JP2018189803A - Electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic device capable of preventing occurrence of image density unevenness resulting from scratch marks on an electrophotographic photoreceptor surface.SOLUTION: An electrophotographic device comprises a toner having toner particles containing crystalline polyester, an electrophotographic photoreceptor having a support and a photosensitive layer on the support, and a cleaning blade configured to clean a surface of the electrophotographic photoreceptor. In the toner particle, distributed crystals of the crystalline polyester are observed from a toner particle surface to a depth of 0.30 μm on a cross section of the toner particle, with a transmission electron microscope. A surface layer of the electrophotographic photoreceptor contains a hardened material of a compound, where 7C or more monovalent hydrocarbon group and polymerizable functional group exist in the same molecule.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an electrophotographic apparatus.

The electrophotographic apparatus has been increased in speed and capacity, and the functions of the toner and the electrophotographic photosensitive member used are required to be improved.
The toner used in the electrophotographic apparatus is required to have low temperature fixability and storage stability. Patent Documents 1 and 2 describe toners in which a crystalline polyester is contained in a binder resin to achieve both low-temperature fixability and storage stability.
An electrophotographic photoreceptor used in an electrophotographic apparatus is required to have wear resistance. Patent Document 3 describes an electrophotographic photoreceptor in which a surface layer contains a polymerizable compound.

JP 2012-063559 A JP 2009-229920 A JP 2010-156835 A

  In an electrophotographic apparatus using an electrophotographic photosensitive member containing a polymerizable compound in the surface layer, rubbing marks may occur on the surface of the electrophotographic photosensitive member. As a result of investigations by the present inventors, it has been found that the developer (toner) carried by the developing unit rubs the electrophotographic photosensitive member, and a rubbing trace in the generatrix direction is generated on the surface of the electrophotographic photosensitive member. When the rubbing mark is generated, density unevenness due to the rubbing mark is generated in the output image.

  Accordingly, an object of the present invention is to provide an electrophotographic apparatus that does not cause uneven image density due to scratches on the surface of the electrophotographic photosensitive member.

The above object is achieved by the present invention described below.
That is, an electrophotographic apparatus according to an aspect of the present invention includes a toner having toner particles containing crystalline polyester, an electrophotographic photoreceptor having a support and a photosensitive layer on the support, and the electrophotographic photoreceptor. An electrophotographic apparatus having a cleaning blade for cleaning the surface of the toner particles, wherein the toner particles have a depth of 0.30 μm from the toner particle surface in a cross-section of the toner particles as observed by a transmission electron microscope (TEM). And the surface of the electrophotographic photoreceptor has a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule. An electrophotographic apparatus containing a product.

  According to the present invention, it is possible to provide an electrophotographic apparatus that does not cause uneven image density due to scratches on the surface of the electrophotographic photosensitive member.

(A): It is a figure which shows an example with a remarkable rub mark of an electrophotographic photoreceptor. (B): It is a figure which shows an example with a slight rubbing trace of an electrophotographic photoreceptor. 4 is a TEM image showing an example of a cross-section of toner particles in one embodiment of the present invention. It is an enlarged view of the crystal | crystallization of the crystalline polyester shown by FIG. 6 is a graph showing an example of the number distribution of the major axis lengths of crystalline polyester crystals observed in a needle shape in a toner particle cross section. 1 is a diagram illustrating an example of a configuration of an electrophotographic apparatus according to one embodiment of the present invention. It is the schematic which shows an example of a structure of the apparatus which acquires the expanded view of the external appearance of an electrophotographic photoreceptor. It is the schematic which shows an example of the press-contact shape transfer processing apparatus which forms a concave shape part in the surface of the electrophotographic photoreceptor which concerns on 1 aspect of this invention. (A): It is a top view which shows the mold used by the Example and the comparative example. (B): It is S-S 'sectional drawing in (a). (C): It is T-T 'sectional drawing in (a).

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.
An example of the scratch mark is shown in FIG. FIG. 1 is a photograph taken with a CCD camera while rotating a cylindrical electrophotographic photosensitive member, and is a development view of the appearance of the electrophotographic photosensitive member. The horizontal direction in FIG. 1 is the generatrix direction of the cylindrical photoconductor, and the vertical direction is the circumferential direction. In FIG. 1, a trace that appears white in the direction of the generatrix of the electrophotographic photosensitive member is a rubbing trace. FIG. 1 (a) is an example in which the rubbing trace is remarkable, and FIG. 1 (b) is an example in which the rubbing trace is slight. The rubbing scar part appears white due to more light scattering than the surrounding area. In an electrophotographic apparatus, image exposure is reduced due to light scattering in the rubbing scar portion, so that the density of the portion corresponding to the rubbing scar portion of the output image is reduced.

  As a result of investigations by the present inventors, it has been found that a rub mark is generated when the developer (toner) carried by the developing unit rubs the electrophotographic photosensitive member. When the rubbing trace portion was examined, the film thickness of the photosensitive layer (surface layer) at the rubbing trace portion was not changed compared to the surroundings, and only light scattering was large. Therefore, it is considered that a minute surface shape change such as sauscle has occurred in the rubbing scar. The electrophotographic photosensitive member containing a polymerizable compound in the surface layer has high film strength, so it does not scrape the entire surface, and the surface shape changes only at the strongly rubbed part, resulting in rubbing marks. it is conceivable that. When the rotation speed of the developer carrier or the electrophotographic photosensitive member is accelerated / decelerated at the time of starting / stopping the electrophotographic apparatus, the frictional force is increased only for a very short time, and a rubbing mark is generated in the direction of the generatrix of the electrophotographic photosensitive member. I think it occurred.

  In order to reduce the frictional force between the developer carried by the developing device and the electrophotographic photosensitive member, the configuration of the electrophotographic apparatus was examined in order to solve the above-mentioned problem of rubbing marks.

  As a result of investigation, a toner having toner particles containing crystalline polyester, an electrophotographic photosensitive member having a support and a photosensitive layer on the support, and a cleaning blade for cleaning the surface of the electrophotographic photosensitive member, An electrophotographic apparatus having the toner particles dispersed to a depth of 0.30 μm from the surface of the toner particles in a cross section of the toner particles observed by a transmission electron microscope (TEM). Crystals of crystalline polyester exist, and the surface layer of the electrophotographic photoreceptor contains a cured product of a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule, It was found that density unevenness caused by scratch marks on the surface of the electrophotographic photosensitive member can be improved by using the photographic apparatus.

  This mechanism is assumed as follows. First, it is known that when the crystalline polyester contained in the toner is melted, the crystalline polyester itself cries. If this crystalline polyester can be transferred to the electrophotographic photoreceptor surface, it is assumed that the frictional force can be reduced. Here, the toner particles containing the crystalline polyester crystals dispersed to a depth of 0.30 μm from the surface of the toner particles are caused by heat generated instantaneously by the cleaning blade contact portion on the surface of the electrophotographic photosensitive member. A part of the crystalline polyester melts and can be released from the toner particles. In order to liberate, it is necessary that crystalline polyester crystals that are dispersed and easily melt are present in the vicinity of the toner particle surface, that is, to a depth of 0.30 μm from the toner particle surface. On the other hand, in order to efficiently transfer the free crystalline polyester to the surface of the electrophotographic photoreceptor, the affinity between the crystalline polyester and the surface of the electrophotographic photoreceptor needs to be high. An electrophotographic photoreceptor containing a cured product of a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule in the surface layer has a high affinity with the crystalline polyester. As a result of calculating the solubility parameter, which is an affinity index, for the high affinity, the monovalent hydrocarbon having 7 or more carbon atoms compared to the compound having no monovalent hydrocarbon group having 7 or more carbon atoms The compound having a group was closer to the crystalline polyester. Further, it is assumed that the crystalline polyester is difficult to be scraped off together with the surface layer due to high wear resistance, and is likely to remain on the surface of the electrophotographic photosensitive member.

  In other words, according to the above configuration, the crystalline polyester released from the toner particles by the heat of the cleaning blade contact portion is transferred to the surface of the electrophotographic photosensitive member having a high affinity, and the developer carried on the developing device and the electrophotographic Reduces frictional force when in contact with the photoreceptor. As a result, it is assumed that rubbing traces are suppressed and the image density unevenness is improved.

  As in the above mechanism, the effects of the present invention can be achieved by the synergistic effects of the components.

〔toner〕
The toner according to the present invention has toner particles containing crystalline polyester. The toner particles have dispersed crystals of the crystalline polyester at a depth of 0.30 μm from the surface of the toner particles in the cross section of the toner particles observed by a transmission electron microscope (TEM).
The components constituting the toner are described below.

<Crystalline polyester>
The toner particles contained in the toner according to the present invention contain a crystalline polyester. The crystalline polyester is obtained by subjecting a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid as main components to a polycondensation reaction.

  The aliphatic diol preferably has 2 or more and 22 or less carbon atoms, and is preferably a chain, more preferably a linear aliphatic diol. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, pentamethylene glycol, hexamethylene glycol , Octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol. Among these, linear aliphatic such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and α, ω-diol are particularly preferable.

In addition, polyhydric alcohol monomers other than the aliphatic diols can be used.
Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomer include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like.
Among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol. 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane And aliphatic alcohols such as trimethylolpropane.

