JP2019008282A - Toner, developer, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

To provide a photoluminescent toner that prevents charge reduction and has excellent hue.SOLUTION: A toner 50 contains a photoluminescent pigment 51 and a coloring pigment, where the photoluminescent pigment 51 is present inside the toner 50; the coloring pigment contains a yellow pigment; and the yellow pigment is an isoindoline pigment. The isoindoline pigment is preferably C.I. Pigment Yellow 185, and the coloring pigment is preferably contained in an amount of 10 to 35 parts by mass based on 100 parts by mass of the photoluminescent pigment.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a toner, a developer, a process cartridge, an image forming apparatus, and an image forming method.

In an electrophotographic image forming method, glitter toner containing a glitter pigment is used for the purpose of forming an image having metallic luster.
In order to give color to the glossy toner, a technique for using the glitter toner and the yellow toner together as in Patent Document 1, and for the purpose of improving the light resistance, a glitter pigment and a yellow pigment are used as in Patent Document 2. The technology used together is known.
However, the glitter pigment has a problem that the chargeability is low because it easily conducts electricity. In addition, there is a problem that the decrease in charge becomes more remarkable by using a glitter pigment and another pigment together. If the chargeability is low, it may cause soiling.

  An object of the present invention is to provide a glittering toner that suppresses a decrease in charge and has an excellent color.

  In order to solve the above-described problems, the present invention provides a toner including a glitter pigment and a color pigment, wherein the glitter pigment is present in the toner, the color pigment includes a yellow pigment, and the yellow pigment includes It is an isoindoline pigment.

  According to the present invention, it is possible to provide a glittering toner that suppresses charge reduction and has an excellent color.

1 is a schematic cross-sectional view of an example of an image forming apparatus of the present invention. It is a cross-sectional schematic diagram in an example of the process cartridge of the present invention. It is a cross-sectional schematic diagram for demonstrating the example of arrangement | positioning of a luster pigment. 3 is an example of a scanning electron microscope (SEM) image of a toner cross section.

  Hereinafter, a toner, a developer, a process cartridge, an image forming apparatus, and an image forming method according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included. Hereinafter, the present invention will be described in more detail.

(toner)
The present invention is a toner including a glitter pigment and a color pigment, wherein the glitter pigment is present in the toner, the color pigment includes a yellow pigment, and the yellow pigment is an isoindoline pigment. And

  The glittering toner is a toner capable of obtaining an image having a metallic luster, and metal particles such as aluminum are used for the pigment. However, the glitter pigment has high conductivity, and the charging ability of the toner becomes low. Further, when a yellow pigment is used in combination for improving the hue, there is a problem that the tendency to decrease the charging ability is increased, and the quality related to charging, for example, deterioration of background stains is caused.

  As a result of investigations by the inventor, it has been found that when an isoindoline pigment is used as a yellow pigment used in combination with a glitter pigment, a decrease in charge can be prevented while having an excellent hue, and both can be achieved. Although the specific reason is unknown, it is presumed that the isoindoline pigment has good dispersibility in the resin and can maintain high toner resistance even when combined with a glitter pigment.

  Further, in the present invention, the glittering pigment having conductivity is disposed inside the toner so as not to contact the adjacent toner. By arranging the glitter pigment in the toner, it is possible to further prevent a decrease in charge, and to further suppress scumming caused by the decrease in charge. As a result, it is possible to obtain a glittering toner that has excellent color tone and in which a decrease in charging is suppressed.

<Brightness pigment>
Examples of the bright pigment used in the present invention include metal powders such as aluminum, brass, bronze, nickel, stainless steel, zinc, copper, silver, gold, and platinum, and metal-deposited flaky glass powder.

  The surface of the glitter pigment is preferably surface-treated from the viewpoint of dispersibility and antifouling properties, various surface treatment agents, silane coupling agents, titanate coupling agents, fatty acids, silica particles, acrylic resins, You may coat | cover with polyester resin etc.

The shape of the metal pigment is preferably a scaly shape (flat plate shape) or a flat shape having a light reflecting surface for the expression of glitter. In order for one particle to have a constant plane with a small volume, it is preferably a flake. The glitter pigment may be contained singly or in combination of two or more. In order to adjust the color tone, various colorants such as dyes and pigments may be used in combination.
Note that it is preferable that the glitter pigment is, for example, scaly or flat and has flatness, because it is easy to form a stacked structure in parallel and stacked inside the toner.

  As described above, in the present invention, the bright pigment is disposed inside the toner. In the present invention, “the glitter pigment is disposed in the toner” refers to a state in which the center in the longitudinal direction of all the glitter pigments is disposed in the toner. By observing the cross section of the toner with a scanning electron microscope (SEM) and performing elemental analysis with energy dispersive X-ray analysis (EDS) or the like, it is possible to confirm the state in which the glitter pigment is disposed in the toner.

FIG. 3 is a schematic cross-sectional view for explaining an arrangement example of the glitter pigment. 3A is an example in which the glitter pigment 51 exists in the toner 50, and FIGS. 3B and 3C are examples in which the glitter pigment 51 does not exist in the toner 50. FIG.
FIG. 4 shows an example of a scanning electron microscope (SEM) image of a toner cross section. 4A is an example in which the glitter pigment 51 is present in the toner 50, and FIGS. 4B and 4C are examples in which the glitter pigment 51 is not present in the toner 50. FIG.
In the example shown in FIGS. 3A and 4A, the center in the longitudinal direction of all the glitter pigments is disposed inside the toner, and the glitter pigment is disposed inside the toner.

  Further, the method of arranging the glitter pigment in the toner can be appropriately changed. For example, in the production of toner, it is preferable to use a luster pigment covered with a hydrophobic substance that is familiar with the toner resin. This can be obtained, for example, by pulverizing and polishing a bright pigment powder in a ball mill together with a long-chain alkyl fatty acid (such as stearic acid or oleic acid). In addition, it is possible to use a dispersion medium substituted with a hydrophobic organic solvent such as toluene, propyl acetate, or ethyl acetate as a dispersion medium, in which polyester resin, styrene, or acrylic resin is dissolved and coated on the surface of the glitter pigment. preferable. It can also be reacted with a surface active hydrogen group such as a silane coupling agent. These treatment methods are particularly effective in the production of chemical toners that are granulated in an aqueous phase.

  The content of the glitter pigment in the electrostatic image developing toner of the present embodiment is preferably 5 to 50% by weight based on the total weight of the toner.

<Coloring pigment>
The color pigment used in the toner of the present invention includes a yellow pigment, and the yellow pigment is an isoindoline pigment. The isoindoline pigment is a pigment containing isoindoline represented by the following structural formula (1).

  By using the glitter pigment and the isoindoline pigment in combination, it is possible to prevent deterioration in charging-related quality due to the combination of the glitter toner and the pigment while having an excellent hue.

