphates, soaps, and the like; amine surfactants, quaternary ammonium salt and other cationic surfactants; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

  In the toner of the present invention, in general, an anionic surfactant has a strong dispersion power and is excellent in dispersing resin particles and colorants. Therefore, an anionic surfactant is used as a surfactant for dispersing a release agent. It is advantageous to use a surfactant. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfone such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Quaternary ammonium salts such as quilts trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And so on.

  The content of the surfactant in each dispersion may be a level that does not inhibit the present invention, and is generally a small amount. Specifically, a range of 0.01 to 3% by mass is preferable, and more Preferably it is the range of 0.05-2 mass%, More preferably, it is the range of 0.1-1 mass%. When the content of the surfactant is less than 0.01% by mass, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion becomes unstable, and thus causes aggregation. Moreover, since the stability between the particles is different at the time of aggregation, the release of specific particles may occur.

Further, as the dispersion stabilizer used in the suspension polymerization method or the like, a slightly water-soluble and hydrophilic inorganic fine powder can be used. Examples of the inorganic fine powder that can be used include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate (hydroxyapatite), clay, diatomaceous earth, bentonite and the like. Among these, calcium carbonate, tricalcium phosphate, and the like are preferable from the viewpoints of easy particle size formation and easy removal.
Also, a room temperature solid aqueous polymer or the like can be used. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like can be used.

If necessary, a charge control agent may be added to the toner of the present invention.
Known charge control agents can be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength (%) and reducing wastewater contamination. The toner in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  In the toner of the present invention, an internal additive may be added inside the toner. The internal additive is generally used for the purpose of controlling the viscoelasticity of the fixed image. Specific examples of the internal additive include inorganic fine particles such as silica and titania, organic fine particles such as polymethyl methacrylate, and the like, and may be surface-treated for the purpose of improving dispersibility. These may be used alone or in combination of two or more internal additives.

  The toner of the present invention may be treated by adding an external additive such as a fluidizing agent or a charge control agent. Examples of external additives include silica fine particles whose surfaces are treated with a silane coupling agent, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, Known materials such as amine metal salts and salicylic acid metal complexes can be used. These may be used alone or in combination of two or more external additives.

<Developer for electrostatic charge development>
The developer for electrostatic charge development of the present invention (hereinafter sometimes referred to as “developer of the present invention”) contains the toner of the present invention described above. The toner of the present invention is used in a method called a two-component developer comprising a toner and a carrier, in addition to a method of using a one-component developer having a charge imparting structure in a developing device.
Hereinafter, the case where the developer of the present invention is a two-component developer will be described.

  The carrier that can be used in the two-component developer is not particularly limited, and a known carrier can be used. For example, the carrier is preferably a carrier in which a resin coating layer is formed by coating a resin (coating resin) with ferrite, calcium powder or the like as a core material. The core material (carrier core material) used is not particularly limited, and examples thereof include magnetic metals such as calcium, steel, nickel and cobalt, magnetic oxides such as ferrite and magnetite, glass beads, and the like. From the viewpoint of using a magnetic carrier, a magnetic carrier is desirable. The average particle diameter of the carrier core material is preferably 3 to 10 times the average particle diameter of the toner.

  Examples of the coating resin include amino resins including acrylic resins, styrene resins, urea, urethane, melamine, guanamine, aniline, amide resins, and urethane resins. These copolymer resins may also be used. Two or more of the above resins may be used in combination as the coating resin for the carrier. Further, for the purpose of controlling charging, resin fine particles, inorganic fine particles or the like may be dispersed in the coating resin.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in a solution for forming the resin coating layer, and a solution for forming the resin coating layer is used for the carrier core material. Spray method for spraying on the surface, fluidized bed method for spraying the solution for forming the resin coating layer in a state where the carrier core material is suspended by flowing air, mixing the carrier core material and the solution for forming the resin coating layer in a kneader coater The kneader coater method that removes the coating resin, and the powder coating method in which the coating resin is finely divided and mixed in the carrier core material and the kneader coater at a melting point or higher of the coating resin and cooled to form a film are mentioned. Preferably used.