  Furthermore, you may use monohydric alcohol to such an extent that the characteristic of crystalline polyester is not impaired. Examples of the monovalent alcohol include monofunctional groups such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. Alcohol.

  The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 2 or more and 22 or less, more preferably a chain, more preferably a linear aliphatic dicarboxylic acid. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid , Fumaric acid, mesaconic acid, citraconic acid, itaconic acid, acid anhydrides or lower alkyl esters thereof hydrolyzed.

Also, polyvalent carboxylic acids other than the above aliphatic dicarboxylic acids can be used.
For example, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, These acid anhydrides or lower alkyl esters are mentioned.
Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Aromatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and the like, These acid anhydrides or derivatives such as lower alkyl esters are listed.

  Furthermore, you may contain monovalent carboxylic acid to such an extent that the characteristic of crystalline polyester is not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples thereof include monocarboxylic acids such as dodecanoic acid and stearic acid.

  By using a combination of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms, the crystalline polyester obtained has an increased order of molecular arrangement and can have high crystallinity. .

  The crystalline polyester according to the present invention can be produced according to an ordinary polyester synthesis method. For example, the above carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction in accordance with a conventional method under reduced pressure or by introducing nitrogen gas. Crystalline polyester can be obtained. The esterification or transesterification reaction can be carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary. The polycondensation reaction can be carried out using a known polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. In the esterification or transesterification reaction or the polycondensation reaction, all monomers may be charged all at once, or after reacting a divalent monomer, adding a trivalent or higher monomer and reacting sequentially. May be.

  The content of the crystalline polyester in the toner particles is preferably 2% by mass or more and 15% by mass or less.

<Binder resin>
The toner particles according to the present invention need to be present in which crystalline polyester crystals are dispersed in the toner particles. In order for the crystals to be easily dispersed in the toner particles, the toner particles preferably contain 70% by mass or more of the binder resin with respect to the entire toner particles.

  Examples of the binder resin include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, and styrene. -Vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Styrene copolymers such as polymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, naturally modified phenol resins, natural Resin-modified maleic resin Acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin (amorphous), polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin Can be mentioned.

Among these, an amorphous polyester resin is preferable, and a polyester resin having a polyhydric alcohol unit and a polycarboxylic acid unit is more preferable. In particular, a polyester resin containing an aromatic diol as a main component is preferable, and examples thereof include bisphenol represented by the formula (1) and derivatives thereof.
(In the formula, R is an ethylene group or a propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less.)

  The amorphous polyester resin is preferably used by mixing a polyester resin A having a low weight average molecular weight and a polyester resin B having a large weight average molecular weight in order to achieve both low-temperature fixability and hot offset resistance. . The mass ratio of the polyester resins A and B is preferably such that (B / (A + B)) × 100 is in the range of 20 mass% to 40 mass%.

The polyester resin A and the polyester resin B are described in detail below.
<Polyester resin A>
It is preferable that the polyester resin A contains 90 mol% or more of polyhydric alcohol units derived from an aromatic diol with respect to the total number of moles of polyhydric alcohol units.

  In addition to the aromatic diol forming the polyhydric alcohol unit, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl Glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1, 2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butane triol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxy methyl benzene.

  The polyester resin A preferably contains 90 mol% or more of a polyvalent carboxylic acid unit derived from an aromatic dicarboxylic acid or a derivative thereof based on the total number of moles of the polyvalent carboxylic acid unit. Examples thereof include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof.

  The polyester resin A preferably contains 0.1 mol% or more and 10.0 mol% or less of a polyvalent carboxylic acid unit derived from an aliphatic dicarboxylic acid or a derivative thereof with respect to the total number of moles of the polyvalent carboxylic acid unit. For example, alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid or anhydrides substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid And unsaturated dicarboxylic acids such as acid and citraconic acid or anhydrides thereof.

  Examples of the polyvalent carboxylic acid unit other than the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid include trivalent or tetravalent carboxylic acid such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and its anhydride.

<Polyester resin B>
From the viewpoint of improving the dispersibility of the crystalline polyester, the polyester resin B contains 0.1 mol% or more and 10 mol% of polyhydric alcohol units derived from oxyalkylene ethers of novolak-type phenolic resins with respect to the total number of moles of polyhydric alcohol units. It is preferable to contain 0 mol% or less.

  The oxyalkylene ether of the novolac type phenol resin is a reaction product of the novolac type phenol resin and a compound having one epoxy ring in the molecule.

  The novolak type phenolic resin is described in, for example, the section of Fenolitz Resins on page 10 of Encyclopedia of Polymer Science and Technology (Interscience Publishers). Specific examples of novolak type phenol resins include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, organic acids such as paratoluenesulfonic acid and oxalic acid, and metal salts such as zinc acetate as catalysts, and phenols and aldehydes. And those produced by polycondensation of

Examples of the phenols include phenol and substituted phenols having one or more hydrocarbon groups having 1 to 35 carbon atoms and / or halogen groups as substituents. Specific examples of the substituted phenol include cresol (ortho, meta, or para), ethylphenol, nonylphenol, octylphenol, phenylphenol, styrenated phenol, isopropenylphenol, 3-chlorophenol, 3-bromophenol, 3, 5-xylenol, 2,4-xylenol, 2,6-xylenol, 3,5-dichlorophenol, 2,4-dichlorophenol, 3-chloro-5-methylphenol, dichloroxylenol, dibromoxylenol, 2,4 , 5-trichlorophenol, 6-phenyl-2-chlorophenol and the like. Two or more phenols may be used in combination. Among these, phenol and substituted phenol substituted with a hydrocarbon group are preferable, and among them, phenol, cresol, t-butylphenol and nonylphenol are preferable. Phenol and cresol are preferable from the viewpoint of imparting cost and offset resistance of the toner, and substituted phenol substituted with a hydrocarbon group typified by t-butylphenol and nonylphenol is intended to reduce the temperature dependence of the toner charge amount. preferable.
Examples of aldehydes include formalin (formaldehyde solutions with various concentrations), paraformaldehyde, trioxane, hexamethylenetetramine and the like.

  The number average molecular weight of the novolac type phenol resin is 300 or more and 8000 or less, preferably 450 or more and 3000 or less, and more preferably 400 or more and 2000 or less. The number average number of phenolic nuclei in the novolak type phenolic resin is usually 3 or more and 60 or less, preferably 3 or more and 20 or less, and more preferably 4 or more and 15 or less. The softening point (JIS K2531; ring and ball method) is usually 40 ° C. or higher and 180 ° C. or lower, preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 130 ° C. or lower. If the softening point is 40 ° C. or higher, blocking is less likely to occur and handling becomes easier. Further, it is more preferable that the softening point is 180 ° C. or less because it is difficult to cause further gelation in the production process of the polyester resin.

  Examples of the compound having one epoxy ring in the molecule include ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, epichlorohydrin. Etc. Further, aliphatic monohydric alcohol having 1 to 20 carbon atoms or glycidyl ether of monohydric phenol can be used. Of these, EO and / or PO are preferred. The number of moles of the compound having one epoxy ring in the molecule relative to 1 mole of the novolak type phenol resin is usually 1 mole to 30 moles, preferably 2 moles to 15 moles, more preferably 2.5 moles to 10 moles. It is as follows. Moreover, the average addition mole number of the compound having one epoxy ring in the molecule with respect to one phenolic hydroxyl group in the novolak type phenol resin is usually 0.1 mol or more and 10 mol or less, preferably 0.1 mol or more and 4 mol or less. More preferably, it is 0.2 mol or more and 2 mol or less.

The structure of the oxyalkylene ether of a novolak type phenol resin is illustrated (formula (2)).
(In the formula, R is an ethylene or propylene group, x is a number of 0 or more, and y1 to y3 are 0 or more of the same or different numbers.)

  The number average molecular weight of the oxyalkylene ether of the novolak type phenol resin is 300 or more and 10,000 or less, preferably 350 or more and 5000 or less, and more preferably 450 or more and 3000 or less. When the number average molecular weight is 300 or more, the hot offset resistance of the toner is sufficiently secured, and when it is 10,000 or less, it is more preferable that gelation is difficult to be caused in the process of producing the polyester resin.

  The hydroxyl value (total of alcoholic and phenolic hydroxyl groups) of the oxyalkylene ether of the novolak type phenol resin is 10 mgKOH / g or more and 550 mgKOH / g or less, preferably 50 mgKOH / g or more and 500 mgKOH / g or less, more preferably 100 mgKOH / g or more and 450 mgKOH. / G or less. Of the hydroxyl values, the phenolic hydroxyl value is 0 mgKOH / g or more and 500 mgKOH / g or less, preferably 0 mgKOH / g or more and 350 mgKOH / g or less, more preferably 5 mgKOH / g or more and 250 mgKOH / g or less.

  A method for producing an oxyalkylene ether of a novolak type phenol resin can be obtained by subjecting a novolak type phenol resin to a compound having one epoxy ring in the molecule, if necessary, in the presence of a catalyst. The reaction temperature is 20 ° C. or higher and 250 ° C. or lower, preferably 70 ° C. or higher and 200 ° C. or lower. The reaction can be carried out under normal pressure, under pressure, or under reduced pressure. The reaction can also be carried out in the presence of a solvent or other dihydric alcohols and / or other trihydric or higher alcohols.