  Examples of isoindoline pigments include C.I. I. Pigment yellow 139, C.I. I. And CI Pigment Yellow 185. Among these, C.I. I. Pigment Yellow 185 is preferable, and the chargeability can be further improved.

The colored pigment may contain a pigment other than a yellow pigment, and examples thereof include a magenta pigment, which is preferably used. When a magenta pigment is included, the hue can be further expanded. Further, the glitter is improved and a more beautiful gold color can be obtained.
The magenta pigment can be appropriately changed. For example, C.I. I. Pigment red 122, C.I. I. And CI Pigment Red 269.

  The addition amount of the color pigment is preferably 10 to 35 parts by weight, more preferably 20 to 30 parts by weight, based on 100 parts by weight of the luster pigment. If it is less than 10 parts by weight, the coloring power is lowered and the desired hue may be deteriorated (a beautiful golden color may not be produced). Also. If the amount exceeds 35 parts by weight, poor dispersion of the pigment in the toner may occur, leading to a reduction in coloring power and a reduction in toner electrical characteristics.

  The color pigment may be used as a master batch combined with a resin. Such a resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

  The master batch can be manufactured by applying a high shear force and mixing or kneading the resin and the color pigment. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the color pigment and the resin. A so-called flushing method is also preferable in that a wet cake of colored pigment can be used as it is, and there is no need to dry it. The flushing method is a method of mixing or kneading an aqueous paste containing water of a color pigment together with a resin and an organic solvent, and transferring the color pigment to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

<Toner production method>
The toner of the present invention can be produced by a known method such as a pulverization method or a polymerization method.
The toner of the present invention comprises, for example, base particles and an external additive. For example, the base particles can be prepared by a dissolution suspension method.

  The dissolution suspension method will be described in detail below. Generally, the dissolution suspension method involves dissolving or dispersing a toner composition containing at least a resin and a color pigment in an organic solvent to obtain a solution or dispersion, Add this to an aqueous medium in which a dispersant is present, and use a normal stirrer, homomixer, homogenizer, etc. to disperse the toner with the desired particle size distribution, and then remove the organic solvent. A method of obtaining a toner slurry by the above method is mentioned. The toner can be isolated by collecting and drying by washing and filtration according to a known method.

In the dissolution suspension method, any resin that can be dissolved in a solvent can be used in production. Specific examples include resins conventionally used in toners, including polyester resins, styrene-acrylic resins, polyol resins, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, silicon resins, phenols. There are resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like.
From the viewpoint of low-temperature fixability, it is preferable to use a polyester resin.

<< Polyester resin >>
Examples of the polyester resin include the following polycondensates of polyol (1) and polycarboxylic acid (2), and any of them can be used, and several types of polyester resins can be used in combination. good.

-Polyol-
Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl); bis (3-fluoro-4-hydroxypheny ) Methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5 -Difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), bis (hydroxy) such as 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Phenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether; adducts of the above alicyclic diols with alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) Alkylene oxides of the above bisphenols (ethylene oxide, pro Alkylene oxide, and the like butylene oxide, etc.) adducts.

  Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  Furthermore, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.

  In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

-Polycarboxylic acid-
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).

Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polycarboxylic acids having 3 or more valences include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1).
In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

-Ratio of polyol and polycarboxylic acid-
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

<< Modified polyester resin >>
The toner of the present invention may contain a binder resin, and the binder resin used in the present invention is a modified polyester resin having a urethane or / and urea group (hereinafter referred to as “modified” for adjusting viscoelasticity). Polyester resin ”).

  The content of the modified polyester resin having urethane or / and urea groups is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less in the binder resin. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated.

  The modified polyester resin having urethane or / and urea groups may be directly mixed with the binder resin, but from the viewpoint of manufacturability, a relatively low molecular weight modified polyester resin having an isocyanate group at the terminal (hereinafter referred to as prepolymer). And an amine that reacts with the binder resin is mixed with a binder resin, and during the granulation / after granulation, chain extension or / and cross-linking reaction to modify the urethane or / and urea group A polyester resin is preferred. In this case, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity.

-Prepolymer-
Examples of the prepolymer having an isocyanate group include a polycondensate of the polyol (1) and the polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). . Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

-Polyisocyanate-
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactams, And a combination of two or more of these.

-Ratio of isocyanate group to hydroxyl group-
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability may be deteriorated. When the molar ratio of [NCO] is less than 1, the urea content in the modified polyester is lowered, and offset resistance may be deteriorated.

  The content of the polyisocyanate (3) component in the prepolymer having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 2 to 20% by mass. If it is less than 0.5% by mass, the offset resistance may be deteriorated. On the other hand, if it exceeds 40% by mass, the low-temperature fixability may deteriorate.

-Number of isocyanate groups in the prepolymer-
The number of isocyanate groups contained per molecule in the prepolymer having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. When the number is less than 1 per molecule, the molecular weight of the modified polyester after chain extension and / or crosslinking may be low, and offset resistance may be deteriorated.

<< Crystalline resin >>
The toner of the present invention may contain a crystalline resin. Preferred examples of the crystalline resin include a polyester resin synthesized from a diol component and a dicarboxylic acid component, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid polymer. Can be mentioned. Further, examples thereof include a urethane-modified polyester resin, a urea-modified polyester resin, a polyurethane resin, and a polyurea resin having a urethane bond and / or a urea bond. Among these, urethane-modified polyester resins and urea-modified polyester resins are preferable in that they exhibit high hardness while maintaining crystallinity as a resin.

-Urethane-modified polyester resin-
The urethane-modified polyester resin can be obtained, for example, by a reaction between a polyester resin and at least a divalent or higher isocyanate compound, or a reaction between a polyester resin having an isocyanate group at a terminal and a polyol component.
Examples of the polyester resin include a polycondensation polyester resin synthesized by polycondensation of a diol component and a dicarboxylic acid component, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester resin of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

--Diol component--
As the diol component, an aliphatic diol is preferable, and the chain carbon number is preferably in the range of 2 to 36. Examples of the aliphatic diol include a linear type and a branched type, and a linear aliphatic diol is preferable, and a linear aliphatic diol having 4 to 6 carbon atoms is more preferable. A plurality of diol components may be used, but the content of the linear aliphatic diol is preferably 80 mol% or more, more preferably 90 mol% or more with respect to the total amount of the diol component. . When it is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between the low-temperature fixability and the heat-resistant storage stability is good, and the resin hardness tends to be improved.

  Specific examples of the linear aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1, Examples include, but are not limited to, 14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like. Is not to be done. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability. 1,4-butanediol and 1,6-hexanediol are more preferable.

  Other diols used as necessary include, for example, aliphatic diols other than those having 2 to 36 carbon atoms (1,2-propylene glycol, 1,3-butanediol, hexanediol, octanediol, decanediol, Dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .; alkylene ether glycol having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol) Polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxides of the above alicyclic diols Hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 1-30); bisphenol AO (EO, PO, BO, etc.) adducts (addition mole number 2-30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene diol, etc. Can be mentioned.