  The amount of the resin coating formed by the above-described method is used by coating the carrier core material in an amount of 0.5 to 10% by mass. The mixing ratio (mass ratio) of the toner and the carrier is in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100.

<Image forming apparatus>
The image forming apparatus of the present invention includes a latent image holding member, developing means for developing the electrostatic latent image formed on the latent image holding member as a toner image with a developer containing toner, and a latent image holding member on the latent image holding member. A transfer means for transferring the toner image formed on the transfer body, a fixing means for fixing the toner image transferred on the transfer body, and the latent image holder by rubbing with a cleaning member to remove the transfer residual component. And a cleaning means for cleaning, wherein the toner is the toner of the present invention described above.

Hereinafter, image formation using the image forming apparatus of the present invention will be described with reference to the drawings.
FIG. 1 is a conceptual diagram showing an example of an image forming apparatus of the present invention.
The image forming apparatus 31 includes a charger 2, an image writing unit 3 such as a laser beam, a developing device (developing unit) 4, and a primary transfer around the photosensitive drum 1 (latent image holding member) sequentially along the rotation direction. A developing device (transfer means) 5, a cleaning device (cleaning means) 6, and the like are disposed, and black, yellow, magenta, and cyan toners are accommodated in the developing devices 4 ₁ to ₄ 4 of the developing device 4. The intermediate transfer belt 7 is in contact with the surface of the photosensitive drum 1, runs between the photosensitive drum 1 and the primary transfer device 5 in the direction of the arrow, and is stretched around the tension rolls 8 a, 8 b, 8 c and the backup roll 9. Yes. A bias roll 10 and a belt cleaner 11 are arranged at positions facing the backup roll 9 and the tension roll 8a, respectively. A voltage application roll 12 is in contact with the backup roll 9.

  A portion where the primary transfer unit 5 presses the photosensitive drum 1 via the intermediate transfer belt 7 is a primary transfer portion, and a portion where the bias roll 10 presses the backup roll 9 is a secondary transfer portion.

  The surface of the photosensitive drum 1 is uniformly charged by the charger 2 and a latent image is formed by the image writing means 3. The latent image formed on the surface of the photosensitive drum 1 is developed with toner constituting the developer layer on the surface of the developer carrying member in the developing device 4 disposed to face the photosensitive drum 1 to form a toner image. The The toner image formed on the surface of the photosensitive drum 1 is electrostatically transferred to the intermediate transfer belt 7 in the primary transfer portion. Then, the toner image is transferred from the intermediate transfer belt 7 to the transfer paper P supplied from the paper feed tray 13 to the secondary transfer portion, and sent to a roll type fixing device (fixing means) 19 to be fixed. In the roll type fixing machine 19, the pressure roll 20 is pressed against the fixing roll 21.

  The residual toner (transfer residual component) is removed by the cleaning device 6 from the photosensitive drum 1 after the toner image on the surface is transferred. In the image forming apparatus shown in FIG. 1, the toner image formed on the surface of the photosensitive drum 1 is transferred to the recording medium (transfer target) p via the intermediate transfer belt 7, but the surface of the photosensitive drum 1 is used. The toner image formed on the recording medium p may be directly transferred to the recording medium p without using the intermediate transfer belt 7.

  Since the image forming apparatus of the present invention uses the toner of the present invention, an image with high gloss and little change in glossiness due to rubbing, contact or the like can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the following Example does not limit this invention. In the following examples, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.
The molecular weight of the binder resin used for the toner of the present invention was measured under the following conditions. As a gel permeation chromatography (GPC), an “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” apparatus was used, and the column was “TSKgel, SuperHM-H (manufactured by Tosoh Corporation), 6.0 mm ID × 15 cm) ”was used, and THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 l, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”. Under this condition, a ratio of 5000 or less was measured and calculated as the molecular weight in terms of weight of the crystalline resin.