  As the component constituting the polyhydric alcohol unit of the polyester resin B, in addition to the oxyalkylene ether of the novolak type phenol resin, the aromatic diol, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedi Methanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentae Thritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, tri Examples include methylolpropane and 1,3,5-trihydroxymethylbenzene.

  Polyester resin B is a polyvalent carboxylic acid derived from an aliphatic dicarboxylic acid having a straight chain hydrocarbon having 4 to 16 carbon atoms as a main chain and having carboxyl groups at both ends with respect to the total number of moles of polyvalent carboxylic acid units. When the acid unit is contained in an amount of 15 mol% or more and 50 mol% or less, the dispersibility between the resins is preferably improved. Examples of such aliphatic dicarboxylic acids include adipic acid, azelaic acid, sebacic acid, alkyldicarboxylic acids such as tetradecanedioic acid and octadecanedioic acid, anhydrides thereof, and lower alkyl esters. In addition, a compound having a structure in which a part of the main chain is branched by an alkyl group such as a methyl group, an ethyl group, or an octyl group, or an alkylene group.

  Other polyvalent carboxylic acid units contained in the polyester resin B include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms. Succinic acid or anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof. Of these, carboxylic acids having aromatic rings such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides or derivatives thereof are preferred because they are easily improved in hot offset resistance. .

<Release agent (wax)>
Wax can be used as a toner release agent. Examples of the wax include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; Deoxidized part or all of fatty acid esters such as deacidified carnauba wax; Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; Unsaturated fatty acids such as brassic acid, eleostearic acid, valinalic acid; saturated alkyls such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol Polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, and melyl alcohol Esters with alcohols; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide, etc. Saturated fatty acid bisamides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N-'dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide; Aromatic bisamides such as m-xylene bis-stearic acid amide and N, N′-distearylisophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (generally metal soap and Waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; vegetable oils and fats Methyl ester compound having a hydroxyl group obtained by hydrogenation of

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance.
The addition amount of the wax is preferably 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

  The wax preferably has a peak temperature of 45 ° C. or more and 140 ° C. or less as the maximum endothermic peak temperature of the wax in the endothermic curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus. It is more preferable that the peak temperature of the maximum endothermic peak of the wax is within the above-mentioned range since toner storage stability and hot offset resistance can be highly compatible.

<Colorant>
Examples of the colorant contained in the toner particles include the following.

  Examples of the black colorant include carbon black; a yellow colorant, a magenta colorant, and a cyan colorant that are toned to black. As the colorant, a pigment may be used alone, or a dye and a pigment may be used in combination in order to improve the sharpness.

  Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of cyan toner dyes include C.I. I. Solvent Blue 70 is exemplified.

Examples of the yellow toner pigment include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of the dye for yellow toner include C.I. I. Solvent yellow 162 may be mentioned.

  The addition amount of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Charge control agent>
The toner may contain a charge control agent as necessary. As the charge control agent, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

  Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a high molecular weight compound, a high molecular weight compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene.

  Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.

The charge control agent may be added internally or externally to the toner particles.
The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Inorganic particles>
The toner may contain inorganic particles as necessary. The inorganic particles may be internally added to the toner particles, or may be externally added by mixing with the toner particles as an external additive. As the inorganic particles, inorganic fine powders such as silica, titanium oxide, and aluminum oxide are preferable. The inorganic particles may be hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As the inorganic particles for improving fluidity, inorganic fine powder having a specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable. In order to improve durability, an inorganic fine powder having a specific surface area of 10 m ² / g or more and 50 m ² / g or less is preferable. A plurality of inorganic fine powders may be used in combination.

  The addition amount of the inorganic particles is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the inorganic particles.

<Magnetic carrier>
The toner can be used as a one-component developer not mixed with a magnetic carrier or a two-component developer mixed with a magnetic carrier.

  Carriers used in two-component developers include metal particles such as oxidized iron powder, non-oxidized iron powder, iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, etc. A known carrier such as a magnetic material such as an alloy particle, oxide particle or ferrite, or a magnetic material-dispersed resin carrier in which the magnetic material is dispersed in a resin can be used.

  The mixing ratio of the toner in the two-component developer is preferably 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 13% by mass or less.

<Toner production method>
For the toner production method, known means such as a pulverization method or a polymerization method can be used. In particular, a pulverization method in which materials are uniformly kneaded and pulverized is preferable in order to make dispersed crystalline polyester crystals exist in the vicinity of the toner particle surfaces.

  Hereinafter, an example of a toner production procedure in the pulverization method will be described. However, the production method is not limited to the pulverization method as long as the dispersed state of the crystalline polyester crystal according to the present invention is achieved.

  First, the materials are mixed. A predetermined amount of materials constituting toner particles such as a binder resin, crystalline polyester, a colorant, and, if necessary, wax, a charge control agent, and inorganic particles are weighed and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.). A mixture of materials is obtained by a mixing process.

  Next, the mixture is melt-kneaded. As the melt-kneading apparatus, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Among these, from the viewpoint of continuity, a single or twin screw extruder is preferable. For example, a KTX type twin screw extruder (manufactured by Kobe Steel), a TEM type twin screw extruder (manufactured by Toshiba Machine), a PCM kneader. (Ikegai), twin screw extruder (manufactured by Kay C.K.), co-kneader (manufactured by Buss), kneedex (manufactured by Nihon Coke Kogyo Co., Ltd.) and the like. A melt-kneaded product is obtained by a melt-kneading process. Further, the melt-kneaded product may be rolled or cooled with a two-roll roll or the like. The dispersion state of the crystalline polyester can be controlled by the temperature condition of melt kneading and cooling.

  Next, the melt-kneaded product is pulverized to a desired particle size. The pulverization is preferably performed in two stages of coarse pulverization and fine pulverization. Examples of the apparatus used for coarse pulverization include crushers such as a crusher, a hammer mill, and a feather mill. Examples of the apparatus used for the fine pulverization include a kryptron system (manufactured by Earth Technica), a super rotor (manufactured by Nisshin Engineering), a turbo mill (manufactured by Freund Turbo), and an air jet system. Toner particles pulverized by the pulverization step are obtained.

  Further, the pulverized toner particles may be classified. For classification, classifiers such as inertial class elbow jet (manufactured by Nippon Steel Mining), centrifugal classifier turboplex (made by Hosokawa Micron), TSP separator (made by Hosokawa Micron), Faculty (made by Hosokawa Micron), Or a sieving machine can be used. Among them, Faculty (manufactured by Hosokawa Micron) can perform spheroidization of toner particles simultaneously with classification. Toner particles classified by the above classification process are obtained.

  Further, inorganic particles may be externally added to the toner particles. For example, a predetermined amount of toner particles and inorganic particles can be blended, stirred and mixed for external addition. Examples of the apparatus used for external addition include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechanohybrid (manufactured by Nihon Coke Industries Co., Ltd.), and a nobilta (manufactured by Hosokawa Micron).

  Further, the surface of the toner particles may be modified using light or heat. By surface modification, for example, the degree of circularity and the adhesion force of inorganic particles can be controlled. In addition, the crystalline polyester crystal near the toner particle surface is made compatible with the binder resin and precipitated again, whereby the crystalline polyester crystal can be refined. Of these, surface modification by heat is preferable from the viewpoint of productivity.

[Evaluation of toner]
The evaluation of various physical properties of the toner will be described below.

<Evaluation of crystalline state of crystalline polyester by TEM observation>
The crystalline state of the crystalline polyester can be evaluated by observing the cross section of the toner (toner particles) with a transmission electron microscope (TEM). By analyzing the obtained cross-sectional image, “whether dispersed crystalline polyester crystals exist to a depth of 0.30 μm from the toner particle surface” or “whether crystalline polyester crystals are dispersed” , "Number distribution of major axis length of crystalline polyester crystal" can be evaluated.

  First, a toner cross-section sample was prepared. Using an osmium plasma coater (filgen, OPC80T), the toner is coated with an Os film (5 nm) and a naphthalene film (20 nm) as a protective film, and embedded with a photo-curing resin D800 (JEOL). A toner cross-section sample having a film thickness of 60 to 70 nm was prepared at a cutting speed of 1 mm / s using a sonic ultramicrotome (Leica, UC7).

Next, the toner cross section sample was dyed with ruthenium. The resulting vacuum electron stainer samples (Filgen Co., VSC4R1H) was used to stain for 15 minutes with RuO ₄ gas 500Pa atmosphere. By ruthenium staining, the crystalline polyester can be identified as a difference in contrast. Crystalline polyester is dyed weaker than the organic components constituting the interior of the toner. This is because the penetration of the dyeing material is different between the crystalline polyester and the organic component inside the toner for reasons such as a difference in density. Since the amount of ruthenium atoms varies depending on the intensity of the staining, the strongly stained portion does not transmit the electron beam, so it is black on the observation image, and the weakly stained portion is easily transmitted through the electron beam, and thus becomes white on the observation image.

  The stained sample was subjected to STEM observation using TEM (JEOL, JEM2800). The STEM probe size was 1 nm, and the image size was 1024 × 1024 pixels.