  In addition, the tri- to octa- or higher-valent alcohol component used as necessary includes a 3- to 8-valent or higher polyhydric aliphatic alcohol having 3 to 36 carbon atoms (alkane polyol and its intramolecular or intermolecular). Dehydrates such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and derivatives thereof such as sucrose and methylglucoside); AO of trisphenols (such as trisphenol PA) Adduct (addition mole number 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl monomers Copolymer, etc.]; It is. Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

--Dicarboxylic acid component--
The carboxylic acid component is preferably an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Examples of the aliphatic dicarboxylic acid include a straight-chain type and a branched type, and a straight-chain dicarboxylic acid is more preferable. Furthermore, among the linear dicarboxylic acids, saturated aliphatic dicarboxylic acids having 6 to 12 carbon atoms are particularly preferable.

  Examples of the dicarboxylic acid include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, etc.); 40 alicyclic dicarboxylic acids [dimer acid (dimerized linoleic acid), etc.], alkene dicarboxylic acids having 4 to 36 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid) , Maleic acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′ -Biphenyl dicarboxylic acid and the like).

  Examples of the tri- to hexa-valent or higher polycarboxylic acid used as necessary include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

  In addition, as the dicarboxylic acid or the polycarboxylic acid having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used. Good.

  Among these dicarboxylic acids, the aliphatic dicarboxylic acids (preferably adipic acid, sebacic acid, dodecanedioic acid, etc.) are preferably used alone or in combination of two or more. Those obtained by copolymerizing dicarboxylic acids (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, and lower alkyl esters thereof) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

--Lactone ring-opening polymer--
Examples of the lactone ring-opening polymer as the polyester resin include monolactones having 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone (one ester group in the ring). ) And the like can be obtained by ring-opening polymerization using a catalyst such as a metal oxide or an organometallic compound. Of these, preferred lactone is ε-caprolactone from the viewpoint of crystallinity.

  Further, it may be a lactone ring-opening polymer having a hydroxyl group at the terminal, obtained by ring-opening polymerization of the above lactone using glycol (for example, ethylene glycol, diethylene glycol, etc.) as an initiator. May be modified so as to be, for example, a carboxyl group. Moreover, you may use a commercial item, for example, highly crystalline polycaprolactone, such as H1P, H4, H5, H7 of the PLACEL series by Daicel Corporation.

--Polyhydroxycarboxylic acid--
The polyhydroxycarboxylic acid as the polyester resin can be obtained by directly dehydrating and condensing hydroxycarboxylic acids such as glycolic acid and lactic acid (L-form, D-form, racemate), but glycolide, lactide (L-form, D-form) A cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to a dehydration condensate of two or three molecules of a hydroxycarboxylic acid such as a meso form of a metal oxide or an organometallic compound From the viewpoint of adjusting the molecular weight, ring-opening polymerization using a catalyst such as Among these, preferable cyclic esters are L-lactide and D-lactide from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

--2 or more isocyanate component-
Examples of the isocyanate component include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and araliphatic isocyanates. Among them, aromatics having 6 to 20 carbon atoms excluding carbon in the NCO group. Diisocyanates, 2-18 aliphatic diisocyanates, 4-15 alicyclic diisocyanates, 8-15 araliphatic diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups) Uretdione group, uretoimine group, isocyanurate group, modified product containing oxazolidone group) and a mixture of two or more of these. If necessary, trivalent or higher isocyanates may be used in combination.

  Specific examples of the aromatic isocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20 mass) %) Of tri- or higher functional polyamine]]: phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m− And p-isocyanatophenylsulfonyl isocyanate It is.

  Specific examples of the aliphatic isocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Etc.

  Specific examples of the alicyclic isocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic isocyanates include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

  Examples of the modified product of diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product. Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified products of diisocyanates such as urethane-modified TDI, and mixtures of two or more of these (for example, modified MDI and urethane-modified TDI) (Combined use with (isocyanate-containing prepolymer)).

  Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanates, and 4 to 15 alicyclic diisocyanates, and particularly preferred are TDI. , MDI, HDI, hydrogenated MDI, and IPDI.

-Urea-modified polyester resin-
The urea-modified polyester resin can be obtained, for example, by a reaction between a polyester resin having an isocyanate group at the terminal and an amine compound.

--- 2 or more amine component-
Examples of the amine component include aliphatic amines and aromatic amines. Among them, aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms are exemplified. If necessary, trivalent or higher amines may be used.

  Examples of the aliphatic diamines having 2 to 18 carbon atoms include alkylene diamines having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.); polyalkylenes having 4 to 18 carbon atoms Diamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; these C1-C4 alkyls or C2-C4 hydroxyalkyl substitutions (Dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.); alicyclic or complex Ring-containing aliphatic diamine {alicyclic diamine having 4 to 15 carbon atoms [1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.], C4-C15 heterocyclic diamine [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3 -Aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like]}; aromatic amines containing 8 to 15 carbon atoms (xylylenediamine, tetrachloro-p-xylylene) Amine) and the like.

  Examples of the aromatic diamine having 6 to 20 carbon atoms include unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine. , Crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4, 4 ′, 4 ″ -triamine, naphthylenediamine, etc.]; aromatic diamines having a nucleus-substituted alkyl group having 1 to 4 carbon atoms [2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyl Tolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, , 4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl- 2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl- 1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3 ′ -Methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldi Phenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5 '-Tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.), and mixtures of these isomers in various proportions; nuclear substituted electron withdrawing groups (halogens such as Cl, Br, I, F; methoxy, ethoxy, etc. An aromatic diamine having an alkoxy group (such as a nitro group) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4 -Bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenedi Amine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, Bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline) ), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2-fluoro) Aniline), 4-aminophenyl-2-chloroaniline and the like]; aromatic diamine having a secondary amino group [the unsubstituted aromatic diamine, the aromatic diamine having a C1-C4 nucleus-substituted alkyl group, and Mixtures of various ratios of these isomers, part or all of the primary amino group of the aromatic diamine having the above-mentioned nucleus-substituted electron withdrawing group was replaced with a secondary amino group with a lower alkyl group such as methyl or ethyl Those] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and the like].

  Trivalent or higher amines can be obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamines (alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

-Polyurethane resin-
Examples of the polyurethane resin include a polyurethane resin synthesized from a diol component and a diisocyanate component. A trivalent or higher alcohol component or an isocyanate component may be used as necessary.
Specific examples of the diol component, diisocyanate component, trivalent or higher alcohol component and isocyanate component are the same as those described above.

-Polyurea resin-
Examples of the polyurea resin include a polyurea resin synthesized from a diamine component and a diisocyanate component, and a trivalent or higher valent amine component or isocyanate component may be used as necessary.
Specific examples of the diamine component, diisocyanate component, trivalent or higher valent amine component and isocyanate component are the same as those described above.