The electrostatic image developing toner of the present invention can be obtained by the following method.
<Method for Producing Crystalline Resin (1) and Crystalline Resin Latex (1)>
600 parts of dodecanedioic acid, 454 parts of 1,10-dodecanediol, and 0.43 part of dibutyltin oxide were stirred at 180 ° C. for 6 hours in a nitrogen atmosphere. Thereafter, the mixture was stirred for 20 minutes under reduced pressure to obtain a crystalline resin (1) having a weight average molecular weight Mw = 4900 and a number average molecular weight Mn = 2300. Moreover, the ratio of Mw5000 or less of this resin was 49.5%. Next, 50 parts of the crystalline resin (1) is dissolved in 250 parts of ethyl acetate, a solution obtained by dissolving 2 parts of the anionic surfactant Dowfax in 300 parts of ion-exchanged water is added, and 10 parts at 8000 rotations using an ultra turrax. The mixture was stirred for 1 minute, and then ethyl acetate was distilled off to obtain a crystalline resin latex (1) having a volume average particle size of 0.17 μm.

<Method for producing crystalline resin (2) and crystalline resin latex (2)>
600 parts of dodecanedioic acid, 454 parts of 1,10-dodecanediol, and 0.43 part of dibutyltin oxide were stirred at 180 ° C. for 6 hours in a nitrogen atmosphere. Thereafter, the reaction temperature was increased to 200 ° C. under reduced pressure, and the mixture was stirred for 6 hours to obtain a crystalline resin (2) having a weight average molecular weight Mw = 26600 and a number average molecular weight Mn = 11200. Moreover, the ratio of Mw5000 or less of this resin was 8.5%. Next, 50 parts of the crystalline resin (1) is dissolved in 250 parts of ethyl acetate, and a solution obtained by dissolving 2 parts of the anionic surfactant Dowfax in 300 parts of ion-exchanged water is added. The mixture was stirred for 10 minutes, and then ethyl acetate was distilled off to obtain a crystalline resin latex (2) having a volume average particle size of 0.20 μm.

<Method for producing crystalline resin latex (3)>
The crystalline resin latex (1) and the crystalline resin latex (2) were mixed with each other so that the mass ratio of the resin amount was 17:83 to obtain a crystalline resin latex (3). The proportion of this latex having a Mw of 5000 or less was 16.0%.

<Method for producing crystalline resin latex (4)>
The crystalline resin latex (1), the resin amount, and the crystalline resin latex (2) were mixed together so that the mass ratio of the resin amount was 25:75 to obtain a crystalline resin latex (4). The ratio of the latex having a Mw of 5000 or less was 19.4%.

<Method for producing crystalline resin latex (5)>
The crystalline resin latex (1) and the crystalline resin latex (2) were mixed with each other so that the mass ratio of the resin amounts to 35:65 to obtain a crystalline resin latex (5). The ratio of the latex having a Mw of 5000 or less was 23.5%.

<Method for producing crystalline resin latex (6)>
The crystalline resin latex (1) and the crystalline resin latex (2) were mixed together so that the mass ratio of the resin amount was 11:89 to obtain a crystalline resin latex (6). The proportion of this latex having a Mw of 5000 or less was 13.5%.

<Method for producing crystalline resin latex (7)>
The crystalline resin latex (1) and the crystalline resin latex (2) were mixed with each other so that the mass ratio of the resin amount was 45:55 to obtain a crystalline resin latex (7). The ratio of the latex having an Mw of 5000 or less was 27.5%.

<Production Method of Amorphous Resin (1) and Amorphous Resin Latex (1)>
194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 133.2 parts of dodecenyl succinic anhydride, 228 parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2 , 2) -2,2-bis (4-hydroxyphenyl) propane (585 parts) and dibutyltin oxide (0.5 parts) were stirred at 160 ° C. for 6 hours in a nitrogen atmosphere. Thereafter, while gradually reducing the pressure, the reaction temperature was raised to 220 ° C., stirred for 6 hours, added with 15 parts of trimellitic anhydride, stirred for about 15 minutes, and further reduced in pressure to obtain a weight average molecular weight Mw = 12600, number average. An amorphous resin (1) having a molecular weight Mn = 5500 was obtained. 500 parts of the amorphous resin (1) is dissolved in 2500 parts of ethyl acetate, a solution obtained by dissolving 20 parts of the anionic surfactant Dowfax in 3000 parts of ion-exchanged water is added, and 20 parts at 8000 rotations using an ultra turrax. The mixture was stirred for 5 minutes, and ethyl acetate was distilled off to obtain an amorphous resin latex (1) having a volume average particle size of 0.16 μm.