  Cross-sectional observation was performed on 20 randomly selected toner particles, and “whether dispersed crystalline polyester crystals exist from the toner particle surface to a depth of 0.30 μm” was determined. Here, the dispersed state is a state in which crystals of crystalline polyester having a major axis length of less than 500 nm are distributed independently. An example of the obtained cross-sectional image is shown in FIG. The crystalline domains of the crystalline polyester can be confirmed as black needles (bars). It can be seen that the toner particles have dispersed crystalline polyester crystals from the toner particle surface to a depth of 0.30 μm.

  Next, the cross-sectional image was binarized with image processing software Image-Pro Plus (manufactured by Media Cybernetics) to extract a crystal, and the major axis length of the crystal was measured. Here, the major axis length of the crystalline domain of the crystalline polyester is the longest distance in the crystalline domain of the cross-sectional image shown by a in FIG. For 20 toner particles randomly selected, a “number distribution of major axis lengths of crystalline polyester crystals” was prepared. From this number distribution, “whether it has a peak at 300 nm or less” and “whether a crystal cross section with a major axis length of 100 nm or more and 250 nm or less exists at 30% by number or more” were obtained. FIG. 4 shows the number distribution of the lengths of the major axes of the crystalline polyester crystals observed in a needle shape in the toner cross section. The broken line is an example of a toner having no peak at 300 nm or less and a crystal cross section having a size of 100 nm or more and 250 nm or less having a crystal cross section of less than 30% by number. The solid line is an example of a toner having a peak at 300 nm or less and having a crystal cross section with a size of 100 nm to 250 nm in an amount of 30% by number or more.

  The toner particles in the present invention can improve scratch marks by the presence of dispersed crystalline polyester crystals from the toner particle surface to a depth of 0.30 μm. In addition, toner particles having a peak at 300 nm or less in the number distribution of the major axis length of the crystal are preferable because the effect of improving scratch marks is high. Further, in the number distribution of the major axis length of the crystal, toner particles having a crystal cross section with a major axis length of 100 nm to 250 nm of 30% by number or more are preferable because the effect of improving the scratch marks is higher. For this reason, when the crystalline polyester is transferred to the electrophotographic photosensitive member, it is necessary that crystals be present in the vicinity of the surface of the toner particles. The finer the particles or the more uniformly the crystals are dispersed, the more the cleaning blade becomes. It is expected to be easily melted by heat and highly effective in improving scratch marks.

<Measurement of endothermic amount ΔH derived from crystalline polyester>
By measuring the endothermic amount ΔH of the crystalline polyester in the toner, the content of the crystalline polyester can be known. The endothermic amount ΔH derived from the crystalline polyester can be measured using DSC Q1000 (manufactured by TA Instruments).
The conditions of the apparatus were as follows.
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
For the temperature correction of the device detector, the melting points of indium and zinc were used, and for the correction of heat quantity, the heat of fusion of indium was used. About 5 mg of toner was precisely weighed and placed in a silver pan for measurement. The maximum endothermic peak was obtained using the toner as a sample, and the endothermic amount (ΔH) was obtained from the peak area by calculation using analysis software attached to the apparatus. When endothermic peaks of other components overlap, the endothermic amount was subtracted.

  If the endothermic amount (ΔH) derived from the crystalline polyester is less than 1.0 J / g, the amount of the crystalline polyester may be small, and if it is more than 5.0 J / g, the crystalline polyester crystal aggregates to form crystals in the toner. There may be a large number of portions where the reactive polyester does not exist. It is preferable that the endothermic amount (ΔH) derived from the crystalline polyester is 1.0 J / g or more and 5.0 J / g or less because the effect of improving scratch marks is higher.

[Electrophotographic photoreceptor]
The electrophotographic photoreceptor according to the present invention has a support and a photosensitive layer on the support, and the surface layer contains a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule. It contains a cured product of the compound in the above.
Examples of the method for producing the electrophotographic photoreceptor according to the present invention include a method in which a coating solution for each layer described later is prepared, applied in the order of desired layers, and dried. At this time, examples of the coating method of the coating liquid include dip coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, and ring coating. Among these, dip coating is preferable from the viewpoints of efficiency and productivity.
Hereinafter, each layer will be described.

<Support>
In the present invention, the electrophotographic photosensitive member has a support. In the present invention, the support is preferably a conductive support having conductivity. Moreover, examples of the shape of the support include a cylindrical shape, a belt shape, and a sheet shape. Among these, a cylindrical support is preferable. Further, the surface of the support may be subjected to electrochemical treatment such as anodic oxidation, blast treatment, cutting treatment or the like.
As the material for the support, metal, resin, glass and the like are preferable.
Examples of the metal include aluminum, iron, nickel, copper, gold, stainless steel, and alloys thereof. Among these, an aluminum support using aluminum is preferable.
In addition, the resin or glass may be imparted with conductivity by a treatment such as mixing or coating with a conductive material.

<Conductive layer>
In the present invention, a conductive layer may be provided on the support. By providing the conductive layer, it is possible to conceal scratches and irregularities on the surface of the support and to control light reflection on the surface of the support.
The conductive layer preferably contains conductive particles and a resin.

Examples of the material of the conductive particles include metal oxide, metal, carbon black and the like.
Examples of the metal oxide include zinc oxide, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, and bismuth oxide. Examples of the metal include aluminum, nickel, iron, nichrome, copper, zinc, silver and the like.
Among these, it is preferable to use a metal oxide as the conductive particles, and it is particularly preferable to use titanium oxide, tin oxide, or zinc oxide.

When a metal oxide is used as the conductive particles, the surface of the metal oxide may be treated with a silane coupling agent or the like, or an element such as phosphorus or aluminum or an oxide thereof may be doped into the metal oxide.
Moreover, electroconductive particle is good also as a laminated structure which has a core material particle and the coating layer which coat | covers the core material particle. Examples of the core material particles include titanium oxide, barium sulfate, and zinc oxide. Examples of the coating layer include metal oxides such as tin oxide.
Moreover, when using a metal oxide as electroconductive particle, it is preferable that the volume average particle diameters are 1 nm or more and 500 nm or less, and it is more preferable that they are 3 nm or more and 400 nm or less.

  Examples of the resin include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, alkyd resin, and the like.

The conductive layer may further contain a masking agent such as silicone oil, resin particles, and titanium oxide.
The average film thickness of the conductive layer is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.

  The conductive layer can be formed by preparing a coating liquid for a conductive layer containing each of the above materials and solvent, forming this coating film, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. Examples of the dispersion method for dispersing the conductive particles in the coating liquid for the conductive layer include a method using a paint shaker, a sand mill, a ball mill, and a liquid collision type high-speed disperser.

<Underlayer>
In the present invention, an undercoat layer may be provided on the support or the conductive layer. By providing the undercoat layer, the adhesion function between the layers can be enhanced, and a charge injection blocking function can be provided.

The undercoat layer preferably contains a resin. Moreover, you may form an undercoat layer as a cured film by superposing | polymerizing the composition containing the monomer which has a polymerizable functional group.
Polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl phenol resin, alkyd resin, polyvinyl alcohol resin, polyethylene oxide resin, polypropylene oxide resin, polyamide resin , Polyamic acid resin, polyimide resin, polyamideimide resin, cellulose resin and the like.
As the polymerizable functional group that the monomer having a polymerizable functional group has, an isocyanate group, a blocked isocyanate group, a methylol group, an alkylated methylol group, an epoxy group, a metal alkoxide group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, Examples thereof include a carboxylic acid anhydride group and a carbon-carbon double bond group.

The undercoat layer may further contain an electron transport material, a metal oxide, a metal, a conductive polymer, and the like for the purpose of improving electrical characteristics. Among these, it is preferable to use an electron transport material and a metal oxide.
Examples of the electron transport material include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, halogenated aryl compounds, silole compounds, and boron-containing compounds. . An undercoat layer may be formed as a cured film by using an electron transport material having a polymerizable functional group as the electron transport material and copolymerizing with the monomer having the polymerizable functional group described above.
Examples of the metal oxide include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, and silicon dioxide. Examples of the metal include gold, silver, and aluminum.
The undercoat layer may further contain an additive.

The average thickness of the undercoat layer is preferably from 0.1 μm to 50 μm, more preferably from 0.2 μm to 40 μm, and particularly preferably from 0.3 μm to 30 μm.
The undercoat layer can be formed by preparing a coating solution for the undercoat layer containing the above-described materials and solvent, forming this coating film, and drying and / or curing it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

<Photosensitive layer>
The photosensitive layer of the electrophotographic photoreceptor is mainly classified into (1) a multilayer type photosensitive layer and (2) a single layer type photosensitive layer. (1) The laminated photosensitive layer has a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. (2) The single-layer type photosensitive layer has a photosensitive layer containing both a charge generation material and a charge transport material.

(1) Laminated Photosensitive Layer The laminated photosensitive layer has a charge generation layer and a charge transport layer.

(1-1) Charge Generation Layer The charge generation layer preferably contains a charge generation material and a resin.
Examples of the charge generation material include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments, and hydroxygallium phthalocyanine pigments are preferable.
The content of the charge generation material in the charge generation layer is preferably 40% by mass to 85% by mass and more preferably 60% by mass to 80% by mass with respect to the total mass of the charge generation layer. preferable.