<< Physical properties of crystalline resin >>
The maximum peak temperature of the heat of fusion of the crystalline resin is preferably in the range of 45 to 70 ° C, more preferably 53 to 65 ° C, more preferably 58 to 62 ° C, from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. Is more preferable. When the temperature is lower than 45 ° C., the low-temperature fixability is improved, but the heat-resistant storage stability is deteriorated, and the toner and carrier aggregates are likely to be generated due to agitation stress in the developing device, which is not preferable. . On the other hand, when the temperature is higher than 70 ° C., the heat resistant storage stability is improved, but the low temperature fixability may be deteriorated.

  The ratio of the softening temperature of the crystalline resin to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is preferably 0.80 to 1.55, more preferably 0.85. It is 1.25, more preferably 0.90 to 1.20, particularly preferably 0.90 to 1.19. The closer this value is to 1.00, the softer the resin, the better the low temperature fixability and heat resistant storage stability.

  The weight average molecular weight (Mw) of the crystalline resin is preferably 10,000 to 40,000, more preferably 15,000 to 35,000, and more preferably 20,000 from the viewpoint of compatibility between low-temperature fixability and heat-resistant storage stability. ˜30,000 is particularly preferred. If it is less than 10,000, the heat resistant storage stability of the toner tends to deteriorate, and if it exceeds 40,000, the low temperature fixability of the toner tends to deteriorate, such being undesirable.

  The weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GPC) measuring device (for example, GPC-8220 GPC (manufactured by Tosoh Corporation)). The column used was TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation). The resin to be measured is made into a 0.15 wt% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus and measured at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C. In measuring the molecular weight of the sample, it was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. Examples of the standard polystyrene sample include Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

  The crystalline resin may be a block resin having a crystalline part and an amorphous part, and the above crystalline resin can be used for the crystalline part. Examples of the resin used for forming the amorphous part include, but are not limited to, a polyester resin, a polyurethane resin, and a polyurea resin. Examples of the composition of these non-crystalline parts are the same as those of the crystalline part, and examples of the monomers used include the diol component, the dicarboxylic acid component, the diisocyanate component, and the diamine component. Any combination can be used as long as it is an amorphous resin.

  The crystalline resin is prepared by using a crystalline resin precursor having a functional group capable of reacting with an active hydrogen group at the terminal in the toner production process, such as a resin having an active hydrogen group, a crosslinking agent having an active hydrogen group, and an extender. It can also be obtained by increasing the molecular weight by reacting with a compound. The crystalline resin precursor has a functional group capable of reacting with the active hydrogen group from the above crystalline polyester resin, urethane-modified crystalline polyester resin, urea-modified crystalline polyester resin, crystalline polyurethane resin, crystalline polyurea resin, etc. It is obtained by reacting with a compound having it.

  Although there is no restriction | limiting in particular as a functional group which can react with the said active hydrogen group, For example, functional groups, such as an isocyanate group, an epoxy group, carboxylic acid, an acid chloride group, are mentioned, Among these, reactivity and stability are mentioned. From the viewpoint, an isocyanate group is preferable. As a compound which has an isocyanate group, the said diisocyanate component etc. are mentioned, for example.

  In order to obtain the crystalline resin precursor, for example, when the crystalline polyester resin is reacted with the diisocyanate component, the crystalline polyester resin includes a hydroxyl group-containing crystalline polyester resin containing a hydroxyl group at the terminal. It is preferable to use it.

  In the hydroxyl group-containing crystalline polyester resin, the ratio of the diol component to the dicarboxylic acid component is preferably 2/1 to 1/1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. More preferably, it is obtained by reacting at 1.5 / 1 to 1/1, particularly preferably 1.3 / 1 to 1.02 / 1.

  The amount of the compound having a functional group capable of reacting with the active hydrogen group is, for example, when a hydroxyl group-containing crystalline polyester resin is reacted with a diisocyanate component to obtain a crystalline resin precursor, the ratio of the diisocyanate component is an isocyanate group. The equivalent ratio [NCO] / [OH] of [NCO] and the hydroxyl group [OH] of the hydroxyl group-containing crystalline polyester resin is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. Especially preferably, it is 2.5 / 1 to 1.5 / 1. In the case of crystalline resin precursors having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

  The resin having an active hydrogen group and a compound such as a crosslinking agent or an extender having an active hydrogen group are not particularly limited as long as they have an active hydrogen group, and can be appropriately selected according to the purpose. For example, when the functional group capable of reacting with the active hydrogen group is an isocyanate group, examples thereof include resins and compounds having a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group, etc. From the viewpoint of reaction rate, water and amines are particularly suitable.

  The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, 4,4′-diamino-3,3′dimethyl. Examples include dicyclohexylmethane, diaminecyclohexane, isophoronediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, hydroxyethylaniline, aminoethyl mercaptan, aminopropyl mercaptan, aminopropionic acid, and aminocaproic acid. . Further, ketimine compounds, oxazolidone compounds, etc., in which these amino groups are blocked with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be mentioned.

<< Wax >>
The toner of the present invention may contain a wax, and examples thereof include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones.

Examples of the polyalkanoic acid ester wax include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, Examples thereof include 18-octadecanediol distearate.
Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate.
Examples of the polyalkanoic acid amide include dibehenyl amide.
Examples of the polyalkylamide include trimellitic acid tristearylamide.
Examples of the dialkyl ketone include distearyl ketone.
Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

  As the needle-like substance, a wax that prevents the glittering pigment from being stacked, or a wax for widening the surface interval is preferably a wax that is branched in the middle to have a certain degree of polarity or a polar group is introduced. The melting point may be high as long as it is about the same as the melting temperature of the resin used for the toner or less than the temperature of the image on paper at the time of fixing.

  Examples of the polar group include a modified wax into which a polar group such as a hydroxyl group, a carboxyl group, an amide group, or an amino group is introduced. Also, oxidation-modified wax obtained by oxidizing hydrocarbons by the air oxidation method, metal salts such as potassium and sodium, polymers containing acidic groups, such as copolymers of maleic anhydride and alpha-olefins, etc. Salts, imide esters, quaternary amine salts, and alkoxylated hydrocarbons modified with hydroxyl groups.

Examples of the esterified carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long-chain hydrocarbon wax include paraffin wax and sazol wax.

  There is no restriction | limiting in particular as melting | fusing point of the said wax, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable and 60 to 90 degreeC is more preferable. If the melting point is less than 50 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 100 ° C., a cold offset tends to occur during fixing at a low temperature.

  The melting point of the wax can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). That is, first, 5.0 mg of wax is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the maximum peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point.