<Preparation of pigment dispersion (1)>
The following composition was mixed and dissolved, and dispersed with a homogenizer (manufactured by IKA, Ultra Turrax T50) and ultrasonic irradiation to obtain a blue pigment dispersion (1) having a volume average particle diameter of 150 nm.
Cyan pigment C.I. I. Pigment Blue 15: 3
(Copper phthalocyanine, manufactured by Dainippon Ink & Chemicals, Inc.) 100 parts, anionic surfactant Neogen SC 10 parts, ion-exchanged water 200 parts

<Preparation of release agent dispersion (1)>
The following composition was mixed, heated to 97 ° C., and then dispersed with a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, the mixture was dispersed with a gorin homogenizer (manufactured by Reiwa Shoji) and treated 20 times under the conditions of 105 ° C. and 550 kg / cm ² to obtain fine particles, thereby obtaining a release agent dispersion having a volume average particle diameter of 190 nm. .
・ Ester wax (manufactured by NOF Corporation: WEP4) 100 parts ・ Anionic surfactant Neogen SC 10 parts ・ Ion-exchanged water 200 parts

<Preparation of release agent dispersion (2)>
The following composition was mixed, heated to 97 ° C., and then dispersed with a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, the mixture was dispersed by a gorin homogenizer (manufactured by Reiwa Shoji Co., Ltd.) and treated 20 times under the conditions of 105 ° C. and 550 kg / cm 2 to obtain fine particles, thereby obtaining a release agent dispersion having a volume average particle size of 200 nm.
・ 100 parts of paraffin wax (Nippon Seiwa Co., Ltd .: HNP-9) ・ 10 parts of anionic surfactant Neogen SC ・ 200 parts of ion-exchanged water

<Preparation of release agent dispersion (3)>
The following composition was mixed, heated to 97 ° C., and then dispersed with a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, the mixture was dispersed with a gorin homogenizer (manufactured by Reiwa Shoji) and treated 20 times under the conditions of 105 ° C. and 550 kg / cm ² to obtain fine particles, thereby obtaining a release agent dispersion having a volume average particle size of 200 nm. .
・ Ester wax (manufactured by NOF Corporation: WEP8) 100 parts ・ Anionic surfactant Neogen SC 10 parts ・ Ion-exchanged water 200 parts

<Preparation of Toner (1)>
A mixture of the following composition was put into a round stainless steel flask, adjusted to pH 3 with nitric acid, mixed and dispersed with Ultra Turrax T50, and the contents in the flask were stirred with an oil bath for heating. Heat to 48 ° C. and hold at 48 ° C. for 1 hour.
-Crystalline resin latex (4) (solid content 30%) 30 parts-Non-crystalline resin latex (1) (solid content 30%) 170 parts-Pigment dispersion (1) (solid content 30%) 20 parts-Release Mold dispersion (2) (solid content 30%) 30 parts / polyaluminum chloride 10% aqueous solution 20 parts / ion exchanged water 300 parts / anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 20% aqueous solution 6 copies

  Thereafter, 100 parts of an amorphous polyester resin latex and 3 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) were added to the mixture. After maintaining the temperature at 48 ° C. for 1 hour, sodium hydroxide was added to adjust the pH to 8. Thereafter, the temperature of the heating oil bath was raised and maintained at 90 ° C., and fusion and coalescence were carried out. Immediately after the stirring was stopped, the solution in the flask was rapidly cooled using a heat exchanger. The temperature lowering rate at this time was 15 ° C./min. Subsequently, the solution in the flask after cooling was filtered, thoroughly washed with ion-exchanged water, and dried to obtain toner (1).

<Preparation of Toners (2) to (8)>
In preparation of the toner (1), the types of the crystalline resin latex and the release agent dispersion were changed as shown in Table 1 to prepare toners (2) to (8). In addition, the domain size of the release agent described in Table 1 is measured under the following conditions.
First, the toner was dissolved in a solvent such as toluene heated to about 180 ° C., and then cooled to separate the release agent. 0.2 g of the obtained release agent was placed on a slide glass and heated to 200 ° C. with a hot plate or the like to be melted. A glass slide heated to 200 ° C. was placed on the molten release agent, and then cooled at a rate of −4 ° C./min. The sample sandwiched between the slide glasses was observed with a polarizing microscope, the domain size of the obtained release agent was measured, and the average value was defined as the release agent domain size.