  The resin includes polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, polyvinyl acetate resin. And polyvinyl chloride resin. Among these, polyvinyl butyral resin is more preferable.

  The charge generation layer may further contain additives such as an antioxidant and an ultraviolet absorber. Specific examples include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

The average film thickness of the charge generation layer is preferably from 0.1 μm to 1 μm, and more preferably from 0.15 μm to 0.4 μm.
The charge generation layer can be formed by preparing a coating solution for a charge generation layer containing the above-described materials and solvent, forming this coating film, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

(1-2) Charge Transport Layer The charge transport layer preferably contains a charge transport material and a resin.

Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these materials. It is done. Among these, a triarylamine compound and a benzidine compound are preferable.
The content of the charge transport material in the charge transport layer is preferably 25% by mass to 70% by mass and more preferably 30% by mass to 55% by mass with respect to the total mass of the charge transport layer. preferable.

Examples of the resin include polyester resin, polycarbonate resin, acrylic resin, and polystyrene resin. Among these, polycarbonate resin and polyester resin are preferable. As the polyester resin, polyarylate resin is particularly preferable.
The content ratio of the charge transport material to the resin (the mass of the charge transport material in the charge transport layer: the mass of the resin in the charge transport layer) is preferably 4:10 to 20:10, and 5:10 to 12:10. Is more preferable.

  Further, the charge transport layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improving agent. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oil, fluorine resin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles Etc.

The average film thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, more preferably 8 μm or more and 40 μm or less, and particularly preferably 10 μm or more and 30 μm or less.
The charge transport layer can be formed by preparing a coating solution for a charge transport layer containing the above-described materials and solvent, forming this coating film, and drying it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. Among these solvents, ether solvents or aromatic hydrocarbon solvents are preferable.

(2) Single-layer type photosensitive layer A single-layer type photosensitive layer is formed by preparing a coating solution for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin and a solvent, forming this coating film, and drying it. can do. The charge generating substance, charge transporting substance, and resin are the same as those exemplified in the above-mentioned “(1) Multilayer type photosensitive layer”.

<Protective layer>
In the present invention, a protective layer may be provided on the photosensitive layer. By providing the protective layer, durability can be improved.
The protective layer preferably contains conductive particles and / or a charge transport material and a resin.

Examples of the conductive particles include metal oxide particles such as titanium oxide, zinc oxide, tin oxide, and indium oxide.
Examples of the charge transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these materials. Among these, a triarylamine compound and a benzidine compound are preferable.
Examples of the resin include polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, and epoxy resin. Among these, polycarbonate resin, polyester resin, and acrylic resin are preferable.

  Further, the protective layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group. Examples of the reaction at that time include a thermal polymerization reaction, a photopolymerization reaction, and a radiation polymerization reaction. Examples of the polymerizable functional group possessed by the monomer having a polymerizable functional group include an acryl group and a methacryl group. As the monomer having a polymerizable functional group, a material having a charge transporting ability may be used.

  The protective layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oil, fluorine resin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles Etc.

The average film thickness of the protective layer is preferably 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 7 μm or less.
The protective layer can be formed by preparing a coating liquid for the protective layer containing each of the above materials and solvent, forming this coating film, and drying and / or curing it. Examples of the solvent used for the coating solution include alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, and aromatic hydrocarbon solvents.

<Surface layer>
The surface layer of the electrophotographic photosensitive member according to the present invention may be the protective layer, the charge transport layer, or the photosensitive layer itself in the case of a single layer type photosensitive member. However, it is a surface layer containing a cured product of a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule. Such a surface layer has high affinity with crystalline polyester and can improve scratch marks.

The monovalent hydrocarbon group having 7 or more carbon atoms may be linear or branched. In the case of a branched hydrocarbon group, the total of the carbon number of the main chain and the carbon number of the branched chain is 7 or more.
When the number of carbon atoms is less than 7, the affinity with the crystalline polyester is insufficient and the transfer of the crystalline polyester to the surface of the electrophotographic photosensitive member becomes insufficient. The number of monovalent hydrocarbon groups having 7 or more carbon atoms contained in one molecule of the compound may be one or more, and may be plural. Examples of the polymerizable functional group include a hydroxyl group, an acryl group, a methacryl group, and an oxiranyl group. The number of polymerizable functional groups contained in one molecule of the compound may be one or more.

As the compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule, a compound of the formula (I) is preferable.
In formula (I), R ¹ is a hydrogen atom or a methyl group. R ² is a linear alkyl group having 7 or more carbon atoms or a branched alkyl group having 7 or more carbon atoms.

  Furthermore, you may further contain the other compound which has several polymeric functional group in order to improve abrasion resistance. The surface layer preferably contains a cured product that is a copolymer of the compound of formula (I) and a hole transporting compound having a polymerizable functional group.

  For the purpose of further stabilizing the behavior of the cleaning blade (cleaning means) brought into contact with the electrophotographic photosensitive member, it is more preferable to provide a concave or convex portion on the surface layer of the electrophotographic photosensitive member.

  The concave portion or the convex portion may be formed on the entire surface of the electrophotographic photosensitive member, or may be formed on a part of the surface of the electrophotographic photosensitive member. When the concave portion or the convex portion is formed on a part of the surface of the electrophotographic photosensitive member, it is preferable that the concave portion or the convex portion is formed at least over the entire contact area with the cleaning blade.

  When forming the recesses, the molds having projections corresponding to the recesses are pressed against the surface of the electrophotographic photosensitive member, and shape transfer is performed, whereby the recesses can be formed on the surface of the electrophotographic photosensitive member.

FIG. 7 shows an example of a press-contact shape transfer processing apparatus for forming concave portions on the surface of the electrophotographic photosensitive member.
According to the press-fitting shape transfer processing apparatus shown in FIG. 7, while rotating the electrophotographic photosensitive member 51, which is a workpiece, the mold 52 is continuously brought into contact with the surface (circumferential surface) and pressurized, A concave portion or a flat portion can be formed on the surface of the photoconductor 51.

  Examples of the material of the pressing member 53 include metals, metal oxides, plastics, and glass. Among these, stainless steel (SUS) is preferable from the viewpoint of mechanical strength, dimensional accuracy, and durability. The pressure member 53 is provided with a mold 52 on its upper surface. Further, the mold 52 is brought into contact with the surface of the electrophotographic photosensitive member 51 supported by the support member 54 with a predetermined pressure by a support member (not shown) and a pressure system (not shown) installed on the lower surface side. Can do. Further, the support member 54 may be pressed against the pressure member 53 with a predetermined pressure, or the support member 54 and the pressure member 53 may be pressed against each other.

  In the example shown in FIG. 7, the pressing member 53 is moved in the direction perpendicular to the axial direction of the electrophotographic photosensitive member 51, so that the surface of the electrophotographic photosensitive member 51 is continuously processed while being driven or driven and rotated. This is an example. Further, by fixing the pressure member 53 and moving the support member 54 in a direction perpendicular to the axial direction of the electrophotographic photosensitive member 51, or by moving both the support member 54 and the pressure member 53, The surface of the electrophotographic photoreceptor 51 can also be processed continuously.

  Note that it is preferable to heat the mold 52 and the electrophotographic photosensitive member 51 from the viewpoint of efficiently performing shape transfer.

  As the mold 52, for example, (i) a finely processed metal or resin film, (ii) a surface of a silicon wafer or the like patterned with a resist, (iii) a resin film in which fine particles are dispersed, (iv ) A metal film coated on a resin film having a fine surface shape.

[Electrophotographic equipment]
An electrophotographic apparatus according to the present invention has the toner and the electrophotographic photosensitive member described so far, and has a cleaning blade for cleaning the surface of the electrophotographic photosensitive member.

FIG. 5 shows an example of a schematic configuration of the electrophotographic apparatus.
Reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow about an axis 2. The surface of the electrophotographic photoreceptor 1 is charged to a predetermined positive or negative potential by the charging unit 3. Although FIG. 5 shows a roller charging method using a roller-type charging member, a charging method such as a corona charging method, a proximity charging method, or an injection charging method may be adopted. The surface of the charged electrophotographic photosensitive member 1 is irradiated with exposure light 4 from an exposure means (not shown), and an electrostatic latent image corresponding to target image information is formed. The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed with toner accommodated in the developing means 5, and a toner image is formed on the surface of the electrophotographic photosensitive member 1. The toner image formed on the surface of the electrophotographic photoreceptor 1 is transferred to the transfer material 7 by the transfer means 6. The transfer material 7 onto which the toner image has been transferred is conveyed to the fixing means 8, undergoes a toner image fixing process, and is printed out of the electrophotographic apparatus. The electrophotographic apparatus includes a cleaning unit 9 including a cleaning blade for removing deposits such as toner remaining on the surface of the electrophotographic photosensitive member 1 after transfer. The electrophotographic apparatus may have a static elimination mechanism that neutralizes the surface of the electrophotographic photosensitive member 1 with pre-exposure light 10 from pre-exposure means (not shown). Further, the process cartridge 11 may be provided with some including at least the electrophotographic photosensitive member 1. The process cartridge 11 may be provided with guide means 12 such as a rail for detachment from the main body of the electrophotographic apparatus.