  The melt viscosity of the wax is preferably 5 mPa · sec to 100 mPa · sec, more preferably 5 mPa · sec to 50 mPa · sec, and particularly preferably 5 mPa · sec to 20 mPa · sec as a measured value at 100 ° C. If the melt viscosity is less than 5 mPa · sec, the releasability may be reduced, and if it is greater than 100 mPa · sec, the hot offset resistance and the releasability at low temperatures may be deteriorated, which is preferable. Absent.

  The total amount of the wax processed into the acicular substance and the other wax in the toner, and the content in the toner is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 10% by mass with respect to the toner. . When the content is less than 5% by mass, the hot offset resistance may be deteriorated, and when it exceeds 10% by mass, the heat resistant storage stability, charging property, transferability, and stress resistance may be deteriorated.

  The wax as a needle-like or plate-like substance is preferably 1% by mass to 30% by mass and more preferably 5% by mass to 10% by mass with respect to the glitter pigment.

<External additive>
Examples of the external additive include inorganic fine particles. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

(Developer)
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.

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

-Carrier core material-
The core material is not particularly limited as long as it has magnetic particles, and suitable examples include ferrite, magnetite, iron, and nickel. In addition, when considering adaptability to environmental aspects that have been remarkably advanced in recent years, if it is a ferrite, it is not a conventional copper-zinc ferrite, for example, manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese- It is preferable to use magnesium-strontium ferrite, lithium ferrite, or the like.

-Protective layer-
The protective layer contains at least a binder resin and may contain other components such as inorganic fine particles as necessary.

--Binder resin--
The binder resin for forming the protective layer of the carrier is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, a crosslinkable copolymer containing polyolefin (eg, polyethylene, polypropylene, etc.) or a modified product thereof, styrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; consisting of an organosiloxane bond Silicone resins or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; Examples thereof include polyimide resins and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

  There is no restriction | limiting in particular as said silicone resin, According to the objective from the generally known silicone resin, it can select suitably, For example, straight silicone resin which consists only of organosiloxane bonds, alkyd, polyester , Silicone resins modified with epoxy, acrylic, urethane and the like.

  Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Specific examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

  The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

--Fine particles--
The protective layer may contain fine particles as necessary, and the fine particles are not particularly limited and can be appropriately selected from conventionally known materials according to the purpose. , Tin oxide, zinc oxide, silica, titanium oxide, alumina, potassium titanate, barium titanate, aluminum borate and other inorganic fine particles, polyaniline, polyacetylene, polyparaphenylene, poly (para-phenylene sulfide), polypyrrole, parylene For example, conductive polymers such as carbon black, organic fine particles such as carbon black, and the like may be used.

  The fine particles may be further subjected to a conductive treatment on the surface. As a method of such a conductive treatment, aluminum, zinc, copper, nickel, silver, or an alloy thereof, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin are formed on the surface of the fine particles. And indium oxide doped with antimony, tin oxide doped with antimony, zirconium oxide, and the like in the form of a solid solution or fusion. Among these, a method of conducting a conductive treatment using tin oxide, indium oxide, or indium oxide doped with tin is preferable.

The content of the protective layer in the carrier is preferably 5% by mass or more, and more preferably 5% by mass or more and 10% by mass or less.
The thickness of the protective layer is preferably 0.1 μm to 5 μm, and more preferably 0.3 μm to 2 μm.

  Here, the thickness of the protective layer is, for example, a carrier cross section of 50 points or more using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) after creating a carrier cross section with FIB (focused ion beam). Can be calculated as an average value of the obtained film thicknesses.

-Method for forming carrier protective layer-
The method for forming the protective layer on the carrier is not particularly limited, and a conventionally known protective layer forming method can be used. The raw material for the protective layer including the binder resin or the binder resin precursor is dissolved. The method of apply | coating a protective layer solution to the surface of a core material using the spraying method or the immersion method etc. is mentioned. It is preferable to accelerate the polymerization reaction of the binder resin or the binder resin precursor by applying a protective layer solution to the surface of the core material and heating the carrier on which the coating layer is formed. The heat treatment may be performed subsequently in the coating apparatus after forming the protective layer, or may be performed by another heating means such as a normal electric furnace or a firing kiln after forming the protective layer.

  Since the heat treatment temperature varies depending on the constituent material of the protective layer to be used, it is not generally determined, but is preferably about 120 ° C. to 350 ° C., and particularly preferably not higher than the decomposition temperature of the protective layer constituent material. The decomposition temperature of the protective layer constituting material is preferably an upper limit temperature of up to about 220 ° C., and the heat treatment time is preferably about 5 minutes to 120 minutes.

-Physical properties of carriers-
The volume average particle diameter of the carrier is preferably in the range of 10 to 100 μm, and more preferably in the range of 20 to 65 μm. When the volume average particle diameter of the carrier is less than 10 μm, carrier adhesion may occur due to a decrease in the uniformity of the core material particles. When the volume average particle diameter exceeds 100 μm, reproducibility of image details is poor and fine. An image may not be obtained.

  The method for measuring the volume average particle size is not particularly limited as long as it is a device capable of measuring the particle size distribution, and can be measured using, for example, a Microtrac particle size distribution analyzer: Model HRA9320-X100 (manufactured by Nikkiso Co., Ltd.). .

  The volume resistivity of the carrier is preferably 9 [log (Ω · cm)] or more and 16 [log (Ω · cm)] or less, preferably 10 [log (Ω · cm)] or more and 14 [log (Ω · cm)]. cm)]] or less. When the volume resistivity is less than 9 [log (Ω · cm)], carrier adhesion occurs in the non-image area, and when the volume resistivity is more than 16 [log (Ω · cm)], it is not preferable at the edge portion during development. The so-called edge effect, in which the image density is enhanced, is not preferable. The volume resistivity can be arbitrarily adjusted within this range by adjusting the film thickness of the protective layer of the carrier and the content of the conductive fine particles as necessary.

  The volume resistivity is measured by filling a cell made of a fluororesin container containing electrodes 1a and 1b having a distance between electrodes of 0.2 cm and a surface area of 2.5 cm × 4 cm, and dropping height: Tapping is performed under the conditions of 1 cm, tapping speed: 30 times / min, and tapping frequency: 10 times. Next, a DC voltage of 1000 V was applied between both electrodes, and a resistance value r [Ω] after 30 seconds was measured with a high resistance meter 4329A (manufactured by Yokogawa Hewlett Packard: High Resistance Meter), and the following formula (3) The volume resistivity R [log (Ω · cm)] can be calculated by calculating as follows.

  R = log {r [Ω] × (2.5 [cm] × 4 [cm]) / 0.2 [cm]} (3)

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably such that the mass ratio of the toner to the carrier is 2.0 to 12.0% by mass, More preferably, it is 2.5-10.0 mass%.