<Preparation of developers (1) to (8)>
Toner (1) was treated with 0.5% hexamethyldisilazane-treated silica (average particle size of 40 nm) as an external additive, and titanium compound obtained by firing after treatment with 50% isobutyltrimethoxysilane in metatitanic acid (average (Particle size 30 nm) 0.7% (both mass ratio with respect to the toner) was added, mixed for 10 minutes with a Henschel mixer, then sieved with a wind sieving machine Hivolta 300 (manufactured by Shin Tokyo Kikai Co., Ltd.), and externally added. A toner was prepared.
On the other hand, for 100 parts of ferrite core having an average particle size of 50 μm, 0.15 parts of vinylidene fluoride and 1.35 parts of a copolymer of methyl methacrylate and trifluoroethylene (polymerization ratio 80:20) resin Was coated using a kneader apparatus to prepare a carrier. The obtained carrier and the externally added toner were mixed at a ratio of 100 parts: 8 parts by a V blender to prepare a developer (1).
Further, in the production of the developer (1), the toner (1) is changed into toner (2), toner (3), toner (4), toner (5), toner (6), toner (7), toner (8). ), And developers (2), (3), (4), (5), (6), (7), and (8) were produced.

The produced developer (1) has a DocuCentreColor 500 modified machine manufactured by Fuji Xerox (latent image holder, developing means, transferring means, fixing means for fixing the toner image transferred onto the transfer target, and cleaning means, Using an external fixing device with a variable fixing temperature, the image is formed on a mirror-coated paper (basis weight of 157 gsm) manufactured by Fuji Xerox Co., Ltd. with a toner loading of 13.5 g / m ^2. And fixing (Nip 6.5 mm, fixing speed 180 mm / sec, fixing temperature 160 ° C.).

For glossiness evaluation, a gloss meter (manufactured by Gardner, trade name: Micro TRI Gloss) was used to measure 60 ° gloss (A) (glossiness before wiping) of a fixed image. Thereafter, the fixed image was wiped off using a cloth, and 60 degree gloss (B) (glossiness after wiping off) was measured again. The results are shown in Table 2. The results are shown in Table 2 with 60 ° gloss (B) -60 ° gloss (A) as Δ glossiness. Furthermore, it evaluated on the following references | standards from the result of 60 degree gloss (B) and 60 degree gloss (A). The results are shown in Table 2 as judgments.
◎: No problem in actual use ○: No problem in actual use ×: Problem in actual use

  From Table 2, Examples 1-3 show that the change of the glossiness before and after wiping with a cloth is small.

1 is a conceptual diagram illustrating an example of an image forming apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Charger 3 Image writing means 4 Developing device 5 Primary transfer device 6 Cleaning device 7 Intermediate transfer belt 8 Tension roll 9 Backup roll 10 Bias roll 11 Belt cleaner 12 Voltage application roll 13 Paper feed tray 19 Roll type fixing machine 20 Pressure roll 21 Fixing roll 31 Image forming apparatus

Claims (3)

  A crystalline resin having a molecular weight of 5000 or less in terms of weight of 15% or more and 25% or less, an amorphous resin, and a colorant are melted at 200 ° C. and cooled at a cooling rate of −4 ° C./min. And a release agent having a domain size of 10 μm or less as observed with a polarizing microscope.   An electrostatic charge developing developer comprising the electrostatic image developing toner according to claim 1.   A latent image holding member, developing means for developing the electrostatic latent image formed on the latent image holding member as a toner image with a developer containing toner, and a toner image formed on the latent image holding member. A transfer unit that transfers onto the transfer member; a fixing unit that fixes the toner image transferred onto the transfer member; and a cleaning unit that cleans the transfer residual component by rubbing the latent image holding member with a cleaning member. An image forming apparatus, wherein the toner is the electrostatic charge developing toner according to claim 1.

Images