[Cleaning blade]
The cleaning unit 9 includes a cleaning blade as a cleaning member of the electrophotographic photosensitive member 1, a waste toner conveying screw, and a housing. The cleaning blade is brought into contact with the electrophotographic photoreceptor 1 at a predetermined angle and pressure by the pressurizing means. As a result, the toner remaining on the surface of the electrophotographic photosensitive member 1 is scraped and removed from the electrophotographic photosensitive member 1 by the cleaning blade.

  There are two types of pressing methods for the cleaning blade: a fixed system and a spring pressing system. The fixed system is a method of generating pressure with a mechanical intrusion amount. The spring pressure system is a method in which the blade is pressed against the electrophotographic photosensitive member by a spring. In the case of the spring pressurization system, the cleaning blade is installed so as to be rotatable with respect to the swing center, and is pressed against the electrophotographic photosensitive member by the spring. The angle in the spring pressure system is the angle formed by the tangent line of the electrophotographic photosensitive member at the contact point between the electrophotographic photosensitive member and the cleaning blade, and the angle formed by the line connecting the swing center and the contact point and the tangent line is defined as the swing angle. Call. In this embodiment, a spring pressurization system is selected. A preferable range of the angle is a set angle of 15 ° to 35 ° and a swing angle of 2 ° to 30 °. The pressure (linear pressure) is preferably 10 gf / cm or more and 60 gf / cm or less.

  As a material for the cleaning blade, a urethane-based elastic material is widely used, and is used in a form in which a flat elastic material is supported by a metal sheet metal. The cleaning blade is required to have toner cleaning properties and wear resistance, and is made of an elastic material having a hardness of 60 degrees to 85 degrees according to the IRHD hardness test method M method (micro method) and a rebound resilience of 10% to 40%. Preferably used. The hardness and impact resilience of the blade may be uniform, or may be changed at the contact portion with the electrophotographic photosensitive member or the blade longitudinal end portion. As a method for changing hardness and impact resilience, there are a two-color molding method in which another material is bonded, and a method in which curing is accelerated by applying a curing agent and then promoting curing.

  The electrophotographic apparatus according to one embodiment of the present invention can be used for a laser beam printer, an LED printer, a copying machine, a facsimile, a complex machine of these, and the like.

  The present invention will be described in more detail with specific examples. In the examples, “part” means “part by mass”.

[Production Example of Polyester Resin A as Binder Resin]
(First reaction step)
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple.
・ 2,2-bis (4-hydroxyphenyl) propane: 64.7 parts by mass (0.18 mol; 100.0 mol% based on the total number of polyhydric alcohols)
-Terephthalic acid: 24.1 parts by mass (0.15 mol; 96.0 mol% based on the total number of polyvalent carboxylic acids)
-Titanium tetrabutoxide (esterification catalyst): 0.5 part by mass After the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180 ° C., and returned to atmospheric pressure.

(StAc conversion reaction step)
Next, the following mixture was dropped with a dropping funnel over 1 hour and held for 1 hour.
Acrylic acid: 0.2 parts by mass Styrene: 8.2 parts by mass 2-ethylhexyl acrylate: 1.6 parts by mass Dibutyl peroxide (polymerization initiator): 1.5 parts by mass

(Second reaction step)
Next, the following materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was performed for 1 hour while maintaining the temperature at 160 ° C.
Trimellitic anhydride: 1.2 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
-Tert-butylcatechol (polymerization inhibitor): 0.1 mass part Polyester resin A whose weight average molecular weight (Mw) is 5000 was obtained as mentioned above.

[Production Example of Polyester Resin B1 as Binder]
(First reaction step)
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple.
・ 2,2-bis (4-hydroxyphenyl) propane: 68.2 parts by mass (0.19 mol; 97.0 mol% based on the total number of moles of polyhydric alcohol)
・ Novolac type phenol resin (ethylene oxide 5 mol adduct having about 5 cores): 4.4 parts by mass (0.01 mol; 3.0 mol% based on the total number of polyhydric alcohols)
-Terephthalic acid: 15.0 parts by mass (0.09 mol; 55.0 mol% based on the total number of polycarboxylic acids)
Adipic acid: 6.0 parts by mass (0.04 mol; 25.0 mol% based on the total number of polyvalent carboxylic acids)
Titanium tetrabutoxide: 0.5 part by mass After the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200 ° C. Furthermore, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, and then returned to atmospheric pressure.

(Second reaction step)
Next, the following materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was performed for 15 hours while maintaining the temperature at 160 ° C.
Trimellitic anhydride: 6.4 parts by mass (0.03 mol; 20.0 mol% based on the total number of polycarboxylic acids)
As described above, a polyester resin B1 having a weight average molecular weight (Mw) of 90000 was obtained.

[Production Example of Polyester Resin B2 as Binder Resin]
In the production example of the polyester resin B1, a polyester resin B2 having a weight average molecular weight (Mw) of 100,000 was obtained using the same production method as the polyester resin B1 except that no novolak type phenol resin was not used in the first reaction step. .

[Production Example of Crystalline Polyester C1]
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple.
-1,10-decanediol: 46.9 parts by mass (0.27 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
-Sebacic acid: 53.1 parts by mass (0.26 mol; 100.0 mol% based on the total number of polyvalent carboxylic acids)
After replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.
Next, the following materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was performed for 4 hours while maintaining the temperature at 200 ° C.
-Tin 2-ethylhexanoate: 0.5 mass part Crystalline polyester C1 was obtained as mentioned above.

[Production Example of Crystalline Polyester C2]
A crystalline polyester C2 was obtained in the same manner as in the production example of the crystalline polyester C1, except that 1,6-decanediol was changed to 1,6-hexanediol and sebacic acid was changed to fumaric acid.

[Production Example of Crystalline Polyester C3]
The following materials were weighed in a reaction vessel equipped with a stirrer, a thermometer, and an outflow cooler.
Diethylene glycol: 108.2 parts by mass (1.02 mol)
・ 1,10-decanedicarboxylic acid: 230.3 parts by mass (1.00 mol)
-Tetrabutyl titanate: 0.50 mass part Then, esterification reaction was performed at 190 degreeC for 5 hours. Next, the temperature was raised to 220 ° C., the pressure inside the system was gradually reduced, and a polycondensation reaction was performed at 150 Pa for 2 hours. After returning to normal pressure, the following materials were added and reacted at 220 ° C. for 2 hours.
Benzoic acid: 24.4 parts by mass (0.20 mol)
Crystalline polyester C3 was obtained as described above.

[Production Example of Crystalline Polyester C4]
The polycondensation reaction was carried out by the same production method as for crystalline polyester C3. After returning to normal pressure, the following materials were added and reacted at 220 ° C. for 2 hours.
Benzoic acid: 24.4 parts by mass (0.20 mol)
Trimellitic acid: 10.5 parts by mass (0.05 mol)
Crystalline polyester C4 was obtained as described above.

<Production example of toners 1 to 5>
The following materials were mixed using a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industries Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, and then a twin-screw kneader (PCM-) set at a temperature of 130 ° C. 30 type, manufactured by Ikegai Co., Ltd.) at the kneading discharge temperature shown in Table 1.
-Polyester resin A as binder resin: 82 parts by mass-Polyester resin B1 or B2 as binder resin: 18 parts by mass-Crystalline polyester C1 or C2: Number of parts (parts by mass) described in Table 1
Hydrocarbon wax (peak temperature of maximum endothermic peak 78 ° C.): 2 parts by mass I. Pigment Blue 15: 3: 5 parts by mass · Aluminum 3,5-di-t-butylsalicylate compound: 0.5 parts by mass

The obtained kneaded product was cooled at a cooling rate shown in Table 1, and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product. The resulting coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo). Further, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions were a classification rotor rotational speed of 130 s ⁻¹ and a distributed rotor rotational speed of 120 s ⁻¹ .

To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica fine particles having a BET specific surface area of 25 m ² / g surface-treated with 4% by mass of hexamethyldisilazane and BET surface-treated with 10% by mass of polydimethylsiloxane. 0.8 parts by mass of hydrophobic silica fine particles having a specific surface area of 100 m ² / g were added and mixed with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industries, Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. Toner particles were obtained.

  As shown in Table 1, toners 1 to 5 were produced by changing the type and number of parts (parts by mass), kneading discharge temperature, and cooling rate after kneading of the binder resin and crystalline polyester.

<Production Example of Toner 6>
After adding 450 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 720 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution. Was added to obtain an aqueous medium containing a dispersion stabilizer.

Separately, the following materials were uniformly dispersed and mixed using an attritor (Nihon Coke Kogyo Co., Ltd.).
Styrene: 74 parts by mass n-butyl acrylate: 26 parts by mass Divinylbenzene: 0.5 parts by mass Crystalline polyester C3: 5 parts by mass Crystalline polyester C4: 5 parts by mass Negative charge control agent (T- 77 (Hodogaya Chemical Co., Ltd.)): 1 part by mass

  This dispersion mixture was heated to 60 ° C., 10 parts by mass of paraffin wax (maximum endothermic peak 78 ° C. in DSC, Mn = 500, Mw = 660) was added and mixed and dissolved. Next, 4.5 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to obtain a polymerizable monomer composition.