(Image forming method and image forming apparatus)
The image forming method includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, and a recycling step. , Including control steps.
The image forming apparatus includes at least a photosensitive member, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. Further, other units appropriately selected as necessary, for example, static elimination Means, cleaning means, recycling means, control means and the like.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on a photosensitive member (also referred to as an electrostatic latent image carrier).
The photoconductor is not particularly limited as to the material, shape, structure, size, etc., and can be appropriately selected from known ones. For example, the shape is preferably a drum shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the photoconductor and then performing imagewise exposure, and can be performed by the electrostatic latent image forming unit.
The electrostatic latent image forming unit includes, for example, at least a charger that uniformly charges the surface of the photoconductor and an exposure device that exposes the surface of the photoconductor imagewise.
The charging can be performed, for example, by applying a voltage to the surface of the photoreceptor using the charger.

The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. Non-contact charger using corona discharge such as a charger, corotron and scorotron.
The charger is preferably one that is arranged in contact or non-contact with the photosensitive member and charges the surface of the photosensitive member by applying DC and AC voltages in a superimposed manner.
Further, it is preferable that the charger is a charging roller that is disposed in close contact with the photosensitive member via a gap tape and charges the surface of the photosensitive member by applying a direct current and an alternating voltage to the charging roller in a superimposed manner. .

The exposure can be performed, for example, by exposing the surface of the photoconductor imagewise using the exposure device.
The exposure device is not particularly limited as long as the surface of the photoreceptor charged by the charger can be exposed like an image to be formed, and can be appropriately selected according to the purpose. Examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of the said photoreceptor.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using the developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the developer, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using the developer, and can be appropriately selected from known ones. For example, it is preferable to have at least a developing device that houses the developer and can apply the developer to the electrostatic latent image in a contact or non-contact manner, and a developing device including the developer-containing container. Is more preferable.

  The developing device may be a single color developing device or a multicolor developing device.For example, a stirrer for charging the developer by friction stirring and a rotatable magnet roller. What has is mentioned suitably.

In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is applied to the surface of the photoconductor by an electric attractive force. Moving. As a result, the electrostatic latent image is developed with the toner to form a visible image with the toner on the surface of the photoreceptor.
The developer accommodated in the developing device is the developer.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.

  The transfer can be performed, for example, by charging the photoreceptor using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.

The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium, and may be performed each time the developer of each color is transferred to the recording medium, or may be laminated on the developer of each color. May be performed simultaneously at the same time. The fixing step can be performed using a fixing device.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.

The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
Depending on the purpose, for example, a known optical fixing device may be used together with or instead of the fixing step and the fixing unit.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the photoconductor, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited and may be any appropriate neutralization neutralizer as long as it can apply a neutralization bias to the photosensitive member. For example, a neutralization lamp is preferable. .

The cleaning step is a step of removing the toner remaining on the photoconductor, and can be suitably performed by a cleaning unit.
The cleaning unit is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the photoconductor can be removed. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, and the like are preferable.

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

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

<One Embodiment of Image Forming Apparatus>
Hereinafter, an embodiment of an image forming apparatus of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic diagram illustrating a tandem type image forming apparatus.
Around the photosensitive drum 01, which is an image carrier, a charging device 02 for charging the drum surface, exposure 03 with a laser beam for forming a latent image on a uniformly charged surface, a latent image on the drum surface Developing device 05 for forming a toner image by adhering charged toner to the surface, transfer device 07 for transferring the toner image on the formed drum to a transfer target, and a cleaning device for removing residual toner on the drum 012 are arranged in order.

  A toner replenishing container 04 for storing replaceable toner, connected to the developing device, and supplying the toner into the developing device is disposed above the developing device. Here, the toner supply container is configured to directly convey the toner into the developing container. However, the toner supply container may be configured to supply the toner to the developing container by providing a supply path in the main body of the image forming apparatus.

  In tandem type electrophotography, monochromatic images such as black, magenta, cyan and yellow are mainly formed on the surface of the photoreceptor. One of these four may be replaced with the glittering toner of the present invention, or a unit for glittering toner may be added. Note that colors other than these, colors having different densities, and those that form a colorless and transparent image may be used in combination.

  In such a configuration, when image formation is performed by a negative positive method (lowering the exposure portion potential and attaching toner), the photosensitive member 01 whose surface is uniformly negatively charged by the charging roller 02 ′ of the charging device 02. , An electrostatic latent image is formed on the surface of the photoconductor by exposure 03, and toner is attached to the surface of the photoconductor by the developing device 05 to visualize the image.

  The toner image is transferred from the surface of the photosensitive drum 01 by the transfer device 07 including the transfer belt 013 and the residual toner component that has not been transferred from the photosensitive member 01 to the transfer belt 013 is photosensitive by the cleaning blade 011 of the cleaning device 012. It is removed from the body surface. The toner image transferred to the surface of the transfer belt is transferred to the recording paper conveyed from the paper feed tray by applying a bias to the secondary transfer roller 08 at the secondary transfer portion. The residual toner component or the external additive component after the transfer is removed by the cleaning member 014. The toner image transferred to the recording paper is welded onto the recording paper by the fixing device 09 and discharged from the paper discharge port.

  In the figure, reference numeral 015 denotes a sensor used to adjust the image density and alignment by measuring the amount of toner deposited on the intermediate transfer belt 013 and the position of each color, and combines regular reflection and diffuse reflection. .

In the figure, reference numeral 016 denotes a cleaning unit for cleaning the toner remaining on the surface of the intermediate transfer belt, and the cleaning blade 014 is in contact with the belt moving direction so as to be a counter, and is made of metal cleaning so as to face the belt. A counter roller 017 is provided.
The toner removed by the cleaning blade is conveyed by a coil 018 or the like and stored in a waste toner storage unit.

(Process cartridge)
The process cartridge of the present invention has a photoconductor and a developing unit that develops the electrostatic latent image on the photoconductor with a developer, and is detachable from the main body of the image forming apparatus.
FIG. 2 shows a schematic diagram of an embodiment of a process cartridge. This embodiment is an example of a process cartridge connected with a toner supply container. The toner cartridge 031 is connected to the process cartridge of the present embodiment, and it is preferable that the toner supply container is always stirred with a stirring paddle 030 or the like in order to maintain the fluidity of the toner.

  In the toner replenishing container, toner can be transported by a conveying means 032 such as a screw or a coil toward a toner replenishing port corresponding to a connecting portion with a developing device or an image forming apparatus toner replenishing path. The means is configured to be connectable to the main body drive unit, and the main body drive unit and the transport unit can be controlled to be connected or disconnected by a known method such as a clutch, and the toner replenishment drive can be freely performed. The toner replenishment amount can be controlled by the drive time of the drive unit. For example, control such as changing the drive time in accordance with the color of the toner or in response to the change in toner fluidity in a temperature and humidity environment. Is also possible.

  In the developing device 033, a toner transport member 037 such as a screw for transporting the toner replenished from the upper toner replenishing container to the entire longitudinal direction, an agitator 034 for stirring the toner in the device, and a developing roller which is a toner carrier 035, a supply roller 036 mainly made of sponge material that can supply toner to the developing roller, a regulating blade 041 that regulates the amount of toner on the developing roller and rubs and charges the toner to the developing roller, It consists of a power supply that applies a voltage to the supply roller and the regulating blade.

  The toner moved to the developing roller 035 by the supply roller 036 is made uniform on the toner layer adhering to the surface of the developing roller by the regulating blade 041, and then an amount of toner corresponding to the surface potential of the photosensitive drum 042 is transferred to the photosensitive drum 042. Is transferred to the transfer material by the transfer means. As described above, the toner that has moved to the photosensitive drum 042 and remains on the photosensitive member as a transfer residue is removed by the cleaning unit, and then collected by installing a waste toner cartridge in the image forming apparatus.

  In the present specification, a tandem type image forming apparatus is described as an example of an image forming apparatus. However, the present invention is not limited to this, and is used for a rotary type image forming apparatus or an image forming apparatus for only one color. Is included.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. “Parts” represents “parts by weight” unless otherwise specified.

Example 1
<Preparation of aqueous phase>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 16 parts of sodium salt Eleminol RS-30 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) of sulfate of ethylene oxide adduct of methacrylic acid, 83 parts of styrene, 83 of methacrylic acid Parts, 110 parts of n-butyl acrylate and 1 part of ammonium persulfate were added, followed by stirring at 400 rpm for 15 minutes. Next, after heating up to 75 degreeC, it was made to react for 5 hours. Further, 30 parts of a 1% by mass aqueous ammonium persulfate solution was added, followed by aging at 75 ° C. for 5 hours to obtain [Vinyl resin dispersion]. Using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.), the volume average particle diameter of [vinyl resin dispersion] was measured and found to be 14 nm. The vinyl resin had an acid value of 45 mg KOH / g, a weight average molecular weight of 300000, and a glass transition point of 60 ° C.
Next, 455 parts of water, 7 parts of [vinyl-based resin dispersion], 17 parts of 48.5% by weight aqueous solution of sodium dodecyldiphenyletherdisulfonate MON-7 (manufactured by Sanyo Chemical Industries) and 41 parts of ethyl acetate are mixed and stirred. [Aqueous phase] was obtained. (Total 520 copies)

<Synthesis of wax dispersant 1>
In a reaction vessel equipped with a stirrer and a thermometer, 480 parts of xylene and 100 parts of paraffin wax HNP-9 (Nippon Seiki Co., Ltd.) were added and heated until dissolved, then purged with nitrogen and heated to 170 ° C. did. Next, a mixture of 740 parts of styrene, 100 parts of acrylonitrile, 60 parts of butyl acrylate, 36 parts of di-t-butylperoxyhexahydroterephthalate and 100 parts of xylene is dropped in 3 hours, and then kept at 170 ° C. for 30 minutes. did. Further, the solvent was removed to obtain [Wax Dispersant 1].

<Preparation of wax dispersion W1>
In a container equipped with a stir bar and a thermometer, 150 parts of paraffin wax HNP-9 (manufactured by Nippon Seiki Co., Ltd.), 15 parts of [Wax Dispersant 1] and 335 parts of ethyl acetate were added and then stirred at 80 ° C. The temperature was raised to 80 ° C. and maintained at 80 ° C. for 5 hours. Next, after cooling to 30 ° C. for 1 hour, using a bead mill Ultra Visco Mill (manufactured by IMEX), the liquid feeding speed is 1 kg / h, the peripheral speed of the disk is 6 m / s, and the diameter is 0.5 mm. Filled with 80% by volume of zirconia beads and dispersed under conditions of 3 passes, to obtain [Wax Dispersion Liquid W1]. The particle size of the obtained wax dispersion was 350 nm as measured with LA-920 (manufactured by Horiba Seisakusho). (Wax solid content concentration 22.6%)

<Synthesis of Amorphous Polyester Resin R2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen insertion tube, 222 parts of an ethylene oxide 2 mol adduct of bisphenol A, 129 parts of a propylene oxide 2 mol adduct of bisphenol A, 166 parts of isophthalic acid and 0.5 of tetrabutoxy titanate After adding a part, it was made to react at 230 degreeC for 8 hours, distilling off the water to produce | generate under nitrogen stream. Next, after making it react under reduced pressure of 5-20 mmHg and cooling to 180 ° C. (normal pressure) when the acid value becomes 2 mg KOH / g, 35 parts of trimellitic anhydride is added and reacted for 3 hours. Amorphous polyester resin R2] was obtained. [Amorphous polyester resin R2] had a weight average molecular weight of 8000 and a glass transition point of 62 ° C.

<Preparation of oil phase>
In a container equipped with a thermometer and stirrer,
-[Amorphous polyester resin R2] 100 parts-105 parts of ethyl acetate was added and dissolved by stirring.

here,
-[Wax dispersion W1] 22 parts-Bright pigment: 20 parts of small particle size aluminum paste pigment (solid content)
(Toyo Aluminum 2173YC (propyl acetate dispersion, solid content 50%))
Yellow pigment: C.I. I. After adding 1.6 parts of Pigment Yellow 139, the mixture was mixed for 1 hour at 5000 rpm while keeping the internal temperature at 20 ° C. in an ice bath using a TK homomixer (manufactured by Tokushu Kika). To obtain a solid content concentration of 50% by mass to obtain [Oil Phase 1]. (Solid content 48.2%)

  Subsequently, 550 parts of [aqueous phase] were put in a container equipped with a stirrer and a thermometer, and then kept at 20 ° C. on a water bath.

  Next, 450 parts of [Oil Phase 1] maintained at 20 ° C. is added, and while maintaining the temperature at 20 ° C., the mixture is mixed for 1 minute at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). An emulsified slurry] was obtained. The oil droplets obtained by observation with an optical microscope had a flat shape. [Emulsified slurry] was put in a container equipped with a stirrer and a thermometer, and then the solvent was removed at 40 ° C. under reduced pressure to obtain 80% slurry in terms of solid content in oil droplets.

  While maintaining the obtained slurry at 20 ° C., the mixture was mixed at 8000 rpm for 5 minutes using a TK type homomiser (manufactured by Tokushu Kika Kogyo Co., Ltd.), and a shear stress was applied to the slurry. Observation with an optical microscope revealed that the obtained oil droplets had a shape close to an ellipsoid. Further, the solvent was removed at 40 ° C. under reduced pressure to obtain a slurry in which the volatile portion of the organic solvent was 0%.