  The polymerizable monomer composition was charged into the aqueous medium, and granulated by stirring at 15,000 rpm for 10 minutes using a TK homomixer (manufactured by Primics Co., Ltd.) in a nitrogen atmosphere at 60 ° C. Then, after stirring for 5 hours at 70 ° C. while stirring with a paddle stirring blade, the temperature was raised to 90 ° C. and stirring was continued for 2 hours. After completion of the reaction, the suspension was cooled and hydrochloric acid was added to dissolve the dispersant, followed by filtration, washing with water and drying to obtain toner particles.

To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica fine particles having a BET specific surface area of 25 m ² / g surface-treated with 4% by mass of hexamethyldisilazane and BET surface-treated with 10% by mass of polydimethylsiloxane. 0.8 part by mass of hydrophobic silica fine particles having a specific surface area of 100 m ² / g was added and mixed with a Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min to obtain toner 6. .

  When the cross-section of the toner 6 was observed using a TEM, it was confirmed that the crystalline polyester was not in a finely dispersed state but existed as a lamellar structure having a major axis length of about 1400 nm.

<Evaluation of Toners 1 to 6>
For the toners 1 to 6, the crystalline state of the crystalline polyester was evaluated by TEM observation and the endothermic amount ΔH derived from the crystalline polyester was measured by the method described in the toner evaluation. The results are shown in Table 2.

[Production example of magnetic carrier]
Magnetic core particles were produced.

(Process 1: Weighing and mixing process)
The ferrite raw material was weighed as follows.
・ Fe ₂ O ₃ : 60.2 mass%
· MnCO _3: 33.9 mass%
Mg (OH) ₂ : 4.8% by mass
・ SrCO ₃ : 1.1% by mass
Then, it was pulverized and mixed for 2 hours in a dry ball mill using zirconia (φ10 mm) balls.

(Step 2: Temporary firing step)
After pulverization and mixing, firing was performed at 1000 ° C. for 3 hours in the air using a burner-type firing furnace to prepare calcined ferrite. The composition of the ferrite was:
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.39, b = 0.11, c = 0.01, and d = 0.50.

(Process 3: Grinding process)
The calcined ferrite was pulverized to about 0.5 mm with a crusher. Using zirconia (φ10 mm) balls, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite, and the mixture was pulverized with a wet ball mill for 2 hours. Subsequently, it was pulverized for 4 hours by a wet bead mill using zirconia beads (φ1.0 mm) to obtain a ferrite slurry.

(Process 4; Granulation process)
To the ferrite slurry, 2.0 parts by mass of polyvinyl alcohol was added as a binder with respect to 100 parts by mass of calcined ferrite, and granulated into spherical particles of about 36 μm with a spray dryer (manufactured by Okawara Chemical Co., Ltd.).

(Step 5; main firing step)
Firing was performed at 1150 ° C. for 4 hours in an electric furnace in a nitrogen atmosphere (oxygen concentration of 1.00% by volume or less).

(Step 6; selection step)
After the aggregated particles were crushed, coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain magnetic core particles.

Next, a coating resin was produced.
The following materials were added to a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube and stirrer.
-Cyclohexyl methacrylate monomer: 26.8 parts by mass-Methyl methacrylate monomer: 0.2 part by mass-Methyl methacrylate macromonomer: 8.4 parts by mass (a macromonomer having a methacryloyl group at one end and having a weight average molecular weight of 5000)
-Toluene: 31.3 parts by mass-Methyl ethyl ketone: 31.3 parts by mass

  Subsequently, nitrogen gas was introduced to make a nitrogen atmosphere sufficiently. Thereafter, the mixture was heated to 80 ° C., 2.0 parts by mass of azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried under vacuum to obtain a coat resin.

A magnetic carrier was produced using the obtained magnetic core and magnetic carrier.
The following materials were dispersed and mixed with a bead mill to obtain a resin liquid.
・ Coat resin: 20.0% by mass
-Toluene: 80.0% by mass
100 parts by mass of magnetic core particles were added to a Nauta mixer, and a resin solution was added so as to be 2.0 parts by mass as a resin component. The mixture was heated to 70 ° C. under reduced pressure and mixed at 100 rpm for 4 hours to remove the solvent and apply. The obtained sample was transferred to a Julia mixer, heat-treated at 100 ° C. for 2 hours in a nitrogen atmosphere, and then classified with a sieve having an opening of 70 μm to obtain a magnetic carrier having a volume distribution standard 50% particle size of 38.2 μm.

<Example of production of two-component developer>
Each of the toners 1 to 6 was mixed with a magnetic carrier to obtain two-component developers 1 to 6. The toner and the magnetic carrier are weighed so that the toner concentration is 8.0% by mass, and mixed with a V-type mixer (V-10 type: manufactured by Tokuju Kosakusho Co., Ltd.) at 0.5 s ⁻¹ and a rotation time of 5 min. Two-component developers 1 to 6 were prepared.

<Production example of electrophotographic photoreceptors 1 to 11>
(Support)
A cylindrical aluminum cylinder having a diameter of 29.92 mm, a length of 357.5 mm, and a thickness of 0.7 mm was used as the support.

(Undercoat layer)
As a metal oxide, 100 parts by mass of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) was stirred and mixed with 500 parts by mass of toluene. To this, 0.8 part by mass of a silane coupling agent (compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and 6 Stir for hours. Thereafter, toluene was distilled off under reduced pressure, followed by heating and drying at 140 ° C. for 6 hours to obtain surface-treated zinc oxide particles.

  Next, 15 parts by mass of a butyral resin (trade name: ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 15 parts by mass of a blocked isocyanate (trade name: Sumidur 3175, manufactured by Sumitomo Covestrourethane Co., Ltd.) as a polyol resin Was dissolved in the mixed solution. The mixed solution is a mixed solution of 73.5 parts by mass of methyl ethyl ketone and 73.5 parts by mass of 1-butanol.

  To this solution, 80.8 parts by mass of surface-treated zinc oxide particles and 0.4 parts by mass of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The dispersion was carried out for 3 hours in an atmosphere of 23 ± 3 ° C. using a sand mill apparatus using glass beads. After dispersion, 0.01 parts by mass of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning), crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-103, Sekisui Plastics Co., Ltd.) 5.6 parts by mass, average primary particle size 3.1 μm) was added and stirred to prepare an undercoat layer coating solution.

  This undercoat layer coating solution was applied onto the support by dip coating, and the resulting coating film was dried at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

(Charge generation layer)
The following four substances were placed in a sand mill using glass beads having a diameter of 1 mm, dispersed for 4 hours, and then 700 parts by mass of ethyl acetate was added to prepare a charge generation layer coating solution.
-Crystalline hydroxygallium phthalocyanine crystal (charge generation material) having strong peaks at 7.4 ° and 28.2 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction: 20 parts by mass • Polyvinyl butyral ( Product name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.): 10 parts by mass. Compound represented by the following structural formula (A): 0.2 parts by mass. Cyclohexanone: 600 parts by mass.

  This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 80 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.18 μm.

(Charge transport layer)
The following five substances were dissolved in a mixed solvent of 600 parts by mass of xylene and 200 parts by mass of dimethoxymethane to prepare a coating solution for charge transport layer.
-Compound represented by the following structural formula (B) (charge transport material): 30 parts by mass-Compound represented by the following structural formula (C) (charge transport material): 60 parts by mass-represented by the following structural formula (D) Compound (charge transport material): 10 parts by mass Polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type polycarbonate): 100 parts by mass Polycarbonate represented by the following structural formula (E) (Viscosity average molecular weight Mv: 20000): 0.02 parts by mass
This charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was dried at 110 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

(Protective layer)
Next, materials selected from the following compound group were mixed in the types and parts by mass shown in Table 3, and stirred for 12 hours to obtain a coating solution for a protective layer.

[Compounds having a monovalent hydrocarbon group and a polymerizable functional group in the same molecule]

[Other compounds]
(Compound G-1)
Trimethylolpropane triacrylate (Compound G-2) manufactured by Shin-Nakamura Chemical Co., Ltd.
(Compound G-3)
・ The above structural formula (D)

[solvent]
A mixed solvent of 100 parts by mass of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) and 100 parts by mass of 1-propanol 200 masses of toluene Part

  This protective layer coating solution was applied onto the charge transport layer. Next, the obtained coating film was dried at 50 ° C. for 6 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.6 seconds while rotating the support (irradiated body) at 200 rpm in nitrogen. The electron beam conditions were set such that the absorbed dose was 8000 Gy at an acceleration voltage of 70 kV. Subsequently, the temperature was raised from 25 ° C. to 120 ° C. in nitrogen over 30 seconds to heat the coating film. The oxygen concentration in the atmosphere during electron beam irradiation and subsequent heating was 15 ppm. Next, a protective layer having a thickness of 5 μm was formed by performing heat treatment at 100 ° C. for 30 minutes in the air.

  As shown in Table 3, electrophotographic photoreceptors 1 to 11 were obtained by changing the compound and the number of parts (parts by mass) used in the protective layer coating solution. As the coating method, electrophotographic photoreceptors 3, 4 and 7 were dip coated, and otherwise spray coating was used. In this way, electrophotographic photoreceptors 1 to 11 were produced.