  Next, the obtained slurry was filtered under reduced pressure. 200 parts of ion-exchanged water was added to the filter cake, mixed for 5 minutes at 800 rpm using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.), reslurried and then filtered. Further, 10 parts of a 1% by mass sodium hydroxide aqueous solution and 190 parts of ion-exchanged water were added to the filter cake, reslurried in the same manner, and then filtered. Next, 10 parts of 1% by mass hydrochloric acid and 190 parts of ion-exchanged water were added to the filter cake and reslurried in the same manner, followed by filtration. Further, 300 parts of ion-exchanged water was added to the filter cake, reslurried, and then the operation of filtering was repeated twice.

The filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and then sieved using a mesh having an opening of 75 μm to obtain [base particles].
[Mass particles] 100 parts and 1 part of hydrophobized silica HDK-2000 (manufactured by Wacker Chemie) were mixed for 30 seconds at a peripheral speed of 30 m / s using a Henschel mixer (manufactured by Mitsui Mining). The operation of resting for 1 minute was repeated 5 times. Next, sieving was performed using a mesh having an opening of 35 μm to obtain [Toner] of Example 1.

(Examples 2-9, Comparative Examples 1-2)
The same procedure as in Example 1 was conducted except that the type of yellow pigment and the number of added yellow pigments per 100 parts by weight of the bright pigment were changed to those shown in Table 1, and Examples 2 to 9 and Comparative Examples 1 and 2 were used. A toner was obtained.
“P.Y.” represents “CI Pigment Yellow”, and “PR” represents “CI Pigment Red”.

(Example 10)
Example 1 except that the kind of yellow pigment and the number of added parts of the yellow pigment relative to 100 parts by weight of the bright pigment are changed to those shown in Table 1, and the magenta pigment is also added with the kinds and amounts shown in Table 1. Thus, the toner of Example 10 was obtained.

(Comparative Example 3)
A toner of Comparative Example 3 was obtained in the same manner as in Example 1 except that no yellow pigment was added.

(Comparative Example 4)
A toner of Comparative Example 4 was obtained in the same manner as in Example 1 except that a bright pigment obtained by grinding aluminum powder with a ball mill was used.

(Evaluation method)
<Arrangement of glitter pigment>
The obtained toner was subjected to elemental analysis with EDS while observing the cross section of the toner particles with SEM, and it was confirmed whether or not the glitter pigment was disposed inside the toner. As a result, in the toners obtained in Examples and Comparative Examples 1 to 3, the bright pigment was disposed inside the toner, and the toner obtained in Comparative Example 4 was disposed on the surface.

<Soil dirt>
Using a RICOH color electrophotographic apparatus (RICOH MP C6003), after 10,000 white solid images were output, the toner adhered to the photosensitive member during white solid image printing was peeled off with a scotch tape and pasted on a white paper. . Using a spectrodensitometer, ΔE (color difference) with the tape attached to the same white paper as it was was measured using X-Rite 938, and evaluated in four stages.

〔Evaluation criteria〕
◎: ΔE is less than 3 ○: ΔE is 3 or more and less than 5 △: ΔE is 5 or more and less than 7 ×: ΔE is 7 or more

<Hue>
Using Image Neo Neo C600 Pro (manufactured by Ricoh Co., Ltd.), on the coated paper (POD gloss coated paper, manufactured by Oji Paper Co., Ltd.), the toner adhesion amount is 0.50 ± 0.10 mg / cm ² and the size is 3 cm × 8 cm. A solid image was formed and the output image was evaluated. For the measurement, hue angle was used with X-Rite 938 manufactured by X-Rite. The hue was judged by the hue angle, and the following criteria were used. “△” or higher was regarded as an acceptable level.

〔Evaluation criteria〕
◎: 80 ° or more and less than 95 ° ○: 75 ° or more and less than 80 °, or 95 ° or more and less than 105 ° △: 65 ° or more and less than 75 °, or 105 ° or more and less than 115 ° ×: less than 65 °, or 115 ° or more

When the hue angle falls within the range of the above evaluation criteria, the obtained image is as follows. In the case of Δ or more, it can be said that the glitter and the color are good.
◎: Beautiful gold color ○: Yellow / red is a little anxious △: Yellow / red is anxious ×: It cannot be said to be gold

  Table 1 shows the formulations and evaluation results of the toners obtained in the examples and comparative examples. In Table 1, the addition amount of the yellow pigment is the addition amount with respect to 100 parts by weight of the glitter pigment, and similarly, the addition amount of the magenta pigment is the addition amount with respect to 100 parts by weight of the glitter pigment.

  As shown in Table 1, it can be seen that the toners obtained in the examples have a good background stain evaluation and suppress the decrease in charge. This is because, in addition to the suppression of the decrease in charge due to the use of the isoindoline pigment, the decrease in the charge is further suppressed by arranging the glitter pigment inside the toner. In addition, it can be seen that the toner obtained in the example has a hue angle in a desired range, and a glossy toner having a good color can be obtained.

01 Photosensitive drum (electrostatic latent image carrier)
02 Charging device 02 ′ Charging roller 03 Exposure 04 Toner supply container 05 Developing device 07 Transfer device 08 Secondary transfer roller 09 Fixing device 010 Waste toner receiver 011 Cleaning blade for photoconductor 012 Cleaning device 013 Intermediate transfer belt 014 Cleaning for intermediate transfer belt Blade 015 Sensor 016 Intermediate transfer belt cleaning unit 017 Cleaning counter roller 018 Coil 030 Stir paddle 031 Toner supply container 032 Conveying means 033 Developing device 034 Agitator 035 Developing roller 036 Supply roller 037 Toner transport member 038 Toner chamber 039 Cleaning blade for photoconductor 040 Waste toner conveying screw 041 Regulating blade 042 Photosensitive drum 50 Toner 51 Bright pigment

JP 2014-134636 A JP 2012-163695 A

Claims (8)

A toner comprising a glitter pigment and a color pigment,
The glitter pigment is present in the toner,
The colored pigment includes a yellow pigment,
A toner wherein the yellow pigment is an isoindoline pigment.   The isoindoline pigment is C.I. I. The toner according to claim 1, which is CI Pigment Yellow 185.   The toner according to claim 1, wherein the color pigment is contained in an amount of 10 to 35 parts by weight with respect to 100 parts by weight of the glitter pigment.   The toner according to claim 1, wherein the color pigment includes a magenta pigment.   A developer using the toner according to claim 1. A process cartridge having a photoconductor and a developing unit that develops the electrostatic latent image on the photoconductor with a developer;
The process cartridge according to claim 5, wherein the developer is the developer according to claim 5. A photoreceptor,
Electrostatic latent image forming means for forming an electrostatic latent image on the photoreceptor;
Developing means for developing the electrostatic latent image using a developer to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the visible image transferred to the recording medium,
The image forming apparatus according to claim 5, wherein the developer is the developer according to claim 5. An electrostatic latent image forming step of forming an electrostatic latent image on the photoreceptor;
Developing the electrostatic latent image using a developer to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A fixing step of fixing the visible image transferred to the recording medium,
The image forming method according to claim 5, wherein the developer is the developer according to claim 5.