<Example of production of electrophotographic photoreceptor 12>
An electrophotographic photosensitive member 4 (electrophotographic photosensitive member before formation of recesses) prepared by installing a mold member (mold) in a press-fitting shape transfer processing apparatus as shown in FIG. Surface processing was performed on.
Specifically, the mold shown in FIG. 8 was installed, and surface processing was performed on the produced electrophotographic photosensitive member before forming the concave portion.

  FIG. 8 is a view showing a mold used in the example. FIG. 8A is a top view schematically showing the mold. FIG. 8B is a schematic cross-sectional view in the axial direction of the electrophotographic photosensitive member at the convex portion of the mold (cross-sectional view in the S-S ′ cross-section in FIG. 8A). FIG. 8C is a cross-sectional view in the circumferential direction of the electrophotographic photosensitive member at the convex portion of the mold (cross-sectional view of the T-T ′ cross section in FIG. 8A).

  The mold shown in FIG. 8 has a maximum width (the maximum width in the axial direction of the electrophotographic photosensitive member when the convex portion on the mold is viewed from above). X: 30 μm, maximum length (the convex portion on the mold) Is the maximum length in the circumferential direction of the electrophotographic photosensitive member when viewed from above.) Y: 75 μm, area ratio 56%, height H: 1.4 μm. In addition, an area ratio is a ratio of the area of the convex part which occupies for the whole surface when a mold is seen from the top. At the time of processing, the temperatures of the electrophotographic photosensitive member and the mold were controlled so that the surface temperature of the electrophotographic photosensitive member was 120 ° C. Then, while pressing the electrophotographic photosensitive member and the pressure member against the mold at a pressure of 7.0 MPa, the electrophotographic photosensitive member is rotated in the circumferential direction to form a recess on the entire surface layer (peripheral surface) of the electrophotographic photosensitive member. Formed. Thus, the electrophotographic photoreceptor 12 was produced.

  The surface of the obtained electrophotographic photoreceptor was magnified and observed with a 50 × lens with a confocal microscope (Carl Zeiss Microscopy Co., Ltd., trade name: Zeiss Smart Proof 5), and provided on the surface of the electrophotographic photoreceptor. Recesses were observed.

  The images subjected to magnified observation were aligned horizontally, developed on a plane, and then connected by an image connection application to obtain a square region having a side of 500 μm. And about the obtained result, image processing height data was selected with the attached image analysis software, and the filter process was performed.

As a result of the above observation, the depth of the concave portion was 1 μm, the axial width of the opening was 30 μm, the circumferential length of the opening was 75 μm, and the area was 140000 μm ² . The area is the area of the recess when the surface of the electrophotographic photosensitive member is viewed from above, and means the area of the opening of the recess.

<Example of production of electrophotographic photoreceptor 13>
In Example 12 of the electrophotographic photosensitive member, except that the height H of the convex portion of the mold was 0.6 μm, a concave portion was formed in the same manner to produce the electrophotographic photosensitive member 13.

<Example of production of electrophotographic photoreceptor 14>
In Example 12 of the electrophotographic photosensitive member, except that the height H of the convex portion of the mold was set to 1.8 μm, a concave portion was formed in the same manner to produce the electrophotographic photosensitive member 14.

[Evaluation]
The evaluation of the scratch marks was performed by using both image evaluation and appearance evaluation of the electrophotographic photosensitive member.

(Image evaluation)
The scratch marks were evaluated using iR-ADV C5255 manufactured by Canon Inc.
230 g of the two-component developer produced in the above production example was charged into the developing device. The electrophotographic photosensitive member produced in the above production example was mounted on a drum cartridge. At this time, the cleaning blade is a urethane rubber blade having a rebound elastic modulus of 20% and a hardness of 77 degrees measured by IRHD hardness test method M (micro method) using a Wallace hardness meter (Model: H12 manufactured by Wallace). The line pressure was set to 30 gf / cm, the set angle was 23 °, and the swing angle was 18 ° by a spring press method. Further, the gap between the developing sleeve and the electrophotographic photosensitive member was adjusted to 180 μm. Setting was made such that the charging potential was -700 V, the developing bias was -550 V, and the exposure potential was -300 V, and 5000 sheets of A4 size, 5% print ratio charts were output. The density unevenness of the 5000th image was measured with a spectral densitometer (trade name: X-rite 518JP / LP, aperture 3.4 mm, manufactured by X-Rite).

(Appearance evaluation of electrophotographic photoreceptor)
The electrophotographic photosensitive member after the output of 5000 image evaluations was taken out, and a developed view of the appearance of the electrophotographic photosensitive member was obtained with the apparatus shown in FIG. FIG. 6 shows an apparatus for irradiating an electrophotographic photosensitive member with light, detecting the reflected light with an image sensor, and outputting a reflected light intensity distribution. A halogen lamp was used as the light source 13, and white light 14 was uniformly irradiated in the axial direction while rotating the electrophotographic photosensitive member 15 after outputting the image. The reflected light 16 was received by a line sensor type CCD camera 17 and output as a developed view of a reflected light amount distribution of a cylindrical electrophotographic photosensitive member by a processing device (not shown). An example in which the amount of reflected light is output is shown in FIG.

(Rating mark evaluation rank)
The evaluation criteria were as follows. In this evaluation, A to D were accepted and E was rejected. With respect to the reflected light amount unevenness of the external appearance of the electrophotographic photosensitive member, FIG. 1A is used as a limit sample, and FIG. Note that C to E do not show a significant difference in appearance, and all have “clearly reflected light amount unevenness” at the level shown in FIG. Further, the density step means a difference in density between a portion corresponding to the rubbing trace and a portion appearing as a step between the portion having no rubbing trace adjacent to the rubbing trace.
A: The image density difference is less than Δ0.02 and the reflected light amount is not uneven in the appearance of the electrophotographic photosensitive member. B: The image density step is less than Δ0.02 and the reflected light amount is slightly uneven in the appearance of the electrophotographic photosensitive member. C; The density difference of the image is less than Δ0.02, and the reflected light amount unevenness is clearly in the appearance of the electrophotographic photosensitive member D; The unevenness of the reflected light amount is clearly in the appearance of the image photosensitive member less than Δ0.03 E; The density difference in the image is Δ0.03 or more, and the reflected light quantity is clearly uneven in the appearance of the electrophotographic photosensitive member.

[Examples 1 to 18, Comparative Examples 1 to 6]
As shown in Table 4, the two-component developers 1 to 6 and the electrophotographic photoreceptors 1 to 14 were selected and evaluated. Table 4 shows the evaluation rank.

  In the configuration of the example, rubbing marks were suppressed. In the configuration of the comparative example, since the toner or the electrophotographic photosensitive member is not within the scope of the present invention, a rubbing mark is generated as image density unevenness. In particular, in Comparative Examples 2 and 4, the toner 6 contains crystalline polyester crystals but is not in a dispersed state, so that the cleaning blade portion is not sufficiently melted and the effects of the present invention can be obtained. It is thought that it was not possible.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means 13 Light source 14 White light 15 Electrophotography after image output Photosensitive member 16 Reflected light 17 Line sensor type CCD camera 51 Electrophotographic photosensitive member 52 Mold 53 Pressure member 54 Support member

Claims (5)

A toner having toner particles containing crystalline polyester;
An electrophotographic photoreceptor having a support and a photosensitive layer on the support; and
A cleaning blade for cleaning the surface of the electrophotographic photosensitive member,
The toner particles have dispersed crystals of the crystalline polyester from the surface of the toner particles to a depth of 0.30 μm in the cross section of the toner particles as observed by a transmission electron microscope (TEM).
An electrophotographic apparatus, wherein the surface layer of the electrophotographic photoreceptor contains a cured product of a compound having a monovalent hydrocarbon group having 7 or more carbon atoms and a polymerizable functional group in the same molecule.   In the toner particles, the crystalline polyester crystals are dispersed in the cross section of the toner particles as observed by a transmission electron microscope (TEM), and the number distribution of the major axis length of the crystals has a peak at 300 nm or less. The electrophotographic apparatus according to claim 1. The toner particles further contain an amorphous polyester resin;
In the endothermic curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) device of the toner, the endothermic amount ΔH derived from the crystalline polyester is 1.0 J / g or more and 5.0 J / g or less,
In the toner particles, crystals of the crystalline polyester are dispersed in a cross section of the toner particles observed by a transmission electron microscope (TEM), and the major axis length in the number distribution of the major axis lengths of the crystals. The electrophotographic apparatus according to claim 1, wherein the crystal cross section having a thickness of 100 nm to 250 nm is 30% by number or more. The electrophotographic apparatus according to claim 1, wherein the cured product contained in the surface layer of the electrophotographic photoreceptor is a cured product of the compound represented by the formula (I).
(In formula (I), R ¹ is a hydrogen atom or a methyl group. R ² is a linear alkyl group having 7 or more carbon atoms or a branched alkyl group having 7 or more carbon atoms. Group.) The cured product contained in the surface layer of the electrophotographic photoreceptor is a copolymer of a compound represented by the formula (I) and a hole transporting compound having a polymerizable functional group. The electrophotographic apparatus according to any one of the above.
(In formula (I), R ¹ is a hydrogen atom or a methyl group. R ² is a linear alkyl group having 7 or more carbon atoms or a branched alkyl group having 7 or more carbon atoms. Group.)